Encyclopedia of Chemical Processing and Design: 69 Supplement 1

Rayford G. Anthony John J. McKetta

Marcel Dekker, Inc.

Encyclopedia of Chemical Processing and Design

Rayford G. Anthony John J. McKetta


Supplement 1

Library of Congress Cataloging in Publication Data Main entry under title: Encyclopedia of chemical processing and design. Includes bibliographic references. 1. Chemical engineering—Dictionaries 2. Technical—Dictionaries. I. McKetta, John J. II. Cunningham, William Aaron. Tp9.E66 660.2′8′003 ISBN: 0-8247-2621-9 Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 10016 tel: 212-696-9000; fax: 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-261-8482; fax: 41-61-261-8896 World Wide Web http://www.dekker.com COPYRIGHT  2002 by MARCEL DEKKER, INC. ALL RIGHTS RESERVED. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher.

Chemistry, 75-40646

MARCEL DEKKER, INC. 270 Madison Avenue, New York, New York, 10016

Current printing (last digit): 10 9 8 7 6 5 4 3 2 1


Contributors to Volume 69
Steve Chum, Ph.D. Research Fellow, The Dow Chemical Company, Polyolefins Research, Freeport, Texas: Structure, Properties, and Applications of Polyolefins Produced by Single-Site Catalyst Technology Ray A. Cocco, Ph.D. Senior Specialist, The Dow Chemical Company, Midland, Michigan: Circulating Fluidized Bed Reactors: Basic Concepts and Hydrodynamics David M. Fishbach, P.E. Senior Consulting Engineer, Starfire Electronic Development & Marketing, Ltd., Bloomfield Hills, Michigan: Nanophase Materials in Chemical Process Avery N. Goldstein, Ph.D. Research Director, Starfire Electronics Development & Marketing, Ltd., Bloomfield Hills, Michigan: Nanophase Materials in Chemical Process Manfred Grove Senior Partner, Intermacom A.G., Technology Consultants, Auerich, Switzerland: Introduction to the Selective Catalytic Reduction Technology Dennis Hendershot Rohm and Haas Company, Bristol, Pennsylvania: Fundamentals of Process Safety and Risk Management Trevor A. Kletz Process Safety Consultant, Cheshire, United Kingdom: Fundamentals of Process Safety and Risk Management Fu-Ming Lee, Ph.D. Director of Technology, GTC Technology Corporation, Houston, Texas: Recent Development of Extractive Distillation: A Distillation Alternative Jim Makris Director, Chemical Emergency Preparedness and Prevention Office, U.S. Environmental Protection Agency, Washington, D.C.: Process Safety and Risk Management Regulations: Impact on Process Safety M. Sam Mannan, Ph.D., P.E. Associate Professor of Chemical Engineering, Mary Kay O’Connor Process Safety Center, Texas A&M University, College Station, Texas: Fundamentals of Process Safety and Risk Management; Process Safety and Risk Management Regulations: Impact on Process Industry Rajen M. Patel, Ph.D. Technical Leader, The Dow Chemical Company, Polyolefins Research, Freeport, Texas: Structures, Properties, and Applications of Polyolefins Produced by Single-Site Catalyst Technology H. James Overman Dow Chemical Company, Freeport, Texas: Process Safety and Risk Management Regulations: Impact on Process Industry iii


Contributors to Volume 69 Michael V. Pishko, Ph.D. Assistant Professor, Department of Chemical Engineering, Texas A&M University, College Station, Texas: Recent Advances in Biomaterials Alan W. Weimer, Ph.D., P.E. Professor of Chemical Engineering, University of Colorado, Boulder, Colorado: Effect of Pressure and Temperature in Bubbling Fluidized Beds

Fishbach Process Safety and Risk Management Regulations: Impact on Process Industry M. Jim Makris. Goldstein and David M. James Overman Recent Advances in Biomaterials Michael V. Weimer Fundamentals of Process Safety and Risk Management M. and Trevor A. Properties. and Applications of Polyolefins Produced by Single-Site Catalyst Technology Rajen M. Dennis Hendershot.CONTENTS OF VOLUME 69 Contributors to Volume 69 Conversion to SI Units Bringing Costs up to Date Circulating Fluidized Bed Reactors: Basic Concepts and Hydrodynamics Ray A. Cocco Effect of Pressure and Temperature in Bubbling Fluidized Beds Alan W. and H. Kletz Introduction to the Selective Catalytic Reduction Technology Manfred Grove Nanophase Materials in Chemical Process Avery N. Sam Mannan. Pishko Recent Development of Extractive Distillation: A Distillation Alternative Fu-Ming Lee Structure. Sam Mannan. Patel and Steve Chum iii vii ix 1 35 49 94 150 168 194 207 231 v .


305 2.52 10 2 4.45 10 3 0.0 10 7 1.) grain gram horsepower horsepower (boiler) horsepower (electric) hundred weight (long) hundred weight (short) inch inch mercury inch water kilogram force kip knot (international) league (British nautical) league (statute) To square meter (m 2 ) meter (m) square meter (m 2 ) newton/square meter (N/m 2 ) newton/square meter (N/m 2 ) cubic meter (m 3 ) joule (J) joule (J) joule (J) cubic meter (m 3 ) joule (J) joule (J) joule (J) newton/square meter (N/m 2 ) newton/square meter (N/m 2 ) meter (m) radian (rad) kilogram/meter (kg/m) kilogram (kg) kilogram (kg) cubic meter (m 3 ) newton (N) joule (J) joule (J) cubic meter (m 3 ) meter (m) meter (m) cubic meter (m 3 ) cubic meter (m 3 ) cubic meter (m 3 ) kilogram (kg) kilogram (kg) watt (W) watt (W) watt (W) kilogram (kg) kilogram (kg) meter (m) newton/square meter (N/m 2 ) newton/square meter (N/m 2 ) newton (N) newton (N) meter/second (m/s) meter (M) meter (m) Multiply by 4.386 10 3 2.457 10 2 9.806 4.888 10 3 3.46 10 2 50.01 10 2 4.S.056 10 3 1.054 10 3 3.54 10 2 3.0 10 2 1.81 10 3 7.) foot furlong gallon (U.559 10 3 4. dry) gallon (U.697 10 6 1.404 10 3 3.046 10 3 1.48 10 5 1.96 10 5 0.457 1.184 1.0 10 10 1.49 10 2 9.Conversion to SI Units To convert from acre angstrom are atmosphere bar barrel (42 gallon) Btu (International Steam Table) Btu (mean) Btu (thermochemical) bushel calorie (International Steam Table) calorie (mean) calorie (thermochemical) centimeter of mercury centimeter of water cubit degree (angle) denier (international) dram (avoirdupois) dram (troy) dram (U.60 10 19 1. fluid) dyne electron volt erg fluid ounce (U.06 0.183 10 4 6.0 10 7 2.36 2.S.055 10 3 1.785 10 3 1.190 4.333 10 3 98.772 10 3 3.S.0 10 5 1.80 45.0 10 3 7. liquid) gill (U.159 1.745 10 2 1.S.013 10 5 1.187 4.S.83 10 3 vii .0 10 5 0.5144 5.

dry) pint (U.S.46 10 15 0.333 10 2 79.58 0.448 0.555 10 3 5.072 10 2 1. liquid) rod roentgen second (angle) section slug span stoke ton (long) ton (metric) ton (short. nautical) mile (U. liquid) poise pound force (avoirdupois) pound mass (avoirdupois) pound mass (troy) poundal quart (U. statute) millibar millimeter mercury oersted ounce force (avoirdupois) ounce mass (avoirdupois) ounce mass (troy) ounce (U.229 1.609 10 3 100.S.03 2.333 10 2 0.S.914 meter (m) cubic meter (m 3 ) meter (m) meter (m) meter (m) meter (m) newton/square meter (N/m 2 ) newton/square meter (N/m 2 ) ampere/meter (A/m) newton (N) kilogram (kg) kilogram (kg) cubic meter (m 3 ) newton/square meter (N/m 2 ) cubic meter (m 3 ) kilogram (kg) cubic meter (M 3 ) cubic meter (m 3 ) newton second/square meter (N ⋅ s/m 2 ) newton (N) kilogram (kg) kilogram (kg) newton (N) cubic meter (m 3 ) cubic meter (m 3 ) meter (m) coulomb/kilogram (c/kg) radian (rad) square meter (m 2 ) kilogram (kg) meter (m) square meter/second (m 2 /s) kilogram (kg) kilogram (kg) kilogram (kg) newton/square meter (N/m 2 ) meter (m) . 2000 pounds) torr yard To Conversion to SI Units Multiply by 9.S.138 1.835 10 2 3.278 2.0 10 6 2.4536 0.732 10 4 0.11 10 2 2.10 10 3 9.S.016 10 3 1.96 10 5 1.001 1.0 10 4 1.852 10 3 1.579 10 4 4.10 4.0 8.46 10 4 5. dry) quart (U.S.85 10 6 2.0 10 3 9.506 10 4 4.81 10 3 1. fluid) pascal peck (U.373 0.) pennyweight pint (U.S.59 0.0 1.59 10 6 14.S.54 10 6 1.viii To convert from light year liter micron mil mile (U.

2 368.0 303.4 323.5 182.8 342.9 322.5 355.6 852.1 381.1 398.5 239.3 84.2 359.6 797.3 332.0 316. quarterly Marshall and Swift (M&S) Equipment Cost Index.4 182.3 180. The differences in overall results of each index are due to uneven price changes for each element.1 915.1 964.7 261.2 234.2 107.8 102.4 81.1 285.1 381.3 137.2 109.4 103.6 190.6 943. In other words.2 238.0 101. updated monthly CE Plant Cost Index (Chemical Engineering).3 358.9 80.2 297.4 444.5 M&S Index 344. the proportion allotted to each element differs with each index.6 119.6 813.1 165.1 505.4 659.1 204.5 99.1 229.4 1027.3 93.7 113. However.9 98.2 1056.1 88.3 321.7 386.2 M&S Index 167.7 325. updated monthly ENR Construction Cost Index (Engineering News-Record).0 314.5 262. updated quarterly All of these indexes were developed with various elements such as material availability and labor productivity taken into account.6 361.6 208.9 180.0 125.0 895.7 237. Several published cost indexes are widely used in the chemical process industries: Nelson Cost Indexes (Oil and Gas J.8 780.3 599. TABLE 1 Chemical Engineering and Marshall and Swift Plant and Equipment Cost Indexes since 1950 Year 1950 1951 1952 1953 1954 1955 1956 1957 1958 1959 1960 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 1972 CE Index 73.7 86.5 1039.). updated weekly Vatavuk Air Pollution Control Cost Indexes (VAPCCI) (Chemical Engineering).9 252.6 721.7 101.0 102.2 993.1 218.1 930.0 Year 1973 1974 1975 1976 1977 1978 1979 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 CE Index 144.5 237.Bringing Costs up to Date Cost escalation via inflation bears critically on estimates of plant costs.2 241.3 472.3 745.4 357. Historical costs of process plants are updated by means of an escalation factor.4 545.3 104.7 132.4 789.4 192.3 318.5 102.6 760.5 184.8 244.9 273.8 225.8 ix .8 238.

3 421.1 756.2 163.4 280.0 364.0 122.8 415.3 739.0 445.7 1252.0 286.9 222.9 622.7 575.1 732.9 1025.4 684.0 137.6 220.x Bringing Costs up to Date TABLE 2 Nelson-Farrar Inflation Petroleum Refinery Construction Indexes since 1946 (1946 100) Materials Component 100.3 254.9 1121.9 206.9 423.4 1487.4 578.1 190.7 161.2 832.8 211.5 827.5 294.0 291.8 438.3 172.9 1044.9 250.5 192.2 707.2 183.2 471.5 1164.0 748.2 157.9 331.1 261.1 234.3 516.8 441.9 226.6 1330.7 304.4 174.0 951.4 310.2 208.4 231.1 144.0 1405.8 903.1 515.9 545.4 206.5 468.3 268.5 265.6 730.4 139.2 623.0 153.9 204.0 164.1 232.7 653.0 1370.1 824.1 121.8 665.6 673.6 207.2 1234.9 213.5 1195.5 143.5 769.1 200.8 656.8 829.6 585.1 158.8 184.6 241.2 122.1 228.8 1061.0 117.6 1440.6 176.6 822.0 438.5 164.2 474.0 701.8 1278.5 179.6 126.6 220.1 174.0 113.8 160.7 278.7 573.0 132.0 1074.4 361.6 712.6 173.7 205.5 Nelson Inflation Index 100.8 239.4 1089.9 249.2 693.5 180.3 205.6 252.3 373.7 146.2 1154.7 237.5 139.8 268.4 201.8 207.6 198.7 224.4 196.8 201.5 198.3 209.4 258.4 703.3 Miscellaneous Equipment 100.9 406.1 192.9 802.4 735.9 Date 1946 1947 1948 1949 1950 1951 1952 1953 1954 1955 1956 1957 1958 1959 1960 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 1972 1973 1974 1975 1976 1977 1978 1979 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 .4 391.3 357.3 189.1 629.1 228.1 1297.0 114.1 879.1 329.1 499.2 219.2 195.8 292.6 678.4 774.5 128.9 1225.0 522.7 1533.0 216.5 729.8 976.6 212.6 149.5 615.0 152.5 163.3 Labor Component 100.4 273.2 277.1 647.6 243.0 199.1 207.8 832.9 797.2 145.

2 1664. A the size of units for which the cost is known.9 1449. and for 1974 it was 165. To approximate a current cost. CB C A (B/A) n (I B /I A ) (3) For example. Since CB C A (B/A) n (1) Here. equipment.7 1392.1 923.1 1418.000. multiply the old cost by the ratio of the current index value to the index at the date of the old cost: CB C A I B /I A (2) index value at the date old cost.2 918. C A actual cost of unit A. n 0.8 1349. . find the cost of plant B at a throughput of 300 million lb/yr on the same basis for 1986.e. Via Eq. and I A Here. It is recommended that the CE Index be used for updating total plant costs and the M&S Index or Nelson-Farrar Index for updating equipment costs.1 879. Combining Eqs. be equal to 0. the CE Index for 1986 was 318.2 the total escalation derived by each index will vary because different bases are used. n.6 842. (1) and (2). expressed in the units of A.000 for 200million-lb/yr capacity in 1974.6.9 Labor Component 1579. if the total investment cost of plant A was $25.5 910. or volume. Let the sizing exponent. throughput. the six-tenths exponent). labor..5 1799.4. I B current index value.8 851.7 1708.Bringing Costs up to Date TABLE 2 Continued Materials Component 824.3 1310.1 1753. and general refinery inflation.7 877.6 (i. (3).5 903. The engineer should become familiar with each index and its limitations before using it. C A of old cost. B the size of unit for which a cost is required.2 1620.0 917. Table 1 compares the CE Plant Index with the M&S Equipment Cost Index. Table 2 shows the Nelson-Farrar Inflation Petroleum Refinery Construction Indexes since 1946. The Nelson-Farrar Indexes are better suited for petroleum refinery materials. From Table 1.5 xi Date 1992 1993 1994 1995 1996 1997 Nelson Inflation Index 1277. and C B the cost of B being sought for the same time period as cost C A .4.5 Miscellaneous Equipment 837.6 846. expressed in terms of capacity.

0 104.6 (318.1 108.4) $61.3 104.5 101. john j.5 100. see the Vatavuk Air Pollution Control Cost Indexes article in volume 61. see the article.3 1995 (Avg.5 104.5 100.7 107.5 105.8 103.3 108.2 119.0 108.0 102.8 CB C A (B/A) n (I B /I A ) 25.2 102.3 101.9 107.9 112.200.8 100.4 101. Control Device Carbon adsorbers Catalytic incinerators Electrostatic precipitators Fabric filters Flares Gas absorbers Mechanical collectors Refrigeration systems Regenerative thermal oxidizers Thermal incinerators Wet scrubbers 1994 (Avg. Editor’s note: For a more thorough explanation of updating costs. mcketta .0 104.7 107.xii Bringing Costs up to Date TABLE 3 Vatavuk Air Pollution Control Cost Indexes (VAPCCI).8 100.0 103.4 106.4 107.3 100.) 101.5 1996 (Avg. For details. ‘‘Tower Cost Updating’’ in volume 58.0 (index values have been rounded to the nearest tenth).000 Table 3 shows the Vatavuk Air Pollution Control Cost Indexes (VAPCCI) since 1994.0 (300/200) 0.) 106.4/165.4 105. First Quarter 1994 100.6 103.2 102.) 110.

Encyclopedia of Chemical Processing and Design 69 .


Standard Oil of Ohio (SOHIO) developed a fluidized-bed reactor for the ammoxidation of propene to acrylonitrile. However.000 tons per year [4]. 1 . nearly all large-scale acrylonitrile plants are based on the SOHIO design. The addition of steam. 2. With the addition of a stripping section after the reactor. as shown in Fig. or other inerts would remove the product from and around catalyst particles flowing toward the regenerator. the evolution of the FCC unit has results into several basic designs. The inherent hydrodynamics of fluidized beds. The separated particles are fed to an optional fluidized bed and then back to the riser. Today. even higher yields were obtained. The large-scale commercial realization of CFBs occurred in the early 1940s. circulating fluidized beds contributed to another breakthrough process for the petroleum and chemical industry. 1.e. In 1960. One design involves a fast-fluidized bed where high gas velocities convey a substantial amount of solids to one or more cyclones. The second basic design uses a riser to convey solids to one or more cyclones.and J-valves or using a mechanical slide valve. with capacities up to 180. SOHIO redesigned the acrylonitrile reactor to more of a ‘‘tube-and-shell’’ fluidized-bed unit [6]. where high catalyst circulation rates allowed a balance between the exothermic burning of coke on the catalyst in the regenerator and the endothermic hydrocracking of petroleum in the reactor. With the increased demand for gasoline during World War II. 3. Today. The result was a fluidized catalyst cracker (FCC). the Houndry Process) used at that time. CO 2. Solids flow rates can be controlled using nonmechanical L. major efforts were underway to develop reactors to crack petroleum feedstocks into usable fuels more productively than the moving bed or snake reactors (i. where solids and. as shown in Fig. To overcome backmixing. Previous technology was done in tube-and-shell fixed-bed reactors. would have a deleterious effect on acrylonitrile selectivity. gas circulate from the top of the bed to the bottom. then to the top again. The greatest challenge in developing the SOHIO process was in the management of backmixing. The high heat transfer characteristic of fluidized-bed reactors made them ideal for the production of acrylonitrile.Circulating Fluidized Bed Reactors: Basic Concepts and Hydrodynamics Introduction Circulating fluidized beds (CFBs) consist of two basic designs.. SOHIO developed sieve trays to compartmentalize the gas flow in the fluidized-bed reactor to resemble a more plug-flow characteristic [5]. The continuous circulation or regeneration of catalyst provided fresh catalyst for petroleum cracking and thereby resulted in high sustainable productivities. although some coal gasification was done in a fluidized bed as early as 1926 [1]. the high heat of reaction of 160 kcal/mol limited the economic feasibility of those units. In 1979. to a lesser extent. as shown in Fig. The separated particles are fed back to the fluidized bed using a standpipe.

2 and 3. (Adapted from Refs. (b) UOP. (c) Kellogg.2 Circulating Fluidized Bed Reactors FIG. 1 Basic design of circulating fluidized beds. FIG. and (d) Exxon.) . 2 Typical FCC units based on the designs of (a) Standard Oil Development.

The high-heat-transfer capabilities of these reactors resulted in lower operating temperatures.Circulating Fluidized Bed Reactors 3 FIG. oxychlorination Developer SOHIO BASF.) During the late 1970s and early 1980s oil crisis. oxidaton of methane Oxidation Ammono-dehydrogenation Butane oxidation Butane oxidation Butene oxidation Chlorination Naphthalene oxidation Ethlyene polymerization Fisher–Tropsch Ethylene chlorination. circulating fluidized beds are used in a wide array of chemical processes. With the surplus of oil starting in the late 1980s. Toatsu. With fluidized beds having the unique distinction of excellent heat transfer and continuous in situ regeneration. Monsanto . the economic attractiveness of processing thermally sensitive chemicals or using catalysts that require TABLE 1 Some Fluidized and Circulating Fluidized Bed Reactor Processes Product Acrolynitrile Aniline Chloromethanes Goal gasification Hydrocyanic acid Maleic anhydride Maleic anhydride Maleic anhydride Perchlorethlyene Phthalic anhydride Polyethylene Synthesis gas Vinyl chloride Process Propene ammoxidation Nitrobenzene hydrogenation Cat. Mitsui. as shown in Table 1. As of the early 1990s. Kellogg Ethyl. Cyanamid. Today. Lonza Asahi Glass Winkler Shawinigan Alusuisse & Lummus (Alma Process) DuPont Mitsubishi Diamond Shamrock Badger/Sherwin-Williams Union Carbide (Unipol) SASOL. fluidized-bed combustors became economically less attractive. thereby reducing NO x and SO 2 emissions. which provided uniform temperatures in the combustor. In addition. circulating fluidized beds found applications in coal combustion. only Dynergy (via the Destec process) and Lurgi and Ahlstrom are practicing this technology [7]. (Adapted from Ref. 5. the high gas velocities resulted in significant turbulence. Hoechst. 3 Two-dimensional schematic of the SOHIO acrylonitrile processes.

At first. the top of the bed becomes less defined. these reactors often set the standards in reactor design. Group C powders. The onset of bubbles in the fluidized bed is commonly referred to as bubbling fluidization. may even show signs of bubbling prior to minimum fluidization. As the gas velocity continues to increase. and attrition have been addressed. The gas permeates through the bed without the formation of bubbles. Particles move in a limited fluidlike fashion and the bed pressure drop becomes constant. but regular. This regime is referred to as smooth fluidization and is only observed for Geldart Group A powders (see Appendix A). Large amounts of particles are ejected into the freeboard region above the bed. With increasing velocity and under ideal conditions. These powders require noticeably higher gas velocities to promote the formation of gas bubbles after minimum fluidization. on average. Concurrently. fluctuations with time. as it was in the minimum and smooth fluidization regimes. Further increases in gas velocity results in further bed expansion and particles appear to freely move throughout the bed. Here. gas bubbles form at or near the distributor and grow to a maximum bubble size as they propagate through the bed. The pressure drop across the bed is still constant. the gas velocity is insufficient to fluidize the particles and the bed remains fixed. . At this point. sizeable regions of voidage and particle clusters are seen FIG. Basic Concepts As the gas velocity through a bed of solids increases. this is usually the result of channeling. the bed undergoes several regimes. 4. however. The top of the fluidized bed is still well defined. In contrast. 4 Various fluidization regimes with increasing superficial gas velocity.4 Circulating Fluidized Bed Reactors frequent regeneration are more realized. Once the obstacles of backmixing. Group B powders begin bubbling shortly after minimum fluidization. but starts exhibiting large. the bed is commonly referred to as undergoing minimum fluidization. being cohesive. the fixed bed expands smoothly and uniformly. mass transfer. as shown in Fig.

To overcome the losses of particles due to entrainment. In this regime. Minimum and Smooth Fluidization As a gas permeates through a fixed or packed bed. a core–annulus radial variation in particle density begins to take shape. Particle clusters and streamers are readily observed and. clusters and streamers are readily observed. This regime is commonly referred to as pneumatic conveying. axial variation in particle density is no longer observed. With the cost of these units running in the tens of millions of dollars for large-scale plants. In order to gain better understanding of these regimes. Thus. the pressure drop can be described by the Ergun equation [8]: ∆P gc L (1 ε bp )2µu g (1 ε bp )ρ g u 2 g ε 3 (Φd p ) 2 bp 150 ε 3 (Φd p ) 2 bp 1. attrition. suggesting that some sort of bed exists. nearly all the particles are entrained from the bed. from conveying in the riser to a bubbling fluidized-bed regime in the regenerator). Keep in mind that most of the correlations are empirical and may not fully represent every system. In the design of fluidized beds. The gas velocity at the onset of this type of fluidization is referred to as the minimum fluidization velocity or u mf. The particles become mobile and the bed becomes fluidized. the methodology used to determine the onset of each fluidization regime is discussed in the following sections. For dense systems. the bed reaches a point where the drag force exceeds the force of gravity on the particles.75 (1) With increasing gas velocity. knowledge of the fluidization regimes is paramount. At very high gas velocities. Particle density is still higher at the bottom of the unit compared to the top. and entrainment rates. Group C and D powders may show a slugging behavior prior to the turbulent fluidization regime. The simple transition from one regime to another can have significant impacts on reaction. Particle entrainment is high and the total disengagement height may be well beyond the physical dimensions of the fluidized-bed unit.Circulating Fluidized Bed Reactors 5 in the bed itself. this transition from the bubbling fluidized-bed regime is called the onset of turbulent fluidization. increases in the gas velocity results in dramatic and sometimes sharp transitions in the hydrodynamics.. Assuming that the weight . where several regimes may exist in a single unit (i. in some cases. heat transfer. experimental validation of the expected regimes is critical when designing these processes. for gas–solid systems. except maybe in entrance and exit regions. cyclones may be used to capture entrained particles and recirculate them back into the bed. For Group A and B powders. the gas velocity is sufficient enough that the surface of the bed can no longer be discerned.e. For circulating fluidized beds. During fast fluidization. it is crucial that one knows the fluidized regime that will exist at operating conditions. Radial variation in particle density can vary dramatically and range from a core–annulus profile to a uniform profile.

(6) can be rewritten as Re p. is defined as d 3 gρ g (ρ s p µ2 ρg) Ar (4) and Re p is the particle Reynolds number having the expression d p u mf ρ g µ Re p. mf Ar (6) By solving for Re p. mf. the Ergun equation can be written as 1. (7) .mf ε3 Φ 2 mf 1. Ar.75 2 Re p.6 Circulating Fluidized Bed Reactors of the particles in the fluidized bed corresponds to ∆P/L. Eq.mf K 2 Re p. Many correlations for the minimum fluidization velocity are based on Eq.mf (5) Equation (3) can be written as a quadratic with the coefficients K 1 and K 2 having the form K 1 Re 2 p.75 d p u mf ρ g ε3 Φ µ mf 2 150(1 ε mf ) d p u mf ρ g ε3 Φ 2 µ mf d 3 gρ g (ρ s p µ2 ρg) (2) or 150(1 ε mf ) Re p.mf ε3 Φ mf Ar (3) where the Archimedes number. mf K1 2K 2 2 Ar K1 0.5 K1 2K 2 (7) where the particle Reynolds number at minimum fluidization is a simple function of the Archimedes number and two constants (K 1 /2K 2 and 1/K 1 ).

2 28. 5 Minimum fluidization curve for smooth and round alumina particles. . round. Figure 5–8 demonstrate the results of such an experiment. less scatter in the data is obtained from larger or higher beds. the minimum fluidization velocity is the intersection of the linearly increasing line with the constant-pressure-drop line. With further increases in the gas velocity. the constants of Wen and Yu are most often used.0365 0.ave 60 µm.5-in.0494 Comments For fine particles Dolomite at high temperature and pressure For large particles for the constants K 1 /2K 2 and 1/K 1. [14] Source: Adapted from Ref.7 25. [12] Grace [13] Chitester et al. the pressure drop remains constant. When measuring the minimum fluidization velocity.0571 0. these correlations are specific to a group of particles with common characteristics and may not represent a less-thanideal particle morphology and texture.0651 0.3 27. For smooth.3 25.7 1/K1 0. (7) Reference Wen and Yu [9] Richardson [10] Saxena and Vogel [11] Bubu et al.5 cm/min. 5 suggests that perhaps a higher bed should have been used. d p.0408 0.-inner diameter fluidized bed unit. Hence.7 25.0408 0. The diameter of the fluidized bed used in this type of experiment is also FIG. These constants are presented in Table 2 for a wide range of studies. and noncohesive particles. For typical Geldart Group A powder. 7 K2 /2K1 33. Figure 5 is the pressure-drop curve for alumina particles with a mean particle diameter of 60 µm in a 4. The minimum fluidization velocity for these particles was determined to be 6. 7. The scatter in Fig. The minimum fluidization velocity can be experimentally determined by measuring the pressure drop across a bed of particles with increasing superficial gas velocity. the pressure drop increases linearly with gas velocity until the minimum fluidization velocity is reached.Circulating Fluidized Bed Reactors TABLE 2 K1 and K2 Values for Eq. However.

rough. the two curves should overlap each other. The black data points are the pressure drop with increasing gas velocity and the gray data points are the subsequent pressure-drop measurements with decreasing gas velocities. Figure 6 shows two pressure drop versus superficial gas velocity curves for the same particles used in Fig. a hysterisis effect is typically observed. d p. 6. and noncohesive particles. bed diameters less than 3 in. For the coarser Group B powders. This is obvious in Fig.ave 92 µm.ave increasing and decreasing gas velocities. with critical to obtaining accurate data. 7 Minimum fluidization curve for rough alumina particles. for irregular. as shown in Fig. can result in experimental data that are influenced by frictional effects at the wall. However. 5. . 7 for rough and irregularly shaped alumina particles with FIG. For Geldart Group A powders. 6 Minimum fluidization curve for smooth and round alumina particles. d p. or cohesive particles. 60 µm. smooth. the minimum diameter is much larger. For round.8 Circulating Fluidized Bed Reactors FIG.

8 is the result of another channel achieving fluidization while the majority of the bed remains fixed. Also. smaller bubbles tend to be completely spherical.ave 68 µm. Oddly enough. it is almost impossible to detect the minimum fluidization velocity. a mean particle diameter of 92 µm. Here. Higher pressures or temperatures result in a decrease in the maximum bubble size (due to changes in the gas physical properties) and tend to make fluidization smoother [1]. depending on bed conditions. gas bubbles in all fluidized beds behave similarly to gas bubbles in low-viscosity liquids [7]. As in liquid systems. This resulted in higher solid shear forces during fluidization such that the pressure drop is dependent on previous conditions or is path dependent. 8 Minimum fluidization curve for cohesive iron catalyst particles. gas bubbles in fluidized beds can coalesce into larger bubbles or split into smaller bubbles. d p. This behavior is typically of Group C powders. beds with Group A powders pass from minimum fluidization to smooth fluidization to bubbling fluidization with increasing gas velocity. Large gas bubbles are typically spherical on top and flattened or even inverted on the bottom. For Geldart Group A and C powders. Abrahamsen and Geldart [15] proposed that the minimum bubbling velocity can be calculated from . as gas bubbles approach the top of a fluidized bed. Each peak or spike in Fig. Figure 8 shows the pressure-drop curve for a catalyst supported on alumina with a mean particle diameter of 68 µm. Group B and D powders exhibit bubbling fluidization at the onset of minimum fluidization. The minimum velocity for bubble formation is referred to as the minimum bubbling velocity or U mb. High cohesive forces result in a fluidized bed prone to channeling.Circulating Fluidized Bed Reactors 9 FIG. they collapse such that solids are propagated into the freeboard region. Bubbling Fluidization As discussed earlier.

e.72P 45 µm ) in SI units d (ρ s ρ s )0. Geldart [1] found that Eq. B.1 in SI units (9) For Geldart Group B and D powders. the higher the probability of a bed exhibiting slugging. Group C powders may also exhibit slugging behavior even in large-diameter beds due to the cohesive forces.ave (8) This expression is based on observations that the minimum bubble velocity is strongly dependent on P 45 µm. (8) can be simplified into the form u mb ρ 33d p g µg 0.max 2u t g (11) where u t is the terminal free-fall velocity of the particle (see Appendix B). For these cases. the bubble size increases until a maximum or equilibrium size is achieved.7d p (12) For Group D powders.8 p. If the bed diameter is small and the bed is sufficiently high. Eq. the fluidized bed will slug before entering the turbulent fluidization regime. (11) provided a better fit to experimental data if an effective f(d′ )]. For calculations where less information regarding the system is known. u t p p effective diameter is defined as d′ p 2. Turbulent Fluidization Further increases in the gas velocity result in a slugging or turbulent fluidized bed.. the minimum bubbling velocity is near the minimum fluidization velocity. the larger and more cohesive the particles or the smaller the bed diameter. was used to calculate the terminal velocity [i.52 g g exp(0. and D powders. the onset of fluidization and the formation of gas bubbles nearly coincide and u mb u mf (10) As gas bubbles rise through the fluidized bed. For Group A and B powders. Davidson and Harrison [16] proposed that the maximum stable bubble size can be determined from d b. Thus. the maximum stable bubble size is so large that in realistic fluidized-bed applications the bubbles size is restricted by the bed diameter. For Group A. provided that the bed is high enough. Thus.93 0.13 u 0. The wall stabilizes the bubble such that almost the entire bed is translated up to the top of the bed or even higher. the probability of finding a particle with a diameter less than 45 µm.10 u mb u mf Circulating Fluidized Bed Reactors 2300ρ 0. The diameter. . d′ . slugging is basically the result of a bubble diameter that exceeds about two-thirds the bed diameter.

higher gas velocities result in the onset of turbulence fluidization directly from the bubbling bed regime. This transition can be observed by detecting a sudden change of pressure drop with respect to entrainment rate for increasing superficial velocities. They noted that the onset of fast fluidization correlated to the point where significant particle entrainment was observed. For Groups A and B powders.45 µ ρgdp (16) .45 (14) where 2 Ar 1 108 or. can be calculated using the expression of Bi and Grace [20]: µ ρg dp u mt 1.Circulating Fluidized Bed Reactors 11 the minimum slugging velocity. where the maximum bubble diameter is smaller than two-thirds the bed diameter. can be estimated using the expression of Stewart and Davidson [17]. The onset of turbulent fluidization is defined as the point where the standard deviation of the pressure fluctuations reaches a maximum [18].07(gD)0. Yerushalmi [21] proposed that this transition occurs when a significant number of particles become entrained from the fluidized bed. Re mt 1. U ms.53 Ar 0. Schnitzlein and Weinstein [22].24 Ar 0.24 Ar 0. Fast-Fluidization Regime Detecting the point of transition between the turbulent fluidized bed and the fastfluidized bed regimes has been under debate for many years.45 (15) where 2 Ar 1 108. Bi and Grace [20] measured the entrainment rate versus superficial velocity for a wide range of fluidized-bed systems.5 (13) For Group A or B powders in large-diameter beds. in terms of dimensionless numbers. this minimum transport velocity can be estimated with the expression u mr 1. u mt. The superficial gas velocity corresponding to this point is referred to as the minimum transport velocity or u mr. The minimum velocity for the onset of turbulence fluidization. Higher velocities cause this balance to shift toward a dominating bubble breakup mechanism. however. Grace and Bi [19] noted that fluidization at this point reflects the balance between bubble coalescence and breakup. were unable to determine u mr using Yerushalmi’s method. where u ms u mf 0. Their observations suggested that the value of u mr was strongly dependent on the location and the distance separating the two pressure taps used to measure the pressure drop.

2 (17) Regime Map The bed hydrodynamics associated with each powder classification used in fluidized beds are summarized in Fig. with the exception that smooth fluidization is typically not observed. the onset of fluid- FIG. This transition marks the onset of the pneumatic conveying regime and the superficial velocity corresponding to this point is called the minimum conveying velocity or u mc. fast fluidization. turbulent fluidization. . increasing the gas velocity results in bed hydrodynamics that start in the fixed-bed regime and continue through smooth fluidization. For the larger Group D powders. the axial transition between the dense and lean regions disappears.. Group B powders exhibit the same types of transition. Pneumatic Conveying As the velocity continues to increase in a fast-fluidized bed. 9 Flow regime map for various powders. bubbling fluidization. 9.12 Circulating Fluidized Bed Reactors where 2 Ar 4 106. Yang [23] proposed that this velocity can be estimated with the equation 4. Eq. The superficial gas velocity where the suspension collapse (i.7 2gD(ε mc u mc /ε mc 1) ut ρ 681. Slugging for Group A and B powders depend on vessel diameter. choking) is observed corresponds to the minimum conveying velocity [19]. pneumatic transport. Increasing the gas velocity through a powder bed results in the transition of several regimes. Under these conditions. finally. The onset of pneumatic conveying is readily measured by starting with a high superficial gas velocity and decreasing its value while holding the entrainment rate constant. the minimum transport velocity should be set to equal the terminal velocity [19]. Group C powders tend to slug and Group D powders almost always exhibit slugging. which are dependent on the particle properties. For Group A powders. and.000 g ρs 2.e. 16 may underpredict u mr compared to using the terminal velocity as the minimum transport velocity.

and Yang [23]. Group D powders often exhibit slugging during the onset of fluidization. 10 and the relatively simple calculation of d* and u*. [35]. but more of a gray area between two adjacent regimes. In each of these cases. For instance. Kunii and Levenspiel describe this transition as not being well defined. with the dimensionless gas velocity. Li and Kwauk [26] and Avidan and Yerushalmi [27] took a different approach to developing a unified flow regime map by comparing the relationship of the superficial gas velocity to solids voidage. J-valves. the p flow behavior of most gas–solid systems can be readily obtained. It is interesting to note that Kunii and Levenspiel’s [7] demarcation from fast fluidization to pneumatic conveying is not identical to that first proposed by Grace. to the inverse of the drag coefficient. who compared the superficial gas velocity to the solid flux. L-valves. Group C powders also have a higher tendency to exhibit slugging prior to turbulent fluidization. With the aid of Fig. Horio et al.Circulating Fluidized Bed Reactors 13 ization corresponds with the onset of bubble formation. 1/CD. C powders may not be observed in large commercial units where the effective bed diameter often exceeds the maximum stable bubble size. and. slide valves). Grace [31] resolved this problem by generating a unified flow regime map based on the dimensionless variables d* and u* of Zenz and Othmer [32]. Mechanical or nonmechanical valves provide better response for this counterbalancing. special attention needs to be given to the pressure-loop calculations. the transition from the fast-fluidized bed to a pneumatic transport regime was not well defined. Pressure Balance in a CFB In designing a circulating fluidized bed (CFB). that the boundary for each regime shown in Fig. however. Keep in mind. Kunii and Levenspiel [7] further modified Grace’s work by including the observations of van Deemter [33]. The large particle sizes and/or high densities of Group D powder result in the formation of large maximum bubble diameters that often exceed the diameters of commercial-scale fluidized beds. In contrast. d * Ar 1/3. and Catipovic et al. The higher pressure in the standpipe coun- .e.. Figure 10 shows the result of this effort. This correction results in a higher standpipe bed height and pressure drop. 10 should not be considered as sharp transitions. By comparing the dimensionless particle p diameter.or J-valve to prevent backflow. Re p. various attempts have been made to quantify the flow regimes for gas–solid flow. Further modification to Reh’s map were made by Werther [25]. slugging for Group A. Klinzing [30]. another approach was taken by Leung [29]. u* Re p /Ar 1/3. an increase in the gas flow rate in a riser would require a constriction in a slide valve or less aeration in a L. Reh [24] first made the attempt for a unified flow regime map by comparing the particle’s Reynolds number. In an effort to develop a design guide for fluidized unit operations. however. to a lesser extent. Grace p was able to discern the transition to pneumatic conveying. B. This approach was further modified by Rhodes [28]. smooth and bubbling fluidization are often replaced by channeling due to large solid stresses or large cohesive forces on these particles. Yet. For Group C powders. The bed height in a standpipe counterbalances the dynamic pressure drop occurring in the riser or fast-fluidized-bed section. This is especially true in the proper design of standpipes and mechanical or nonmechanical valves (i. [34].

1.) terbalances the increased pressure in the riser. 11. The pressure drop in the riser or fluidized-bed section must equal the pressure drop in the cyclone. 10 Flow regime diagram proposed by Kunii and Levenspeil. Similarly. the pressure drop in the fluidized bed can be approximated by ∆P| fluid bed L bρ s g(1 ε) (20) where L b is the height of the fluidized bed. (From Ref. Figures 11–13 give qualitative examples of the pressure-loop behavior in the CFBs shown in Fig. Counterbalancing can also happen without the aid of mechanical or nonmechanical valves. in Fig.14 Circulating Fluidized Bed Reactors FIG. For example. the freeboard can be described . the pressure loop is defined as [(P 4 P 3 )] fluid bed [(P 5 P 4 )] freeboard [(P 6 P 7 ) (P 5 [(P 8 or ∆P| fluid bed ∆P| freeboard ∆P| cyclone ∆P| standpipe (19) P9) (P 7 P 6 )] cyclone P 8 )] standpipe (18) Assuming that particle frictional (both particle–particle and particle–wall) and particle acceleration effects are negligible. but the response time is slow and the probability for backflow is much greater. and control valve sections. standpipe. fluidized bed. 7.

(21) can be approximated by using the average voidage in the freeboard ε. (18). Because the voidage profile. Eq. This pressure drop can be . the pressure drop in the cyclone can be determined using the expression described by Muschelknautz and Greif [36]. in the freeboard region is rarely known.67 in SI units 1. 11 Pressure loop for a CFB of Design I in Fig. using ∆P| freeboard ρsg Lu [1 Lb ε(z)] dz ρ s g(1 ε)(L u Lb) (21) where L u is the height of the unit. The second terms accounts for momentum losses in the vortex.8Q g (23) The pressure drop in the vortex depends on the average velocity in the vortex tube and the tangential velocity in the vortex tube or exit. ε(z). 1. For the right-hand side of Eq. Under the assumption that the flow over the wall of the cyclone is similar to flow over a flat plate.Circulating Fluidized Bed Reactors 15 FIG. the pressure drop due to wall friction in a cyclone can be calculated using ∆P| wall friction λp ρ g A surface (u 0 u b )0. where ∆P| cyclone ∆P| wall friction ∆P| vortex losses (22) The first term of this expression corresponds to the friction losses at the wall due to gas.

lean phase ρsg Ls . 0 L s. 12. 0 [(1 L s. For the dense-phase region of the standpipe. The pressure drop in the lean phase of the standpipe can be estimated as ∆P| standpipe.b are the height of the standpipe and the dense-phase bed in the standpipe.b (27) For the CFB in Fig.0 and L s. 12 Pressure loop for CFB with a fluidized bed as shown in Design II of Fig. respectively. the pressure drop is approximated as ∆P| standpipe. the pressure drop is determined in a method similar to that used for the fluidized bed under the same assumptions. dense phase ρ s g(1 ε)L s.b ) (26) where L s.33 u0 v0 2 in SI units (24) where the average velocity in the vortex tube is v0 ˙ Vg πr 2 0 (25) For the standpipe. 1.b ε)(z)] dz ρ s g(1 ε)(L s . the pressure loop has the expression FIG. .16 calculated from ∆P| vortex losses ρgv 2 2 0 3 Circulating Fluidized Bed Reactors u0 v0 1.

the pressure loop for the CFB in Fig. 13.Circulating Fluidized Bed Reactors 17 FIG. the only new expressions needed to complete the pressure-loop calculations in Figs. Compared to the pressure-loop calculations used for the system in Fig. 1. 12 and 13 are the pressure drop across the L-valve. Yang and Knowlton [37] noted that the . 13 can be described as (P 4 P 3 ) riser [(P 5 P 4 ) (P 6 P 5 )] cyclone [(P 7 P 6 ) (P 8 P 7 )] standpipe [(P 9 P 8 ) (P 3 P 9 )] L-valve (30) or ∆P| riser ∆P| cyclone ∆P| standpipe ∆P| L-valve (31) A similar set of expressions can be obtained for the CFB in Fig. 13 Pressure loop for CFB with no fluidized bed as shown in Design III of Fig. (P 4 P 3 ) riser [(P 5 P 4 ) (P 6 P 5 )] cyclone [(P 7 P 6 ) (P 8 P 7 )] 1st Standpipe [(P 9 P 8 ) ] 2nd standpipe [(P 10 P 9 ) (28) (P 3 P 10 )] L-valve or ∆P| riser ∆P| cyclone ∆P| 1st standpipe ∆P| 2nd standpipe ∆P| L-valve (29) Similarly. 11.

Their results showed that the opening area can be expressed as Ao 1. detailed design calculations cannot neglect these effects. Using computation fluid dynamics. a clear understanding of the hydrodynamics is needed to fully describe pressure loss in CFBs. Sinclair and Mallo [39] demonstrated that this may be due to the fact that smaller particles dampen the wakes generated by larger particles or bubbles. For an L-valve. Hence.0623 πD 2 L-valve L L-valve in Foot Pounds Seconds (FPS) units ut (33) Thus. Yang and Knowlton [37] found an empirical expression for this opening area of the L-valve based on 158 experimental data points. pressure drops through a CFB can be estimated and can provide the basic foundation for design. the addition of fines to a Group A powder can result in reduced pressure drops for fluidized beds and risers. A o. However. sphericity. however. particle properties such as roughness. and particle size distribution can also have a significant effect on the pressure drop. Indeed. it is important to understand this macro-scale behavior in order to provide the correct riser design for the desired solids concentration and velocity profiles. Although this may be a safe assumption for rough estimates of the pressure loop.41 Q aeration ut 0. A o. the valve opening area. Macro-scale behavior is mostly concern with solids concentration profiles and solids velocity on a large scale. Hence. the pressure-drop calculations presented assume that frictional and acceleration effects are negligible. fast-fluidized beds and risers have shown evidence of dynamic meso-scale flow behavior in the form of particle agglomeration called clusters and streams. Fortunately. may vary during operation but is always known. this has been the focus of intensive research in the last few years. In addition. For instance. Gas–Solid Hydrodynamics In general. this procedure may not be enough. The size and frequency of these clusters . the opening area. as these units become more complicated or are operated at higher and higher solid circulation rates. the hydrodynamics of a riser can be divided into macro-scale and mesoscale flow behavior. To make matters even more complicated. Indeed. the design of the entrance and exit regions of a riser can influence the solid profile throughout the riser. depends on the amount of aeration and is not known.18 Circulating Fluidized Bed Reactors pressure drop across an L-valve is similar to that used by Jones and Davidson [38] for a mechanical valve where ∆P| mechanical 1 2ρ s (1 Ws ε mf ) C D A 0 2 (32) For mechanical valves. Risers typically exhibit a wide and diverse range of axial and radial solids profiles that are highly dependent on operating and design conditions.

Fortunately. and Rhodes et al. pneumatic conveying region) where higher gas velocities are used. fast-fluidized beds and risers can be designed with the solids concentration and radial profile in mind. Unfortunately. it was surprising that this axial gradient also exists in a riser (i. a clearer understanding of these macro-scale and meso-scale behaviors are under intensive investigations. 14 Axial solids concentration profile in (a) a fast-fluidized bed and (b) a riser. Indeed. riser length to diameter ratio. [42]. As the gas velocity increases through a fluidized bed. data on large units are limited and the solids concentration profiles in these units are still a subject of debate. this can only be achieved if one has an understanding of gas–solid hydrodynamics. .Circulating Fluidized Bed Reactors 19 and streams are also highly dependent on operation and design conditions. Reh noted that there exists an axial gradient of solids concentration in a riser similar to that observed in a fast-fluidized bed. having a distinguishable bed height is one of the indicators for fast fluidization (see the subsection Fast-Fluidized Regime). such as atmospheric fluidized-bed combustors.e. Horio [43] suggested that this S-shaped curve is restricted to units with a large L/D. However. the boundary between the dense fluidized-bed region and the lean freeboard region becomes indistinguishable. who found that the axial gradient of the solids concentration exhibited an S-shaped curve. [40].. FIG. However. Weinstein et al. [41]. This behavior was later quantified by Li and Kwauk [26]. Figure 14 illustrates these subtitle differences in the axial solids concentration profile commonly observed throughout a fast-fluidized bed and riser. may not exhibit this axial profile. Both the cluster size and frequency have a substantial impact on both catalytic reaction rates and heat transfer. Large-scale units. Macro-Scale Behavior: Solids Profile Axial Profile of Solids in a Fast-Fluidized Bed and Riser In 1971. Today. Hartge et al.

15 Length-normalized pressure drop in a riser with increasing solids flux. as shown in Fig.48. as illustrated in Fig. 16 [46. whereas the annulus consists of a dense concentration of particles. Furthermore. At some point beyond the entrance region of the fast-fluidized bed or riser. Radial Profile of Solids in a Fast-Fluidized Bed and Riser The radial profile of solids that exists in fast-fluidized beds and risers is even more surprising. particles segregate toward the wall to form a core–annulus profile. At moderate solids fluxes. and fiber optic probes were able to resolve this core–annulus profile [1. As illustrated in Fig. a γ-ray densitometer.20 Circulating Fluidized Bed Reactors FIG. Kostazos et al. [44] were able to further substantiate this effect by examining the radial profile in a riser at varied feed ports. 16. Using an x-ray absorption technique.49]. 15. Their results showed that the core consists of a lean concentration of solids moving up the riser. this effect becomes more pronounced with higher solids fluxes. particles in the annulus region actually exhibit a downward velocity. can be affected by the entrance design for 20 to 30 L/D’s. versus the riser length to diameter ratio. Karri and Knowlton were able to quantify this downflow as a function of radial profile by measuring the solid mass fluxes in a 20-cm-diameter by 14-m-high riser [49]. normalized by the distance between pressure taps. Their results showed that an asymmetric position of the feed manifested itself in the asymmetry of the radial profile at an axial position of up to 30 L/D’s.45–48]. Figure 17 presents their results where downflow in the annulus regions was observed for solid mass fluxes of 49 and 93 . L/D. Recent studies have shown that the design of the entrance and exit region in a riser can have a substantial effect on the resulting performance. the pressure drop. Studies using kinetic sampling probes.

For example. 17 The effects of solids mass flux on the radial net solids mass flux profile. Similar findings FIG. to a lesser extent.) . Miller and Gidaspow [50] showed that the largest magnitude of annular downflow flux at and near the wall was near the bottom of the riser. backmixing near the feed region and. 16 Representation of the core–annulus profile in a riser where downflow is observed near the walls. Fortunately.5-cm-diameter riser. results in a core–annulus profile where particles at the wall move in the same direction as those in the core region (positive solids mass flux of 1 kg/m2 s). The implications of this behavior can be substantial. At less than 2 m from the inlet of Miller’s 7. up throughout the riser can have a significant impact on productivity.Circulating Fluidized Bed Reactors 21 FIG.) kg/m2 s. 49. 17 shows that operating Karri and Knowlton’s riser [49] at or above solid fluxes of 195 kg/m2 s. many of these reactions require very high solids fluxes where downflow may be less of an issue. (Adapted from Ref. downward fluxes were several times the average feed flux [51]. 48. In this case. (Adapted from Ref. Fig. For many catalytic reactions. backmixing was limited.

this effect appears to only occur for downflow operations. 20.) have also been reported by Issangya et al. noted that the asymmetries in solids radial distribution were more noticeable in the interphase between the dense and dilute regions. depending on the design of the feed region.09-minner diameter by 7. In contrast. With upflow at the wall. but backmixing is less severe in this region.2-m-high riser. As shown in Fig. the exit configuration of a riser can have an impact on the solids profile for several L/D’s below the exit region. Particle segregation was not observed for core–annulus upflow profiles for either very high or low solid mass fluxes [49]. using . Of course. 19. [42] used a nonisokinetic sampling probe to examine the radial solids loading in a 0. a nonuniform radial profile may exist throughout many industrial risers. the low shear may not generate strong enough eddies to effect the particle size distribution across the riser diameter. the Laser Doppler Velocimetry (LDV) of particle-laden jets. the added attrition caused by baffles needs to be factored into the design process. as depicted in Fig. Their results showed that a side solids feed resulted in a nonuniform radial distribution of solids beyond 40 L/D’s. (Adapted from Ref. A representation of this behavior is presented in Fig. As with the axial profile. Particle segregation appears also to be influenced by the core–annulus profile in a riser. 18. [52]. Thus. Rhodes et al.22 Circulating Fluidized Bed Reactors FIG. A core–annulus profile may still develop further up the riser. [53] examined this phenomena using. Hence. Jones et al. Karri and Knowlton [49] observed that in the presence of downflow. 49. Their results showed that eddies or recirculation zones were responsible for this particle segregation. Rhodes et al. In addition. the high shear and resulting recirculation zones generated from the solids downflow near the wall may be responsible for the segregation effect observed by Karri and Knowlton [49]. 18 Representation of the core–annulus profile in a riser where upflow is observed near the walls. which limit the core–annulus profile. Baffles can induce wakes and turbulence. the particle size distribution in the annulus region was larger than that found in the core. the design of the entrance and exit region can have a substantial effect on the solid radial concentration profile. Another option is to use secondary feeds to produce a higher plug flow or uniform solids velocity profile at the entrance region. Brereton and Grace [54] observed this effect for smooth and abrupt riser exits. In a similar fashion. There are also design features that can reduce backmixing in risers.

.1 m/s. initial solids flux of 73 kg/m2 s. and 148µm sand particles. 20 Effect of exit configuration on solids volume fraction for a 0. 19 Illustration of the nonuniform solids radial profile in a riser due to solids feed on the side of the riser (not drawn to scale).) FIG.15-m-diameter by 9. 54). 28. (Adapted from Ref.3-m-high riser with a superficial gas velocity of 7.Circulating Fluidized Bed Reactors 23 FIG. (From Ref.

solids flux of 50 kg/m2 s. asymmetric feed designs and abrupt exits are less critical.4-mdiameter by 15. resulted in backmixing. 21 Solids flux ratio with respect to radial position for a riser with a smooth. 21 and 22. For combustors. and 80-µm sand particles.1-m-high riser. solids flux of 71 kg/m2 s.) . However. rounded exit at a superficial gas velocity of 4. an abrupt bend. and 80-µm sand particles.2 m/s. (From Ref. wide-radius bend to terminate the riser resulted in little deviation in the axial solids concentration profile.) a smooth.24 Circulating Fluidized Bed Reactors FIG. where backmixing is tolerable and sometimes even desired. 55. 55. substantially less downflow is observed compared to the abrupt exit configurations. 22 Solids flux ratio with respect to radial position for a riser with an abrupt. the region of downflow for the abrupt exit configuration was over twice the size of that observed for the smooth configuration. These results provide a good example of the importance of riser design for chemical production. Similar effects for solids fluxes are reflected in the data of Kruse and Werther [55] who compared normalized solid fluxes to radial solids loadings for a 0. as shown in Figs.2 m/s. such as a square bend or tee. For smooth bends. (From Ref. In addition. squared exit at a superficial gas velocity of 4. which affected the overall riser solids volume fraction profile up to 20 L/D’s below the exit region. How- FIG.

. both the entrance and exit can be designed such that minimal asymmetric solids profiles and backmixing ensues. in chemical production such as in oxidation and chlorination. For the entrance region. Fortunately. stripper) for a more uniform solids loading profile.e. One such design is shown in Fig. 24. ever. A fluidizing gas is used to distribute incoming solids. the exit region should have either a long radius bend or a disengagement section. asymmetric solids profiles and backmixing can seriously reduce selectivity and activity. care needs to be taken such that entering solids are well mixed with the entraining gas. 23 Illustration of riser entrance region for a more uniform solids loading profile. as shown in Fig. Meso-Scale Behavior: Clusters and Streamers Riser sections in circulating fluidized beds exhibit a core–annulus profile with downward flow resulting in the formation of clusters and streamers of particles.. FIG. industrial risers have a stripper section at the top of the riser to not only strip gas but also minimize exit effects on the riser. 23. Similarly. 24 Illustration of riser exit region (i. and one or more jets are used to entrain catalyst into the riser.Circulating Fluidized Bed Reactors 25 FIG. Typically.

25 An illustration of the cluster or streamers often observed in risers. infrared imagining [59]. ε cl. In general. cluster and streams are frequently observed.26 Circulating Fluidized Bed Reactors This phenomenon was proposed by Squires et al.027 10d p ) 32 ε 6 cl (36) FIG. and fiber-optic probes [60–62] all reveal the presence of wave packet of particles near the riser wall moving with the downward annulus flow in continuous but dynamic and unstable sheets. [63] experimentally measured the cluster length and time-averaged local solid volume fraction in riser flow. laser sheet [58]. replaced the average local solids volume fraction of particles. High-speed movies [24]. These sheets of particles (commonly called clusters. Because the slip velocity cannot exceed the terminal velocity. Their results were in agreement with Yerushalmi and Avidan’s [57] earlier empirical correlation of dc dp ε s (0. in a core–annulus profile with downward flow at the walls. as dc dp ε cl (0. [56] and Yerushalmi and Avidan [21. Laser sheet and fiber-optic studies of Horio [43] and Rudnick and Werther [61] have further demonstrated that these clusters are three dimensional in nature and can be found in the annulus and core regions. . In other words. swarms. Soong et al. Under the assumption that the pressure drop equals the weight of the solids in suspension. Soong et al. calculated as v slip vg Gs ρs εs (34) was found to be several times larger than the terminal velocity [51]. 25. or strands) are represented in Fig. by the solids volume fraction of a cluster.027 10 d p ) 32 ε 6 s (35) However. streamers. it was observed that clusters move in a direction parallel to the flow of the suspension phase. it was postulated that the particles must be forming clusters that effectively act as larger particles. Today. strings. the resulting slip velocity. ε s. clusters in the annulus region flow downward and clusters in the core region flow upward.57].

wall collisions would need a coefficient of restitution of less than 0. As a result. or decreasing pipe diameter. whereas larger particles.and 200µm-diameter glass beads readily accumulated at the wall. the clusters were 2–3 cm in length in the down-flowing annulus region. What is interesting here is that if particle collisions with the wall help create the formation of clusters. For this to happen. did not. is 0. Furthermore. Instead. The downward motion of a cluster is caused by the net lift forces on a cluster being less than the sum of the forces on each individual particle. Senior and Grace [66] proposed that inelastic wall collisions cannot account for all the energy loss needed to form clusters. Senior and Grace proposed that the balance between shear-induced lift and drag forces on a particle act to momentarily detain particles at the wall region of the riser. for Group A powders.5–5. Perfectly elastic collisions have a coefficient of restitution of 1. Senior and Grace [66] were able to model these trajectories and found similar conclusions. cluster density increased with increasing solids flux. Lee and Durst [67] found that 100. Particle migration to the wall is not only dependent on axial and lateral velocities but also on the particle diameter.max 1 εs ε s. The mechanism for the formation and degeneration of clusters in a riser is still under some dispute.Circulating Fluidized Bed Reactors 27 Gu and Chen [64] further correlated Soong’s data such that the solids volume fraction of a cluster can be related to the local solids volume fraction of particles using the expression ε cl ε s. lift forces acting in the opposite direction move the particle away from the wall to the near-wall regions. concentrations were found to be an order of magnitude larger at the wall than that found for 230-µm particles with lateral velocities ranging from 3 to 22 cm/s. For 40-µm particles. When the particle-to-wall friction slows the particle below the local gas velocity. Particles hit the wall. For particles larger than 500 µm in diameter. Tsuo and Gidaspow [65] observed that. Tsuji et al.5 cm/s. Tsuo and Gidaspow [65] proposed that clusters are the result of partially inelastic collision with the walls. This process continues until a cluster is formed. Furthermore. [68] was also able to measure this crossover of particles to the wall for smaller particles.max.1. Clusters form when many particles undergo this lateral-velocity-reduction process. After a particle collides with the wall. each time losing more lateral velocity. a significant concentration of particles was predicted to accumulate near the wall for initial lateral velocities of 4. ε s.57. no range of lateral velocities was found that slowed the particle significantly enough for crossover to the wall. lose energy. how do cluster form in the core region as observed by Horio [43] and Rudnick and Werther [61]. the particle continues to hit the wall. Yet. Karri and Knowlton [49] . it has insufficient momentum to counteract the lift force. with a 400–800-µm diameter. and fall. The larger particles were traveling at significantly lower axial velocities and were less influenced by lift forces directed to the wall. which is unlikely. decreasing gas velocity. for 230-µm particles. to collide with another particle.max 3.4 (37) where the maximum local solids volume fraction.

This is not a daunting task. a complete description of the CFB hydrodynamics is not possible even after decades of intensive research. whereas two particles aligned parallel with the flow tend to attract each other due to the nearest-neighbor effect on lift and drag. a broad knowledge base exists for the design of fluidized catalyst crackers using empirical-based models. Horio noted that buoyancy forces dominate in lean-phase regions. in riser flow. Yet.28 Circulating Fluidized Bed Reactors observed that particles in the annulus region with a downward flow had a larger particle size distribution than that in the core. Both of these results contradict the above postulate of Senior and Grace in which a wall is needed for cluster formation and larger particles prefer the core region. These macroscopic properties may also need to be considered. and gas and solid residence times is still more art than science. the design. The combination of nonelastic processes and the parallel-aligned particle flow may provide the attractive force needed to promote clustering. Unlike the petroleum industry where FCC catalysts have similar properties. particle alignment is not stable. heat transfer. as particles undergo collisions. For the design. Two particles traveling perpendicular to the gas flow tend to repeal each other. In a core–annulus profile where both regions have an upflow profile. This may be the very mechanism to ensure clustering. Thus. construction. Most likely. and operation of CFBs in the chemical industry. Hence. Yet. just careful consideration of each design aspect of the CFBs needs to be addressed. Horio [43] proposed that another mechanism may be responsible for cluster formation. no particle size distribution effects were observed. where a homogeneous suspension evolved into clusters [69]. and other nonelastic processes. tumbling. Furthermore. Closing Remarks To date. A particle in flight can have either attractive or repulsive forces with nearby particles. bumping. predicting accurate pressure profiles. Indeed. Even though a fundamental understanding of the physics behind gas–solid flow is limited. reaction productivities. The interaction of these forces controls the development of particle groups to form steady but turbulent structures of a certain characteristic length. This results in a shear between clusters and the lean-phase region. it is more important to understand and apply at least the known physics in gas–solid flow. whereas gravitational forces dominate in dense-phase regions. the physical properties of the catalyst commonly used in the chemical industry are diverse. circulating-fluidized-bed reactors have been in productive use for more than 50 years. construction and operation of these units can be done in a relatively short period of time. the magnitude of the solids flux or solids concentration may have a significant impact on the locality of cluster formation and particle-size-segregation effects. . this is not the case. Two-dimensional simulations of particles show this very event.

or J-valve Volumetric flow rate of the gas Radius Vessel radius Particle Reynolds number Particle Reynolds number at minimum fluidization Superficial gas velocity Superficial gas velocity at the onset of pneumatic conveying in a fluidized bed Superficial gas velocity at the onset of bubbling in a fluidized bed Superficial gas velocity at minimum fluidization Superficial gas velocity at the onset of fast fluidization in a fluidized bed Superficial gas velocity at the onset of slugging in a fluidized bed Superficial gas velocity at the onset of the turbulence regime in a fluidized bed Inlet velocity of a cyclone Tangential velocity at the wall of a cyclone Dimensionless gas velocity Particle terminal velocity Volumetric gas flow rate Slip velocity Distance Solids void fraction Solids void fraction for a packed bed Average solids void fraction of a cluster .8 m/s2 or 32.Circulating Fluidized Bed Reactors 29 Nomenclature Ar A surface db d b.2 ft/s2 Solids flux rate Length Height of fluidized bed Height of L-valve (distance between L-valve feed and horizontal leg into reactor) Height of fluidized-bed vessel Proportion of particles with a diameter less than 45 µm Volumetric flow rate of the gas for L. 9.ave d* p D D L-valve g gc Gs L Lb L L-valve Lu P 45µm Q aeration Qg r R Re p Re pmf ug u mc u mb u mf u mr u ms u mt ui u0 u* ut ˙ Vg v slip z ε ε bp ε cl Archimedes’ number Surface area Bubble diameter Equilibrium bubble diameter Cluster diameter Particle diameter Effective particle diameter Average particle diameter Dimensionless particle diameter Vessle diameter Diameter of an L-valve Acceleration of gravity Newton’s law proportionality factor.max dc dp d p′ d p.

As the superficial gas velocity increases. For the aggregate particles. Jackson [71]. these particles move further apart in an independent fashion. In contrast. These particles are considered cohesive and almost always exhibit significant channeling during fluidization. Group C powders are usually fluidized with the aid of baffles and/or mechanical vibration. these groups are referred to as Geldart Group A through D. Today. most FCC units are designed for Group A powders. This graph is the basic foundation of modern-day fluidization engineering. To address this shortcoming. the ‘‘type’’ of fluidization can be determined. such as Group B powders. For example. By comparing the particle density (less the gas density) with the mean particle diameter. To limit this effect. Geldart Group C powders are typically less than 50 µm in diameter and are the most difficult to fluidize. the resulting dense phase remains unchanged in terms of solids concentrations after initial fluidization. and Verloop and Heertjes [72] suggested that the fluidization of particles can be classified into two categories: particulate and aggregative. The particulate category is limited to a small group of particles leaving the aggregative category to describe everything else. The particulate category pertains to powders that fluidize in a liquidlike fashion. particles in the aggregates catagory would exhibit bubble formation with increasing gas velocities. the design and operation of a fluidized-bed unit containing a Group A powder would not be the same as that used for a Group B powder. Sometimes.73] demonstrated that particles could be classified into four distinct categories or groups. which . Geldart Group A powders are the most common type of powder used in fluidization. In general. this two-category methodology falls short in adequately describing fluidization behavior. Most particles adhere to the aggregative behavior. Unfortunately. larger particles. a description of the fluidization behavior is presented in the order of increasing particle size. Figure A1 illustrates how the fluidization behavior of a particular powder can be predicted using the Geldart Group classification. Geldart and Rhodes [1. To better clarify these differences.30 ε ms ε mf εs ∆P λp µ ρg ρs Φ Circulating Fluidized Bed Reactors Solids void fraction at the onset of pneumatic conveying in a fluidized bed Solids void fraction for a bed at minimum fluidization Average solids void fraction Pressure drop Dimensionless solids friction coefficient Gas viscosity Gas density Solids density Sphericity Appendix A: Geldart Powder Classification Simpson and Rodger [70]. are added to the bed to promote smoother fluidization. Group A powders undergoing fluidization behave significantly different than the other groups. Thus.

some powders fluidize well as a Group A powder. gas requirements for fluidization are large. a Group B powder may behave as a Group A powder Furthermore. These powders are sometimes referred to as Group AC powders. As a result. In some cases. At low gas velocities. the transition from one group to another is not well defined.e.. (Adapted from Ref. where smooth fluidization is observed. Group A powders tend to exhibit significant bed expansion without the formation of bubbles (i. but become permanently defluidized as a Group C powder in nonaerated horizontal sections of a CFB. bubbles appear and rise more rapidly than the gas in the rest of the bed. on the order of feet in some cases. Geldart Group B powders have particle diameters typically ranging from 200 to 800 µm.Circulating Fluidized Bed Reactors 31 FIG. . Unlike Group A powders. Group A powders do not promote maximum bubble size greater than 10 cm [7]. At higher gas velocities (i. During fluidization. These powders are typically processed in spouting beds where gas requirements are less than that needed in standard fluidized beds.. A1 Geldart powder classification at ambient conditions.) typically have a mean particle diameter of 75 µm and a particle density of 1. Care should be taken that slugging does not occur in smaller fluidized beds. greater than u mb ).0 g/ cm3. Geldart Group D powders have the largest particle diameters of all other Geldart groups. the behavior of a powder can be classified under more than one group. Typically. these powders exhibit the formation of bubbles at the onset of fluidization. Group B powders fluidize easily and are used in a wide range of fluidization unit operations with little difficulties. Under high pressures. Gas in the dense or emulsion phase tend to percolate through the bed compared to the residence time of the gas in the bubbles. 7.e. For example. Group D powders have enormous bubble diameters and slugging is commonly observed even in large fluidized beds. smooth fluidization). It should be noted that Figure A1 was developed for particles at ambient conditions. The bubble size in Group B powders can be large.

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Y. eds. and H. Powder Technol. Rodger. 125–146 (1982). Chem. vol. 71. Haider and O. ‘‘Cluster Formation in Dispersed Gas–Solid Glow: Effects of Physical Properties of Particles. J. Tanaka. S. J.’’ in Fluidization IX (L-S. We i∞ will also summarize the reported effect of pressure on chemical reaction conversion because reactor performance is the result of all combined effects the pressure and temperature may have on hydrodynamics as well as on the reaction. pp. Levenspiel. H. Y. Temperature and pressure affect fluidized-bed systems because they affect the gas density and gas viscosity. D. Basu. u mf. The reader is referred to two in-depth reviews of the subject [1. pp. Shiomi. Eng. Rhodes. ing Fluidized Bed Risers. L. J. pp. T. RAY A. Inst. Kyoto. Geldart and M. M. 68. bubble diameter. Trans. Chem. Multiphase Flow. dense phase voidage. 70. as particle size dramatically impacts fluid–particle interactions. Pergamon Press. Yonemura. These effects cannot be considered independently of particle size. 58. PT4-25–PT4-30. Simpson and B. 3. Sci. Hence. J.2]. u mb. 74. C. K * . ε mf. Lee and F. R. minimum bubbling velocity. Eng. Tsuji. Fluid Mech. Verloop and P. 417–434 (1984). Chem.’’ in Circulation Fluidized Bed Technology (P. Durst. ed.. 41. and Y. 21–31. bed voidage at minimum fluidization velocity. 1998.. COCCO Effect of Pressure and Temperature in Bubbling Fluidized Beds Introduction Typical commercial gas fluidized-bed processes operate at up to 7. and particle entrainment and elutriation rates. 13–28 (1963). In this section. we will summarize the impact of pressure and temperature on the critical hydrodynamic parameters of minimum fluidization velocity. 16. 63–70 (1989).. Fan and T.). d b. M. 8. 139. Heertjes. ε D. 25. 1986. 73. 69. Int. Tsuji. Sci. 153–180 (1961).1 106 Pa ( 70 atm) pressure and 1273 K (1000°C). Eng.). Morikawa. f.. bubble frequency. A. W. 165–172. S. Engineering Foundation. ‘‘From Minimum Fluidization to Pneumatic Transport: A Critical Review of the Hydrodynamics. 1995. an understanding of the effect of pressure and temperature on hydrodynamics is critical for propert fluidized-bed system design. . 825 (1970). New York. two critical parameters impacting bed operation. J.’’ Proceedings to 2nd International Conference on Multiphase Flow.Pressure and Temperature in Fluidized Beds 35 67. 72. New York. Knowlton. Jackson.

Mass and heat transfer (interchange) occur between the jets and the dense phase gas. FIG. q D /q B). Heat is also transferred by the dense phase to internal heat-exchange surfaces. Small bubbles provide higher mass-transfer rates and increased residence time in the bed. . A critical factor affecting the overall performance of a fluidized bed is the interchange between the dilute and dense phases. Interchange rates can be increased by (1) increasing the ratio of the gas jet volume to the bubble volume in the bed (i. It is imperative to note that although we want bubbles to be small.e. phases. Bubbles must be present in order to achieve rapid mixing in the reactor. contributing to high heat-transfer rates to internal surfaces. The gas that enters a fluidized bed at the volumetric flow rate q G(in) enters in the form of gas jets. and between the dense phase gas and solids. this gas is distributed between bubbles that form (q B) and the interstitial dense phase gas (q D) that flows through the solid particles. bubbles must not disappear. (2) increasing the ratio of the gas flowing through the dense phase to the gas flowing as bubbles (i. between the bubbles and the dense phase gas.. 1 Transport. 1): (1) a dense (or emulsion) phase of solid particles with a surrounding interstitial dense (or emulsion) phase gas and (2) a dilute phase consisting of gas jets which protrude up through a perforated gas distributor or series of nozzles. At the top of the jets. and gas bubbles that form at the top of the jets.36 Pressure and Temperature in Fluidized Beds Two-Phase Flow Model A bubbling fluidized bed can be considered as consisting of two phases (Fig.e. VJ /VB). and (3) maintaining a small bubble size throughout the bed. and pressure in fluidized beds..

flow predominates.75–33. or viscous. various investigators have proposed values of C 1 and C 2 on the basis of experimental results to be in the range 18. respectively [3]. The following relationship can be shown to hold (see the Nomenclature section for terms): Ar or Ar where Ar d 3 ρ g(ρ p p µ2 g C1 ρ g)g . At minimum fluidization conditions.and heat-transfer rates. For small particles (Re mf 20).7 and 0. (1) and (2) is u mf C2 2C 1 d 2 (ρ p p µg ρ g)g (5) . or inertial. is a fundamental characteristic of a fluidized bed.Pressure and Temperature in Fluidized Beds 37 Pressure and temperature can have a significant effect on the distribution of gas between the bubble and dense phases and the mass. flow predominates in the system. The first terms on the right-hand sides of Eqs. whereas the second terms are important if turbulent. (1) and (2) are important if laminar. the drag force by upward-moving gas equals the weight of particles lifted in the fluidized bed. the simplified form of Eqs.0651.75 2 Re mf φε 3 mf (1) (4) Working on the assumption that the particles constituting the bed can be approximated by a constant value of φ and that ε mf remains constant over the entire range of operating conditions of temperature and pressure.86(1 φ C2 φε 3 mf 1. u mf. 42. Minimum Fluidization Conditions The minimum fluidization velocity. Its accurate prediction is important for the successful design and operation of a fluidized-bed process.75 Re mf ε mf) d p u mf ρ g µg (3) 2C 1 Re mf C2 1 Re 2 mf C2 (2) 150 1 mf 2 3 mf ε φε Re mf 1.0313–0.

increases with temperature. using fixed C 1 and C 2. For large particles. (5) indicates that u mf is relatively unaffected by changes in pressure for fine particles. The effect of temperature and pressure on ε mf has been studied by a number of investigators. However. Using this effective particle diameter. or (7). Eq. almost independent of pressure and because ρ p ρ g for most materials. The effect of temperature on ε mf has been reported to be much more significant [7–10] and to affect fine-particle systems more than coarse-particle systems. (2) can be rearranged and used: u mf µg [(C 2 1 dpρg C 2 Ar)0. which are independent of temperature and pressure.10]. Several studies [5. A recommended method for improving the accuracy of u mf is to first determine u mf experimentally at ambient conditions and to back-calculate an effective particle diameter (i. indicating that u mf decreases for increasing pressure. (5). (6) indicates that u mf will increase with temperature because an increased temperature results in a decreased ρ g.6] have indicated that pressure has essentially no effect on ε mf for fine particles and a slight increasing effect on ε mf for larger particles. Because the gas viscosity. µ g.0494 [5] for coarse-particle systems. use C 1 33. according to Eq. Eq. the absolute values of the predictions may be incorrect because of the difficulty in determining a representative value for d p and φ. On the other hand.e. d eff) from Eq. . however. calculate u mf at the desired conditions of temperature and pressure.7 and C 2 0. the simplified form becomes u2 mf C2 d p (ρ p ρg ρ g)g (6) With gas viscosity. For changes in temperature. (6). u mf decreases with an increase in temperature for fine-particle systems in which viscous forces dominate.5 C 1] (7) The trends that u mf is relatively unaffected by changes in pressure and decreases for increases in temperature for fine-particle systems and that u mf decreases for increases in pressure and increases for increases in temperature for large-particle systems are consistent with those reported experimentally. it does not account for any changes in ε mf which might occur for changes in temperature and pressure.. The dependence of ε mf on temperature can be expressed in linear form as [8] ε mf ε mf(amb) k(T T (amb) ) (8) where the parameter k is a function of particle properties. µ g. The temperature effect appears to be the result of interparticle forces which affect packing properties [8. or estimating ε mf. (5) indicates that u mf varies with 1/µ g . (6). Eq.5. u mf for larger particles will vary with (1/ρ g)0. Eq.0408 [4] for fineparticle systems and C 1 28.38 For large particles (Re mf Pressure and Temperature in Fluidized Beds 1000). This method substitutes an effective value for d p and φ. In the absence of reliable data. For systems in the intermediate regime (20 Re mf 1000).7 and C 2 0.

523 exp(0. However. Abrahamsen and Geldart [12] observed that u mb and. u mb u mf).209 Ar 0. it is clear that incorporating an accurate value of ε mf with an effective particle size. εD As the gas velocity is increased above that required to incipiently fluidize the bed of particles.e..e. q D /q B).716F)u mf g g d 0. In fine-particle systems at high pressures. (1) will allow an accurate calculation of u mf. the voidage of the dense phase. for fine-particle systems. u mb (i. for u mf u0 u mb). it is possible to observe a particulately (or homogeneously) fluidized bed without bubbles for intermediate gas velocities between u mf and minimum bubbling.8 g 0. Hence. ε D. gas bubbles eventually form (at u 0 u mb) and rise through the dense phase..687)0.934 p (9) Equation (9) indicates that u mb will increase for an increase in gas temperature and pressure (via increased u g and ρ g) and that the sensitivity to viscosity is more significant than the sensitivity to pressure.934(ρ p ρ g)0. The minimum gas velocity at which bubbles appear. has been found to equal u mf for coarse-particle systems [11]. no reliable correlations are available for predicting ε mf for a given system. Without experimental data. overall reaction rates for catalytic and gas– solid fluidized-bed reaction processes involving fine particles will increase with . The effect of u mb u mf and ε D ε mf is to increase the interchange between feed gases and solid particles because more feed gas flows directly through the dense phase (i. weight fraction of particles 45 µm) to a fluidized bed of fine Group A powders: u mb u mf 2300ρ 0. For fluidized beds of fine Group A powders that particulately fluidize (i. d eff. µ D.e.Pressure and Temperature in Fluidized Beds 39 Although substantial data have been reported in the literature. hence.209 (10) It is important to note that an increase in ε D results in a decrease in dense phase viscosity. This voidage has been shown to be adequately described for high-pressure systems of fine powders [14] by the empirical correlation of Kmiec [15]: εD (18Re 2. the region of particulate expansion is increased by adding fines (increased F. Minimum Bubbling Velocity. The velocity range over which this ‘‘delayed bubbling’’ occurs can be extended with an increase in operating pressure. However.126 µ 0. in Eq. the use of Eq. This equation has been shown to be valid over a wide range of pressures for fine-particle systems [13]. there is a range of velocities between u mf and u mb over which the bed expands uniformly. exceeds ε mf. umb and Dense Phase Voidage. (7) with the recommended values for C 1 and C 2 is suggested for calculating u mf. u mb.7Re1..

The contribution of pressure and temperature impacting the jet length. In applying the Taylor theory to bubbles in fluidized beds.19] have shown that the penetration of the gas jets into the fluidized bed increases substantially with an increase in operating pressure. heat transfer.68 dp do 0.40 Pressure and Temperature in Fluidized Beds increased pressure due to the effect of pressure on fluidization hydrodynamics alone. Overall reaction rates depend on the size of bubbles because bubble size is a primary contributor to bubble rise velocity. the dense phase over the bubble is the heavy fluid and the gas in the bubble is the lighter fluid.05 ρg ρp 0. h j. Several investigators [18. The effect of gas viscosity was not found to be significant [20]. it enters a fluidized bed in the form of gas jets. indenting the upper surface of a bubble. An initial.37 Re 0.2Fr 0. and fine-particle elutriation. gas rate of exchange between phases. among others) has high gas–solid contacting efficiencies relative to the bubbling region above. grows to split it from above. It has been suggested that this splitting results from a Taylor instability [23] wherein a heavy fluid overlies a lighter one [24]. increased pressures yield smaller-sized bubbles. Studies have indicated [21] that the smaller bubbles result from a decrease in the stability of bubbles leading to their breakup into smaller voids. Fine-Particle Systems For fine-particle Group A systems. X-rays [22] of gas bubbles in fluidized beds have shown that an initial disturbance.24 (11) Bubbling Region Bubble size is one of the most important parameters of conventional gas–solid fluidized beds. is through their effect on gas density via the equation [19]: hj do 21. small disturbance with amplitude η 0 is assumed to perturb the essentially horizontal upper surface of the bubble and to grow according to η η 0 exp(nt) (12) . Jetting Region As gas flows through a perforated or multinozzle distributor plate. random. 16 and 17. This jetting region (Refs.

d bmax. Clift et al. according to the Taylor instability theory. Observations of splitting bubbles suggest that disturbances usually develop in a regular pattern on either side of the node. It is clear from Eq. The likelihood of splitting can be estimated by comparing the 1/n) with the maximum time constant for the growth of a disturbance (i. For each ν p. The major difficulty in testing the ability of using the .5 ln 1 tan(θ/2) (16) If the time available for growth. d f . Smaller particles and higher pressures are known to lower ν p [26] and thus.e. t e. 2.Pressure and Temperature in Fluidized Beds 41 where n is a parameter depending on the physical properties of the system and on the wavelength of the disturbance. (13) has been presented elsewhere [25]. hence. and the corresponding ν p is shown in Fig. the maximum stable bubble size. t am. there is a specific wavelength called the ‘‘most dangerous’’ wavelength. the prediction of the effect of system properties on the bubble stability depends on the prediction of the effect of system properties on ν p. λ max. (13) and from Fig. and. Assuming a node is located λ/4 from the bubble nose so that the node is an antinode in the initial disturbance. is greater than the required growth time. the most dangerous wavelength. which exhibits the maximum growth rate. 2 that ν p is the dominant factor determining the growth of the instabilities. t e time available for growth [25]: t am R0 g 0. Thus. In practice. [25] have noted that disturbances initiated on the roof of a bubble are swept around the periphery. θ λ 2θ π kR 0 (17) The relationship between the stable bubble frontal diameter. the disturbance grows so slowly that it does not achieve an amplitude large enough to cause splitting before it is swept around the bubble equator. n may be obtained from [25] R4 where k 2π λ (14) 2R 2 4R 1 g (k 3ν 2 ) p 0 (13) is the wave number of the disturbance and R 1 n(ν p k 2) (15) A numerical solution for Eq. Otherwise. In gas fluidized beds. a bubble does not split unless the disturbance has grown sufficiently before the tip of the growing spike reaches the side of the bubble.. the bubble is liable to split. λ max. result in smaller d f .

The actual bubble volume is approximately 75% of that of a sphere of diameter equivalent to d f [22]. no suitable relationship exists today to allow the calculation of d bmax for fine-particle systems as impacted by temperature and pressure. d bmax is dependent on ν p. correlations. increased pressure and temperature result in a decrease in d bmax. However. Because ν p decreases with an increase in ε D and ε D increases with an increase in pressure and temperature. Although such a relationship is not currently available. to system parameters. Hence. particularly for fineparticle systems. Taylor instability theory to explain observed limited bubble growth in high-pressure fluidized beds is the lack of data. The relationship between the stable bubble frontal diameter. 2. and theory relating the kinematic viscosity of the dense phase. the effect of particle size must be taken into consideration because the effect of pressure and temperature on d bmax is minimal for coarse-particle systems compared to fine-particle systems. Hence. calculations using equations developed for systems of solid spheres in liquids have been shown to be consistent with µ D needed to limit bubble growth in high-pressure systems [14]. and the corresponding ν p is shown in Fig. d f . 2 Effects of kinematic viscosity on stable bubble frontal diameters. d f and d b are related: df 1.42 Pressure and Temperature in Fluidized Beds FIG. ν p. A suitable relationship for estimating µ D from variations in ε D for gas fluidized beds is needed in order to predict d bmax a priori. experimentally determined values for d b indicate .1d b (18) For Taylor instabilities governing the maximum stable bubble size in fluidized beds. Nonetheless.

For PFBC (P in Pa). It has generally been reported that the bubble frequency.Pressure and Temperature in Fluidized Beds 43 that higher pressures and temperatures yield smaller-diameter bubbles in gas fluidized beds. Chan and Knowlton [32] also found that the TDH increased linearly with pressure in the range 1–30 atm. more and more particles are transported to greater heights above the bed surface and there exists a particle density gradient extending some distance above the surface.06(u 0 f {exp[ 1.42 14 P2 0.8P 0. [31] for pressurized fluidized-bed combustors (PFBC) on the basis of a comprehensive analysis of previous work. For sufficiently tall freeboards. there will be a certain height at which the density gradient eventually falls to zero.1905h0.25(u 0 u mf)2 1 10 6P(u 0 u mf)]} (20) Particle Entrainment and Carryover Entrainment occurs when gas bubbles break at the top of the fluidized bed and throw particles up into the freeboard region above the bed surface.1002L 0. Coarse-Particle Systems A generalized correlation for bubble size has been developed by Cai et al.4 10 u mf)0. An increase in the operating pressure increases the carrying capacity of the gas and increases the amount of solids carried over [32. These results are consistent with decreases in bubble size for increases in temperature and pressure. The correlation takes into account the different flow regimes at different pressures and gas velocities. If the bed solids have a wide size distribution and the gas velocity in the freeboard exceeds the terminal fall velocity of the smaller ones. They investigated temperatures in the range of ambient to 1033 K . and above this height.4 10 u mf)0.06(u 0 {exp[ 1. the entrainment flux will be constant.42 14 P2 0. At low gas velocities. these particles quickly fall back into the bed and are retained. as well as the special variation of bubble size within the lower-pressure range of the bubbling regime. Findlay and Knowlton [20] studied the effect of increasing temperature on entrainment.25(u 0 u mf)2 1 10 6P(u 0 u mf)]} (19) The equivalent bubble size of the entire bed is d be 0.33]. Entrainment from fluidized beds is affected by changing pressure and temperature. increases with increases in temperature [27–29] and pressure [30]. but as the fluidizing velocity is increased. particularly for fine-particle systems. db 0.8P 0. then these will be carried out of the system or elutriated. This height is called the transport disengagement height (TDH). f.

Increasing the temperature will cause a reduction in the terminal velocity for particles in the Stokes region (small particles) and an increase for those in Newton region (large particles). the elutriation rate will increase for a decrease in the particle terminal velocity. u t.7 and B′ 31. The Zenz–Weil [34] equation is recommended for particles of diameter d p 100 µm and superficial gas veloci1. Geldart [11] recommended various elutriation rate constants for particle size fraction d pi. and in the Newton region (large particles) according to (1/ρ g)0. The increased gas viscosity decreased the terminal fall velocity and increased the rate of entrainment for a given fluidizing velocity. Effect of Hydrodynamics on Reaction Conversion Because the conversion of fluidized-bed chemical reactors depends on the contact of solids (either catalyst or reacting) with reactant gases. and other low-density solids: K* i∞ (µ gu 0) where A A 1.4 and B′ 49. For the discharge point exceeding TDH.4 for higher velocities and coarser particles 4. as the gas pressure is increased at constant gas velocity.2 m/s when the entire bed is potentially entrainable (even the largest ties u 0 particles have a terminal velocity u t u 0).31 107 and B 104 and B 1. coal char.44 Pressure and Temperature in Fluidized Beds while maintaining the system pressure constant. (21) and (22). Hence.88 when [(u 2 /(gd pi ρ 2 ) 0 ρ 1. slightly in the transition region. the dominant effect was the increase in gas viscosity. it is advantageous to be . according to Eq.1 and B′ 5. Terminal velocities are unaffected by the gas density in the Stokes region (small particles). thus.27 for beds consisting largely of 1-mm solids 4 for 2.5-mm coarse particles in the bed A′ exp B′u t u0 (22) It is clear that the elutriation rate constants will increase for increases in gas viscosity and gas density according to Eqs. Some of the applicable materials include cracking catalyst.5.26 4. (22).18 when [(u 2 /(gd pi ρ 2 ) 0 ρ 3 3 10 10 4 4 A u2 0 gd pi ρ 2 p B (21) Geldart [11] proposed that K* i∞ (ρ gu 0) where A′ A′ A′ 23. the size of the particles carried over will increase slightly. Also.

X CO 0.e. At nominal P 6996 kPa. Bubbles were reported to be d b 5 cm in diameter for the P 3549 kPa operation and to 2 cm in diameter for the P 6996 kPa operation.8 cm inner diameter 22 cm long) and fluidizedbed (15 cm inner diameter 2. This contacting can be improved by forcing more feed gas to flow directly into the dense phase (i. For GHSV 1000 h 1 and T 623 K.74 in the fixed bed versus X CO 0. one would expect that higher pressures would result in improved reactor conversions. Nomenclature A A′ Ar Constant in Eq. Their results showed that for nominal pressures of P 3549 kPa. which do form. increasing q D relative to q B) and to keep the bubbles. The investigators believed that even better results could have been achieved if finer particles were being fluidized ( 100 µm). the conversion of carbon monoxide (X CO) was noticeably higher for the fixed-tube reactor. The better agreement between results at nominal P 6996 kPa versus P 3549 kPa was believed due to smaller bubbles at the higher pressures. the number of times the bubble gas was exchanged with the dense phase gas as bubbles rise in the bed) was calculated to be between 5 and 6 for the smaller bubbles at higher pressures versus 1 for the larger bubbles at lower pressures. [21] presented the only comparative results ever reported for a pilot-scale tubular fixed-bed (3. Results reported in the literature indicate that the highpressure.Pressure and Temperature in Fluidized Beds 45 able to improve the amount of feed gas contacting the solids. (22) Archimedes number d 3 ρ g(ρ p p ρ g)g/µ 2 g . Normally. They investigated the exothermic Fischer–Tropsch synthesis of syngas at pressures of P 3549 and 6996 kPa and temperatures between T 613 and 663 K. X CO 0. The number of gas be d b interchanges for bubbles traversing the bed (i. fluidized-bed scale-up is complicated by the fact that the wall for small-particle systems limits bubble growth and that bubbles grow as the bed gets larger.7 m long) catalytic process operating at comparative gas hourly space velocities (GHSV) and temperatures.7 in the pilot fixed bed versus 0.55 for the pilot fluidized bed. These results indicate that the smaller bubbles resulting from higher pressures in fine-particle systems contribute to substantial improvement in mass interchange.e. (21) Constant in Eq. For GHSV 1600 h 1 and T 621 K. Weimer et al. fluidized-bed bubble size can be controlled by proper selection of fineparticle size.71 in the fluidized bed. the fixed-bed X CO conversions were only slightly higher than those in the fluidized bed were. fine-particle fluidized beds from laboratory data is simplified because bubble growth is limited by hydrodynamics. small (improved mass transfer between dilute and dense phases). The scale-up of high-pressure. Because higher pressures increase gas–solid contacting for fine-particle systems. allowing fixed-bed-type conversions... The fluidizable particle size was measured to be around d p 100 µm.

46 B B′ db C1 C2 d bmax df do d be dp d eff d pi F Fr f g h hj K* i∞ k Lf n P qB qD q G(in) R R0 Re mf T T (amb) t am te u0 u mf ut VB Vj X CO Pressure and Temperature in Fluidized Beds Constant in Eq. (12) Pressure (Pa) Volumetric flow rate of gas as bubbles (m3/s) Volumetric flow rate of dense phase gas (m3/s) Volumetric flow rate of gas (m3/s) Defined by Eq. (22) Bubble diameter (m) C 1 42. (21) Constant in Eq.75 mf Maximum bubble diameter (m) Frontal bubble diameter (m) Jet nozzle or distributor orifice diameter (m) Equivalent bubble diameter.86(1 ε mf)/φ C 2 φε 3 /1. (15) Frontal radius of a bubble (m) Particle Reynolds number d pu mf ρ g/µ g Temperature (K) Ambient temperature (K) Time available for growth (s) Required growth time (s) Superficial gas velocity (m/s) Minimum fluidization velocity (m/s) Terminal velocity (m/s) Bubble phase volume (m3) Jet phase volume (m3) Conversion of carbon monoxide Greek εD ε mb ε mf ε mf(amb) Dense phase voidage Voidage at minimum bubbling Voidage at minimum fluidization Voidage at minimum fluidization at ambient temperature . averaged over bed height (m) Particle diameter (m) Effective particle diameter based on experimental u mf calculation (m) Diameter of particle size fraction I (m) wt fraction of fine particles 45 µm in diameter Froude number u 2 /gd p 0 Bubble frequency (1/s) Gravitational force (m/s2) Distance up the bed axially (m) Distance the jets protrude up the bed (m) Elutriation rate constant for size fraction d pi(kg/m2 s) Linear slope for rate of change of ε mf with temperature (l/K) Expanded bed height (m) Parameter used in Eq.

Lignola. 951–961 (1998). Kornosky. Arnaldos. 247– 256 (1986). Geldart. Engineering Foundation. Danko. E. Knowlton. Zhang.. Casal. Toman. ‘‘Mechanics of Fluidization.’’ Chem. Potter and D. . J. ‘‘Hydrodynamic Characteristics of Gas– Solid Fluidized Beds over a Broad Temperature Range. Mathur. 253–261 (1984). 33(10). 637–640 (1991). ‘‘Influence of Pressure on the Minimum Fluidization Velocity. A. 3. Chichester.’’ Chem.’’ AIChE J.’’ in Fluidization VII (O.. 1698–1707 (1987). Geldart. Sci. 27–46. R. Jacob and A. 121–132 (1986). Formisani. T. Formisani. 9. (12)] Maximum wavelength of disturbance Gas viscosity (kg/m s) Kinematic dense phase viscosity Angular position where disturbance originates Gas density (kg/m3) Particle density (kg/m3) 47 References 1.’’ Powder Technol. Saxena. Lucas. and Z. G.’’ in Gas Fluidization Technology (D. 46(2). F. M. ‘‘High Temperature Incipient Fluidization in Mono and Polydisperse Systems. and J.’’ Powder Technol. M.. R. Yuregir. 123–154. 51(2). 2. G. Eng. P. 35–46 (1980). Commun. J. Wiley.. 1986. and P. Eng. ed. ‘‘Behavior of Gas Fluidized Beds of Fine Powders I. 11. New York. 72. C. Weimer and G..’’ Powder Technol. Quarderer. 1019–1028 (1985). K. 26. C. ‘‘High-Pressure Particulate Expansion and Minimum Bubbling of Fine Carbon Powders. 1992. B.. R. pp. 14. D. Olowson and A. E. Raso. Eng. V. J. M.’’ AIChE J. Chichester. B..). W.). (12)] Initial amplitude of disturbance for Taylor theory [Eq. Weimer.-S. ‘‘Particle Entrainment and Carryover. Sci. 4. L. Y. 53(5). (12)] Particle sphericity Wavelength of disturbance for Taylor theory [Eq. Y. Homogeneous Expansion.’’ Chem. ‘‘Effects of Temperature and Pressure on Gas–Solid Fluidization. A. 10.. Progr.’’ Chem. Abrahamsen and D. J. Ser. Yu. H. ‘‘On Dense Phase Voidage and Bubble Size in High Pressure Fluidized Beds of Fine Powders. P. and K. S.. Puigjaner. Sci. S.’’ Powder Technol. 41. 6. eds. ‘‘Characteristics of Fluidization at High Pressure. 62. 100–111 (1966). ‘‘The Influence of Temperature on the Properties of the Particulate Phase at Incipient Fluidization. Mancuso. 12.. ‘‘The Effect of Operating Temperature on the Velocity of Minimum Fluidization Bed Voidage and General Behaviour. A. Wen and Y. Eng. J. 71–76 (1992). R. J. 13. C. Geldart. 8.’’ Chem. D. ‘‘Analysis of the Fluidization Process of Particle Beds at High Temperature. Botterill. G. Symp. 7. Yates. ‘‘Pressure and Temperature Effects in Fluid-Particle Systems.. pp. and L. 31(6). Eng. 47. M. 101–110 (1982).’’ Chem. 39(2). A. Eng. Fan.Pressure and Temperature in Fluidized Beds η η0 φ λ λ max µg νp θ ρg ρp Amplitude of disturbance for Taylor theory [Eq. 167–205 (1996).. Sci. Nicklin. D’Amore. A. Girimonte. Almstedt. W. and L. 31. 5.

. L. Toei. and M. Taylor. R. M. 29. ‘‘Equilibrium of Forces in a Fluidized Bed—Experimental Verification. Sci. 26. Grace. Cai. G. Kunii. K. Fluidization 5 (K. Weil. F. F. and D. Engineering Foundation.. J. AIChE J. 2309 (1972). 45 (1974). eds. Hemisphere. Engineering Foundation. ‘‘The Grid Region in a Fluidized Bed Reactor.’’ Proc.’’ Powder Technol. 100–102 (1973).. Yates. G. 79–86. 23. Shemilt. 1984. Knowlton. 133 (1982). ‘‘Mass Transfer from a Grid Jet in a Large Gas Fluidized Bed. Final Report for Department of Energy. WEIMER . ‘‘Quantitative Estimation of Bubble Size in PFBC. Shishtla. M. Hirsan. 283–290. 43. M. Washington. Miccii. M. ‘‘Behaviour of Rising Bubbles in a Gas-Fluidized Bed at Elevated Temperature. and D. Kunii and R. Pemberton and J. R. Ostergaard and S. eds. 19. R. Yoshida. Bergougnou.48 Pressure and Temperature in Fluidized Beds 15. M. G.’’ Powder Technol. Eng. F. A. Clift. 25. 99–109 (1994). Chicago. J.. Shishtla. and M. S. Bergougnou. H.). K. ‘‘An X-ray Study of Bubbles in Fluidized Beds. Engineering Foundation. ‘‘The Effect of Bed and Jet Parameters on Vertical Jet Penetration Length in Gas Fluidized Beds. Sorenson. Kunii. ‘‘The Instability of Liquid Surfaces When Accelerated in a Direction Perpendicular to Their Planes. 34. Chan. and T. Harrison. 16. Japan. C. 8. L. A. Soc. J. ‘‘Dense Phase Viscosities of Fluidized Beds at Elevated Pressures. A. 20. 27.’’ Chem. J. W. ‘‘Stability of Bubbles in Fluidized Beds. Weimer. pp. A. 388– 392. and T. Grace. 55 (1981). C. Project DE-AC21-83MC20314 (1985).’’ in Fluidization (D. Chem. ‘‘The Effect of Pressure on Bubbling Gas Fluidized Beds. Cochran. Ueno. DC. G. 19. 192 (1950). N. ed. A. Mii. 23. Roy. 18. and D. F. Otake. Kmiec. A. G. Grace. Eng. 28. 275–282. Engineering Foundation. 1986. Cheesman. M. I. Vol. H. Fundam. Chem. Japan. and M. T. 24. Toei. 1070 (1973). Eng. M. 6. New York.). Eng.’’ in Fluidization (D. 17. 1976. Clift and J. 31. 53. A. 1983. 157 (1965). New York. R. 1989. Partridge. J. A. 472 (1958). and C. Kawashima.’’ Powder Technol.). De Michele. King. V. D.. T. S. T. ‘‘Temperature Effects on the Characteristics of Fluidized Beds. and T. pp. Knowlton. Davidson. 33. 32. 217–235 (1987). C. ‘‘Mechanism of Bed to Wall Heat Transfer in a Fluidized Bed at High Temperatures. 21. 1980.. Keairns. A201. Yoshida. Eng. E. 1.).. Quarderer. 77–82 (1974). Conway. 22. Grazzini. I. G.. M. p. Bejcek. Rowe and B. G. Findlay and T. New York. ‘‘The Mechanism of Bubble Break-up in Fluidized Beds. R. Zenz and N. ‘‘The Effect of Pressure on Entrainment from Bubbling Gas Fluidized Beds. and M. New York.. P. 80. I. Chem. J. IL. Knowlton. Schiavetti.’’ 73rd Annual AIChE Meeting. ‘‘Jet Penetration into Fluidized Beds at Elevated Pressures. 28. 261. L. R. D. W.. eds.’’ Trans. Kunii and R. and D. Knowlton. A.’’ in Fluidization VI (J. Sci. 27.’’ in Fluidization Technology. G. Weber. Baker. ALAN W. A. 30.’’ AIChE J. Shibata. Tone. T. Behie. Mitchell. Eng. 4. eds. Chan and T. J.). pp. ‘‘Elutriation of Fine Particles from Bubbling Fluidized Beds. Kehoe.’’ Chem. I. G.’’ J. 13. L.’’ J. ‘‘Design and Performance of a High-Pressure Fischer-Tropsch Fluidized Bed Reactor.’’ Chem. Chem. P.’’ Ind. Inst. 29.. Behie and P.

There is a direct payoff in savings on a company’s workers’ compensation insurance.Process Safety and Risk Management 49 Fundamentals of Process Safety and Risk Management Introduction The growth of industry and.’’ In fact. Recently. it is important to study the concept of multiple barriers and its role in preventing process plant accidents. It is important to study these patterns in order to be able to develop management systems to prevent these accidents. and the impact of operating conditions. .). Also. had at least one of the ‘‘barriers’’ not failed. The ingraining of safety as second nature in day-to-day activities requires a paradigm shift and can only be accomplished when safety is viewed as an integral and comprehensive part of any activity as compared to being a stand-alone or add-on activity. It is even more important now to design the process and equipment to precise standards based on a complete understanding of the underlying hazards. These more complex processes require in-depth analysis and knowledge of process chemistry and hazards. Managing safety is no easy task. especially in the chemical industry. However. but it makes bottom-line sense. and exotic chemistry. and impact of operating conditions are the root cause of many process plant incidents. However. as a result. whose premiums are partly based on the number of claims paid for job injuries [1]. much attention has been paid to human factors and its impact on chemical plant incidents. Accident Process and Multiple Barrier Concept Most chemical plant accidents follow a typical pattern. it can be argued that many of these accidents may not have occurred. It starts with sustained support of top management followed by implementation of appropriate programs and practices that institutionalize safety as a culture as compared to add-on procedures. more reactive chemicals. flow rate. the economy are dependent on technology advances and innovations. pressure. these same activities often lead to more complex processes. chemistry. and understanding of the process hazards. process chemistry. Thus. etc. information. The indirect benefits are far larger. This is based on the concept that inadequate knowledge. which is using comparatively severe operating conditions (temperature. many accidents occur as a result of the failure of multiple systems or ‘‘barriers. one can also say that process knowledge and understanding is the most human factor. for safe plants tend to be well run in general and more productive. The recipe for safety is remarkably consistent from industry to industry.

or condition which allows the accident process to continue. some corrective actions might include the following: • • • Using a pump with an improved design. which stop the accident The following is an example of the process: • • • • • A seal on a sulfuric acid pump leaked. 1 . and improving procedures and training to ensure timely washing of equipment and use of protective equipment (reducing likelihood of propagating events) Training the mechanic to assume the pump contains sulfuric acid and to drain it to a safe place before he begins his work (provide a safe terminating event by safely removing the acid) Multiple Barrier Concept (Layers of Protection) Chemical processes traditionally rely on multiple layers of protections. we must modify this accident process. between a hazardous agent and the people. which would require less frequent seal repair (reducing the likelihood of the initiating event) Providing a double block between the sulfuric acid supply and the pump. but some time passed before maintenance began (propagating event). and property which might be adversely impacted by an incident. or by providing terminating events to interrupt the accident sequence before unacceptable consequences can occur. An isolation valve between the pump and the sulfuric acid supply was leaking (propagating event). which starts the accident process Propagation: the event.50 The Accident Process Process Safety and Risk Management Most chemical accidents follow a three-step process. series of events. but failed to wear rubber boots (propagating event). requiring replacement (initiating event). The pump was drained and washed. For the example described. or barriers. environment. The mechanic wore most of the required personal protective equipment. reducing the ability of propagating events to increase the magnitude of the accident. as described by Crowl and Louvar [2]: • • • Initiation: the event. When the mechanic began to work on the pump. This can be done by eliminating or reducing the likelihood of initiating events or propagating events. he was splashed on the foot when a small amount of sulfuric acid was released. resulting in an acid burn (terminating event—all of the acid in the pump was released). or which expands the magnitude of the accident Termination: the event or events. This concept is illustrated in Fig. To prevent accidents.

2. physical containment systems such as catch tanks and spill containment dikes. (Based on Fig. safety interlocks.) [3]. basic process controls and operating procedures. 3. 1 Typical layers of protection for a chemical process. emergency equipment such as rupture disks and pressure relief valves.2 of Ref.Process Safety and Risk Management 51 FIG. critical alarms and process shutdown procedures. emergency response equipment and services such as sprinkler sys- . The layers of protection might include the basic process design.

or property—hazard analysis or hazard evaluation. The U. there may be no need for additional protective layers at all. and an understanding of the mechanisms or scenarios by which those hazards might result in harm to people. This requires a complete understanding of the hazards of the process and plant-hazard identification. The American Petroleum Institute (API) and the American Chemistry Council (ACC) started to work with their members to develop organizational guidelines. Regulations During the past 15 years. and the fire and radiation release in Chernobyl. and extent of each document differed. the liquefied petroleum gas explosion in Mexico City in 1984. and personnel evacuation procedures. The final OSHA rule on Process Safety Management of Hazardous Chemicals (29 CFR 1910.52 Process Safety and Risk Management tems and fire-fighting equipment and personnel.119) was published in the Federal Register [7] on February 24.S. the environment. although the layers of protection may be highly reliable and the risk of an accident may be small. Also. Department of Labor directed the Occupational Safety and Hazard Administration (OSHA) to develop federal standards for managing process safety. were reported worldwide. 1992. such as the vapor cloud explosion in Flixborough in 1974. Although the language. a number of chemical or related incidents in the petrochemical industry have adversely affected surrounding communities. Both governmental agencies and trade organizations responded by developing standards and regulations to improve process safety. A few of these incidents. The API published Recommended Practice 750: Management of Process Hazards [4] in January 1990. the contents and objectives were almost the same. OSHA published the proposed federal process safety rule [5] in July 1990. In October 1990. if the hazard is sufficiently small. An inherently safer process (discussed elsewhere in this article) will reduce or eliminate the hazard and will require fewer or less robust layers of protection—and. application. A consensus started to emerge in 1990. This is highly desirable because the layers of protection may require significant initial capital investment and ongoing operating costs to ensure their continued effectiveness. A matrix showing the relevance of OSHA Process Safety Management (PSM) elements to the Center for Chemical Process . the Clean Air Act Amendments of 1990 directed OSHA and the Environmental Protection Agency (EPA) to develop process safety management regulations to protect workers and the environment. it can never be zero—there is always a possibility that all of the layers of protection will fail simultaneously and the accident will occur. The number and required reliability of the barriers or layers of protection must be established through the use of the various hazard and risk analysis techniques described in the following sections. In addition. the toxic material release in Bhopal in 1984. the ACC published its Resource Guide for Implementing the Process Safety Management Code of Practices [6]. Multiple barriers are generally required because no barrier will be perfect— all are subject to potential failure.

In response to the 1976 chemical dioxin release in Seveso. Process and Equipment Integrity 53 Relevant paragraphs of OSHAs PSM rule Process Safety Information § 1910. Accountability: Objectives and Goals 2. The Norwegian Petroleum Directorate issued rules [8] in 1981 requiring quantitative hazard analyses for offshore petroleum operations. expansions.119 (n) Incident Investigation § 1910. following the recommendations of the widely distributed Cullen Report.119 (l) Process Hazard Analysis § 1910. 11. 12. Codes.119 (i) 7. a European Directive [9] (commonly called the Seveso Directive) on process safety management was issued in 1982. Process Knowledge and Documentation 3.119 (d) Pre-Startup Safety Review § 1910.119 (f ) Operating Procedures § 1910.119 (g) Pre-Startup Safety Review § 1910. The international chemical and petroleum community has also been addressing process safety management through regulations and recommended practices. EPA published the Risk Management Program in June 1996. the International Labor Office in Geneva has issued hazard analysis recommendations [12]. Capital Project Review and Design Procedures (for new and existing plants. the British government has issued process safety management regulations [10] for North Sea petroleum operations. Similarly. and Laws Audits and Corrective Actions Enhancement of Process Safety Knowledge Mechanical Integrity § 1910. More recently.119 (j) Process Hazard Analysis § 1910. . Training and Performance 9.119 (m) Compliance Audits § 1910. 10. Human Factors 8.119 (e) Pre-Startup Safety Review § 1910.119 (o) Safety’s (CCPS) chemical process safety management elements is given in Table 1. Process Risk Management 5.119 (i) Emergency Planning and Response § 1910. Management of Change 6.119 (f ) Mechanical Integrity § 1910. and acquisitions) 4. Italy.119 (e) Operating Procedures § 1910. which investigated the 1985 Piper Alpha offshore platform tragedy. Outside of Europe.119 (f ) Training § 1910. the World Bank [11] has provided process safety management guidance for third-world projects.Process Safety and Risk Management TABLE 1 Summary Comparison of OSHA Elements with CCPS Elements CCPS 12 elements of chemical process safety management 1.119 (i) Management of Change § 1910.119 (j) Process Hazard Analysis § 1910. Incident Investigation Standards.119 (e) Operating Procedures § 1910.

the EPA promulgated the regulation for Risk Management Programs for Chemical Accident Release Prevention (40 CFR 68). the scenario assumes an . and management practices. The regulation requires a comprehensive management program: a holistic approach that integrates technologies. the local emergency planning committees. The objective of the regulation is to prevent or minimize the consequences of catastrophic releases of toxic. Segments of the hazardous chemicals industry have for sometime practiced some or all of the required programs. processes that involve flammable liquids or gases on-site in one location. and processes that involve the manufacture of explosives and pyrotechnics. procedures. The promulgation of the regulation formalized the requirements and established a minimum criterion. For liquids. oil or gas well drilling or servicing operations. reactive. the state emergency response commission. the worst-case release scenario assumes the quantity is released in 10 min. The process safety management regulation requires a systems approach for managing safety. in quantities of 10. prevention program. The Risk Management Program In 1996. flammable. The RMP includes a description of the hazard assessment. 1992 [7]. the regulation does not apply to retail facilities. For gases. including administrative controls and passive mitigation that limit the total quantity involved or release rate.54 Process Safety and Risk Management The Process Safety Management Program The 14 elements of the OSHA Process Safety Management (PSM) regulation (29 CFR 1910. or normally unoccupied remote facilities. The regulation requires regulated facilities to develop and implement appropriate risk management programs to minimize the frequency and severity of chemical plant accidents. are included if the fuel is part of a process covered by this regulation. subsequently. EPA required a performance-based approach toward compliance with the risk management program regulation. This federal regulation was mandated by section 112(r) of the Clean Air Act Amendments of 1990. because of the same reason. This is both good and bad. The regulation now requires everyone to establish the management systems and apply the technologies needed to comply with the regulation. In keeping with regulatory trends. The process safety management regulation applies to processes that involve certain specified chemicals at or above threshold quantities. or more (subject to few exceptions).000 lbs. Facilities submit the RMP to the EPA and. The risk management program regulation defines the worst-case release as the release of the largest quantity of a regulated substance from a vessel or process line failure. or explosive chemicals.119) were published in the Federal Register on February 24. and communicated to the public. and the emergency response program. which may be excluded if used solely as a fuel. it is made available to governmental agencies. Hydrocarbon fuels. In addition. However. The EPA regulation also requires regulated facilities to develop a Risk Management Plan (RMP). there is a tendency to look for ‘‘paper compliance’’ as compared to making real improvements in safety programs and technologies.

A mixture of a vinyl monomer and a peroxide initiator has significant potential chemical energy of reaction. the environment. or property. For alternative scenarios (note: EPA used the term alternative scenario as compared to the term more-likely scenario used earlier in the proposed regulation). Sulfuric acid is corrosive.Process Safety and Risk Management 55 instantaneous spill and that the release rate to the air is the volatilization rate from a pool 1 cm deep unless passive mitigation systems contain the substance in a smaller area. they are intrinsic to the material or its conditions of use. Appendix A of the final regulation lists endpoints for toxic substances to be used in worst-case and alternative scenario assessment. Therefore. Hazard and Risk Hazard A hazard is a physical or chemical characteristic of a material or process which has the potential to cause harm to people. the scenario assumes an instantaneous release and a vapor cloud explosion using a 10% yield factor. which make the material or system useful. A 600 psig steam pipe is at elevated temperature and also contains a lot of energy from the pressure of the steam. Gasoline is a flammable liquid. or it can be the result of an interaction among two or more materials or sources of energy. will produce a valuable product. To do this. when polymerized under controlled conditions. Although it is generally preferable to eliminate or reduce hazards (see later discussion on inherent safety). The flammable endpoints represent vapor cloud explosion distances based on overpressure of 1 psi or radiant heat distances based on exposure to 5 kW/m2 for 40 s. may be the same as the properties. Then. facilities may take credit for both passive and active mitigation systems. it can be a result of the conditions of use of the material. However. These hazards cannot be changed. this is not always possible. The properties of a material or system. Some examples of hazards include the following: • • • • • • Chlorine is a toxic gas. A highly reactive monomer. which create a hazard. A hazard can be a characteristic property of a material. the result could be overpressurization of a reactor and a possible explosion. The toxic endpoints are based on ERPG-2 (Emergency Response Planning Guidelines—Level 2) or level of concern data compiled by the EPA. you must understand how . it is often necessary to manage and control the hazards of a process and plant. you must first identify and understand the hazards—hazard identification. A cylinder containing compressed air contains significant potential energy from the pressurized gas. The only way to eliminate or reduce hazards is to change the material or conditions of use. if the polymerization is not controlled. For flammables.

and incident likelihood: Risk f (incident. two employees. or loss. All of these risks must be understood and managed to successfully operate a profitable plant and business over the long term. and others. consequence. incident consequence. for example. or property can be realized from the hazardous material or condition—hazard evaluation or hazard analysis.56 Process Safety and Risk Management the harm to people. Risk can be considered to be a function of the potential incident occurrence. There are many different measures for each of the risks associated with a chemical manufacturing facility. or property loss expressed in terms of both the likelihood of the incident and the magnitude of the injury. etc. risk of damage to the plant or other property. safety risk to plant workers. likelihood) There can be many different kinds of risk associated with a chemical process or plant. environmental damage. damage.) Average risk of injury to an employee The CCPS Guidelines for Chemical Process Quantitative Risk Analysis [13] describes many different measures of safety risk which might be used in understanding the risk of a chemical plant and also provides quantitative methodologies for calculation. risk of various kinds of environmental damage. including the hazards associated with the following: . Risk Risk is a measure of human injury. For example. health risk to neighbors. business risk that the product cannot be sold. the environment. risk of loss of business due to a plant outage. Hazard Identification and Hazard Evaluation Objective of Hazard Identification and Evaluation The objective of hazard identification is to fully understand the hazards of a chemical process. three employees. some measures of risk to employees in a plant include the following: • • • • • Average risk of fatality from a process accident to an employee in the plant Maximum risk of fatality from a process accident to the employee at greatest risk Average risk to a specific employee in a plant over the course of a normal working day as he does various specific jobs An estimate of the distribution of likelihood of accidents of various size (impacting one employee. risk of producing product which does not meet specifications and cannot be sold. health risk to workers.

Process Safety and Risk Management


• • •

Materials; for example, toxicity, reactivity Process conditions; for example, high temperature, high pressure Potential interactions among one or more materials; for example, chemical reaction, decomposition, corrosion

A full understanding of all hazards of a process is the essential first step in eliminating, minimizing, or managing those hazards. The objective of hazard evaluation is the identification of specific mechanisms by which the potential harm associated with the process hazards can be realized. Hazard evaluation techniques can also include the identification of protective measures which have been incorporated into the process design to manage the hazards, qualitative assessment of the risk of the specific incident scenarios identified, and evaluation of the adequacy of existing protective features or recommendation for additional safeguards.

Hazard Identification Hazard identification is based on a complete knowledge of the properties of the materials being handled and the chemical and physical processes used. Hazards of materials can be identified from literature searches, publications such as Sax’s Dangerous Properties of Industrial Materials [14], and libraries of Material Safety Data Sheets. The best source of hazard information for raw materials is often the material supplier. Bretherick’s Handbook of Reactive Chemical Hazards [15] provides a comprehensive summary of reactive chemical hazard literature. Checklists are a good mechanism for identifying process hazards (checklists as a hazard evaluation technique will be discussed later). Two specific tools for hazard identification, which are particularly useful in understanding chemical reaction hazards, are discussed in more detail in the following sections.

Interaction Matrix
The interaction matrix (Fig. 2) is intended to identify chemical reaction hazards among materials and energy sources in a chemical process. This tool is particularly useful early in the development of a new chemical process. To create an interaction matrix, list all of the materials, materials of construction, likely contaminants, potential sources of energy, process utilities (such as steam, water, nitrogen, compressed air, ethylene glycol coolant, and heat transfer oil), and other relevant parameters along each axis of the matrix. It is a good idea to also include ‘‘people’’ on one of the axes, to prompt questions about toxicity and other adverse impacts of materials on people. Then, ask what happens for each interaction where the matrix columns and rows intersect. The matrix should go beyond a simple yes– no answer, but rather should provide some detailed information on the nature of the interactions identified. Often an interaction matrix will generate more questions than answers, particularly early in development. In this case, it may be appropriate to recommend a literature search or laboratory experiments to understand potential interactions.


Process Safety and Risk Management

FIG. 2 Example interaction matrix.

Chemistry Hazard Analysis The Chemistry Hazard Analysis (CHA) is derived from the Hazard and Operability (HAZOP) study methodology. The thought process of a HAZOP study can be applied at any stage in process development. The CHA is a HAZOP applied to a chemical reaction, without the detailed plant design information required for a traditional HAZOP study. For the CHA, the chemist or engineer usually assumes that the deviation identified by the application of the guide word to the chemical reaction does occur for some reason, not developing specific causes, and investigates the consequences. If the consequences are known, the designer should determine if they represent a hazard which must be understood and managed as a part of the process development, and document this information for future action or reference. In many cases, early in process development, the consequences may not be known, and additional research or experiments may be needed.

Hazard Evaluation: Selection of Procedure A number of different hazard evaluation techniques are in common use in the chemical industry, as listed in Table 2. Some techniques, particularly those based on logic models, require more detailed plant design information and it may not be possible to apply them early in process development. Table 3 provides some

Process Safety and Risk Management
TABLE 2 Category Brainstorming techniques Process Hazard Analysis Tools Commonly Used in the Chemical Process Industries Process Hazard Analysis Tool Safety review Preliminary hazard analysis What If Hazard and Operability Study (HAZOP) Failure Mode and Effect Analysis (FMEA) Description and Comments


Checklist techniques

Checklist What If/checklist

Risk-ranking techniques

Relative ranking

Logic model techniques

Fault-tree analysis Event-tree analysis

Relatively unstructured brainstorming techniques to identify hazards and potential accident scenarios. A structured analysis procedure that focuses brainstorming activities, including use of a specific set of guide words or knowledge and checklists of known equipment failure modes. Predefined checklists based on previous experience compare a design to specific standards or good practice. When combined with What If analysis, the checklists are used to prompt brainstorming activities. A general category that includes a large number of quantitative and semiquantitative techniques which use checklists or equations based on material properties, quantities, and handling conditions to numerically rank risk. Examples include the Dow Fire and Explosion Index and the Dow Chemical Exposure Index. Logic models which identify specific causes combinations of events which lead to a potential accident scenario. These techniques require much detailed design information and usually focus on analyzing a few specific accident scenarios in detail. These techniques can be quantified and are important tools in quantitative risk analysis

guidance on how the various techniques have commonly been applied through the life cycle of a chemical process.

What-If Analysis What-If Analysis is a brainstorming technique in which a team with expertise on the process asks ‘‘what-if ’’ questions about the process to identify potential hazards or incident scenarios. The Preliminary Hazard Analysis and Safety Review techniques are forms of What-If Analysis. In a What-If Analysis, a team of experts on the process and plant meet in a free brainstorming session to ask ‘‘what-if ’’ questions to identify what can go wrong. The technique is very flexible and can


Process Hazard Analysis Technique

Process Hazard Evaluation Techniques

Chemical Process Life-Cycle Stage Safety Review Checklist What-If Relative Ranking What-If/ Checklist

Preliminary Hazard Analysis

Failure Mode and Effect Analysis (FMEA)

Hazard and Operability Analysis (HAZOP)

FaultTree Analysis

EventTree Analysis

Research and development Conceptual design Detailed engineering Construction Start-up Routine operation, modifications, and expansions Decommissioning Demolition
: PHA technique rarely used or not appropriate.

Process Safety and Risk Management

Note.— : PHA technique commonly used; Source: Based on Ref. 5.

Process Safety and Risk Management
TABLE 4 Example of the Results of a What-If Analysis for a Batch Process What-If...? 1. Reactant feed rate is too high? Hazard or consequence Safeguards



2. Reactor temperature is too low?

1. Heat generation 1. High reactant 1. Establish prevenrate exceeds heat flow rate intertive maintenance removal capabillock shuts down and testing proity, increased temfeed. High reactor gram for flow perature, potentemperature inand temperature tial runaway terlock shuts interlocks. reaction. down feed. Rupture disk sized adequately to protect reactor for maximum feed rate with no cooling. 2. Reaction may 2. Low reactor tem- 2. Evaluate rupture stall, resulting in perature alarm disk size relative a buildup of rewarns operator. to potential poolactants. This pool ing of unreacted of unreacted matematerial. Based rial has signifion result, detercant potential enmine if additional ergy, possible protection is runaway reaction needed. if temperature is subsequently increased.

be applied at any stage in the process life cycle. The unstructured nature of WhatIf Analysis can be both an advantage and a disadvantage. With an experienced and knowledgeable team, the technique can be powerful. The discussion and interaction among team members in the meeting can enhance the identification of hazards. However, the unstructured nature may result in an incomplete analysis by an inexperienced team. Table 4 is an example of the results of a What-If Analysis. WhatIf is often combined with a checklist to ensure that a minimum set of ‘‘What-If’’ questions are covered by the review team.

Checklist Analysis A checklist is a list of items used to verify that a plant or process is designed and operated consistently with a predetermined set of good practices defined by the checklist. A checklist is often used to confirm that a plant complies with codes, standards, or regulations. Checklists vary from general lists of questions describing common chemical hazards and processing concerns to detailed lists of specific requirements of a standard. Many checklists are simple, requiring only ‘‘yes, no,

Checklist completeness depends on the experience of the checklist authors. The use of checklist analysis depends on the availability of suitable checklists for the plant being reviewed. the team determines as many potential causes of the deviation as possible. a piece of process equipment such as a reactor or heat exchanger. The following are basic guide words: • • • • • • • No More Less Part Of Reverse As Well As Other As an example. The output of a checklist analysis is a list of responses to the checklist questions.62 Process Safety and Risk Management not applicable’’ answers. as intended. or a step in a batch process. with areas of noncompliance highlighted and recommendations for bringing the facility into compliance. including values of the process parameters—the process intention. and are unlikely to be available for unique process operations.’’ Once a deviation has been identified. or nodes. which are analyzed individually. Hazard and Operability Study A Hazard and Operability Study (HAZOP) is a guide word hazard evaluation technique normally done by a review team. A Hazard and Operability Study is best applied when specific process and plant information is available (e. the process is first divided into sections. and the checklist ensures that the team considers a specified list of hazards based on prior experience.. the guide word ‘‘less’’ can be combined with a specified reactor temperature intention to arrive at the deviation ‘‘less (lower) reactor temperature. incorrect temperature set point. The team states the intended operation of each process node. and the team must agree that this is true.’’ causes might include a cooling water control valve stuck open. Combining a What-If Analysis with a checklist can be a very effective hazard identification and evaluation technique. The team determines the consequences of each deviation. and the review team determines the consequences of those deviations. HAZOP begins with the premise that the process is safe if operated. a detailed plant design or an operating plant). The team then applies guide words to the parameters to identify potential deviations from intended operation. such as flammable-solvent storage facilities. Guide words are used in conjunction with the process operating parameters to identify potential deviations. To do a HAZOP. For the deviation ‘‘less reactor temperature. Good checklists are most likely to be available for common types of installation. Incidents are assumed to result from deviation from intended operation. and others. The What-If allows creative brainstorming of a team to identify hazards. cause . addressing the concern about completeness of the What-If analysis.g. A node might be a transfer line from one vessel to another.

It then qualitatively judges the effectiveness of the safeguards to determine if they are adequate. The analyst begins with a specific undesired event and develops a model using Boolean ‘‘AND’’ and ‘‘OR’’ logic gates to identify the immediate causes. Event-Tree Analysis An event tree is a graphical logic model which shows the possible outcomes resulting from an initiating event.. Table 5 shows a part of the output of a typical HAZOP study. If the existing safeguards are judged to be inadequate. Event trees are very useful in understanding the effectiveness of . Fault trees can also be quantified by assigning failure rate and probability data to the basic events. A semiquantitative risk-ranking system is often used to aid the team in evaluating the significance of the hazards identified. the team should recommend appropriate action to mitigate the potential hazard. 4 shows an event tree for the sulfuric acid splash incident used to describe the accident process. Fault-Tree Analysis A fault tree is a logic model which identifies the multiple ways in which equipment and human failures in a system can combine to cause an undesired event (the ‘‘Top Event’’). These outcomes may vary in severity. Human error can be incorporated into a fault tree by including specific operator actions (e. A fault tree can be solved using Boolean algebra techniques to identify specific combinations of individual equipment failures and human errors. The cut sets can be used to identify areas where the system can be improved. The team continues to apply the guide words to each node until no additional deviations can be identified.g. which can cause the undesired top event. until the entire process has been reviewed. basic events are at the level of failure of individual plant components (e. also using Boolean logic gates. a pressure sensor failing to detect high pressure). The development of the tree continues until it reaches a level of resolution judged to be adequate for understanding potential incident sequences and identifying system improvements. These combinations of failures and errors describe specific potential incident scenarios and are called minimal cut sets. a pump failure to run..Process Safety and Risk Management 63 combination. and existing safeguards. opening the wrong manual valve) or errors (e.g. These immediate causes can then be further developed to identify their causes. and the event tree is useful in understanding the full range of possible outcomes that can result from a single system failure. a shutoff valve stuck in the open position. These steps are repeated for each process node. For example. An event tree describes the response of a system to a disturbance created by the initiating event. failure to act in response to a high temperature alarm). These data can be mathematically manipulated to estimate the likelihood of the top event and to understand the relative contribution of individual basic events and cut sets to the total probability of failure. Fig. Normally..g. Figure 3 is an example of the top levels of a fault tree for a fire. These events are not further developed and are called basic events. An event tree describes a number of potential outcomes from a single initiating event.

FIC-301-01 control value stuck open C. 1. MORE than 160 lbs/h Raw Material A flow Process Safety and Risk Management Note. Deviation 1.—Intention: Feed 150–160 lbs. Reactor R-310 agitator is running at 50 rpm. B. Reactor R-310 temperature increases. Confirm that operator training includes proper response to FIC-301-01 and TAH-310-05 high alarms. High temperature alarm TAH-310-05 on Reactor R-310 warns operator. Raw Material A solution temperature is 20–35°C. C. Same as A./h of 42–44% aqueous Raw Material A solution from Feed Tank F-101 using Pump P-110 through line 10436 and flow controller FIC301-01 to Reactor R-310. While feeding.64 TABLE 5 Causes Consequences Safeguards A. Same as A. A-2 only applies. A-1 will not provide an alarm because the flow sensor is miscalibrated. A. . Plant experience indicates this is not likely. High flow alarm on FIC-301-01 warns operators. C. B. 2. even for maximum possible flow rate. Wrong set point (too high) on FIC-301-01 B. product will not meet specifications if R-310 temperature increases above 90°C. heat balance indicates there is no potential for runaway reaction. FIC-301-01 flow sensor miscalibrated—reads low Example of Partial Results of a HAZOP Recommendations A. A. Same as A.

g. Quantitative event tree analysis is often combined with fault-tree analysis: Fault trees are used to quantify the frequency of the initiating event and the probability of failure of the protective systems at the event-tree branch points. Failure Mode and Effect Analysis A Failure Mode and Effect Analysis (FMEA) lists the known failure modes of specific pieces of equipment in a plant and determines the impact of those failures on the plant. the main difference is the starting point for identifying potential hazardous incident scenarios. like a fault tree. the multiple layers of protection. 3 Top levels of a fault tree for a fire.. FMEA and HAZOP are similar.Process Safety and Risk Management 65 FIG. Each independent layer of protection is a branch point in the event tree. which are often present in a chemical process. can also be quantified by estimating a frequency for the initiating event and the probabilities of success and failure at each branch point in the event tree. An event tree. more flow) and asking what kind of equipment failures or operating errors might have caused that devia- . HAZOP starts by postulating a deviation in the value of a process parameter (e. with the branches corresponding to the success or failure of the layer of protection.

unit operations. These risk indices provide a relative ranking of specific types of process hazards (e. and other factors. Table 6 shows a part of the output from a typical FMEA study. operating conditions.66 Process Safety and Risk Management FIG. control valve stuck open) and asks what impact this failure will have on the operation of the process. . chemical reactions. These steps are very similar to the corresponding step in a HAZOP study. identifies existing safeguards. FMEA starts by postulating a known equipment failure mode (e. determines if a potentially hazardous incident will result. tion and what the process impact will be.. understanding the parts of a plant or process which are the major sources of risk. A good understanding of the equipment and potential failure modes is required.g. and develops recommendations for action where appropriate.. Risk-Ranking Techniques Risk-ranking techniques such as the Dow Fire and Explosion Index [16] and the Dow Chemical Exposure Index [17] develop a numerical risk-ranking index based on various process characteristics such as material properties. 4 Example event tree. The FMEA determines how the process will respond to the potential equipment failure. and prioritizing other hazard evaluation and risk management activities.g. The FMEA starts with a functional description of each piece of process equipment and identifies ways in which that piece of equipment might fail to perform as designed. evaluates their effectiveness. fire and explosion hazards) and are useful for comparing alternate process or plant designs (including location and siting).

fails closed on air supply failure B. A. Valve stuck in closed position Example of Partial Results of a Failure Mode and Effects Analysis Safeguards A. Recommendations A. Air failure to FIC-30110 67 . B. Pneumatically operated valve. Possible uncontrolled reaction generating high temperature and pressure. Review maintenance procedures and make sure Valve FIC-301-10 is regularly inspected and tested.Process Safety and Risk Management TABLE 6 Failure mode Effects A. Cooling Water Control Valve FIC-301-10. Full cooling is sufficient to control temperature at maximum raw material feed rate. High temperature interlock TAH-310-08 on Reactor R-310 closes raw material feed valve. Valve will open. Unable to increase flow of cooling water to reactor to control temperature of batch during exothermic reaction. putting full cooling on the reactor. Confirm that there is no buildup of unreacted material and stopping feed will stop reaction. Item and Description 1. B.

Consequence models can be quite complex and can only be described in general terms in this discussion. it is recognized that there is a wide variety of other potential consequences of incidents and a correspondingly wide variety of tools used to understand these consequences. there is a number of different tools which may be useful in analyzing these impacts. orifices. providing a wide variety of plant and process experience and interactive discussion to understand the process and identify potential hazards and incident scenarios. Because there is a wide range of potentially harmful impacts of chemical process incidents. rate. and pipes. liquid. risk is defined as a function of incident occurrence. Source Models Source models quantitatively estimate the magnitude. which are readily adapted to describe flow from a leaking pipe or vessel. gas. or a combination). Consequence Analysis As mentioned earlier. Les [25] also provides a detailed description of incident consequence models. There are also a number of public domain and proprietary commercial computer-modeling systems available for chemical release consequence analysis. the environment. Two-phase flashing flow models are based on technology developed by the Design Institute for Emergency Relief Systems (DIERS) [26]. duration. CCPS [18] and Wells [19] provide more information on the application of these and other hazard evaluation tools in the chemical industry. Consequence analysis is the quantitative estimation of the consequence of a chemical process incident—an estimate of the magnitude of the potential harm to people. the consequence analysis tools described will be limited to those commonly used to estimate the potential for injury or fatality to people as an immediate result of exposure to harmful materials or energy. or property. A number of publications by the Center for Chemical Process Safety [20–24] describe specific types of consequence analysis models in detail. and temperature or other physical condition of a chemical release based on the physical and chemical parameters associated with a particular release scenario. and consequence.68 Process Safety and Risk Management Summary of Hazard Identification and Evaluation This section has briefly described a number of commonly used hazard identification and evaluation tools. These include single-phase and multiphase flow models for flow-through holes. physical state (solid. Two-phase or flashing jet release models must also consider the formation of fine aerosols in the discharge and the potential for the small drops . Most source models are well developed in chemical engineering theory and are essentially the same as the models used for similar material flow scenarios used to design plant equipment. However. Most of these tools are best used in a multidisciplinary team environment. In this discussion. frequency.

gravity spreading resulting from the depth of the pool. The vapor release rate is determined from an estimate of the total heat transfer into the pool and the heat of vaporization of the liquid. Evaporation models are based on standard methodologies for estimating convective mass transfer from a liquid into a gas. viscosity. volatile liquid pools.g. composition. total quantity released. For a discharge of material from a reactive system. pressure) . The evaporation of vapor from this pool is another potential source term for atmospheric dispersion models. and relatively nonvolatile liquid pools. both from the ground and from the surrounding atmosphere. it will form a pool on the ground.Process Safety and Risk Management 69 to remain suspended in the atmosphere rather than ‘‘raining out’’ into an evaporating pool on the ground. and they estimate the vapor concentrations at specific locations in the cloud. If a release is wholly or partially in the form of a liquid. and the liquid physical properties (e. Some of the data required for a vapor cloud dispersion model include the following: • • Characteristics of the release. location of the release Characteristics of the release (phase. The evaporation of relatively nonvolatile liquid pools is primarily determined by mass transfer at the surface of the pool. In this case. surface tension. the models required to fully understand the system may be quite complex and data from reaction calorimetry tests may be required. Pool size models consider the momentum of the liquid stream entering the pool. velocity. Vapor Cloud Dispersion Vapor cloud dispersion models estimate the area covered by the vapor cloud from a chemical release as it disperses in the atmosphere. The first step in estimating evaporation from a liquid pool is to estimate the size of the pool. including rate. • • • Boiling liquid pools occur when the pool liquid boils at a temperature below that of its surroundings (the ground and atmosphere). Evaporation models for volatile liquid pools consider both heat transfer into the pool and mass transfer rates into the atmosphere from the pool surface. which estimate the downwind concentration of the vapor. which are typically modeled: boiling liquid pools. and surface wetting properties). Because the evaporation rate is low.. direction. There are three major pool evaporation situations. the pool temperature will be essentially the same as the temperature of the surroundings after any initial temperature differences equilibrate. vapor generation is controlled by heat transfer into the liquid pool. temperature. Physical constraints such as dikes and containment systems may also determine the size of a pool of spilled liquid. Volatile liquid pools exert a significant vapor pressure but are at a temperature below the liquid boiling point.

pressure Characteristics of the surface. including surface roughness Some of the complex vapor cloud dispersion models may require additional information to characterize the release. and geometry of the fire relative to the receiving source. atmospheric stability. the geometry of the pool. surface emissive power. Pool fire models estimate the thermal effects based on the properties of the material burning in the pool. The CCPS [22] provides a more condensed summary of some of these models. The output of these models describes the concentration of the released material in both time and space as the vapor cloud travels downwind.70 Process Safety and Risk Management • • Atmospheric conditions. usually from a pipe or vessel Flash fire: nonexplosive combustion of a flammable mixture of a combustible vapor in air Pool Fire The primary mechanism of damage from a pool fire is thermal radiation from the flame. temperature. including all of the major types of dispersion models and release types. Vapor cloud dispersion models consider three typical types of behavior: • • • • • Neutrally buoyant gases (having a density close to the density of air) Positively buoyant gases (having a lower density than air) Dense or heavy (negatively buoyant) gases Two major types of releases must also be considered: Instantaneous (puff releases) Continuous releases (plumes) The CCPS [20] describes vapor cloud models in detail. all of which are well established in the literature. and atmospheric transmissivity. the atmospheric conditions. Pool fire models are well developed. Pool fire models provide an estimate of the thermal radiation at locations of interest surrounding the fire. . including wind speed. atmospheric characteristics. flame height. and surface conditions. They are based on empirically determined characteristics such as burning rate. Fires Incident consequence analysis may require consideration of one or more of several different types of fire: • • • Pool fire: a burning pool of a flammable or combustible liquid Jet fires: burning of a flowing jet of flammable liquid or gas.

In this case. Confined explosions: explosion resulting from a rapid chemical reaction generating high temperature and pressure inside a confined space such as a vessel or a building. which is normally for a brief time of a few tenths of a second. like pool fires. If the liquid is flammable. the damage from a jet fire results primarily from thermal radiation from the fire. . due to a vessel defect or excess pressure in the vessel). Explosions Chemical incident consequence analysis may need to consider four types of explosion: • • • • Physical explosions: the failure of a vessel containing material under pressure without chemical reaction (e. characteristics of the atmosphere. As for pool fires. Flash fires are normally modeled by determining the dimensions of the flammable cloud using vapor dispersion models and estimating the thermal radiation resulting from combustion of the cloud. The primary hazard is from direct contact with the flame and from thermal radiation. Vapor cloud explosions: explosion of a cloud of flammable vapor dispersed in the atmosphere. the burning cloud will not generate pressure and an explosion.22] describes commonly used explosion models in detail. Jet fire models require an understanding of the characteristics of the jet (discharge rate and velocity. Boiling liquid expanding vapor explosions (BLEVE): the catastrophic failure of a vessel containing a superheated liquid. The CCPS [20. Such a cloud can explode under the proper conditions (size and degree of confinement).. ignition may result in a fireball. the cloud may still ignite and burn. material burning properties) and. but the flash fire is still capable of causing significant damage. If the conditions required for a vapor cloud explosion are not present. Jet fire models are primarily empirical but are derived from much data and experience. resulting in a vapor cloud explosion.g.Process Safety and Risk Management 71 Jet Fire Many jet fire models are based on models used for the design of flare systems. The models produce an estimate of the thermal radiation at locations surrounding the jet fire. Flash Fire A flash fire results from the ignition of a cloud of flammable gas (a cloud containing a flammable material at a concentration between its lower and upper explosive limits in air).

This estimated energy is then converted to an equivalent amount of TNT. Vapor cloud explosions are modeled using three types of model: • TNT Equivalency Models. which could cause local partial confinement. which may not be known for a particular material or cloud configuration. Mass of the cloud. and these can be used to estimate damage. TNT equivalency models are empirical. a flammable vapor cloud can burn as a flash fire. It may also be necessary to consider the potential impact of the vessel fragments. and volume to atmospheric pressure. Combustion properties of the fuel. The CCPS [21] reports studies indicating that this minimum mass is in the range of 1 to 15 tons for typical hydrocarbons. which is empirically estimated. structures. Vapor Cloud Explosions If ignited. A number of correlations of explosion pressure as a function of distance from a TNT explosion have been published. which result from a vessel explosion. or other factors. their travel distance. if the flame speed accelerates sufficiently. TNT equivalency models also do not characterize the vapor cloud explosion well in the area close . The total energy available from the combustion is estimated from the mass of fuel in the cloud and the heat of combustion of the fuel. or. Materials with a high fundamental burning velocity such as ethylene oxide and ethylene are reported to be more readily inclined to propagate to a vapor cloud explosion. A number of factors have been found to be important in determining whether a vapor cloud explosion occurs when a flammable vapor cloud is ignited. pressure. Empirical models to estimate the number and size of fragments. This combustion energy is then converted to an equivalent mass of TNT and reduced by an ‘‘explosion efficiency’’ factor. Partial confinement of the vapor cloud as a result of obstacles. it can produce significant blast pressure from a vapor cloud explosion. The explosion overpressure and other characteristics can then be estimated as a function of distance from the cloud using readily available experimental data for TNT explosions.72 Process Safety and Risk Management Physical Explosions Physical explosion models generally estimate the amount of energy which would be released by the sudden expansion of the material contained in a vessel from its initial temperature. and the results are strongly dependent on the explosion efficiency. Experimental studies have demonstrated that there is a minimum mass of flammable material required to transition to a vapor cloud explosion. and energy are available. The explosive combustion in the locally confined cloud can propagate into the rest of the cloud. These include the following: • • • • Turbulence in the vapor cloud. This turbulence may arise from the energy from the release of the fuel itself (from a jet or catastrophic loss of containment) or from the interaction of the cloud with its surroundings during the combustion process.

and the degree of confinement created by the obstacles in the confined volume.Process Safety and Risk Management 73 • • to the cloud. It often occurs as a result of weakening of a pressure vessel caused by direct flame impingement on the vessel above the liquid level. BLEVE models are based on the expansion energy of the flashing liquid. These models are discussed in detail in Refs. and the impact of the fireball. Then. Blast characteristics are then estimated using a set of correlations and charts. BLEVE fireball models empirically estimate the fireball dimensions based on the quantity of material released. it can also ignite. increasing its volume several hundred times and generating a pressure wave and fragments. is the more important source of damage. Confined explosions are modeled by estimating the peak pressure that can be generated from the chemical reaction. Multienergy Method. geometry of the confined volume. . where they may predict much higher pressure than typically result from the combustion of a flammable cloud. and the potential damage is estimated from empirically derived correlations. The combustion or reaction products are often gases. This model is based on the assumption that the blast characteristics of a flammable vapor cloud depend more on the level of congestion and confinement than on the fuel. It also considers burning characteristics and reactivity of the fuel. If the released liquid is flammable. resulting in a fireball. The models are specific to the reaction and may require considerable reaction thermodynamic and kinetic data. the damage resulting from vessel failure and the potential for damage or injury from fragments can be estimated using the methods for physical explosions discussed earlier. Confined combustion reactions may occur with flammable vapor–air mixtures or from the dispersion of a cloud of combustible dust in air. Confined Explosions Confined explosions result from combustion or another rapid chemical reaction in a confined vessel or building. and pressure is generated by the gas and also the elevated temperature resulting from the heat of combustion or reaction. The sudden loss of confinement allows the superheated liquid to rapidly flash. The energy from each blast source is estimated. The models require dispersion models to determine the size of the cloud. which usually accompanies a BLEVE of a flammable material. 20 and 22. This model also considers confinement as the basis for the size of the flammable vapor cloud. Baker–Strehlow Method. Blast effects tend to be local. The maximum pressure resulting from the reaction model is then compared to the failure characteristics of the confining vessel or building. areas with different confinement and congestion characteristics are identified and considered to be sources of strong blasts. Boiling Liquid Expanding Vapor Explosions A BLEVE is the rapid release of a large amount of superheated liquid to the atmosphere. This weakens the metal vessel and it can fail rapidly and catastrophically. If the pressure exceeds the expected failure pressure of the vessel.

g. sometimes a generally accepted standard or code of practice tells us what to do. objects. fires. which results from these physical effects. relating severity of burns to intensity and duration of exposure to thermal radiation.. and property. probabilistic risk assessment (PRA). or estimating damage to structures based on peak overpressure and duration). Stages of Risk Assessment Before carrying out a risk assessment. fires. in the chemical industry. the environment. In other cases.e. Models are available to estimate the impact of a hazardous agent using the dose-response relationship (e. the amount of radiant energy at a specific location from a fire.74 Process Safety and Risk Management Thermal radiation characteristics of the fireball are then modeled using a combination of empirically derived relationships and fundamental models for the geometry of the fireball with respect to the receptor and atmospheric transmission of the thermal radiation. at least for the time being? Often.) There are then three questions to answer: . we have to identify the hazards (i. the decision is not obvious and we use a numerical method known as quantitative risk assessment (QRA). and explosions.. Risk Assessment However many the resources we devote to the prevention of accidents. is the probability that injury or damage will occur. Effect Models The result of the application of the models discussed in this section so far is an estimate of some type of physical parameter at various locations surrounding a chemical release: a concentration of toxic gas in the atmosphere. These models are generally empirical and are based on experimental data and evaluation of the consequences of past incidents. The CCPS [22] provides a summary of effect models commonly used to estimate the impact of toxic vapors. (A risk. in contrast. Effect models estimate the damage. and the peak pressure and impulse duration from an explosion. There are a wide range of possible effect models corresponding to the wide range of potential damage to people. which can result from exposure to toxic materials. hazard analysis (Hazan). some are obviously intolerable large or acceptably small. and explosions on people. the substances. we can never eliminate every risk. relating probability of fatality to concentration and duration of exposure by inhalation of a toxic gas. the judgment is qualitative: Some risks are illegal. The result is an estimate of the radiant energy flux level and duration at various locations surrounding the BLEVE. or situations that can give rise to injury or damage) using one of the methods described earlier. or. We have to decide our priorities: Which risks should we deal with first? Which are so small compared with the other risks to which we are exposed that we should tolerate them.

but often there is no experience. then the average cost of the damage (including consequential loss) is compared with the cost of prevention. The extent to which this approach is used and the risk levels are made explicit differs from country to country. Other governments have been reluctant to admit that even trivial and infrequent risks should be tolerated and this has hindered the use of QRA. the risk can be tolerated. The risk considered tolerable for members of the public is much lower than that considered tolerable for employees. based on the known failure rates of its components. in money. Risks above an upper level are considered intolerable. we reduce the risks if we can. the risk being insignificant in relation to the cost. Risks below a much lower level are considered acceptable and need not be reduced. Thus. In between the two levels. and trouble. but we tolerate them if it is impracticable or very expensive to do so. the plant should not be built (or should not be operated if it is already built). If damage is possible but injury is not. The answer to the third question depends on the nature of the consequences. If there is a gross disproportion between them. in fact. We then estimate a failure rate for the equipment as a whole. if they cannot be reduced. but this risk is. . The pressure to reduce them is great if the risk is near the intolerable level and reduces as we approach the acceptable level.Process Safety and Risk Management 75 • • • How often will injury or damage occur? What is the extent of the injury or damage? What action should we take? Whenever possible. They are similar to those used by many organizations elsewhere. Those below this level can be left alone. usually based on the risk to life. there are two levels of risk. tolerated in some industries. Similarly. QRA is a method for determining priorities. as described earlier. the answer to the first question should be based on experience. Risk of death per person per year Maximum tolerable risk (employees) Maximum tolerable risk (public) Maximum tolerable risk (public—nuclear risks) Broadly acceptable risk (employees and public) 10 10 10 10 3 4 5 6 The maximum tolerable risk to employees seems rather high. The United Kingdom has long accepted the principle that we should compare the size of a risk with the cost. as the equipment is new or failure has never occurred. time. If injury is possible. then the QRA approach is to set a target or criterion. In a later development. The actual risk levels suggested for the United Kingdom are as follows. the answer to the second question should be based on experience whenever possible but can be estimated as by one of the methods described earlier. of removing it (although the ability to pay is not a deciding factor). QRA was therefore accepted readily and the regulatory authority has suggested figures for the tolerable and acceptable risk levels. Risks above a certain level should be removed or reduced as a matter of priority. at least for the time being.

. We try to explain the benefits of the industry and the low levels of risk. 4 for Public Attitudes Quantitative risk assessment is difficult to explain to the public. this is democracy in action. Many people have an opportunity to prevent almost every incident. The public tends to oppose risks with the following traits: • • • • • • • • Imposed rather than accepted voluntarily Not under the individual’s control Of no obvious benefit to them Man-made rather than natural Unfamiliar Dreaded (e. The death of 10 people once in 10 years is given far more publicity than the death of 1 person per year for 10 years. and the spokesmen for the industry are often outsiders. not under his control. but we cannot say that accidents will never happen. They pick on the fact that a number of people could be killed in an industrial accident but ignore the fact that the probability that this will occur is extremely low. past experience has been unpleasant. the annual risk of death from all causes is about 10 someone aged 20 years and about 10 3 for someone aged 60 years. it is giving the most to those that shout the loudest. As a result. After some months. cancer is more dreaded than heart disease though the latter kills far more people) Immoral (e. they judge the messenger.76 Process Safety and Risk Management For comparison..g. At its best. most of these concerns make the man in the street oppose the chemical industry: The risks are imposed.. Incident Investigation The purpose of incident investigation is to find out why the incident occurred so that we can prevent it from happening again. nuclear power reminds us of atomic bombs) When the public cannot judge the message. There is no easy way of countering this perception. at its worst. it leaked and a passing vehicle ignited the escaping vapor. public pressure often compels industry and government to reduce risks which are already low but which the public perceives as high. crime is feared more than road accidents) Associated with unpleasant events (e. man-made. and dreaded.g. Unfortunately. Damage . Figure 5 shows by example the opportunities that are available to prevent a fire or minimize the consequences of an apparently simple incident: An expansion joint (bellows) was incorrectly installed in a pipeline so that it was distorted.g. the industry does not obviously benefit him. unfamiliar. The purpose is not to find out who should be blamed.

by better design methods (using HAZOP. caused no injury or damage. We should investigate all incidents. better design standards. The fire could have been prevented by better detailed design (not using expansion joints for hazardous materials). which. Many people in various functions could have prevented the incident or minimized the consequences. An expansion joint (bellows) was incorrectly installed so that it was distorted. including those. 5 An example of an accident chain. but might easily have done so. consulting experts. they may. and by not tolerating poor workmanship in the past. not just the fitter who installed the expansion joint incorrectly. as the surrounding equipment had not been fire-protected to save the cost. Many people could have prevented the fire. . as the surrounding equipment had not been fireprotected to save the cost. by better inspection of workmanship. After some months. Damage was extensive. it leaked and the escaping vapor was ignited by a passing vehicle. Next time. by better training of the fitter. was extensive. better training of designers). by good fortune.Process Safety and Risk Management 77 FIG. by keeping eyes open on plant visits.

or better compliance with instructions and. If not. Draw up a list of everyone who may be able to help. Ask if the cost of each recommendation is proportional to the size of the risk. perhaps with less serious results. Ask if it was foreseen. Avoid questions to which the answer is ‘‘yes’’ or ‘‘no. better instructions.’’ Make it clear that the objective of the investigation is to find out the facts. not to establish blame. why? If it was foreseen. to ask why it occurred when it did and not at some other time. for example. if so. ask if we need better training. so that we can prevent the incident happening again. Record information on damage and injuries so that others can use it for prediction. were the results followed up? Preventing leaks is a more effective way of preventing liquid and gas fires than removing sources of ignition (although we should also do what we can to remove known sources of ignition). designers. Beneath the immediate technical causes. make it clear who will carry it out and when. what recommendations were then made. Look for causes that lead to actions. have occurred before. why did it occur? Was the right material of construction used? Were operating conditions outside the design range? Was monitoring carried out? If so. It is also useful to ask if similar incidents. Instead. such as poor training or instructions or turning a blind eye to previous failures to follow instructions. Otherwise. Consider alternative solutions as well as the obvious ones. look for ways of removing opportunities for error. Inform any authorities who have to be notified. Look also for weaknesses in management. quote corrosion as a cause and stop there. Managers should not accept reports that fall short in any of these respects. Avoid the use of the term ‘‘human error’’ and never recommend someone to take more care. Drawing Conclusions from the Facts Accident investigation is like peeling an onion. If an error was due to a slip or lapse of attention. look for ways of avoiding the hazard.78 Finding the Facts Process Safety and Risk Management • • • • • • • Include people with a variety of experience on the investigating panel. Do not disturb evidence that may be useful to experts who may be called in later. experts. . say how this will be achieved. Concentrate on prevention rather than causes. It is often useful. Do not put ideas into people’s minds. Valuable information may be missed if we try to take police-type statements. four or five people are usually sufficient. especially when investigating fires and explosions. such as witnesses. Be patient when questioning witnesses. For each recommendation. inevitable from time to time. Avoid long shopping lists of possible recommendations. such as inherently safer design. and if they were effective or allowed to lapse. It should not be too large. Bring the report forward at that time. nothing will happen except a repeat of the incident. and people on other shifts. Do not.

we have a duty to pass it on. There is no need to say where the incident occurred. Keep in every control room a folder of reports on past accidents. code. but this will not prevent the incident from happening again. Remember that the first step down the road to an accident occurs when someone turns a blind eye to a missing blind. Procedures lapse or the equipment falls out of use and the incident happens again. For example. acted on. We should circulate the essential messages throughout the company. they may tell us about theirs. Remember that incident reports grab people’s attention and are read. Follow up at regular intervals to see that the recommendations made after accidents are being followed. After a few years. and then filed and forgotten. Pragmatic: If we tell other organizations about our accidents. so that others can learn from them. There are several reasons for doing so. Circulate reports containing new or forgotten information throughout the industry. even in the plant where it happened before. . in design as well as operations. Economic: We would like our competitors to spend as much as we do on safety. people forget the reasons for the changes that were made. • • • • Moral: If we have information that might prevent another accident. we can recover some of the cost by turning it into a learning experience. Never remove equipment before you know why it was installed. Remembering the Message Incident reports are written. if they had been followed up.Process Safety and Risk Management 79 They should look out for what is not said. and standard a note on the reasons for it and accounts of accidents that would not have occurred if the instruction. could have prevented the accident. Having paid the high price of an accident. To prevent this from happening we should do the following: • • • • • • • Include in every instruction. Giving the message once is not enough. Include important accidents of the past in the training of undergraduates and company employees. The industry is one: Every accident affects its reputation. writers of accident reports are naturally reluctant to draw attention to similar incidents that had occurred elsewhere and. It should be read by all new arrivals and others should browse it during quiet shifts. code. Never abandon a procedure before you know why it was adopted. whereas advice and instruction are put aside to be read when we have time (if we ever do). Spreading the Message Many companies restrict the circulation of incident reports. or standard had been followed. Describe prior accidents as well as recent ones in safety bulletins and discuss them at safety meetings.

which may fail or be neglected. when it is practicable. Only when we cannot do so. can’t leak. not safe.80 Process Safety and Risk Management • Devise better retrieval systems so that we can find. Microreactors promise much greater intensification than has been possible in the past. by changing designs or reaction conditions rather than by adding on protective equipment. . When we control a hazard. Thus. is the first choice. as it brings about greater reductions in cost. confident that they could keep it under control.’’ This may seem obvious but until the explosion at Flixborough. details of past accidents in our own and other companies and the recommendations made afterward. When we remove a hazard. it may be possible to replace flammable solvents by nonflammable ones and processes that use hazardous raw materials or intermediates by processes that use safer ones. Attenuation or moderation: Another alternative to intensification is attenuation—using a hazardous material under the least hazardous conditions. or the safety procedures may lapse. Note that we refer to inherently safer. the safety is inherent in the design and cannot be lost. we need smaller pipes and vessels and smaller structures and foundations. If less material is present. after the hazards have been identified (see the section Hazard Identification and Hazard Evaluation). liquefied chlorine and ammonia can be stored as refrigerated liquids at atmospheric pressure instead of storing them under pressure at ambient temperature. it is better to prevent overheating by using steam or oil at a safe temperature than by using a hotter medium and a control system. Bhopal almost destroyed it. Intensification. ‘‘What you don’t have. using a safer material in place of a hazardous one. is to see if they can be removed. Engineers simply designed a plant and accepted whatever inventories the design required. The Management of Safety Inherently Safer Design The first step in the management of safety. UK in 1974 little thought was given to ways of reducing the amount of hazardous material in a plant. The principle routes to inherently safer design are as follows: • Intensification or minimization: Using so little hazardous material that it does not matter if it all leaks out. should we look for ways of keeping them under control or mitigating their consequences. then an alternative is substitution. For example. the protective equipment may fail. more easily than at present. Thus. • • • Substitution: If intensification is not possible. and 10 years later. or be neglected. if ever. Flixborough weakened that confidence. The lower pressure results in smaller leaks through a hole of a given size leak and the lower temperature results in less evaporation. design as we can rarely. remove every hazard. Limitation of effects.

whether they are designers. Some violations occur because all people carrying out routine tasks tend to cut corners after a while. • • Some errors. or managers. its failures. Human Factors Engineers are interested in equipment. Many more occur because people think they know a better way . Defense in Depth The hazards that cannot be removed have to be controlled. occur because people do not know what to do. However. Provide fire-fighting equipment. Install automatic detectors so that leaks are detected promptly and people not required to deal with the leak can leave the area. They are usually also cheaper.Process Safety and Risk Management 81 • Simplicity: Simpler plants are safer than complex plants. as they provide fewer opportunities for error and contain less equipment that develop faults. therefore. we use defense in depth. Install remotely operated emergency isolation valves in places where leaks are most likely to occur or where a large quantity could leak. we use some or all of the following: • • • • • • Prevent leaks by good design. If instructions are not being followed. are they too complex? Can the job be simplified? Some errors. supervisors. should understand the way people react with equipment and why they sometime fail to act in the way we instruct them or expect them to act. Engineers. Passive equipment such as fire insulation is usually better than active equipment such as water spray turned on by automatic equipment. and ways of preventing them and often less interested in people. Minimize damage by installing fire protection. construction. However. Because we depend on equipment and people. Employers should provide adequate training and instructions and should not write the sort of instructions that are designed to protect the writer rather than help the reader. maintenance. Remove all known sources of ignition. usually called mistakes. This is better than active equipment turned on by people. should be trained in flexibility (i. If we handle flammable liquids or gases and an inherently safer design is not possible. usually called violations or noncompliances. and operation. It is essential to carry out regular audits—tests and inspections to make sure that automatic equipment is in working order and those procedures have not lapsed. all systems involve both equipment and people. problems will arise that are not covered by them and so people. both of which may fail.e. particularly operators. The intention was wrong. for many instructions we write. occur because someone knows what to do but makes a deliberate decision not to do it.. the ability to diagnose and handle unforeseen situations).

or was not correctly identified and the wrong equipment was opened up. and are able to do it. or underloaded. Some errors (mismatches) occur because the job is beyond the physical or mental ability of the person asked to do it. Before any change is made. they were not followed. Management Systems Some management systems have been discussed in earlier sections on risk assessment. an incorrect method will be used. procedures were poor. Carry out checks from time to time to see that instructions are being followed and do not turn a blind eye if they are not. The management of change: Many accidents have occurred because a change to plant. whenever possible. was not freed from hazardous materials.82 Process Safety and Risk Management of doing the job. The following are also important: The preparation of equipment for maintenance: Many accidents have occurred because equipment was not isolated correctly. errors occur if people are overloaded. the intention is correct but is not fulfilled. intend to do it. There is a fine line between showing initiative and breaking the rules. We should change the plant design or method of working. All we can do is to change the plant design or method of working so as to remove opportunities for error (or minimize the consequences or provide opportunities for recovery). process. it should be examined by professionally qualified people using HAZOP (or a simpler technique if the change is minor) and then inspected after completion to make sure that the intention has been followed and that the modification . For example. we should do the following • • • • • Explain the reasons for the instructions. design inherently safer plants which can withstand errors (and equipment failures) without serious effects on safety (and output and efficiency). noncompliance may achieve the intention. To prevent or reduce violations. simplify the job. and accident investigation. They want to know the reason why. They happen to everyone from time to time and cannot be prevented by telling people to be more careful or by telling them to keep their minds on the job. The fourth category is the commonest—a momentary slip or lapse of attention. hazard identification. If the correct method is difficult. slip and lapses of attention are infrequent. or organization had unforeseen effects. Sometimes. We should. or asked to break well-established habits. Managers and designers as well as operators make errors. Compared with mistakes. but because they usually have time to check their work. If possible. sometimes. sometimes beyond anyone’s ability. We do not live in a society in which people will simply do as they are told. People know what to do. but it slips their mind. Note that if the instructions are wrong. Most of their errors are mistakes or violations.

the failure is usually hidden and regular testing is necessary. • Spare pumps. • Drain valves in tank bunds. • Emergency equipment such as diesel-driven firewater pumps and generators. if their failure can affect the safety of the plant. which have to be used in an emergency.Process Safety and Risk Management 83 looks right. the rest is useless. discussed in the subsection Remembering the Message. If they choke. Test results should be displayed for all to see. They vanish with remarkable speed and regular checks should be made to make sure that they are still there. interfering with the smooth operation of the plant. Training should emphasize that protective equipment is there for their protection and they should ‘‘own’’ it. Remembering the past: A most important system. is not forgotten and that the information can readily be retrieved. These are the simplest possible sort of relief device and should be treated as relief valves. If they are left open. The following equipment is often overlooked but should be tested or inspected regularly: • Drain holes in relief valve tailpipes. • Trace heating (steam or electrical). • Flame arrestors. If passive equipment such as fire insulation is missing. especially the moveable ones used for earthing road tankers. • Nonreturn valves and other backflow prevention devices. • Steam traps. • Valves. is one to ensure that the lessons learned from past accidents. . If 10% of the fire insulation on a vessel is missing. rainwater will accumulate in the tailpipe. but. Operators sometimes regard tests and inspections as a nuisance. for example. this is visible. the bund is useless. • Hired equipment. • Ventilation equipment. it should be checked regularly. • Mechanical protective equipment such as overspeed trips. When active equipment such as relief valves and interlocks fails. • Water sprays and steam curtains. • Open vents. • Earth connections. nevertheless. Who will test it. Testing and inspection of equipment: All protective equipment is liable to fail and should be tested or inspected at regular intervals. All protective equipment should be designed so that it can be tested or inspected. on a board in the control room. in our own and other companies. the owner or the hirer? • Labels are a sort of protective equipment. • Fire and smoke detectors and fire-fighting equipment. • Nitrogen blanketing (on tanks. especially those fitted with auto-starts. remotely operated and hand-operated. What does not look right is often wrong and should always be checked. stacks and centrifuges).

Safety auditing should not be a police activity. All the systems can do. Audits We need audits of equipment and procedures by outsiders because of the following: • • • Those who work in a plant do not notice the hazards they see everyday. and testing protective equipment and whether or not these procedures are actually followed. These have much more impact than mere procedures and bring out the need for the changes. Limitations of systems: Some managers seem to believe that good safety management systems will ensure a safe plant. people will not achieve their full potential. ignorance. Senior managers should systematically assess the levels of knowledge and experience needed and ensure that they are maintained. or lack of time. This is a particular danger at times when companies are reducing manpower and experienced people are leaving. Discussions will allow the manager to check that the message has been received and understood and he may discover that it is impracticable or difficult to use in its present form. Procedures for investigating accidents. Auditors should pay particular attention to the following: • • • • The quality of the training and instructions and the knowledge and experience of employees. who may miss hazards through familiarity. they should be discussed with those who will have to operate them and not just sent to them through the mail. People will go through the motions. however. is ensure that people’s knowledge and experience are applied systematically. Without knowledge and experience. passing on the lessons learned. Discussions should start with descriptions of incidents that would not have occurred if the systems had been in operation at the time. . The procedures for preparing equipment for maintenance. it is intended to help the local management. Continuous monitoring is necessary to make sure that systems continue in use. Process hazards as well as mechanical ones. Without a system. Auditors have more time for investigation in depth than those who work regularly on a plant. systems will achieve nothing. controlling modifications. then the systems are empty shells.84 Process Safety and Risk Management Introducing and maintaining systems: When systems are introduced or changed. Auditors may have specialized knowledge and thus see hazards not apparent to others. but the output will be poor. All systems are subject to a form of corrosion more rapid than that which affects the steelwork and can vanish without trace once managers lose interest. If the staff lack knowledge and experience. and ensuring that they are not forgotten.

It can involve actions such as the following: • • Promoting sound land use planning based on known hazards Buying flood insurance to protect your belongings . the lost-time accident rate. engineering process plants to be inherently safer. mitigation measures can help reduce disaster losses and suffering so that there is less demand for money and resources in the aftermath. we should provide a numerical measure of the success of each management function. and creating and enforcing effective engineering codes to protect employees. not just during the day. The number of faulty permits-to-work found by routine inspection. Unlike many other measures of safety. In addition. process hazards should be reassessed every few years in the light of new knowledge and new techniques. this one tries to detect falling standards before an accident occurs. and other natural hazards. A monthly summary of the cost of incidents. Mitigation is defined as ‘‘sustained action that reduces or eliminates long-term risk to people and property from hazards and their family and belongings are better protected from floods. Mitigation technologies can be used to strengthen hospitals. it never measured process safety. and other critical service facilities so that they can remain operational or reopen more quickly after an event. An annual report of the progress made in reducing inventories of hazardous substances. fire stations. Auditors (and managers) should visit the plant at night and at weekends. hurricanes. In practice. It is the ongoing effort to lessen the impact disasters have on people and property. The Measurement of Safety Whenever possible. the public. mitigation can take many forms. Mitigation involves keeping homes and populated areas away from industry. In any case.Process Safety and Risk Management 85 • • Places where others do not look. Mitigation Mitigation is the cornerstone of emergency management. and the environment from potential process plant upsets and incidents. The number of faulty protective systems found by routine testing. merely measures luck and the willingness of injured people to remain at work. Possible additional or alternative measures are as follows: • • • • • An index based on audit results. earthquakes. behind. Accident rates in good companies are now so low that the usual measure of safety. and underneath equipment. Although it may be a separate exercise. They can be utilized to help business and industry avoid damages to their facilities and remain operational in the face of catastrophe.

some plants may choose to employ very sophisticated sensor systems. For example. less chemicals stored or less in process vessels).e. training for vapor release prevention and control. mitigation should be addressed only after the following options have been exhausted: • • • Inherent safety: These include inventory reduction (i. include water sprays. . which have been very effective in mitigation. and use of lower temperatures and pressures. Another common technique utilized to protect high-hazard pipelines is the installation of labeled warning ribbons approximately 1 ft below grade over the pipeline. Depending on the nature and extent of the chemical hazards. equipment testing. in the industry as Teledyne Geotech’s ‘‘LASP’’ [27. The system known.. and air curtains. Some of the common mitigation techniques employed by process plants are as follows: • • Early vapor detection and warning: Detection by sensors or personnel.86 Process Safety and Risk Management • • • • • • Relocating or elevating structures out of the floodplains Having hurricane straps installed to more securely attach a structure’s roof to its walls and foundation Developing. Some of the engineered systems. ensuring proper operating conditions and material purity. Use of engineered and management systems to impede the progress of the released chemicals. steam curtains. maintenance program. procedures for forced dilution of contaminant. which is analyzed for H2S contamination at regular intervals.28] (Leak Alarm System for Pollutants) consisted of a semipermeable tubing which is laid above the sour gas pipeline under the ground. and enforcing effective engineering codes and standards Engineering process plants to be inherently safer Using fire-retardant materials in new construction Developing and implementing a plan in your business or community to reduce your susceptibility to hazards In the multiple-barriers concept and development of inherently safer layers of protection. For example. water curtains. Management: Examples include consistent operating policies and procedures. Engineering design: Examples are use of better seals or materials of construction. and procedures to mitigate or suppress released chemicals by the use of foams and other suppressants. mitigation is a much lower-level activity and should be looked at only when all other measures in the inherently safer hierarchy are exhausted. The tubing is capable of drawing air through it. and general plant security. and installing dikes and spill vessels. substitution of a less hazardous chemical for one more hazardous. management of modification and changes to prevent new hazards. a pipeline company handling sour gas mixtures with very high H2S content decided to install an early warning H2S-sensing system. adopting. Management systems may include standing procedures to deliberately ignite explosive clouds. audits and inspections.

Questions that should be settled in advance include emergency shutdown criteria. Mitigation measures such as active and passive scrubbers. perhaps considering prevailing directions as well. Separating the process from vulnerable populations affords both attenuation of the effects and time to provide emergency response. Process integrity involves the chemistry of plant design and operation. . incident commander designation. curbs. a hazards analysis early in the design stage may identify one particular unit as having the greatest potential for a toxic release and that unit may then be located on the site as far as possible from off-site neighbors. Response Emergency response plans for process plants should be developed in accordance with applicable governmental regulations and operating company requirements. flares. whereas this type of mitigation measure is not useful for the protection of on-site personnel. The isolation distances needed to appreciably reduce blast effects and impact from toxic releases is significantly large. Mitigation after loss of containment can also be effective and usually must be provided for in the process design stage. In addition to being quickly and effectively warned of a dangerous situation. personnel need to know ahead of time the best response to minimize their chances of being affected by the vapors. Other hazard mitigation measures should be used for protection of on-site personnel. Results or risk assessment studies and hazard zone calculations should be used in the formulation of emergency response actions contained in the emergency plans. Dikes. catch tanks for vapor–liquid separation. Secondary containment by double-walled piping or double-walled vessels may be needed. adsorbers. Other issues that should be settled in advance include circumstances which would warrant shelter-in-place for the employees and the affected public. help keep the liquid source of the vapor away from the most sensitive areas of the plant. and trenches leading away from storage vessels to strategically located impoundments can be used to reduce the rate of evaporation. CCPS’s Guidelines for Vapor Release Mitigation [29] provides detailed discussions on these mitigation techniques. absorbers. stacks. explosion hazards may warrant the construction of blast-resistant buildings or blast walls. and the appropriate operating personnel should be trained in their proper use. Some process plants use consequence modeling in deciding the layout of the plant. incinerators. accident investigation protocol and procedures. and limit the extent of emergency response activities. and condensers are used widely for reducing the impact after loss of containment. Written emergency response procedures. For example. Toxic release hazards may require the availability of shelter-in-place facilities or escape respirators. For example. and repair procedures should be prepared.Process Safety and Risk Management 87 Isolation by distance of a chemical process from on-site and off-site surrounding populations is generally a very effective consequence–mitigation measure. Process integrity may also be addressed in the engineering design. and the roles of incident commander and other emergency personnel.

The procedures should clearly indicate what constitutes an emergency situation. Systems which are being considered include single-phase viscous liquids and gas flows. equipment. many companies are also moving toward the installation of automatic telephone dialing and alerting systems or communicating hazard warnings to downwind personnel. air–liquid) two-phase flows of gases and viscous liquids. A discussion of three major areas of development is given here. and risk management. Other advanced features of the APTAC include in situ additions to the sample cell of reactants or catalysts with a high-pressure syringe pump. The extent and nature of steps taken to bring the process back under control should also be clearly indicated. closed-cell sample pressures are continuously matched by an external pressure of nitrogen so that sample cells of low mass and therefore low thermal inertia can be used for highly sensitive measurements of sample thermal behavior. Every plant should establish clearly defined procedures for emergency shutdown of equipment.g. Finally. In this calorimeter. Technology Advances Advances in the understanding of chemical hazards have led to the development of new technology in the arena of process design. Recently. ‘‘frozen’’ (e. Relief Valve Sizing and Overpressure Alternatives Recent research on relief valve sizing and overpressure protection alternatives has focused on the development of validated engineering design procedures for the proper sizing of safety relief valves for systems. Warnings can be communicated through the use of public address systems. One such calorimeter is the Reactive Systems Screening Tool (RSST). Personnel authorized to make the decision to shutdown should be aware of their responsibilities and the role of other personnel. Reactive Chemistry In the Reactive Chemistry arena. and flashing flows of viscous and nonviscous liquids. Another apparatus is the Automatic Pressure Tracking Adiabatic Calorimeter (APTAC) for detailed analyses of thermal behavior of larger samples (up to 130 cm3) for temperatures up to 450°C and pressures up to 2000 psia. alarm systems. Preprogrammed computers can be used to dial thousands of preselected numbers in very short periods of time. which involve two-phase flows of viscous fluids. calorimeters are being used increasingly for studying the thermal behavior of reactive systems.88 Process Safety and Risk Management Communicating warnings to potentially exposed personnel is essential in an emergency. and sirens. .. the conditions which would unambiguously require a shutdown should be spelled out. which is designed for rapid measurement of thermal behavior of small samples (10 cm3) for temperatures up to 400°C and pressures to 500 psia.

For each sample. the cost of designing and installing large flare systems has continued to rise. Traditionally. In the process industry. a key safety consideration is the control and response to overpressure situations. Although there are no specific performance criteria in the Case Code. Thermal energy released or absorbed by the sample (as defined by sample temperature changes of 0. The SIS should be designed to meet a safety integrity level. The ruling is intended to enhance the overall safety and environmental performance of a facility by utilizing the most appropriate engineered option for pressure protection. the substitution is generally intended for limited services where the PRV may not work properly due to process condition (e. ASME Code Case 2211. The overpressure protection can be provided by a safety instrumented system in lieu of a pressure-relieving device under the following conditions: One of the most important criteria for safety instrumented system (SIS) design is the requirement that the User assign and verify the safety integrity level (SIL) for the SIS [30]. Safety integrity levels per draft IEC 61508 [31.04°C/min) is measured by the calorimeter as a nearly adiabatic excursion from the thermal scan baseline.01 [33–37] are designated in Table 7.32] and ANSI/ISA S84. . in turn. plugging. In many communities and countries around the world.Process Safety and Risk Management 89 During typical experiments with each calorimeter. Division 1 and 2. Safety Integrity Levels Industry is moving toward the use of high-integrity protection systems to reduce flare loading and alleviate the need to upgrade existing flare systems when expanding facilities. Industry standards from the American Petroleum Institute (API) and American Society of Mechanical Engineers (ASME) provide criteria for the design of vessels and the protection of these vessels from overpressure. In addition. The assignment of SIL is a corporate decision based on risk management philosophy and risk tolerance. fail-safe equipment operation.. provide alternatives in the design of overpressure protection systems. or trip systems. Consequently. These alternatives revolve around the use of an instrumented system that exceeds the protection provided by a pressure relief valve and flare system.g. which. Flare loading calculations gave no credit for operator intervention. multiple phases. etc. pressure relief valves and flares were used to handle the relieving of vessels in the worst credible scenario. approved in 1996. investigations of thermal behavior of wide ranges of reactive systems and systems of questionable chemical compatibility can be performed. With this experimental capability. the belt is tightening on the venting and combustion of gases. the sample temperature is measured during temperature scans when the temperature is increased at a steady rate or held isothermally (in the APTAC).). API 521 and Case 2211 of ASME Section VIII. is used to design safe processes and choose safe operating conditions. which is appropriate for the degree of hazard associated with the process upset. the substitution of the high-integrity protection systems for the pressure relief valve should provide a safer installation. the thermal peaks can be identified and measured from ambient up to 450°C (up to 400°C in the RSST). It is simply not acceptable to flare large volumes of gas. sets the conditions under which overpressure protection may be provided by an instrumented system instead of a pressure relief valve (PRV).

The practical impact of the toxicological and industrial hygiene research programs on the workplace largely depends on the actions of employers. both acute and long term associated with chemicals. and increasing the number of workplaces with rehabilitation and safety and health programs.90 TABLE 7 Safety Integrity Levels Safety integrity level IEC 61508: 4 ISA S84: 3 2 1 Process Safety and Risk Management Availability required 99. there is much work to be done.00% Probability to fail on demand 10 10 10 10 5 1/PFD 100.000 1. employees. Clearly. workplace hazards continue to inflict a tremendous toll in terms of human and economic costs. Thus. In the coming years.000–1. managers. The work of governmental agencies and research organizations has had and will continue to have an impact on improving health and safety at the workplace.90–99.99% 99. Although workers are often exposed to contaminant mixtures. determining the toxicological effects of these chemicals and. as a result.90% 90.000 10. Examples are reducing work-related deaths and injuries. With this information.00–99.00–99. labor.000–100 100–10 to 10 to 10 to 10 to 10 4 4 3 2 3 2 1 Industrial Hygiene and Toxicology As the world becomes more industrialized in an attempt to increase the quality of life. there are 500 new chemicals marketed each year [38]. and deaths (such as musculoskeletal problems. the scientific research and development of databases on the toxicity of mixtures are needed. It is quite apparent that industrial hygiene requirements in the coming years will be dictated to a large extent by the upcoming findings on carcinogenesis and mutagenesis. reducing lost work days and incidences of cumulative trauma and skin disorders. illnesses. injuries. To remedy this situation. Although substantial progress has been made in the United States toward improving worker protections since 1970 (largely a result of occupational safety and health research). The stated objectives in this area include target levels of improvements in work-related conditions. more and more environmental problems will require the attention of engineers. one of the most dreaded is cancer. and community organizations. findings and advances on chemical toxicity will require the implementation of stringent industrial hygiene standards. Although there are many toxic effects. and planners. developing industrial hygiene programs to protect people from these effects will command significant attention and resources from process safety personnel. .99% 99. therefore. By one estimate. academia. exposure regulations do not take into account the effects of the various types of contaminant interactions capable of modifying toxicity. it will help address many of the issues related to workrelated hazards. and partners in governmental agencies. industry. health and safety specialists will be able to quantify contaminant interactions for any given situation.000–10.

so that an accident would require the failure of several systems.. Recent advances. the use of hazardous processes and complex technologies. employee stress. with the identification of activities necessary to accomplish the goals and the development of a measurement system to measure progress toward the goals. Given a baseline assessment. Regulatory programs and industrial standards and practices in the United States have quite often been reactive (i. In fact. In addition. Another novel approach to . in response to catastrophic accidents or other events). In addition. The pros and cons of establishing national process safety goals and evaluation approaches include the following: 1. thereby helping to establish baseline and trend information in the occupational safety and health area. farm workers. in future processes. the public outcry for improved safety performance also creates significant pressure on the industry. Future Developments Increasingly. Identification of where we want to be and by when in relation to national chemical safety goals 3. Process safety and risk management requires the application of the basic sciences and a systematic approach. and adolescents. and back injuries) as well as categories of workers and prevention strategies for mine workers. the process safety requirements for chemical plants will become more and more stringent. List of activities that need to be implemented to accomplish Step 2 above 4. safety performance will quite likely be dictated by national goal setting. the pressure to operate safely from the point of view of competitiveness and profitability will also keep increasing. Finally. surveillance efforts will assist the development of comprehensive databases. and extreme operating conditions. plants are designed with several layers. As a result. Agreement on some common metrics for measurement of progress toward national chemical safety goals Summary and Conclusions The industrial revolution brought prosperity and. Stakeholder consensus on national chemical (process) safety goals 2. allow safer design and operation of processes.Process Safety and Risk Management 91 skin diseases. This would require the establishment of a baseline assessment of the status of process safety incidents.e. In the multiple-barriers concept. National Chemical Safety Goals can be established. Growing economies and global competition has led to more complex processes involving the use of hazardous chemicals. exotic chemistry. such as overpressure protection alternatives and reactive chemistry. a fundamental understanding of the hazards and associated risks is essential. along with it. violence in the workplace.

Inherently safer design consideration should be first in the hierarchy. February 24. Chemical Process Safety: Fundamentals with Applications. Center for Chemical Process Safety. Recommended Practice 750: Management of Process Hazards. A. 1990. In fact. L230 (June 1982). ‘‘Techniques for Assessing Industrial Hazards. 11. DC. 9. No single partners can claim exclusive credit for the progress. followed by prevention systems. Englewood Cliffs. 5. 1988. 12. 1990. Guidelines for Safe Automation of Chemical Processes. European Community Directive. Chemical Manufacturers Association. 4. mitigation. state and local agencies. Connors. Chemical Manufacturers Association. labor. Chronic as well as catastrophic consequences resulting from toxic and flammable substances can be reduced and/or eliminated through appropriate design and operating practices. 2. 8.119. 10. API. Washington. Washington. International Labour Office. ‘‘On the Major Accident Hazards of Certain Industrial Activities. 1992. Norway.’’ Fortune. measurable progress has been made in the period 1970 to 1995.’’ World Bank Technical Paper #55. Health and Safety Executive. ‘‘The Battle for Industrial Safety. . 1990. References 1. Community. and others. ‘‘Safety Evaluation of Platform Conceptual Design. DC. Washington. In the end. We have also seen a 25% decline in the rate of occupational injuries and illnesses from 1973 through 1994. National Institute of Occupational Safety and Health. New York. The success of these systems is dependent on the fundamental understanding of the process and the associated hazards. if further progress is to be made. Louvar. 1993. Federal Register. Washington. Offshore Installation (Safety Case) Regulation 1992. all of the partners must act—from identifying the causes of disease and injury through controlling or eliminating the hazards or exposures at the worksite. Occupational Safety and Health Administration. Geneva. M. Mining Safety and Health Administration. UK. D. These reductions are the result of the combined efforts of all the partners in occupational safety and health: industry. 1997). 3. 1992. Major Hazard Control. 1990. 6. Washington.119. 1988. London. a Practical Manual. Eur.’’ Stavanger. American Petroleum Institute. academic researchers. during which the rate of workplace fatalities fell by 78% and the number of workplace deaths has declined by 62%. Thus. 7.92 Process Safety and Risk Management process safety and risk management is to consider various actions in a descending hierarchical order. DC. DC. 1981. American Institute of Chemical Engineers. DC. F. Resource Guide for Implementing the Process Safety Management Code of Practices. NJ. progress toward the improvement in safety performance can be measured only by a reduction in occupational injuries. Federal Register. illnesses.’’ 82/501/E. and fatalities. ‘‘Final Rule on Process Safety Management of Highly Hazardous Chemicals’’: 29 CFR 1910. July 17. Prentice-Hall. J. 116[C-P] (August 4. Norwegian Petroleum Directorate. Crowl and J. ‘‘Notice of Proposed Rule Making on Process Safety Management of Highly Hazardous Chemicals’’: 29 CFR 1910. and response.

6. 29. New York. 1992. Guidelines for Use of Vapor Cloud Dispersion Models. 31. 24. 23. American Institute of Chemical Engineers. Methods for the Calculation of Physical Effects. 34. Final Standard. 27.’’ International Electrotechnical Commission.’’ International Electrotechnical Commission. 34– 35 (June 10. 32. Draft. American Institute of Chemical Engineers. Center for Chemical Process Safety (CCPS). Lantzy. and C. H. New York. American Institute of Chemical Engineers. 15. G. Forrest. S. Institution of Chemical Engineers. 20. Loss Prevention in the Process Industries. 1995. D. 9th ed. 26. 21. Mannan. 1991). 2nd ed.. 83–87 (June 3. 28.. ‘‘Techniques for Assigning a Target Safety Integrity Level. Shaw. G. 1992. Dow Chemical Company. 1995.Process Safety and Risk Management 93 13. New York. 2nd ed. 1989. 16. Mannan. Hazard Identification and Risk Assessment.. Final Draft International Standard. New York. E. Huff.’’ Oil Gas J. Muller. P. J. 65A/255/CDV. The Hague. 33. and D. D. IEC 61508. American Institute of Chemical Engineers.0. King. A. Emergency Relief System Design Using DIERS Technology. 25. Parts 2. March 1998. 1994. R. and C. 1996. January 1999. Butterworth-Heinemann Boston. 1994. Guidelines for Evaluating the Characteristics of Vapor Cloud Explosions. Warwickshire. New York. A.02.. ‘‘Sour Gas Pipeline—Conclusion: Line. 19. Wells. UK. A. D. New York. 1996. 3. New York. Understanding Atmospheric Dispersion of Accidental Releases. P. Fisher. 1997. American Institute of Chemical Engineers. New York. American Institute of Chemical Engineers.. H. Bretherick’s Handbook of Reactive Chemical Hazards. 65A/255/CDV.. G. and 5. Part 1 and 2 CPR-14. and B. A. New York. R. and 7. Zinn. Center for Chemical Process Safety (CCPS). Parts 1. American Institute of Chemical Engineers. E. J. Center for Chemical Process Safety (CCPS).’’ ISA Trans. Urben (ed. M. Dow Chemical Company. ‘‘Safety Instrumented Systems (SIS)—Safety Integrity Level (SIL) Evaluation Tech- . Version 4. ‘‘Functional Safety of Electrical/Electronic/Programmable Electronic Safety Related Systems. Center for Chemical Process Safety (CCPS). IEC 61508. American Institute of Chemical Engineers. Part 1: Introduction. D. 17. New York. 1996. Guidelines for Consequence Analysis of Chemical Releases. 4. 1988. with Worked Examples.). New York. Grossel.). Summers. and BLEVES. SdU Uitgevers. ‘‘Functional Safety of Electrical/Electronic/Programmable Electronic Safety Related Systems. D.. 37. 1996. 1999.. Pfenning.. R. Lees. December 1998. ‘‘Sour Gas Pipeline—1: Risk-Analysis Procedures Ensure System Safety. Guidelines for Hazard Evaluation Procedures. Flash Fires. A. J. The Netherlands Organization for Applied Scientific Research (TNO). 2nd ed. Center for Chemical Process Safety. Boston. Dow’s Chemical Exposure Index Guide. Tilley. 30. Butterworth-Heinemann. J. 7th ed. S. B. F. M. 95–104 (1998). Guidelines for Chemical Process Quantitative Risk Analysis. 14.’’ Oil Gas J. 3rd ed. G. Center for Chemical Process Safety (CCPS). Sax’s Dangerous Properties of Industrial Materials. 18.’’ TR84. 1994. American Institute of Chemical Engineers. E. ‘‘Safety Instrumented Systems (SIS)—Safety Integrity Level (SIL) Evaluation Techniques. 22. Rugby. 1991). 5th ed. Zinn. Dow’s Fire and Explosion Index Hazard Classification Guide. Fontaine. Pfenning. Weather Conditions Among Variables to Determine Public Risk. J. Guidelines for Vapor Release Mitigation. DeVaull. John Wiley & Sons. J. S. J. Noronha. Lewis (ed. American Institute of Chemical Engineers. B.

This at the expense of major increases in CO emissions. Part 4: Determining the SIL of a SIS via Markov Analysis. France). due to low-cost energy.0.’’ TR84. Version 4. Version 3. March 1998.02. Part 3: Determining the SIL of a SIS via Fault Tree Analysis.02. Part 5: Determining the PFD of SIS Logic Solvers via Markov Analysis. KLETZ 35. by a 4-degree time-retard timing. In the United States. and SCAQMD). Draft. (Source: BACT best available control technology of U. T. Draft. and carcinogenic particulate matter (PM) emission. ‘‘Safety Instrumented Systems (SIS)—Safety Integrity Level (SIL) Evaluation Techniques. Version 4. EPA. March 1998. Part 2: Determining the SIL of a SIS via Simplified Equations. Prentice-Hall. 38.’’ TR84. The United States with approximately 5% of the world population accounts for about 28% of the world’s fossil fuel consumption (International Energy Agency.02. The process is being discussed within the framework of air-pollution control policies and practices of industrialized countries. F. excess fuel is often used to reduce NOx of IC engines. 1999. ‘‘Safety Instrumented Systems (SIS)—Safety Integrity Level (SIL) Evaluation Techniques. March 1998. ‘‘Safety Instrumented Systems (SIS)—Safety Integrity Level (SIL) Evaluation Techniques. accounting for about 20% of the world population and generating 80% of the global combustion air-pollution. Cal. The ozone is formed primar- . 37. Stringent Energy Conservation and Emission Reductions Policies have a much longer tradition in Europe and Japan than in the United States.02. fuel consumption. Draft.S. Yen.0. M.’’ TR84. 36. more than twice the per-capita consumption of other major industrial countries. Paris. April 1998. SAM MANNAN DENNIS HENDERSHOT TREVOR A. Englewood Cliffs. a precursor of regulated low-level ozone (O3) emission. which accounts for over 50% of the United States’ total NOx inventory. Environmental Chemistry: Essentials of Chemistry for Engineering Practice.0.’’ TR84. NJ.-ARB.0. Introduction to the Selective Catalytic Reduction Technology Introduction Overview The selective catalytic reduction (SCR) process has been originally developed for reducing oxides of nitrogen (NOx).94 Process Safety and Risk Management niques. The SCR process has been designed to reduce oxides of nitrogen (NOx). Version 4. Draft.

including mobile applications such as heavy-duty diesel (HDD) trucks. in the 1980s. 1). SCR technology is being used in retrofit and integrated emission control systems. However. May 1993.and gas-burning industrial boilers. Then. diesel. The SCR combustion pollution control technology is able to overcome the target conflict of IC combustion equipment. and so forth. The SCR utility applications have to compete with pollution control processes. coastal and ocean-going vessels. and stationary gas. In the United States. Also. because the number of utility plants are relatively few in comparison to the number of other nonutility SCR applications to be considered for OEM and retrofit applications in future.Selective Catalytic Reduction 95 ily by the two precursor NOx and volatile organic compounds (VOC) in the presence of sunlight through photosynthesis. However. FIG. in recent years. portable generation sets. and dual-fuel IC engines were added. earth-moving equipment. accounting for over half of the total U. Figure 2 shows high-dust and low-dust utility boiler applications. diesel locomotives. (Source: German Engineering Society (VDI). NOx pollution inventory. Originally developed in the 1970s for stationary utility power generation equipment. gas turbine applications were introduced in the 1980s and many coal-burning utility power plants require SCR retrofit system installations by 2004. the SCR process can be used to reduce emissions of practically all types of combustion equipment. The earliest SCR applications were located primarily in oil-burning utility boiler facilities in Japan in the 1970s. increasing the NOx emission by reducing the fuel consumption or increasing the PM and CO emission by increasing fuel consumption through fuel-based emission controls (see Fig. Today. 1 The target conflict of IC equipment emission reduction versus fuel consumption. European application engineering technology developments have broadened the application of SCR technology. the nonutility and the new mobile combustion sources are being emphasized in this article. advanced SCR developments have been achieving VOC/HC (hydrocarbons) and particulate matter (PM) emission reductions simultaneously with the NOx reduction.S. European SCR applications for hard-coal-burning utility and oil.) .

96 Selective Catalytic Reduction FIG. Hence. depending on the type and size of the SCR equipment. as shown by Fig. which are almost completely oxidized in the SCR process. air quality regulators cooperated with the trucking industry and the SCR equipment industry in the development and field testing of SCR systems for heavy-duty diesel truck engine applications in the 1990s. railroad. 3: From (clockwise) a coal-burning utility plant to HDD truck. natural-gas. These truck field tests have lasted for some 4 years. and gas turbine applications. depending on custom engineering requirements and the number of systems of the same design fabricated (Siemens).) such as the selective noncatalytic reduction process (SNCR). 20–50% PM. cost-effective technology available to reduce combustion emissions. due to the development of a diesel SCR catalyst with an operating temperature window of 300–1020 F (150–550° C). SCR technology is considered the most promising. Today. Today. the range of SCR applications is rather broad.and fuel-oil-burning industrial boilers and IC engines and turbines were equipped with SCR systems in a few regional nonattainment areas for ozone since the 1980s and gas. In Europe. (Courtesy of Siemens. construction equipment. The SCR systems will go to market in 2002. pipeline pump station. the SCR technology allows the simultaneous reduction of combustion emission of 70–95% NOx. In the United States. featuring low capital investment but high operating costs. It may be interesting to note that the emission reduction of VOC include air toxins such as aldehydes and polycyclic aromatic hydrocarbons (PAH). The capital investment cost of SCR systems are US$ 10 to 50 per BHP h. . Various cost-effectiveness calculations showed annualized costs of $500 to 1500 per annual ton of NOx reduction. enabling air quality regulators worldwide to achieve more drastic emission reductions of combustion equipment than thought possible just a few years ago. and 85–95% VOC/HC at minimum fuel consumption and CO2 emission.and coal-burning utility boilers since the 1990s. This process is limited to a small operating temperature window of usually 1350–1550 F (750–900°C) and requires an ammonia or urea consumption of up to four times the stoichiometric requirements of the SCR process. 2 Utility boiler applications. vessel. portable generator set. accumulating approximately 3 million road and highway miles with 20 Class 8 type HDD trucks.

and so forth. The various emission inventory data for the United States for NOx indicate that the leading sources of combustion emission are from on-road and off/nonroad emission sources.) Environmental Policies After the United Nations summits on the environment in the 1990s in Rio. have been equipped with three-way catalyst systems for many years. finally.Selective Catalytic Reduction 97 FIG. PM. however. commercially available solution to reduce NOx. at the expense of higher fuel consumption and N2O (laughing gas) secondary emission. global warming gas emissions. The air quality regulations. PM. and VOC/HC emissions substantially and simultaneously existed until the early 1990s. as mentioned above. increasing the fuel consumption of engines and other combustion equipment and. Global warming is becoming an increasing concern domestically and internationally. as no considerations were given to the capability of reducing VOC and PM simultaneously with NOx at no extra cost. no cost-effective. Therefore. fuel is often used today to reduce emissions. were developed in a piecemeal approach: first NOx. • • Health effects of NOx. environmental policy-makers around the world have been focusing on the reduction of emission generated by combusting fossil fuel. Japan. Brazil and Kyoto. The industrialized countries must reduce their fossil-fuel combustion emission substantially to allow developing nations to generate more power for their growing economies. and. Increases of 10–13% in CO2 . This has been a major disadvantage for SCR technology applications. 3 The Range of SCR applications. PM. Gasoline engines. the diesel engine. then VOC/HC to reduce ground-level ozone. (Courtesy of Siemens. and VOC/HC have been the driving force for air quality legislation in the past. shorelines of the ocean. For the most fuelefficient device in converting fossil fuel into useful energy and power. considering changes in weather pattern. with it.

S. EPA NOx emission reductions versus exponential increases in fuel consumption. therefore.12 parts per million (ppm).S. The U. EPA’s BACT mentioned earlier. CO2. Ambient Air Quality Act was passed and then amended in 1990. Therefore. The various state implementation plans for combustion emissions in the United States. (Courtesy of Siemens. CO. VOC/HC.S. exhaust gas aftertreatment technologies will be required in mobile and other applications. unit electronic–hydraulic injection.S. 4 Target conflict: reduction of NOx versus increase in fuel consumption.08 ppm ozone at an 8-h average and introduced a new PM 2. call for substantial further NOx reductions of the U. and PM emission of Class 8 HDD truck engines.S. Combustion emission reductions through fuel savings and internal combustion equipment design modifications such as electronic engine management systems. ARB meetings in 1999 and 2000. EPA). . In Fig. inventory of approximately 25 million tons of NOx per year (U. 4.S. Environmental Regulations In 1970. the U. was never met throughout the United States. to avoid higher fuel cost and to achieve future U. and exhaust gas recycling is limited.S. That increased the nonattainment areas in the United States substantially (Fig. EPA further reduced the ground-level ozone standard due to late health data and increased health concerns to 0. intercooling. Serious nonattainment areas for ozone (O3) such as in the Northeast and in California still exist and new ones were added recently. and PM. National Ambient Air Quality Standard (NAAQS). allowing a maximum ground-level ozone concentration of 0. is shown by reducing NOx emissions of engines by modifications such as U.5 standard of 65 µm/m3 at a 24-h average. In 1997. however. the U. 5).98 Selective Catalytic Reduction FIG.) • and up to 70% of PM emission of diesel engines were reported at public Cal. the target conflict of the U. EPA emission reduction goals beyond 2002 and 2004.S.

The SCR process equipment layout is pictured in Fig. finally received an ozone transfer regulation for about 20 states. GA. According to NESCAUM data presented at the ICAC Forum 1998. Figure 6 shows the different emission source categories by area in Texas in 1996.. 7. East coast states. TX became serious or extreme nonattainment areas. requiring midwest states to reduce NOx substantially. the NOx emission in the midwest was caused by utilities ( 33%). and by mobile equipment (on-road 34% and off/nonroad 14%). cities such as Atlanta. after years of complaining about Mid-west combustion pollution transfers to the East. on-road.5. using an engine as an example for combustion equipment. . SCR technology has been advanced considerably in Europe in recent years. Dallas. Technology As stated earlier. Chicago. In addition to major cities in California and the Northeast. by independent power producers (14%). the basic SCR process is still the same. California) are more like 30% each for stationary.Selective Catalytic Reduction 99 FIG.e. 5 Nonattainment areas in the United States for ozone (dark areas) based on the EPA’s new standards for ground-level ozone and PM 2. however. TX and Houston. and nonroad combustion equipment after 20 years of stationary emission source regulations in that State. IL. Other estimates (i.

20% nonroad. 6 NOx emission by source category in tons per year at selected areas of Texas in 1996. 2000. using a diesel engine SCR application as an example. mobile.) . 25% on-road. (Courtesy of Siemens. clockwise: 2% area. (Source: TNRCC. 7 The SCR process.) FIG.100 Selective Catalytic Reduction FIG. and 53% stationary emission sources. Example: Houston.

200 ppm NO. 10% H2O. Figure 8b shows the reversible side reactions and their equilibrium at threshold temperatures (EESI/Steuler. a well-supported estimate of a SCR-based NH3 slip rate of 2–5 ppm for 200. depending on weather conditions and the type and intensity of fertilizer usage. aqueous urea. a leading SCR system supplier) at a specific chemical exhaust gas composition. typically in the 2–30-ppm range as secondary emission. 8b. Secondary Reactions and Emissions The effects of high SOx levels in the exhaust gas is given in Fig. There are several reducing agents in use today. using an exhaust gas of a specific chemical composition: 72% N2. the reducing agent NH3 reacts with the NOx to yield molecular nitrogen (N2) and water vapor (H2O) with very limited ammonia slip. and SCR-based NH3 slip emission do not account for more than 0. In a U. required a much safer reducing agent. Also. leading to the reactor. the area NH3 emission may be as high as 5– 30%. is used primarily in stationary industrial and utility applications. ARB. Some typical chemical reactions of the SCR process are shown by Fig. nitric acid production. yielding two NH3 and one CO2 in the exhaust duct upstream of the SCR catalyst. The mobile SCR system application developments of the 1990s. mass flow. Ammonia slip has been a concern of health experts and air quality regulators when considering SCR exhaust emission reductions.S. Germany.5–2% of the total NH3 emission inventory (Bavarian-EPA. However. 60–75% of the total local NH3 emission is caused by animal droppings. raw or uncontrolled. and some sensor probes. through the SCR reactor and other exhaust gas system components such as the muffler into the atmosphere. a certain amount of a reducing agent is injected and homogenously mixed upstream of the catalyst bed.S. 1000 ppm SO2. The exhaust gas duct.Selective Catalytic Reduction 101 The exhaust gas generated by a diesel engine passes from the engine through the exhaust pipe or duct.000 MW utility applications would just cause an NH3 emission increase . depending on the life stock concentration. study. The industrial applications such as air conditioning. Cal. When subsequently passing through the SCR catalyst bed. 15% CO2. and California show that. turning vanes. and 200 ppm HCL. A safer ammonia reducing agent. 3% excess O2. hazardous. Depending on the exhaust gas temperature. NH3 Emission Inventory Studies in the Netherlands. and other studies). and permitted or controlled NOx concentration and other variables. 50 ppm SO3. Figure 8b shows a few of the reversible side reactions and their equilibrium threshold temperatures (EESI/Steuler). containing 25–29% ammonia gas in demineralized water. was introduced to SCR applications in the 1980s. United States air quality regulators for gas turbine SCR applications have imposed extremely costly low levels of NH3 slip emission limits of 2–5 ppm. A European university study on the effects of high SOx levels in the exhaust gas duct concluded that temperature and SO2 SO3 control is key to avoid ammonia salt emissions. Anhydrous ammonia (NH3). static mixers. houses the gas flow straightener. aqueous ammonia. and flammable gas. from which ammonia is generated through hydrolysis. The SCR reactor houses the SCR catalyst and other sensor and instrumentation probes. 10 ppm NO2. 8a. a toxic. however. pollution control experts point out that this ‘‘NH3-slip hype’’ is not based on facts: European and U.

and so forth. (Courtesy of L. control/monitoring system requirements. 3. (c) NH3 /NOx ratio and the effects of overinjection and underinjection of ammonia. emission reduction. 4.) of less than 10.102 Selective Catalytic Reduction Reducing Agent Urea: Ammonia generation through hydrolysis in the exhaust or flue gas. 4. 8 (a) Typical chemical reactions of the SCR process. (b) Equilibrium threshold temperatures at which ammonia salts is formed/dissolved.000 tons per year equal to less than 1% of the total U.S. 3. NH3 emission inventory. (a) Effects of high SOx levels in the exhaust gas Temperature (°C) 1. 1. Pruce. 5. . 5. upsteam of the SCR catalyst. System Controls The component selection will vary depending on the type of combustion equipment. (NH2)2 CO H 2O → 2 NH3 → → → → CO2 NOx Reduction with Ammonia 2. (b) 22 219 209 113 88 Chemical Reactions H2O SO2 2NH3 2NH3 H2O SO3 NH3 H 2O SO3 NH3 HCl NH3 H2O (1/2)O2 i i i i i (NH4)2SO3 (NH4)2SO4 NH4HSO4 NH4Cl 2NH4NO3 4NO 6NO 2NO2 6NO2 4NH3 4NH3 4NH3 4NH3 O2 O2 4N2 5N2 3N2 7N2 6H2O 6H2O 6H2O 12H2O 2NO2 (c) FIG. 2.

incorporating continuous emission monitoring systems (CEMS) or sensors. The inlet duct or piping houses the gas flow straightener. Utility applications for large boilers or gas turbines are therefore custom engineered. and housing design Proper selection of materials. certified systems. However standardized. alternate fuels. The new mobile SCR applications for diesel and lean-burn gas engines will be such standardized and volume-produced SCR systems. Also. 9. This industrial approach. developed and adopted for the first time in the HDD truck program by Siemens and the European trucking industry. and injection spray heads or nozzle as well as the static mixers. and control system design The SCR system component selection and system configuration may vary considerably depending on the application. requiring a calculated amount of reducing agent to achieve the permitted NOx emission rate. The first is the open-loop. flow turning vanes. An even flow rate . SCR System Design Considerations The following basic design considerations are common to all SCR systems: • • • Proper exhaust gas flow and temperature distribution at the front face of the catalyst bed Proper selection of the catalyst material formulation. system components. in most cases. bypass valves are incorporated in ducts to cope with certain operating conditions such as cold start-ups. and connects the combustion equipment with the SCR reactor. feed-forward control with a computer-based ‘‘map. Only in very special cases. SCR System Component Summary The Exhaust or Flue Gas Piping or Duct This is usually heat insulated. and so forth. Such a system is also called a Predictive Emission Monitoring System (PEMS). is already benefiting the custom-engineered SCR systems as well. the catalyst bed. made of heat-resistant nonscaling steel such as molybdenum alloys. which could harm the SCR catalyst of earlier developments. Independent Power Producer (IPP) and industrial applications such as cogeneration and standby generation sets are still primarily custom engineered. sensor probes. volume-produced small gas turbine and engine SCR applications will be more cost-effective and thus more common in future.Selective Catalytic Reduction 103 Basically. The feedback systems are.’’ a correlation function of NOx emission generated at certain combustion equipment loads. Maximum reduction rates at minimum unreacted ammonia (slip) can be achieved by adding to the rapidly responding open-loop system a slower closedloop system. two types of reducing agent injection control are being used. Such inlet ducts with the SCR reactors downstream are pictured in Fig.

the permitted NOx reduction rate was finally negotiated and increased by the local regulator without hearing expert witnesses. even major improvements in the ammonia/exhaust gas mixing system and a major increase in the catalyst volume could not solve the original problem. in a gas turbine project in southern California. They house the SCR catalyst and any oxidation catalyst or sound deadening material as may be required by the specific application. they house instrumentation probes for monitoring operating conditions and emission .104 Selective Catalytic Reduction (a) (b) FIG. (b) SCR inlet duct and catalyst location. As a case in point. and temperature distribution at the front face of the catalyst bed are most crucial and prerequisites of any well-performing SCR system design. The Reactor Housing and Stack Duct These are normally heat insulated. Figure 10 pictures such a flow modeling case and how an even gas flow can be achieved through turning vanes and a static mixer in front of the SCR catalyst bed. made of heat resistant nonscaling molybdenum alloy steel rather than stainless steel. 9 (a) SCR inlet duct and catalyst location. The uneven gas flow rate and temperature distribution at the front face of the catalyst still deviated by 20–40% due to improper turning vanes and lack of static mixers that the contractor had refused to install. which is sensitive to stress corrosion in welded areas. In addition. To obtain a Permit to Operate. gas turbine application. stationary engine application.

dust clogging of the catalyst. reductions. 11. These problems gave the SCR technology in the early developments prior to the 1990s a bad name. Manholes. improving the uneven (32%) to a more acceptable (9%) flow rate deviation at the front face of the catalyst bed. (See Fig. causing an increase in back pressure and/or reducing catalyst reactivity/ performance. an irreversible degradation of the catalyst surface Plugging. washable flue gas deposits reduce the reactive catalyst surface temporarily Poisoning. Initially. Since then major R&D and .Selective Catalytic Reduction 105 FIG. catalyst ‘‘fouling’’ was a major problem.) The SCR Catalyst This is the ‘‘heart’’ of SCR systems and much research and development work went into catalyst material formulations. loading and unloading equipment. and production processes over the last 20 years. Most custom-engineered SCR systems have space available for adding a row or layer of catalyst at a later date to reduce the emission even further or to meet certain catalyst replacement strategies. and excess doors for handling catalyst modules are required in larger. 10 Flow modeling: before and after computer and scale modeling. The operating temperature window was limited to 570–850°F (300–450°C) to avoid ammonia sulfate formations at low reactivity and ammonia combustion problems at high temperature. with the following concerns: • • • Masking. structures. stationary SCR applications as well.

’’ the diesel catalyst from Siemens was selected by the European trucking industry for the field tests in the early 1990s. toxic. requires professional handling. The operator of supply piping and anhydrous ammonia storage tanks is . Aqueous Ammonia. Today. several different types of SCR catalyst are commercially available from several suppliers.S. ammonia slip.000 operating hours or 3 years. on-road applications. Upon the completion of these tests. and so forth. in stationary and several hundred thousand kilometers in mobile. whichever occurs first. or Aqueous Urea Anhydrous ammonia. Today. arsenic resistance. Also. 12.106 Selective Catalytic Reduction FIG. the best performing ‘‘Catalyst A. Various catalysts from different European and U. Germany of 1989–1991 are shown in Table 1 and Fig. a phosphorus and zinc compound containing lubricating oils. a pollution control industry. the SCR catalyst service life was guaranteed for 1 year only during early developments. 11 Reactor housing with SCR catalyst in shelf system. the standard process or performance guarantee for SCR systems worldwide is 20. a hazardous. trucking industry and air quality regulator partnership conducted lab/bench and field tests with several technical universities and certified test labs in Europe. and flammable gas. The diesel SCR catalyst did overcome past SCR problems related to high-sulfur fuel. (Courtesy of EESI/Steuler. Tank and Piping System for the Reducing Agent Anhydrous Ammonia. Like most oxidation catalyst guaranties today. manufacturers were evaluated in late 1980s to early 1990s Some test results from the technical university RWTH-Aachen.) application engineering work was carried out in Europe. maintaining the emission reduction. and high-dust loads and allows operating temperatures as low as 300°F (150°C) and as high as 1020°F (550°C).

8 A/V(m2 /m3) 850 1400 1250 1250 570 1250 V2O5 /TiO2 /WO3 V2O5 /TiO2 V2O5 /TiO2 V2O5 /TiO2 /WO3 Fe/molecular sieve Cu/zeolite 45 100 100 100 21 100 107 . SV space velocity.8 6.0 5.0 6.8 7. Catalyst Selection Cpi A. D. extruded Coated substrate (CS-based) CS based CS based Homogeneous extruded zeolite CS based Channels per inch.Selective Catalytic Reduction TABLE 1 European HDD Truck Tests.8 6. Note: Cpi SV(m3 /hm3) 5100 8200 8200 8200 4000 8200 AV(m3 /hm2) 6. A/V area/volume. AV area velocity. E. F. Homogeneous. C. B.

Aqueous ammonia is safer but requires the same handling and storage precautions as for anhydrous ammonia. Again. usually does not require such certified tanks. To achieve proper mixing of the reducing agent into the flue gas. Engineers with little or no corrosion engineering experience sometimes specify carbon steel rather than SS316 for piping and lower-grade stainless steel for storage tanks in case aqueous ammonia is used. Examples of SCR systems with anhydrous and aqueous ammonia are shown in Fig. not realizing that aqueous ammonia is highly corrosive in the vapor phase. and off/nonroad applications. Aqueous urea. is nonhazardous. This tank corrosion has been causing extensive downtime due to rust particles. the reducing agent is heated and diluted with hot air or recycled exhaust gas prior to . The Ammonia and Urea Supply. spray nozzles. 25% ammonia concentration in demineralized water is standard. however. on-road. clogging valves. 13. 12 NOx (a) and VOC/HC (b) reduction rates at different temperatures during 30–50 operating hours with NH3 slip of 30 ppm. sometimes 27–29% ammonia concentrations are common. now benefiting the new and retrofit stationary combustion applications as well. 14.108 Selective Catalytic Reduction (a) (b) FIG. and Injection Systems These systems are due to the corrosive nature of the reducing agents made of SS316 steel. and nonflammable and is primarily used as fertilizer and animal feed. In Europe. nontoxic. requiring pressurized tank certifications and routine maintenance in some states (i. Metering.. as salt dissolved in demineralized water. and federal regulations. state. It required extensive R&D and application engineering development to make urea SCR systems work properly and reliably. New Jersey).e. and so forth. Data on aqueous urea is presented in Fig. Ammonia with a concentration of 20%. this gave the SCR technology a bad name in the United States. In the United States. The urea SCR system engineering development work in Europe was a prerequisite for applying the SCR technology to mobile. required to strictly adhere to safety instruction of the manufacturers as well as to local.

(Courtesy of EESI/Steuler. 13 (a) Gas turbine application with PEMS and CEMS controls. aqueous urea requires a certain reaction time to convert to ammonia in the exhaust duct. aqueous ammonia and aqueous urea may be co-injected and atomized with compressed air directly into the exhaust pipe.8MW engine cogeneration plant. Also. . (b) Gas/diesel (dual fuel) 4. temperature control and other design considerations have to be met. determining the injection nozzle location upstream of the static mixer.) being injected into the exhaust gas stream in front of the catalyst bed. Because the dissolved urea salt may crystallize again and deposit around the spray nozzles. Alternately.Selective Catalytic Reduction 109 (a) Anhydrous Ammonia Tank (b) Aqueous Ammonia Tank FIG.

(Courtesy of Siemens. engine bench tests or gas turbine.1 0. The alternate system incorporates corrosion-resistant.110 Aqueous Urea: (NH2)2 CO Safety Aspects: Consumption: Selective Catalytic Reduction H2O. which operates on historical emission data measured at different loads of the combustion equipment during (for example. On-Line SCR Operating Control and Emission Monitoring System This features a Predictive Emission Monitoring System (PEMS).5 0.4°C or 11.00 Urea in demineralized water (%) 30 – 40% 11.5 F at 32.5 8. 15.38 3. operating on historical computer memory data. but fine-tuning feedback control.26 (1. The correlation function of engine-load values versus NOx emission values generated is combined with an algorithm in the software of the SCR control system. industrial grade Virtually nonodorous. or boiler SCR system) start-ups. The reducing agent is metered and injected continuously in accordance with the signals received from the microprocessor or Process Logic Controller (PLC)based SCR electronic operating control system. Such custom-designed SCR systems used to occupy an entire row of control cabinets. or the feed-forward control plus a slower.0 1105–1125 1.1 Dimension % g/cm3 mPa s kJ/kg K m S/cm Concentration: Crystallization: Salting-out temperature: Specification: Typical industrial grade Example. and nonflammable 1:0.87 Molecular weight ratio NO2: Urea NO: Urea 1:1.5 0. The mobile SCR system developments reduced such controls to less than laptop computer size. Such system may feature either a feed-forward PEMS-based injection control.0–9. engine. and injection system designs currently being used.1 0. The first is a constant high-pressure common rail piping system with needle valves or unit electronic hydraulic injectors.2–1. The feedback system incorporates either a Continuous Emission Monitoring System (CEMS) or sensors. (See Fig.) There are basically two types of supply.3) 10 4 0–35°C (32–95 F) 0. variable speed or variable stroke metering pumps of different designs.6°C or 33. metering. calculating the amount of reducing agent required to reduce the NOx to the specified .0 F at 40% concentration Value 40 0. Urea pH Density at 15°C Viscosity (at 25°C) Specific heat (at 25°C) Electrical conductivity Temperature range without temperature control Biuret Fe PO4 Mg Ca % mg/kg mg/kg mg/kg mg/kg FIG. 14 Aqueous urea data. nonhazardous.) The Integrated.5% concentration 0.

Figure 16a shows the highest temperature of 900–950 F at 1000 rpm and medium torque. 16a–16c. An example of this ‘‘mapping’’ process is shown in Fig. a typical truck operating condition.) (b) Laptop-size SCR operating and injection control system. Figure 16b shows that the highest NOx emission is generated at medium speed and torque as well. (Courtesy of EESI/Steuler. 15 (a) SCR control system cabinets with PEMP and CEMS.Selective Catalytic Reduction 111 (a) (b) FIG. (Courtesy of Siemens. .) permitted emission rate.

Engine test standards should therefore emphasize those operating conditions. achieving NOx reductions of up to 90%. EPA regulations such as 40 CFR Part 60. Again.) Figures 16c and 16d show that the highest NOx reduction takes place at medium speed and medium torque (Fig. The control system monitors all SCR system functions such as tank level control with high. . the system communicates with. (c. reordering. and low limit. d) PEMS mapping: correlation functions of NOx reduction rates and break-specific fuel consumption. In many stationary applications. Thereby. Appendix B for IC engines. the local air quality regulator requires the use of certified CEMS in accordance with U. operating parameters such as exhaust gas temperature and pressure drop of the SCR catalyst as well as all required maintenance and trouble-shooting management functions. the accurate but expensive gas-analyzerbased CEMS are often more capital-intensive than the SCR emission reduction equipment. for example. 16 (a.b) PEMS mapping: correlation functions of uncontrolled NOx and operating temperatures of a 12-L HD diesel truck engine rated 400 HP. 16d) as well. the electronic engine management system and the remote central control panel or On-Board Diagnostic (OBD) system by CAN bus or via 4–20-mA or 0–5 V analog signals. where the lowest fuel consumption is achieved (Fig. (Courtesy of Siemens. 16c). Thereby. this gave the SCR technology a bad name.112 Selective Catalytic Reduction (a) (b) (c) (d) FIG.S.

the SCR catalyst meeting the performance characteristics best is selected.Selective Catalytic Reduction Catalyst Selection Process 113 The type of SCR application determines the material and component selection. as well as the chemical analysis thereof Fuel operation: different fuels as percentage of total operating time Flue gas analysis: NO/NO2 ratio. uncontrolled NOx and emission such as CO.e. max. per hour. per hour. Not all SCR catalysts and system components perform well in all SCR applications. 2. permitted NOx rate [kg or lb. wood chips. natural gas. The following is a partial list of parameters that may have to be considered while designing a SCR system: • • • • • • • • • • • • • • • Fuels and fuel analysis: No. for example. digester or landfill gas. at front face of catalyst at different loads H2O concentration in the flue gas O2 concentration in flue gas . and min. 200 to 300 cells/in. causing high corrosion through SO3 conversion and reducing the NOx emission reduction by up to 80% SO2 converting more than 50% of NO NO2. VOC/HC. chemical waste. and 6 fuel oil. N m3 per hour or scfm) and gas density Flow rate (m/s) and uneven gas flow and temperature deviations (%) at front face of catalyst bed. 1. SCR Catalyst and System Performance Parameters Depending on the application.2. or changing the catalyst structure such as the cell density of honeycomb catalyst from i. and space-velocity data Catalyst space availability: maximum cross section and length Temperature range. oxidation catalyst manufacturers in the United States also included oxidation catalysts upstream of the (SCR) catalyst. ppm vd (dry by volume)] at stack or tail pipe Exhaust gas mass flow rate (kg or lb. area-. reducing the reactivity to avoid exhaust duct corrosion through SO2 SO3 conversion (SO3 H2O H2SO4). In some cases. as shown in Fig. this is not sufficient and the SCR catalyst is optimized through changes in catalyst material formulations. 17a–c. Then. total from combustion equipment to stack or tail pipe exit Sound attenuation requirements (dB A) Free-flow. PM and NH3-slip as well as the emission reduction requirements NOx —in: raw/uncontrolled emission at different loads of the combustion equipment NOx —out: reduced. The SCR catalyst selection begins with a careful analysis of the performance and guarantee requirements. requiring computer and/or scale-flow-modeling and static mixer applications Maximum allowable pressure drop of the catalyst bed Pressure drop. liquid or gas. In several cases. different operating conditions and performance requirements have to be met. 3. to reduce the weight and the size of the SCR catalyst for a mobile on-road application where it matters most.

(VDI-Report 1995.114 Selective Catalytic Reduction (a) (b) (c) FIG.) (c) NOx reduction rate at increased pre-oxidized NO NO2 at 500 F (250°C).) . (Courtesy of Dudoco 1995.) (b) Catalytic reactivity of noble metal catalyst for SO2 SO3. 17 (a) Metal-substrate based noble metal oxidation catalysts. (Courtesy of Miratech/Hug.

The reaction of NOx with ammonia takes place at the catalyst macropore surface. SCR Catalyst Material There are basically three types of material used for SCR catalysts. 18. For some basic calculations equations are provided in Fig. which would also form in exhaust gas ducts if SO2 oxidizes to SO3 catalytically H2O H2SO4). Ammonia slip rates as low as 3–10 ppm have been achieved in continuous operations. which is desorbed in a subsequent operation. noble. This allows the adsorption of unreacted ammonia spikes (ammonia slip) rather than passing through the stack as secondary emission. vanadium (V2O5). to enhance the SCR NOx reduction by partially oxidizing NO to NO2. 7%. PM by up to 50% and NOx by up to 95% at no extra cost. and palladium. today’s efficient HD diesel engines emit only minimal amounts of CO and VOC/HC. Base-metal-type SCR catalysts have nondiscrete mac(SO3 ropores and channels. . Due to the high cost. base metal. The material formulations and manufacturing processes are usually proprietary developments of the manufacturers. tungsten (WO3). primarily oxides of base metal are being used for SCR catalysts. Noble metal oxidation catalysts may be used upstream and/or downstream of the SCR catalyst: for upstream. or 15% O2 Acceptable process guaranties and equipment warranties Calculated catalyst bed dimensions and number of catalyst modules Oxidation catalyst requirements Particulate filter requirement Other There are several SCR and Oxidation Catalyst and Application Engineering Calculations required to layout a SCR system. oxidation catalysts are generally not recommended because additional PM would be generated when burning sulfur fuel. however. They can be used for both NOx reductions and for the oxidation of VOC/HC. is counterproductive if SO2 is converted to SO3 as well. Noble catalyst metals are platinum. Catalysts with a high V2O5 content are used in the production of sulfuric acid (H2SO4) as well. the exothermic reaction takes place inside the vast micropore structure of over 200 m2 per gram of zeolite. 21. PM. CO. which in some cases. adsorbing ammonia. In HD diesel engine SCR applications using the Siemens diesel SCR catalyst. V2O5 is highly reactive and used in small amounts of up to 2% only. Although originally developed for NOx reduction only. and additive and ceramic binders. The advanced diesel SCR catalyst development allows NOx emission reductions at temperatures as low as 300 F (150°C). the plate-type and the extruded-type base metal catalyst packaging are pictured. In the case of the ceramic-zeolite-type catalysts. Base-metal-based SCR catalysts contain oxides of base metals such as titanium (TiO2). rhodium.Selective Catalytic Reduction 115 • • • • • • O2 concentration of air quality regulator’s standard for emission rate calculations at 5%. for downstream. Also. the advanced SCR catalysts is able to simultaneously reduce VOC/HC by up to 95%. which may amount to 60 m2 / per gram of material of noble or base metal catalyst materials. and zeolite. In Fig. to reduce possible ammonia slip spikes and CO/ HC not oxidized by the SCR catalyst.

is the volume of air consumption times O2 content times NG consumption (N m3 /h). may vary greatly. and n is the emission reduction rate (i. VEGF (N m3 /h) (m3) SV (1/h) Keff.) Vcat. natural gas combustion.3/1. the catalyst surface area per catalyst volume (m2 /pm3).000. 95% 0. is the actual oxygen (O2) concentration of the exhaust gas. is the volume of air with 21% O2 required to oxidize total HC (N m3 /h). (d) Reducing Agent Consumption. 18 (a) Reactivity of SCR catalysts.000 (kg/h) using aqueous ammonia with a 25% ammonia concentration. AV is the area volume. and NGcons. (b) Catalyst Volume (Vcat. the volume of the exhaust gas flow (N m3) per hour at normal conditions divided by the volume of the catalyst (m3) resulting in (1/h).) (6) where VEGF min.] (c) Exhaust Gas Flow. SV AV ln(1 n). (1) ln(1 n) (2) SV where VEGF is the total exhaust gas flow at standard or normal condition (N m3 /h) and SV is the space velocity. stand (ppmvd compound) O2 stand. l is the percentage O2 in the air used during combustion. and structure of catalyst Keff. (mg/N m ). 2(Cx 21 NGcons.4 64 (molecular weight)/22.4 21 21 (9) O2act vs. [For each proprietary catalyst formulation and structure variation. (c) Exhaust gas flow calculations. (d) reducing agent consumption. Example Aqueous NH3 Consumption NH3 cons. (b) catalyst volume calculation. O2 act. material.116 Selective Catalytic Reduction (a) The K values. NOx —Reduction ppm NO ppm NO2 ppm NH3 ppm SO2 ppm NO ppm NO2 ppm NH3 ppm SO2 (NOx in NOx out)(ppm). (mg/N m ) (mg/N m3). (mg/N m3). (VEGF) VEGF VEGF min. (1) where SV is the space velocity.4 17 (molecular weight)/22.e. (ppm vd) O2 actual.95). (10) FIG. the reactivity value of catalysts. VEGF min. AV see Eq. ln is the natural logarithm. VEGF(N m3) NOx reduction (ppm) (7) 3. VAIR min. VAIR min. 3 3 (8) 30 (molecular weight)/22. depending on type. is the natural gas consumption (N m3 /h). Cx Hy is the various hydrocarbons (HC) of the NG analysis making up the total HC.4 46 (molecular weight)/22. (N m3 /h) NGcons. . the manufacturer has developed proprietary space velocity table values for reactivity and NOx reduction rate (1/h). VAIR min. (N m3 /h) Hx) (N m3 /h) (3) (4) (5) l (21 21 (%) O2act.

) Zeolite. incorporating either corrugated foil . others like the ZSM5 of Mobile Oil is produce synthetically. Some other more novel combinations of zeolite with noble or base metal materials are presently being researched for PM and other emission reductions. for example. N2 and H2O vapor. The extruded honeycomb-type zeolite-based SCR catalyst has a very large micropore structure of over 2000 ft2 or 200 m2 per gram of material. which are unable to enter the micropore structure through the discrete openings. (Courtesy of SCAQMD. are disposed of. The exothermic reaction of ammonia and NOx takes place inside the micropore structure through electrostatic forces. and gasoline from natural gas processes. The pellet-type catalyst. is a ceramic material. and thereby extending the service life of the SCR catalyst considerably. the zeolite catalyst has superior resistance to many compounds such as heavy metals. Oil refineries heavily depend on them for their gasoline cracker. This reaction is relatively slow. base metal catalysts. synthetic lubrication oil. and the coated-substrate-type catalyst. the extruded monolithic. honeycomb-type catalyst using either oxides of base metals or zeolite. Some zeolite structures occur naturally. 20. The reaction products. requiring a higher volume of catalyst than. This enormous sponge effect compensates for major spikes of NH3 and NOx during rapid load changes.Selective Catalytic Reduction 117 FIG. also called molecular sieve. NOx and NH3 are attached to the micropore surface ˚ upon passing through the discrete pore openings of 6–10 A in size. 19 Pellet-type catalyst. However. One example of the over 1000 known different zeolite crystals is shown in Fig. SCR Catalyst Structure There are three types of SCR catalyst structure. back into the exhaust gas.

21 Left: Coated stainless-steel mesh/expanded metal-substrate-based plate-type catalyst for high-dust applications. the catalyst bed shrinks and unreacted exhaust gas will bypass together with the injected ammonia over the top of the catalyst bed into the atmosphere. and dust. Pellet-type catalysts are filled in containers through which exhaust gas is passed. base metal diesel catalyst. there are still several such reactors operating in southern California today. clogging the catalyst bed and prevents an even gas flow. right: extruded. monolithic. or plate-type stainless-steel sheet metal or extruded Corderite ceramic substrates. The pulsing exhaust gas flow. (Courtesy of Siemens.) . 20–22). cause the pellets to vibrate. Thus. Due to the erosion of the pellets.118 Selective Catalytic Reduction FIG. however. FIG. The dust settles. However. 20 A zeolite crystal. abrade/ erode. There is also a novel catalyst development incorporating fiber-based substrates. (See Figs. honeycomb. pellet catalysts do not work most of the time and were replaced as soon as the honeycomb-type catalysts became available.

containing high-dust loads. Long-term operating experiences in Europe showed that the erosion of the reactive catalyst material at the face of the SCR catalyst bed will terminate upon the exposure of the stainlesssteel substrate. review basically 10–20-year-old designs for coal and gas utility boilers). 22 Macropore structure of extruded base metal catalyst. industrial and municipal solid-waste incineration. monolithic. and other applications. the coated-type catalyst is less reactive. the aluminized washcoat to which the third layer. extending the service life. Conclusion It would be beyond the scope of this introduction to the SCR technology to go into further details of the process and the application engineering (i. is bond. engines.e.. the catalytically active material. honeycomb-type SCR catalyst has low back pressure and is widely used for gas turbines and boilers. The extruded. 23. the higher the reactivity/active surface area and the smaller the catalyst for a specific application.3–1. see Fig. corrugated stainless-steel foil or mesh plates. The corrugated foil substrate is primarily used for noble metal catalysts.Selective Catalytic Reduction 119 FIG. The future of .08 mm containing the macropore structure. The plate-type catalyst has been developed for flue gases. Due to the smaller macropore structure and surface area and thus absorption capability. The lack of a ‘‘sponge effect’’ may also be the reason for the lower emission reduction rates achieved by the coated-substrate-based catalyst at temperatures below 480 F (250°C). such as the hard coal utility boiler. The coated-type SCR and oxidation catalyst has usually three layers: the corrosion-resistant substrate (such as the extruded Corderite monolith. and other industrial applications. This advanced catalyst development allows NOx emission reductions at temperatures as low as 300 F (150°C). whereas the Corderite monolith is used for noble and base metal. Advanced base-metal-type SCR catalysts are available with 14–300 cps with channel wall thicknesses of 0. The higher the number of extruded channels per square inch (cps).

) the SCR technology lies in distributed power generation applications such as generation sets. There are already close to 1000 IC engine and turbine applications in service worldwide today (Intermacom AG).2) at space velocity of 60. and mobile on-road and non-road applications. cogeneration sets. However.6 and 0. This number could multiply when HDD trucks and other mobile SCR applications come to market in 2001 through 2010. application engineering. SCR systems engineers will have to pay more attention to design and application engineering details in future (Table 2).120 Selective Catalytic Reduction (a) (b) FIG.000/h. (b) Standardized test: relative reactivity of extruded ( 1) versus coated-catalyst structures depending on thickness of coating ( 0. (Courtesy of Siemens. . because some past design. and operation deficiencies gave the SCR technology a bad name in the United States. In the following section. 23 (a) Extruded monolithic honeycomb catalyst macropore structure versus the reduced coatedmetal substrate-based macropore structure. a few examples of SCR projects are summarized.

Selective Catalytic Reduction TABLE 2 Why Certain SCR Systems Have Not Performed in the United States Failure Catalyst 1. shutdowns. confirming equipment manufacturer’s long-term performance claims during a 3-year performance guarantee Controls and Other 1. and lawsuits of poorly maintained system or new/unproven technology. Reactivity loss Cause Pellet type catalyst Masking. Clogging and bypass of NOx and NH3 slip 2. and low back-pressure static mixers such as Parmix TM/ TM Siemens Feed-forward PEMS-based control with optional feed back CEMS or sensor-based control Electric–chemical sensorbased accurate spot check analyzer with periodic emission testing by third party Independent test lab certification. and PM itself Operators avoiding fines. Not cost effective 3. scaling/ particles due to temperature cycling Uneven gas flow at front face of catalyst bed or insufficient mixing of exhaust gas/NH3 121 Advanced (SCR) Technology Solutions Honeycomb or plate-type catalyst Special lean burn/diesel catalyst. allowing up to 3% sulfur fuel and an operating temperature window of 300–1020 F Diesel catalyst with micropore structure/‘‘sponge effect’’ with adsorption/ desorption features 3. VOC. Clogging of injection system valves or nozzles 2. scale model tests. Politics: Operator’s good references but bad performance of air pollution control equipment in actual operation . Low emission reduction Gas flow modeling. or delamination of catalyst coating with metal or Corderite-based substrates Little to no adsorption/ desorption capability of catalyst (nonmonolithic catalysts) at 500 F (250°C) Heavy corrosion/particle volume due to carbon steel aqueous ammonia tank and piping material Carbon steel reactor housing. Emission spikes at rapid load changes System Design 1. Clogging of catalyst All stainless-steel storage. which is often more costly than the SCR emission reduction system for NOx. delivery and injection system Heat-resistant steel such as low Molly steel 3. High emission spikes at load changes Relying only on a downstream CEMS with long feedback/response time Including a fully certified CEMS. homogeneous material. poisoning. ‘‘promoted’’ by the regulator 2.

2 diesel fuel upon start-up in Summer 2000. Fairbanks (UAF) has a 9000-kW electric Fairbanks– Morse reciprocating engine. both pumps will run. University of Alaska. A system of duplex metering pumps was furnished. The system was designed with a vertical exhaust flow. A soot-blowing system has been installed above the catalyst. Injection rate control utilizes a feedforward system. This allows the PM to pass through more easily. exhaust temperature. this data are then used to ‘‘trim’’ or fine-tune the reducing agent injection. a coal slurry as an alternative fuel. a zeolite catalyst was selected. and exhaust flow rate between the two fuels. When operating on coal slurry. from top to bottom. When running on diesel fuel. When running on diesel. The SCR system is designed to reduce NOx emissions independently of the fuel used. the system had to be designed with a wide operating range. the extruded monolithic honeycomb SCR catalyst was designed with a larger than normal pitch or channels per square inch (CPSI). An SCR system was proposed to reduce NOx emission. and because urea would require a great deal of temperature control during winter operation. A control feedback is used which measures NOx emissions upstream and downstream of the catalyst. which currently is fueled on No. In order to deal with the high-PM load. The continuous emission monitoring system (CEMS) analyzer (furnished by UAF) alternately reads emissions upstream and downstream of the catalyst and thereby . Because there is a large difference in NOx emission. has been constructing a demonstration project to test the feasibility of pulverized coal mixed in water. Ammonia was selected over urea because it is easier to source in the region. the engine produces large amounts of particulate matter (PM). The reducing agent flow is adjusting by varying the speed of the metering pumps. UAF. in partnership with Fairbanks–Morse and the Department of Energy (DOE). When operating on coal slurry. only one pump is required. exhaust temperature and flow. The system is designed to use aqueous ammonia (20% NH3 in demineralized water by weight) as the reducing agent. Because of the relatively high sulfur content of the fuel and the required low SO2 to SO3 conversion. An exhaust waste heat recovery system generates steam.122 Selective Catalytic Reduction Summary of SCR Application Case Studies Diesel/Coal-Slurry Fueled Diesel Engine Cogeneration Plant. the exhaust gas PM or soot concentration is low enough to operate without the soot blower. The engine will provide electrical power for the campus. 1999 System Overview The University of Alaska. allowing the PM to pass through and being collected in an ash hopper below the catalyst housing. When operating on diesel. Power not used by the campus is sold to the local electric utility. Fairbanks–Morse had already developed and tested the engine modifications in their research facility in Wisconsin so that the long-term field tests could commence in 2000. The soot blower automatically blows down the PM from the catalyst at regular intervals when the engine is running on coal slurry. which sets pump speed based on engine load. which is used for heating and cooling campuswide. and NOx emissions are higher than when running on coal slurry.

Zeolites ˚ are crystalline microporous ceramic solids with pore openings of 3–10 A. Ammonia reacts with NO and NO2 within the zeolite catalyst micropore structure to form nitrogen gas (N2) and water vapor (H2O). SCR Catalyst and Housing CER-NOx (SCR) Abatement Catalyst. The catalyst cartridge weight is 1510 kg (3329 lbs. with ammonia slip of 10 ppm or less. since the system start-up in Summer 2000. The system is designed to reduce NOx emissions by 90%. the process and instrumentation diagram (P&ID) and modified summary excerpts of the operating and maintenance manual are presented. . Each module has openings with a 6-mm pitch/cps (channels per square inch) to allow particulate matters (PM) to pass through without plugging. molecular sieve. During commissioning. The CER–NOx* (SCR) NOx abatement catalyst is a honeycomb-type. Currently. on diesel fuel. Electrostatic forces generated inside the micropores decrease the activation energy for the reduction process.Selective Catalytic Reduction 123 provides the feedback necessary to ensure that the SCR system is operating at peak emission reduction with minimal ammonia slip. * CER-NOx is a trademark of EEST/Steuler. the system is operating within these parameters. based on the concentration gradient. The 2 micropores provide over 1500 ft of surface area per gram of zeolite material. all-zeolite catalyst. which protects them from mechanical damage. thus allowing reactions to occur in a temperature range of 300° C/570° F to 480° C/900° F. Chemical Process. before the heat recovery boiler. 26. Seventy-two modules are wrapped in a stainless-steel cartridge. Figure 25 shows the Table of Contents of the summary excerpt of the Operating and Maintenance Manual. Each catalyst module has dimensions of 152 mm 152 mm 1000 mm long. 24. a 90% NOx reduction and almost zero ammonia slip was measured. which forcibly expels the reaction products N2 and H2O from the micropores. Design Parameters The SCR system is designed based on the parameters shown in Fig. The engine is scheduled to run primarily on coal slurry by late 2001 or early 2002. Nitrogen oxides and the injected aqueous ammonia are removed from the exhaust gas through adsorption into the catalyst micro pores of the zeolite. The construction on the coal–water slurry production facilities will start in 2001.) and its dimensions are 1920 mm 960 mm 1365 mm height. The reaction releases energy. In Fig. without wrapping. The SCR catalyst is located in the exhaust gas stream downstream of the Fairbanks–Morse engine.

124 Selective Catalytic Reduction FIG. 24 Process and instrumentation diagram (P&ID) of the Alaska cogeneration plant. (Courtesy of EESI/Steuler.) .

an injection spray nozzle. Design Parameters 2. The system includes control valves. Operating System Control a) Condition b) Analysis c) Action 5. The reducing agent supply and injection system consists of a storage tank. 125 SCR Reactor Housing. Daily Log. A static mixer is welded into the inlet of the reactor housing to properly mix the reducing agent and to evenly distribute the . and drive motors. Aqueous Ammonia Supply & Injection System a) General Description b) Ammonia Metering Panel c) Compressed Air Subsystem d) Electric Sub-panel e) Ammonia Injection Lance Assembly f) Static Mixer g) Ammonia Pump Station h) Ammonia Storage Tank i) Ammonia Tank-Truck Unloading Station 4. It includes the following: • • • • A 90° inlet transition from the exhaust duct to a turning vane assembly to distribute the exhaust gas evenly across the catalyst bed A shelf system with one row for catalyst One soot-blowing system to blow ash off the catalyst bed during coal–water fuel operation. Maintenance Routines 7. Operating Routines a) Start Up b) Normal Operation c) Shut Down 6. The housing is fabricated of A36 carbon steel. and interconnecting piping. an ammonia pump station. Visual Inspection FIG. isolation valves. catalyst is loaded into the housing after the housing has been installed Aqueous Ammonia Supply and Injection System General Description. 25 Table of Contents of the CER–NOx SCR system.Selective Catalytic Reduction CER-NOx (SCR) NOx ABATEMENT SYSTEM Overview and Component Description Table of Contents 1. controlled from the Co-gen plant control system Bolt-on access doors provided in order to load and unload catalyst. a metering panel. (SCR) Catalyst & Housing a) CER-NOx (SCR) Abatement Catalyst b) Chemical Process c) (SCR) Reactor Housing 3.

volume SO2 Ash/particulate. wet 0.800 837 665 8. lb/hr Exhaust temp. 24. P-104). Two metering pumps (P-103.126 Selective Catalytic Reduction • • Emission source: Fairbanks–Morse dual-fuel engine.6 13. weight % N2. °F Exhaust temp. maximum 120 psi 32 SCFM FIG. which controls how much reducing agent is injected into the gas stream. lb/hr —SCR System Performance NOx Reduction. When the engine runs on distillate fuel. (Courtesy of EESI/Steuler.3 3. SIC-104).75″ water column.) exhaust gas across the front face of the catalyst. Ammonia Metering Panel. The metering panel is controlled by the Co-gen plant’s Distributed Control System (DCS). P-103 is run at full speed and P-104 is operated at varying speed to provide the balance of the reducing agent volume required.. A 240-VAC single- . wet 2. only P-103 is operated.18 vol.2 600 ppmv 79 ppmv 350 90% — 10 ppmvd (15% O2) 0.500 BHP Combustion Process Information: Diesel Fuel Exhaust flow rate. weight % H2O. Each drive is controlled by the DCS via a 4–20-mA signal (for speed setting) and dry contacts (for starting/stopping the drive).5 74. measured from inlet hood to end of catalyst bed Aqueous ammonia. Refer also to Fig. one for each metering pump motor. max. The metering panel is divided into two subsystems: one for reducing agent control. weight % O2. % Ammonia slip SO2 to SO3 conversion Pressure drop. During coal–water fuel operation. 26 Design parameters for the SCR system.400 800 765 11. nominal 25% in water Technical grade in demineralized water only! 53.2 Coal Slurry Fuel 105. An ammonia pump station provides pressurized ( 40 psi) ammonia to the ring line.016 vol.. The reducing agent subsystem consists of the following components: • • • One fine filter (7 µm) on the pump outlet. for clean system —Reducing Agent —Reducing Agent consumption —Atomizing Air Requirements Pressure Consumption 155.%. The metering panel contains metering pumps. max.1% max 1. design. °F CO2. %. the other for control of atomizing compressed air..4 0.1 gal/h 21 gal/h Minimum 70 psi. The reducing agent is supplied via stainless-steel pipe to the metering panel. Two variable-speed drives (SIC-103. 9000 kW(e)/ Fuel type: either diesel fuel or coal–water slurry fuel 12.3 11.6 70. weight % NOx.9 6.

It is controlled automatically by the DCS. The injection lance is inserted into the exhaust duct upstream of the first static mixer. Mounted on the Metering Panel. to remove particulate matter and moisture from the compressed air. The lance’s spray head shall point in direction of flow. Compressed Air Subsystem. One magnetic-inductive flow meter (FE/FIT-101) which provides feedback to the DCS to close the feed rate control loop. Two pulsation dampeners to absorb pulsations from the diaphragm pumps. which transfers the atomized reducing agent into the exhaust duct. Ammonia Injection Lance Assembly. This valve closes off the airflow when the system is not running. Two relief valves (PSV-103. One normally closed (energized to open) solenoid shutoff valve (FV-101). This valve gives a positive shutoff of the reducing agent feed when the system is turned off. signaling the DCS. The drives are located in an electrical subpanel mounted on the side of the metering panel. If the air supply pressure drops below 50 psig. One pressure switch (PSL-201). 104) to protect the metering pumps. One pressure gauge (PI-105) on the pump discharge to monitor injection pressure. . Electrical Subpanel. to provide a local disconnect of the 240-V power supply to the metering panel One 24-VDC power supply to provide power for the solenoid valves and flow meter Three circuit breakers to distribute AC power to the two variable speed drives (SIC-103 and SIC-104) and 24-VDC power supply One circuit breaker to switch on the outlet of the 24-VDC power supply Two loop isolators for the variable-speed drives (SIC-103 and SIC-104) speed setting input Four 2PDT pilot relays with 24-VDC coils. One filter/dryer. the pressure switch contacts open. The valve is opened when a metering pump is started and closed when the metering pump is stopped. The lance consists of an air/liquid atomizing nozzle and a carrier pipe. to take control inputs from the DCS for SIC start/stop control. The valve is controlled by the DCS. This subpanel consists of the following components: • • • • • • One 20-A disconnect switch. to maintain air pressure at 43 psig. One normally closed (energized to open) solenoid valve (FV-201). This subsystem consists of the following components: • • • • One pressure regulator (PCV-201). variablefrequency output to the metering pump motor.Selective Catalytic Reduction 127 • • • • • phase input to each drive is converted to a 240-VAC three-phase.

NEMA 4 enclosure. Ammonia Storage Tank. M-102. 190 µm. in NEMA 4 enclosure. One back-pressure control valve (PCV-102) to set ring line pressure. is made of 304 stainless steel. One static mixer is provided.128 Selective Catalytic Reduction Static Mixer. to shut down the pump if flow is lost. Ammonia Tank-Truck Unloading Station. One inlet strainer. Control panel. One control panel. FE/FS-101. and a level transmitter. to remove larger particle from the aqueous ammonia. with capacity of 100 gal/min. with manual start/stop control switch and interlock with the flow switch above and the ammonia tank level switch (LIS101). main disconnect. and is resistant to the highly corrosive ammonia vapor above the liquid. The tank is designed for atmospheric pressure. TEFC to drive P-102. to remove pulsations from the pump outlet. A 3 HP. One motor. 3450 rpm. diaphragm type with fixed speed and capacity of 90 gal/h. 1/3 hp. This panel also houses the ammonia tank level indicator/ switch (LIS-101) which indicates the tank level in gallons. One pressure/vacuum gauge (PI-103) on the inlet and one pressure gauge (PI104) on the pump outlet. P-102. One pulsation dampener. The unloading station is used to transfer aqueous ammonia from the delivery tank truck to the bulk storage tank. interlocked to the motor. Ammonia Pump Station. One pressure/vacuum gauge (PI-101) on the inlet and a pressure gauge (PI102) on the pump outlet. See the detailed program description for pin assignments and input/output requirements. It consists of the following: • • • • • • • • One supply pump. The ammonia pump station supplies aqueous ammonia to the ring line feeding the metering pumps. a safety valve. the return side of the ring line is connected to the PCV. Flow switch. which is welded into the duct upstream of the reactor-housing inlet. shown on Fig. with HOA switch. 24. Operating System Control The SCR system is controlled by the central DCS of the Co-gen plant. 460VAC motor. to protect the pump. M-101. . PSV-101. the unloading pump will be shut down. It is supplied with ball valves. Cam-and-groove fittings for the tanker to connect. Upon a ‘‘high tank level’’ alarm. The aqueous ammonia storage tank holds 8000 US gals. 115-VAC single phase. It consists of the following: • • • • • • Centrifugal transfer pump. motor contactor. One pressure relief valve. The general operating sequence should follow the program in Table 3. The mixer ensures proper ammonia/exhaust gas mixing. P-101.

wires. allow 1 min time delay from start of pump before writing alarm Ammonia flow below min value (from FIT-101) and metering pump start signal is given. Operating Routines Start-up. the following restart checks have to be performed: No maintenance is being performed at the NOx abatement system. close ammonia valve FV-101 Stop metering pumps Stop metering pumps.Selective Catalytic Reduction TABLE 3 Operating System Control Condition On start of engine Analysis Begin purge of injection lance Start pump P-102 DCS decision on which metering pump to run Exhaust temperature for SCR Process OK. and so forth. • • • • • • Open all hand valves in the reducing agent supply and injection lines Atomizing compressed air supply (compressor) available Open all hand valves of the atomizing compressed air supply and aqueous ammonia injection lines Verify that the DCS available Verify power is available to metering panel Start the system via the DCS upon determine permissive conditions to start . and metering pump speed signal above min value On shutdown of engine Open ammonia valve FV101 Start metering pump P-103 (if CWF) and P-104 (if distillate fuel) Stop metering pumps Close ammonia valve FV101 Stop metering pumps. a visual inspection shows no disconnected or broken pipes. close air valve FV-201. and the reducing agent supply is available. close ammonia valve FV-101. close ammonia valve FV-101 Stop metering pumps. ammonia injection permitted Actions 129 Send ‘‘start’’ signal to P102 Advice from Engine control if running on distillate or coal–water fuel Exhaust gas temperature (570 F) (from TIT-301) Exhaust gas temperature (896 F) (from TIT-301) Ammonia storage tank low level Atomizing air pressure low Exhaust temperature for SCR Catalyst too high The ammonia tank empty Failure of compressed air system Failure of metering pump. Upon a complete equipment shutdown. stop ammonia pump P-102 Source: EESI/Steuler.

Under normal operating conditions. Note that these intervals assume continuous operation. Daily Log Table 5 is the inspection checklist. pump oil changes. Natural Gas/Liquid Fuel Fired at Bridgeport Harbor. It is generally not required to make adjustments or continuously monitor the system. Fuel efficiencies of over 85% versus 50–60% max. Connecticut Overview Cogeneration and distributed power generation will be the preferred and most fuelefficient way of the future to generate heat and electricity as fuel cost increases and the utility industry becomes fully deregulated. and so forth. and periodic replacement or cleaning of filters. Under intermittent operation.130 Selective Catalytic Reduction injection based on temperature. Rather than ‘‘destroying’’ the so-called ‘‘waste heat’’ in cooling systems. the excess electricity can easily be wired away. especially in Japan and Europe. these intervals could be extended. Gas Turbine Combined Cycle Power Plant Rated 2 170 MW. routine maintenance on the CER-NOx SCR system is limited to occasional visual inspections. If the system will be shut down for maintenance. the system can be quickly checked out in conjunction with other maintenance activities. the DCS controls the speed of the reducing agent pumps in accordance with the NOx signal received from the continuous emissions monitor-based feedback. Shutdown. The operator shall determine if the intervals can be lengthened based on operating experience. Fuel efficiency has been a driving force of air-pollution control regulator outside the United States in the power generation community. the following steps have to be taken: • • • Shut down aqueous ammonia injection and allow system to purge lines and lances with compressed air Shut off power supply to the metering panel Close air and ammonia hand valves at inlet and outlet of metering panel Maintenance Routines In general. the local heat requirement will be the driving output/product and the by-product. in . lack of alarm signals. Usually. and other operating parameters Normal Operation. Table 4 outlines how often certain maintenance procedures should be performed.

gas/steam turbine projects have been achieved. utilizing the steam generated from the ‘‘waste heat’’ of the gas turbine for electricity generation. reducing CO2 emission by over 15% in the prior 10 years. utility companies have rarely opted for the highly fuelefficient cogeneration plant alternative yet. In the United States. Replace every 1000 h of operation Drain differential pressure gauge (PDIT-301) condensate lines for SCR reactor Record differential pressure indication for SCR reactor Clean/replace reducing agent in metering panel Clean atomizing air filter in metering panel Clean reducing agent strainer at ammonia pump station Check/replace metering pump and transfer pump diaphragms Check metering panel and pump station pulsation dampener charge Check/rebuild metering panel solenoid valves (FV-101/201) Check metering panel pressure relief valve setting (PSV-103/104) Check air pressure switch (PSL-201) setting Check injection lance nozzle for cleanliness Calibrate all 4–20-mA loops to DCS Source: EESI/Steuler. however.N. The Saarbruecken utility company in Germany. Environmental Award at the summit of world leaders in Rio.Selective Catalytic Reduction TABLE 4 Maintenance Routine Operation Visual inspection (see: Visual Inspection Daily Log) Check reducing agent supply tank level Check/replace metering pump (P-103/ 104) and ammonia transfer pump (P-102) oil. . providing heating to the town nearby. received the U. The new or upgraded power plants. A Swedish utility company operates a 1200-MW cogeneration power plant. usually incorporate gas turbines and downstream steam turbines. 131 Daily Weekly Monthly X X X Biannual Annual X X X X X X X X X X X X combined-cycle. Brazil in 1990. primarily through cogeneration.

Verify no leaks exist and that isolation valves are fully open. Verify that they are not damaged and are properly positioned (high. and that no air or reducing agent is leaking inside or outside of enclosure. Verify no leaks exist. 28a and Fig. 2 Inspect supply line between reducing agent storage tank and metering panel.3A gas turbine project is rated 170 MW electric per gas turbine. Verify that no obvious exhaust leaks exist (indicated by soot tracks at insulation joints). and when finished. The SINOx (SCR) system features the use of either aqueous urea or aqueous ammonia as the reducing agent to meet future. condensate lines closed). that no physical damage exists (internal or external of enclosure). and stainer for good physical condition. The process and instrumentation diagram (P&ID) of the SINOx exhaust gas cleaning system is shown in Fig. 9 Inspect the SCR differential pressure gauge and its associated block and bleed valves. If system is running. bypass valve closed.and low-pressure input valves open. Verify no leaks exist and that isolation valves are fully open. and that isolation valves are open. The system ensures State of Connecticut EPA compliance with the emission reduction of 91% to 4. and correct pressure is available (75–120 psi 4 Check metering panel for proper position of its isolation valves (fully open). 27. Project Summary The (2) Siemens V 84.5 ppmvd at 15% O2. The SCR system design is based on the exhaust gas data listed in Figs. proper draining of condensate drains. 5 Inspect air and reducing agent lines between metering panel and injection lance for good physical condition. dry basis for nitrogen oxides (NOx. more restricted safety regulations. 8 Check thermocouple probe at inlet of SCR housing that no exhaust leaks exist and that termination cover is in place. as NO2). The SINOx system was delivered as two preassembled units. 3 Inspect atomizing air source.132 TABLE 5 Inspection Checklist Inspection check list Selective Catalytic Reduction Initial when done 1 Inspect reducing agent storage tank. that the door is closed and latched. that it is making normal operation noises. Verify that no leaks exist in air supply lines between atomizing air source and metering panel. . 7 Inspect insulation on exhaust duct and SCR housing for condition and proper installation. 6 Check that injection lance is in good physical condition (no bent or cracked hook-up ports). 28b. 10 Verify that the DCS is operating normally and that no alarms are displayed.

27 P&ID of a (2) gas turbine power generation plant. the Cal. irrigation/pump drives) and garden equipment should be prime targets. and various agriculture (i.Selective Catalytic Reduction 133 FIG.e. HC. diesel-powered coastal vessels and construction/mining equipment. . 1999. During the University of California–Irvine Technology Meeting on October 6. 29 and a system maintenance schedule is given in Fig. NOx emission inventory of 25 million tons per year and close to 60% of PM emissions is generated by portable. Summary of Recent Market Data on Retrofit Emission Reduction Target Markets.S. on-road.S. Portable and Other Applications Background Summary California ARB (Air Resources Board) Strategy for Additional Emission Reductions by 2007/2010. and PM emissions. Over 50% of the total U. Retrofit emission reduction applications for diesel locomotives. 30.-ARB presented its objectives to substantially reduce NOx. portable generation sets. To achieve California SIP (U.. Mobile. and off-road vehicles and equipment. EPA’s State Implementation Plan) goals by the year 2007/2010 emission of onroad and off/nonroad vehicles and equipment could be reduced by market incentive and monetary incentive programs. A brief technical description of the systems function is provided in Fig.

134 Selective Catalytic Reduction (a) (b) FIG. (b) project data. system utilities. . 28 (a) Project data. operating conditions of the (2) gas turbines.

caused by 1.6% were assumed from Class 8 HD diesel trucks. • A total of 2. However. for which engine manufacturers were fined in a con- . an additional 1. 29 Brief description of the SINOx system process.3 million tons of NOx per year had to be added.328 million Class 8 trucks.Selective Catalytic Reduction 135 FIG. due to excess ‘‘off-test-cycle’’ emissions of 15.758 million tons during 1988 through 1998.2 million tons/year of NOx from the United States representing 8.

This increased HDD truck NOx emission resulted in over 3. the State of New York. • sent decree.S.5 million tons of NOx emission per year. according to industry. EPA. Justice Department and the U.-ARB with the engine manufacturers did not incorporate any short-term remedies but only engine-rebuilt solutions for this large fleet of highly fuel-efficient HDD trucks. NOx inventory. is the unrealistic U. and Cal. The Consent Decree of the U. 30 System maintenance schedule. FTP (Federal Transient Protocol) test cycle with heavy emphasis on low torque/low rpm and high rpm.S.S. equal to 12% of the total U.136 Selective Catalytic Reduction FIG. One reason. whereas most truck operations take .S.

SINOx SCR System. 31 Product summary. 20. 2000. Feb.) . (From Intermacom AG.ARB. Draft for the WebPages of Cal.Selective Catalytic Reduction 137 FIG.

6 gr. Two most promising retrofit technologies were identified achieving over 70–80% NOx and VOC/HC and substantial PM emission reduction: The UREA–SCR and the NOx Absorber Technology.000 miles and the initial target price is estimated to be US$ 2000–3000 per HDD truck. transportable.S. it is claimed that only a 20. almost neglecting the low torque/low rpm operation. • • The NOx Absorber Technology has been tested by Cummins. achieving 80% NOx reduction at a 8.S. The technology will be commercially available by 2001.S.000-mile service life with 5–15 ppm sulfur fuel could be expected./BHP h. In a Marathon–Ashland Petroleum commentary to U.9 gr. marine applications lag behind. ships. whereas some of the same engines in trucks have to meet 2 gr. EPA does expect that such 15 ppm sulfur fuel will be readily available in the United States prior to 2007. • Reports on Technology Evaluations. California has an earlier target date and fleet averaging provisions. lube oils with phosphor and sulfur compounds have to be reformulated and tested to avoid loss in engine service life. has been field tested for 4 years./BHP h NOx emission rates in California.4 gr.5% fuel penalty.S. The UREA SCR Technology for the simultaneous reduction of NOx (70–85%). According to Cal. All other retrofit/post treatment technologies are either years away from any commercialization or achieve only 20–40% NOx reduction rates. By the end of 2001./BHP h by 2002/2004. U. mining. are required to meet NOx HC emission levels of 2. The service life is expected to be over 300. EPA. VOC/HC/AirToxics (80–95%).000 BHP) in Europe. One of these European tests shall now complement the U.S. and agriculture equipment as well as portable equipment such as generation sets have not been a U. The volume-produced SINOx Systems can then be used for mobile. Institute for Transportation Studies) and Diesel Fuel News. even though less than 2 gr. EPA FTP tests. rated 110–600 BHP. EPA priority even though they account for approximately one-quarter of the total U. The U. Currently. and PM (up to 50%) has already been used in HDD truck field tests in Europe and the United States in the 1990s.138 Selective Catalytic Reduction place in medium torque/rpm. Portable generation sets are not required to achieve better than 5. diesel locomotives are required to meet 5./BHP hr NOx in 2002/ 2004. Japanese and European tests cycles emphasize medium torque/rpm./BHP h NOx emission rates have been demonstrated in close to 100 marine diesel engine applications (with engines rated 300 to over 10. The European truck manufacturers and Siemens pioneered this technology. By 2010. Off-road NOx and PM emission from diesel-powered locomotives. no 15 ppm sulfur fuel is commercially available on a large-scale basis in the United States. . In addition. New trucks however. construction. Also. NOx inventory. using the Euro-3 (13 Mode) Steady State Diesel Engine Tests and 5 ppm sulfur fuel. Siemens will go into the SCR system production for Daimler–Chrysler and MAN’s new ultralow-emission HD diesel trucks. In recent publications of UC-Davis’ ITS (University of California.S.-ARB there are 72. In comparison. various emission control strategies for HD diesel engines were discussed.064 portable and stationary diesel engines without emission controls in California. and demonstrate no fuel penalty.

the engine data are listed. and NOx emission limits. Figure 33a shows one of the three engine enclosures with the SCR system and exhaust stack located in front. set by the State of New Jersey. cogeneration. Three 3000-BHP gas engines with low NOx emission exceeded the plants VOC/ HC/AirToxics. VOC/HC. off-the-shelf SINOx products as retrofits kits. 33d. Jet Fuel Pipeline Pump Station for the New York Area Airports. on-road and off/nonroad applications.S. . (b) Simultaneous reduction of NOx. (Courtesy of Siemens. 33b. CO.Selective Catalytic Reduction 139 (a) (b) FIG. The SINOx SCR systems are used in coal and gas-fired utility boilers and gas turbines. 33c. engineering journals in 1998. to use the prefabricated. NJ This SCR application was discussed in two U. However. and various mobile. Figure 32 shows the range of SINOx Applications. In Fig. and PM at stationary and mobile applications. The process guaranteed emission limits are shown by Fig. engine model/application adaptations through local factory trained and licensed dealers are required. 32 (a) Stationary and mobile applications for the diesel SCR catalyst. The system design aspects are listed in Fig.) and stationary engines rated 100–600 BHP. stationary and portable generation sets.


Selective Catalytic Reduction




FIG. 33 (a) Engine enclosure with SCR system and stack in front; (b) Data on the three gas engines of the jet fuel pump station; (c) SCR system design data; (d) Pump station permitting and process guarantee data. (Courtesy of Siemens.)

Selective Catalytic Reduction


Coastal and Ocean-Going Vessels and Other Marine Applications
Two of the vessels equipped with SINOx diesel SCR Systems achieving very low emission rates of equal or less than 1 gr/pBHP h are pictured in Fig. 34.

Heavy-Duty Diesel Truck Field Tests in Germany and the United States, 1995–1999
SINOx (SCR) System Overview. The SINOx after-treatment system is a fully developed and tested diesel exhaust emission reduction system. Figure 35 pictures the first HD diesel truck on the left with a round muffler, replaced by a round SINOx diesel SCR System in the early 1990s. The right photo shows the Daimler– Chrysler HD diesel truck barrel-type SCR reactor/muffler, going into production at the end of 2001. The UREA–SCR System developed by Siemens (Siemens Westinghouse) and the European trucking industry uses aqueous urea as a reducing agent for the SCR process to reduce NOx. The process also reduces VOC/HC, and PM at the same time. The manufacturer has performed laboratory and fleet tests of the SINOx system. Approximately 20 European Mercedes Benz (Daimler–Chrysler), IVECO, and MAN heavy-duty Class 8 trucks were tested in the field. In late 1998, some of these trucks had accumulated over 300,000 miles in common carrier operations. The urea infrastructure, the risks of tampering with the UREA (SCR) system, and other initial operating reliability and other concerns were resolved to the European trucking industry’s and air quality regulators’ satisfaction. The diesel fuel used during the tests had a sulfur content of max. 500 ppm (0.05%). Figures 36a and 36b show program objectives and the aqueous urea pump station, respectively.

FIG. 34 SCR marine applications with extremely low NOx emission. (Courtesy of Siemens.)


Selective Catalytic Reduction

FIG. 35 Pilot-type and preproduction model SCR system for Class 8 HD diesel trucks. (Courtesy of Siemens.)


FIG. 36 (a) SCR truck program objectives; (b) SCR aqueous urea pump station. (Courtesy of Siemens.)

Selective Catalytic Reduction


The SCR system feasibility tests included bench tests using European Stationary Cycle (ESC) ( OICA) and European Transient Cycle (ETC), and the Federal Transient Protocol (U.S. FTP) Test Cycle in the United States. NOx, VOC/HC, and CO of the exhaust gas were measured upstream and downstream of the catalyst, using sample gas conditioning systems, heated sample gas lines, and various gas analyzers. The following analyzers were used: chemiluminescent detector (CLD) for NO and NO2, flame ionization detector (FID) for VOC/HC, a nondisperse infrared analyzer (NDIR) for CO and CO2, and a magnetopneumatic analyzer for O2. Fourier transformation infrared spectroscopy (FTIR) allowed simultaneous, realtime monitoring for multiple gas components. The FTIR was used downstream of


FIG. 37 (a) European steady-state cycle (ESC) test results; (b) European transient cycle (ETC) test results. (Courtesy of Siemens.)


Selective Catalytic Reduction the catalyst for the exhaust gas and for detecting potential traces of secondary emissions, such as ammonia slip (NH3), laughing gas (N2O), cyanic acid (HCN), formaldehyde (CH2O), and so forth. Also, a microwave process analyzer was used to measure ammonia slip during steady-state tests and for periodic verification/ calibration tests of the FTIR analyzer. For analytical hydrocarbon tests, bag samples were taken and analyzed with gas chromatographs. Test results of an European HD diesel engine with a SINOx System are summarized and compared with emission standards, based on the European steady-state cycle ESC (OICA) and the European transient test cycle (ETC) as shown in Figs. 37a and 37b, respectively. The NOx emission reduction was 80% in steady-state


FIG. 38 (a) Urea SCR steady-state/13-mode test results, DDC-S 60, 12 L/400 HP HDD truck; (b) Urea SCR U.S. EPA’s FTP test results, DDC-S 60 engine. (Courtesy of Siemens.)

VOC/HC. EPA emission limits in 1999. A flow control unit in the metering panel meters the amount of reducing agent. The reducing agent storage tank has a volume of 5% of the fuel tank volume.S. The SINOx system is activated by the signals ‘‘engine on’’ (provided by the Engine Management System) and exhaust gas ‘‘temperature above set point’’ (temperature sensor in exhaust pipe). 39). (Courtesy of Siemens. and no other undesirable secondary emissions were detected with the sophisticated analyzer setup described above. 39 SCR system layout.) . The amount of reducing agent is metered and in accordance with the computer-memory-based predicted NOx emission and injected into the gas pipe upstream of the SINOx FIG. the Series 60 Detroit diesel engine. and PM [18]. The emissions measured downstream of the SINOx diesel catalyst was approximately 50% lower than the next lower tier of the European emission limits for NOx. bench tests in Detroit in 1998.S. that is. 38a and 38b. as shown in Figs. the aqueous urea (30–40%) is injected upstream of the SCR catalyst. Ammonia slip is limited to single-digit ppm. A certain amount of the reducing agent. using the most popular Class 8 HD diesel truck engine in the United States. SINOx System Description The exhaust gas generated by the diesel engine is fed into the SINOx catalyst.Selective Catalytic Reduction 145 and 80% in transient tests. which is integrated into the exhaust gas pipe system (Fig. the emission limits achieved in Europe and later in the United States already met the year 2005 European and the 2002/2004 U. The control system data bus provides the data link between the HDD engine’s control unit and the SINOx control unit. This was confirmed in U. Hydrocarbons are simultaneously reduced by over 80%.

.146 Selective Catalytic Reduction (a) (b) FIG. 40 Utility boiler application.

states and has a customer base of more than 4. an international energy company based in Columbus. Redwitz. This project uses urea rather than anhydrous or aqueous ammonia as the reducing agent to overcome local safety concerns about the transport. Active monitoring or supervision of the system by the operator is not required. AEP’s Gavin Plant has two 1300-MW generating units and is the largest utility station in Ohio This AEP Urea SCR project is designed to reduce NOx by approximately 70% to 0.15 lbs. Summary on a Urea SCR Application in a Coal-Burning Utility Operation. head of Siemens’ SCR Business world- . GA (USA) for supporting this project. Germany and Alpharetta.Selective Catalytic Reduction 147 catalyst. Ohio Rated 2 X 1300 MW American Electric power (AEP). In the presence of the highly reactive. AEP and other power generators in the Midwest and Southeast are required by court order to reduce their NOx emission by May 2003. 40. Juergen Zuerbig. handling.S. because the fuel-efficient heavy-duty diesel engines practically produce no CO and very little VOC/HC and PM. (See Fig. depending on the required NOx yield and/or the measured NOx concentration downstream of the catalyst via a feedback control. The SINOx system is controlled automatically by a programmable microprocessor-based process logic control system. extruded SINOx (SCR) diesel catalysts. homogeneous. the nitrogen oxides (NOx) react with the ammonia (NH3) to yield nitrogen (N2) and water vapor (H2O). and storage of ammonia. The reducing agent injection rate can be increased or decreased. The author is especially thankful to Dr.000 MW electricity in 11 U. relative to the load. Oxidation catalysts are even undesirable if sulfur-containing fuel is used. The SCR Process Aqueous urea is converted into ammonia through hydrolysis downstream of the injection nozzle. The operating temperature range is approximately 300–1020F. which are further reduced by 80–90% and 20–30%. An oxidation catalyst is not required if an SCR diesel catalyst is used.8 million. respectively./pBTU of the coal-burning plant’s utility boilers at a cost of US$ 175 million. The SINOx control system uses a correlation function/map PEMS of the NOx mass flow. OH is capable of producing 38. American Electric Power Gavin Plant at Cheshire.) Acknowledgments The author would like to thank Siemens powergeneration’s KPW Group. which was generated during engine bench tests.

SCR Business and their staff for the support received and for the permission to incorporate Siemens material. the author would like to thank the many professionals in the air pollution control community in the United States and Europe. Bibliography H.’’ SAE Report 1999-01-0111 (1999). Germany. ‘‘Exhaust Gas Aftertreatment Systems Onboard Seagoing Vessels. G. ‘‘An Experience Report on Reducing Emissions of Criteria Pollutants of Stationary and Mobile Sources. CA and Hans J. N. professor and head of the Chemical Engineering Department. D. Mueller. C. ‘‘An Urea Lean NOx Catalyst System for Light Duty Diesel Vehicles. Lepperhoff. G. H. Joisten. on IC engines at Cal. Germany who provided valuable information about some CER-NOx zeolite SCR catalyst applications. the author would also like to thank Dr. Texas A&M University and his staff for their valuable guidance and editing effort. ‘‘Test Cycle Development EURO3 for HD Diesel Engines. Fraenkle. at conferences. Raimund Mueller. Huetwohl.’’ SAE 95-2493 (October 1995). and W. H. in particular in mobile SINOx diesel catalyst applications in recent years. used in prior papers and public presentations for this project. ARB. M. with whom he has been associated over the years.W.’’ ICAC Forum ’98. and R.* Head of the U. Finally. ‘‘SCR-De-NOx Katalysatoren. Joisten. Havenith. The author is especially thankful to Nick Detor. Ray Anthony. Li. Cerritos. and M. R. Without sharing their inside information about the European advancements in the SCR technology. and while serving with the author on committees in California. Essen. Roemich. . G. Chmela. Huethwohl. such as the Scientific Review Committee on Best Available Control Technology (BACT) at SCAQMD. S. Koeser. and F. Q..’’ Diesel Fuel News (April 1999). Mueller.148 Selective Catalytic Reduction wide and Dr. J. was most helpful.’’ CSAT. 1992. Engineering and Project Manager of EES Inc. Mathes. Wagner. R. ‘‘UREA–SCR Test Achieves Big Cuts in NOx with Fuel Savings over Competing Technologies. R. Backes. and at joined projects at the University of California. Lueders. J. Raimund Mueller became Manager of Mobile SINOx (SCR) applications worldwide in early 2000. Roemich. R. and A. R. this project would not have been possible. and F. Horreck. 1996. Also.A. ‘‘On-Road Demonstration of NOx Emission Control for Diesel Trucks with SINOx Urea SCR System. Senior Manager of Steuler’s equipment Division.G Hurley. Eidloth. Silini. G. 1999.S. The information shared privately.H. Hammerle. Brussels.’’ Vulkan Verlag.’’ Marine Conference and Exhibition. Cutting NOx Emissions. Fritz. Ketcher. Zuerbig. Hoehr–Grenzhausen. ‘‘Untersuchung der NOx-Reduzierung im Abgas von Dieselmotoren durch SCR-Katalysatoren’’ [NOx Emission Reduction of * Dr. Furthermore. Pischinger. the author would like to thank EESI/Steuler for the support received and the permission to use material from public and internal documentation. (1998).

Zuerbig.O. D. M. South West Research Institute. (NOx) Adsorber Test. 1984.R. F. Fleischer. ‘‘Long Term Stable NOx Sensor with Integrated In-Connector Control Electronics. BACT Guidelines. and J. Diesel Net. ‘‘Massnahmen fuer einen wirtschaftlichen und sauberen Betrieb der SchiffsDiesel-Motoren’’ [Methods to Operate Ship Diesel Engines Efficiently with Low Emission]. R. Southwest Research Institute. 1995. ‘‘NOx Reduction with the CER-NOx (SCR) Process. Grove and W.’’ Marcel Dekker. a Comparative Analysis of European and U. Duponteil. 1997.’’ Power (1981). 1978. Inc. J. 1990–1999. Doelling.S.S. various reports 1998–1999. ‘‘Reducing NOx Emission. South Coast Air Quality Management District (SCAQMD) (1998).K. Miller. ‘‘NOx Control Technology Data Base for Gas-fueled Prime Movers. Sturm.’’ GSF-Forschungszentrum.H. VDI Rep.’’ ICAC. ‘‘Use of Ammonia in NOx Pollution Control. Mueller. 6 & 7. Kirchner.5% Fuel Penalty..T. October 1988. Gleis. 1999. Verbeek.’’ MECA 1998.S. MANFRED GROVE . Department of Energy. 1999. Witzel.com. Kokune. (1998). ‘‘80% NOx Reduction with 8. 15 (198). Kolar and H. ‘‘NOx Reduction Technology Challenges Marine Diesel Builders. Heavy-Duty Trucks. N. Vols. (SCR) Catalysts]. B Lemire and T. ‘‘The Development of UREA-SCR Technology for U. N. M..’’ EPA Stationary Source Symposium. various reports (1998/1999). W. Wasser and R.’’ Power Generation in the 21st Century. J. VOC/Airtoxics and PM Emission. W. F.’’ SAE Paper 1999-01-0202 (1999). Intermacom A. Simbeck. Energy Frontiers & U.Selective Catalytic Reduction 149 Diesel Engine Exhaust Gas. Kato. Khair. ‘‘The Future of Distributed Power Generation. ‘‘Transient Performance of a UREA DeNOx Catalyst for Low Emission Heavy-Duty Diesel Engines.H. ‘‘Using SCR for NOx Control. 1999.’’ California Air Pollution Control Officers Association (CAPCOA) Engineer Symposium. Bruce. Technical University RWTH–Aachen. Mueller. http:/ /www.’’ Ohio State University. Hull. New York.’’ Diesel & Gas Turbine Worldwide. M. various in-house studies.P.’’ Diesel & Gas Turbine Worldwide (April 1995). L.’’ Power Gen Europe. Germany (1996).’’ Diesel Fuel News (October 1999). ‘‘Exhaust Emission Reduction in Existing Ships. Mueller and M. R. ‘‘Demonstration of Advanced Emission Control Technologies Enabling DieselPowered Heavy-Duty-Engines to Achieve Very Low Emission Levels. ‘‘Diesel Engine NOx Control with SCR. November 1988. Klein. ‘‘NOx Abatement System for Glass Melting Furnaces. Grove and W. Davis and G. Walde. Thring and R.’’ ASME Proceedings. 1987. Grove: ‘‘Advanced SCR System Technology for the Simultaneous Reduction of NOx. ‘‘NOx-Minderung in Rauchgasen. Havenith and R. Diesel Fuel News.dieselnet. Power (1986). J. C.‘‘Encyclopedia of Chemical Processing and Design. Peckham.’’ VDI. Joisten and R.G.B. (1987). Report. J. R.’’ SAE Paper 970185. M. ‘‘Experience with the Reduction of NOx Emissions from Diesel Cogeneration Plants and Industrial Incineration Facilities. Sturm. ‘‘Die Bedeutung von Ammoniak and Ammonium fuer Mensch und Umwelt.’’ SAE Paper 2000–01–0190 M. Perry. (1997). J.

nanocrystalline materials. along with the conventional modes of composition and treatment conditions. promising results suggest broad application of nanophase materials in all aspects of future chemical processes. fatigue. Beyond these generic material selection considerations. elastic modulus. size-dependent variables across the nanophase size regime.7]. Nanophase concepts and technologies can be applied in many different configurations. Materials science has experienced substantial progress in the synthesis and characterization of nanophase materials [1]. and mechanical strength [5]. and even ‘‘nanoparticles of vacuum. the effects of process thermal conditions and temperature cycling on material properties are relevant to the durability of the material in a working plant. nanotubules. and creep across a broad range of temperatures and/or pressures. The demand for new materials with an ever-expanding range of properties has led to the exploration of nanophase materials. Nanophase materials are in a unique portion of the ordered length scale of materials between molecular and bulk domains. Thus. The chemical property of corrosion resistance is also a significant factor to consider in process material selection. Engineering materials must satisfy a variety of criteria in order to operate successfully in a process environment. Additionally. These structural configurations combine with the fundamental aspects of nanophase materials to provide tools for the tailoring of desirable mechanical and chemical properties. The practical effect of material properties being adjustable across the nanophase size regime is that material domain size becomes another mode of modifying process material properties. Nanophase materials have properties which vary from those of the bulk including reactivity [2]. The mechanical properties of a material must be satisfactory with regard to tensile strength. and resistance to fracture. As the domain size of a given material increases across the nanometer size regime of between 1.150 Nanophase Materials in Chemical Process Nanophase Materials in Chemical Process Introduction The selection of construction materials for chemical process equipment is a critical factor in the efficient operation of a chemical process plant. nanocomposites. in fact. . many bulk properties of a material considered to be inherent constants are. melting temperature [4]. process-specific material properties are regularly required. This article highlights nanophase material developments relevant to chemical process construction and operation.and 100-nm molecular properties become increasing collective and bulklike in nature. magnetism [3]. Although the high surface area of nanophase materials has long been exploited in catalysis.’’ in which desired materials properties are obtained by introducing nanometer-scaled voids or pores in materials [6. wear. including active nanoclusters.

The former approach relies on atomic orbital hybridization to build a band structure. These characteristics of nanophase systems will be manifest and helpful in understanding the material properties discussed in this article. As N approaches infinity. . Molecular Origin The central effect of an incomplete electronic band structure in a system is that the smaller the dimensions. From a philosophical standpoint. k. . . nanocrystals can be examined as either a summation of a large. in the absence of any interatomic interactions. the resonance energy is given by β φ i | H|φ j (2) The result of a unit of the chain interacting with adjacent units is to lift the degeneracy of orbitals.Nanophase Materials in Chemical Process 151 Nanophase Properties: Origin and Overview Nanophase properties are largely a function of an incomplete electronic band structure and surface sites comprising a non-negligible percentage of the total atoms. and E(k) become continuous variables from 0 to π/a and e 2β to e 2β. . number of interacting atoms or as a small piece of material excised from a bulk crystal. given by e φ i |H |φ i (1) where H is the electronic Hamiltonian. 2. N (3) 2β cos(k j a) where k j j π/(N 1) a. An infinite chain of N ‘‘atoms. ¨ The energy levels of these one-electron orbitals are derived using the Huckel approximation of neglecting orbital overlap: E( j. Because the evolution from atomic orbitals to the band structure associated with the bulk follows directly from atomic hybridization. a linear combination of atomic orbital–molecular orbitals (LCAO–MO) method is invoked to explain nanophase behavior. containing one electron and separated by a distance. the wave vector. When the individual units interact. 1. φ i. j 1. each with an orbital energy. N) e e 2β cos jπ (N 1) . . respectively. a. but finite. has N degenerate orbitals. Changes in electronic structure as a function of size are most easily illustrated by the use of a one-dimensional system [8]. the higher the energy of the lowest excited state. e. as shown in Fig.’’ each possessing one π orbital.

2. as shown in Fig. . such as Pt [9]. as shown in Fig. each with a single electron and an interatomic separation a. the electronic band structure incrementally grows toward the FIG. 1 The result of adjacent orbital interactions serves to lift the degeneracy of the orbitals resulting in the energy levels of N degenerate orbitals splitting into a band. For a finite chain. As the preceding model suggests. This model system shows how adjacent eigenvalue spacings increase as the system shrinks. I N 5 eigenvalues. (—): an infinite energy chain. 2 The band structure for a one-dimensional chain of N atoms. where a′ is the repetition pair spacing. The addition of a twounit repetition pair and Jahn–Teller distortion serves to open a gap between the highest occupied and lowest unoccupied molecular orbitals (HOMO–LUMO) in the middle of the dispersion curve at k π/a′. the eigenvalues are discrete and energetically separated by increasing amounts as the chain shortens. The extreme eigenvalues asymptotically approach e 2β as the chain length increases. It is now apparent that π/a is the limit of the Brillouin zone and each ‘‘atom’’ in the chain is comparable to a unit cell in the semiconductor. Energy in units of overlap energy. 3. as in the case of a metal. The dependence of the electronic properties on particle size shows dramatic changes between the dimensions of atoms and the bulk material [9]. N 9 eigenvalues.152 Nanophase Materials in Chemical Process FIG.

Nanophase Materials in Chemical Process 153 FIG. The effect of a surface can be incorporated into thermodynamic models to account for the modified behavior associated with fine particulate metals and molecular clusters. one might infer that bulk thermodynamic characteristics arise from an additive stabilization of atomic properties. The surface free energy produces a size dependence in the chemical potential. . (5) where γ i is the surface energy of face i and h i is the distance from that face to the particle center of mass. For example. The same equation describes crystalline solids with shapes satisfying the Curie–Wulff equation: γi hi construction. Surface to Volume Ratio The surface of a nanocrystal contains a non-negligible fraction of the total atoms. Likewise. µ. of the particle. ρ is the density. For a constant density liquid droplet. nearly 60% of which occupy surface sites. bulk as the system size increases. the chemical potential is given by µ µ∞ 2γ ρR (4) where γ is the surface tension. and R is the droplet radius. 3 The effect on a uniform chain of the introduction of a two-atom repeat unit and a Jahn–Teller distortion to produce a HOMO–LUMO gap at k π/a′. a 1-nm-radius nanocrystal of arbitrary composition contains about 200 atoms.

50 to 2. but most profound in the size range from 1 to 6 nm. Thermodynamics is also mute as to the kinetic issue of the rate at which the transformation occurs. For example. The depression in melting and annealing temperature is evident throughout the nanocrystal size regime. The reduction in melting temperature as a function of nanocrystal size can be enormous. Softening of Nanocrystalline Metals The properties of bulk materials fail to hold true when dealing with nanophase materials. and in the high concentration limit.5-nm nanoparticles. Nanocrystals of the indirect semiconductor Si also exhibit size-dependent melting [18]. extrinsic defects represent a similar disruption of the long-range order. Melting studies on a range of nanocrystals have established that the melting temperature is size dependent in the nanometer-size regime and is approximately proportional to the inverse particle radius. and Sn [15]. Al [14]. Cu nanoparticles show a significant change in interatomic spacing. dislocations. The loss of long-range order is a characteristic of melting. there is no specification as to the mechanism of melting. Even though semiconductors have directional and somewhat covalent bonds and the crystal facets of binary semiconductors do not all exhibit bulk stoichiometry. thermodynamic theories of melting assume a homogenous process occurring simultaneously throughout the system. nanophase materials often are understood as a manifestation of surface properties which are masked in studies of bulk materials. The size-dependent melting temperature of metallic nanocrystals has included studies of Au [12]. Although thermodynamics rigorously defines T m as the temperature at which the Gibbs free energy of the solid and liquid phases is equivalent. it stands to reason that they play a significant role in melting.56 between Cu 2. Metallic and semiconductor nanocrystals have been shown to possess reduced melting temperatures when compared with the bulk. With the large percentage of constituent atoms or molecules of a nanophase material present on surface sites or within a few atomic layers of the surface. process of a crystalline solid at a distinct temperature. owing to surface tension effects and strained surface geometries associated with nanophase systems. but not simple. nanocrystalline solids often are sought for their increased . with the spacing increasing from 2. By way of example. 4.154 Nanophase Materials in Chemical Process Chemical bond energy and coordination differences also exist between surface and bulk lattice sites within a material [10. The complexity in this seemingly mundane process lies in the atomistic nature of the transformation. As such.10a]. 0. regardless of the material identity. T m undergoing a phase transformation to a liquid. as compared to 1065°C for bulk gold [12]. Properties Melting Melting is a fundamental. as shown in Fig. which often are both thermodynamically and kinetically more reactive to transformation. Because all real solids contain extrinsic (thermodynamically metastable) defects such as surfaces. respectively [11].22 to 2. the size-dependent melting temperature has been shown in the direct band-gap semiconductors CdS [16] and GaAs [17]. and grain boundaries. 2-nm Au nanocrystals melt at about 300°C. For example. and the bulk. Pb and In [13].

Ceramic reinforcement SiC–Si 3N 4 composite powders have been synthesized through a sintering process. plotted as a fraction of nanocrystal melting temperature T m to the bulk melting temperature T b.Nanophase Materials in Chemical Process 155 FIG. resulting in nanophase SiC particles distributed intergranularly and intragranularly throughout the Si 3N 4 matrix [21]. Yet contrary to the Hall–Petch effect. Mechanical alloying is a viable method for homogeneously distributing nanophase particles of TiC in an amorphous Ti–Al matrix [20]. hardness and/or ductility [19]. 4 The melting temperature of materials as a function of particle size. where both hardness and yield stress typically increase as the grain size decreases. . Nanophase Materials Intermetallic Compounds Nanophase materials technology can be used to reinforce an intermetallic compound with a ceramic to obtain desirable characteristics of each type of material. hardness and yield decrease as the grain size decreases [19]. computer simulations of nanocrystalline copper show that as the grain size decreases down to values less than approximately 7 nm. thereby creating one such in situ ceramic-reinforced intermetallic compound. For example. This resulted in a dramatic improvement in high-temperature strength and creep resistance [21]. TiAl) with TiC improves the toughness and retention of strength across a broad range of temperatures while continuing to provide a lightweight material with good oxidation resistance [20]. the reinforcement of titanium and aluminum intermetallic compounds (Ti 3Al. The Hall–Petch effect is observed in polycrystalline metals with random grain orientations.

7 ppmv vapor concentration. The resistance of a chemiresistor changes when the device is placed in the presence of specific chemicals. and water. (From Ref. By selecting the absolute and relative sizes of the gold nanocluster and the ligand thickness. tetrachloroethylene (TCE). FIG. one can selectively detect the presence of various chemicals through changes in electrical resistance. chemiresistors can be developed to target-specific chemical species while ‘‘ignoring’’ others. as both adsorbed and absorbed vapors affect the transfer of electrons across the matrix [22].) . 22. based on 15°C vapor pressures. 1-propanol. Thus. 5 Vapor response isotherms of the Au: C 8 (1 : 1) MIME sensor to toluene. A thin transducer film having gold nanoclusters terminated with alkanethiol ligands is deposited onto an interdigital microelectrode [22]. The inset displays the toluene response down to a 2.156 Nanophase Materials in Chemical Process Chemiresistors High-performance chemiresistors have been developed through the use of a colloidal nanophase structure known as a metal–insulator–metal ensemble (MIME) [22].

show that single-layer antireflective coatings cannot possess the desired refractive indices [23]. such as humidity [22]. 7A) [23]. The mathematics of this destructive interference. 6 A simple two-dimensional sketch of the gold cluster film morphology illustrating the gold core. Polymer Films Although the coating of lenses is an old practice. and region of lower ligand density. alkanethiol ligand shell. (From Ref. 22. Such a chemiresistor serves as the basis for a new class of miniature chemical sensing devices that remain unaffected by typical environmental conditions. Nanocluster technology is being applied to embed metal particles in polymer . and then using a selective solvent to remove one of the source polymers [23].) One such construct has been shown to be extremely sensitive to toluene and tetrachloroethylene (TCE) vapors. Antireflective (AR) coatings function through destructive interference of reflected light (see Fig. high-performance broad-band antireflection coatings have not been commonplace due to materials limitations [23].Nanophase Materials in Chemical Process 157 FIG. but insensitive to water vapor [22]. nanoporous films. with pore sizes much less than the incident light wavelength can be tailored to specific refractive indices. combined with a review of the available dielectrics. The refractive index is dependent on the pore volume ratio of the film [23]. Nanoporous films have been prepared by demixing a binary polymer blend during spin-coating. However.

or infrared absorption capabilities [24]. Although the film in (A) appears opaque. the PS phase was removed by washing the sample in cyclohexane. (From Ref. a lateral phase morphology is obtained. 23. and after evaporation of the solvent. (B) Preparation of a binary polymer film. (C) The film is exposed to a solvent that is selective for one of the polymers. Iron. 23. magnetism. In such constructs.158 Nanophase Materials in Chemical Process FIG. 8 Atomic force microscope (AFM) images of two porous PMMA films 110 nm thick. Applications for such materials include magnetic ‘‘watermarks’’ and heat-absorbent window coatings [24]. both polymers (black and gray) and the solvent form one phase. For a given wavelength and incidence angle. iron oxide. phase separation sets in. light transmission is maximized when the two reflected beams interfere destructively. (B) If low M w PS and PMMA are used. the nanoporous film in (B) is transparent. silver. After spin-casting of a PS–PMMA–THF mixture onto silicon oxide surfaces. (From Ref. the lateral structure size is reduced to 100 nm.) films in order to provide new properties of strength.) . (A) Films prepared from higher M w PS and PMMA show average structure sizes of 1 µm. and copper have been placed successfully into permanent polymer lattice sites [24]. 7 (A) Reflection of light from both interfaces of an AR layer. a small quantity of embedded metal allows the film to remain transparent while still affecting its performance characteristics [24]. with a low effective refractive index. During spin-coating. FIG. producing a porous film. Initially.

as compared to previous instrumentation [27]. These findings illustrate the need for pressure-specific studies of the catalytic be- . vibrational spectroscopy. and gold-coated cobalt–platinum appear to be promising high-performance materials showing dramatic effects in the blocking temperatures (T b ) and coercivities (H c ) (see Table 1) [25]. more compact storage media continues to grow. Nanometer-scaled ferromagnetic particle arrays have reversible rotation and magnetic switching behaviors associated with magnetic core diameters and shape anisotropy that affords a variety of new device design options [26]. SFG studies at high pressures reveal that CO molecules occupy binding states on Pt(111) that are not present at low pressures.0357 0. cobalt–platinum. Such a model is useful in predicting blocking temperatures [26]. magnetization reversal is dependent on thermal activation within a volume that increases with particle diameter [26]. As researchers look to alloys to improve upon the magnetic properties of traditional materials. Catalysts Properties The ability to conduct molecular studies of surface behaviors of nanometer-sized particles and/or nanoporous materials has led to an understanding of surface effects in catalysis [27]. and atomic force microscopy (AFM) have provided information about surface reactions and catalysis at relatively high pressures. Improved scanning tunneling microscopy (STM). High-density media storage requires the nanoparticles to approach monodispersity and a defect-free state.115 0.0166 159 Magnetics As the information revolution continues. The magnetic properties of nanophase cobalt. or near atmospheric pressures approaching actual catalysis conditions has led to a greater understanding of the pressure dependence of metal nanocluster catalysis [27]. The ability to produce nanometer-scaled ordered arrays and then to conduct detailed studies of their surface behaviors at. turnover rates are negligible compared with the overall reaction rate [27]. nanophase metallic alloys are viewed as attractive candidates because of its ability to control properties as a function of domain size [25].Nanophase Materials in Chemical Process TABLE 1 Sample Co Co: Pt Co: Pt3 Au at Co: Pt Summary of the Magnetic Data Obtained on Four Different Samples Tb (K) 70 140 130 30 Hc (G) 1800 2700 2000 1000 µ(eff) (emu/g) 0. the need for reliable. sum frequency generation (SFG). At temperatures above 30 K.0598 0. whereas adsorbates that are readily detectable in low-pressure surface studies often are stationary spectators or totally absent during high-pressure catalytic reactions. Further.

continuous nucleation (steps 1–3). which have been tested successfully in monometallic nanoclusters such as iridium(0) [29]. continuous nucleation. in turn. 9. Nucleation and growth are separated in time because k 1 k 2 [B]. consisting of (a) slow. rate constant k 2 for the pseudoelementary step A B → 2B. because the reaction pressures greatly influence the outcomes in a way that cannot be extrapolated from low-pressure studies [27]. is a key to the observed formation of a nearmonodisperse ( 15%) particle size distribution. can have similarly profound effects on catalysis behaviors [27].5H 2 Ir(0) n → Ir(0) n 1 k2 (4) (COD)Ir(P 2W 15Nb 3O 62 )8 P 2W 15Nb 3O 629 S H Net Reaction: 300 [(COD)IR(P 2W 15Nb 3O 62 )8 ] 750H2 → Ir(0) 300 300 P 2W 15Nb 3O 629 150 H 300S SCHEME 1 Minimum mechanism for the formation of Ir(0) nanoclusters. trimetallic. (From Ref. 9. is shown in Scheme 1 and Fig. the level of surface defects. In additional. and consequently control. or other irregularities.160 Nanophase Materials in Chemical Process havior of metal nanoclusters. and multimetallic transition metal nanocluster systems [29]. nanocluster size [29]. followed by (b) fast autocatalytic surface growth (step 4).5H 2 → Ir(0) H S 2 acetone nIr(0) → Ir(0) n (b) Autocatalytic Surface Growth A B → 2B 2.) . followed by autocatalytic surface growth. in which nanocluster growth is considered analogous to polymer growth [28] and autocatalytic surface growth once M(0) nanoclusters have been nucleated [29]. It is the ratio of the rate of growth to the rate of nucleation [R k 2 (nanocluster active sites)/k] [29] that can be used to predict. which. Such models are predicted to be applicable to bimetallic. The research into these methodologies also has led to an endorsement of the ‘‘magic (a) Nucleation A → B k1 (1) (2) (3) 2 acetone (COD)Ir(acetone) 2 P 2W 15Nb 3O 629 (COD)Ir(P 2W 15Nb 3O 62 )8 (COD)Ir(acetone) 2 2. rate constant k 1 for the pseudoelementary step. An example of this process of slow. A → B. Of interest are the developments in size-control and size-prediction methodologies. investigations continue into the ‘‘living metal polymer’’ model. At the same time.

These experiments were designed in order to study the behavior of a bimetallic colloid with a more electronegative core than the ligand (Au–Pt) and compare it to that of one with a more electropositive core than ligand (Pd–Pt) [30]. However. or surfactants [32]. the more electropositive core seemed to yield superior results. 9 Idealized. which states that because closed-shell structures are stable. 29. Au–Pt had been shown to provide marked improvement over Pt alone in the semihydrogenation of 2-hexyne into cis2-hexene [31]. For this particular commercial synthesis. they will be more common in the size distribution of completed nanocluster formations [29]. experimental verification is required before such findings can be extended to other catalytic systems [30]. in light of the Au–Pt semihydrogenation mentioned. For the sake of clarity. The Ir(0) atoms are known (by electron diffraction) to be cubic close packed as shown. Previously. Further exploration of the catalysis properties of transition metal colloids indicates that their behavior is extremely reaction-specific and dependent on many factors. Using a combination of STM and transmis- . only 17 polyoxoanions are shown. in their monomeric form. (From Ref. For example. whereas Pd–Pt showed marked improvement [30]. the Au–Pt showed no improvement over Pt alone. in the synthesis of silicone polymers.) number’’ theory of nanoclusters. and the 300 Bu 4N and 228 Na cations have been deliberately omitted. in the synthesis of bis(trimethylsiloxyl)octamethylsilane (BTMOS). roughly-to-scale representation of a P 2W 15Nb 3O 629 polyoxoanion and Bu 4N stabilized Ir(0) 300 nanocluster. polymers.Nanophase Materials in Chemical Process 161 FIG. Nanocluster agglomeration is prevented through surface stabilization using ligands. However. [Ir(0) 300(P4W30Nb6O12316 ) 33](Bu4N) 300Na 228. the catalytic performance of bimetallic colloids of Au(core)/Pt(ligand) and Pd(core)/Pt(ligand) was compared to the performance of Pt nanoclusters formed during the induction period of typical industrial reactions [30].

162 Nanophase Materials in Chemical Process FIG. Such a well-defined nanophase catalyst offers the prospect of engineering the ratio of edge atomic surface sites on a particle surface to alter reaction product efficiencies and mixtures. it has been shown that shell thickness is independent of core size and is directly dependent on the size of the surfactant ion. Further. The development of industrial catalysts. Although nanophase metal catalysts supported on substrata have been industry standards for high-throughput reactions. One such example is a hydrogenation of benzene. in which the accepted ionpair catalyst. Lithographic .many of which are composed of metal particles on oxide substrata. Thicknesses observed in this manner are consistent with standard MM2 force-field calculation theoretical values.) sion electron microscopy (TEM) to observe and examine the size relationships between surfactant stabilizers and metal cores. Synthesis Any discussion of nanophase materials in chemical processes must address the topic of catalysis. To this end. 10 A schematic diagram showing how STM and TEM can be used in concert to determine surfactant stabilizer thickness. 32. has been discredited.and [(C 8H 17 ) 3NCH 3] -stabilized Rh(0) nanoclusters [33]. in recent years particle size control has strived to produce stoichiometrically defined particles. catalysis by even trace amounts of possibly highly active nanocluster catalysts cannot be ruled out [33]. This indicates that in the cases of other putative homogenous catalysts where a facile heterogeneous M(0) catalyst is well established. (From Ref. new methodologies and a better understanding of nanoclusters in general are calling into question previously identified catalysts in previously explored reactions [33]. [(C 8H 17 ) 3NCH 3] [RhCl 4] . 10 [32]. transition metal nanocluster systems have been synthesized which behave as isolable and compositionally well-defined soluble heterogeneous catalysts [33]. is a topic of great commercial interest [34]. as shown in Fig. Fabrication and engineered control in order to deposit tailored metal clusters on oxide surface with an ordered structure remain a goal of catalyst research [34]. with the catalyst shown more likely to be Cl . The high surface area to volume ratios associated with nanophase materials makes them exceptional catalysts as compared to bulk materials.

this method of electrode fabrication failed to produce anticipated current density increases expected from the very small crystal size [38]. Methodologies also have been developed to measure the yield of an ion-sputtering process [34]. Methods of nanostructure lithographic fabrication also can be applied to other surface science studies. once the nanocrystalline material was pressed into a usable cathode. these model systems and fabrication techniques were used to demonstrate that the presence of oxygen is the key factor influencing the thermal stability of the silver nanoclusters [34]. Researchers have partitioned transition metal ions. these developments are used to determine surface mechanical properties.) Nanophase catalysts also function in decomposition reactions of harmful greenhouse gases. In fact. with ZnFe 2O 4 showing the most promise [37]. such as the elastic modulus. The platinum nanoclusters’ catalytic performance on polymer-based supports has been compared to performance on oxide supports [35]. In the synthesis of sodium chlorate. with increasing annealing temperature in oxygen.such as CO 2[37]. with the net effect of reducing catalytic performance [36]. especially at room temperatures [35]. This model of catalytic structure and behavior has been tested against ethylene hydrogenation on a platinum nanocluster [34]. the Dimensionally Stable Anode (DSA) has realized extensive energy savings on one side of the oxidation reaction. but high activation overpotentials on the cathodic side still contribute to large energy losses [38]. cluster surface passivation is often the result. Ni. 11. the activation overpotential was reduced dramatically when compared to a standard iron electrode [38]. The experimental production of a solid Ti 2RuFe nanocrystalline cathode has shown promising results. CO 2 is broken down into carbon and oxygen with virtually no CO by-product [37]. Template methods. with diameters ranging from 20 . In addition to the synthesis and use of ligand-stabilized metal clusters. into the interior of polyamidoamine (PAMAM) and have achieved an encouraging combination of particle size control. particle stability. Although stabilizers control particle size and prevent agglomeration. In addition to purely chemical catalysis. nanocluster materials also function as electrocatalysts. Yet. silver cluster surface oxidation occurs at 200°C [34]. combined with chemical vapor deposition (CVD). (See Fig. and electrocatalytic behavior and performance [36]. No migration of silver clusters was observed at 700°C in the absence of oxygen [34]. One proposed solution to this dilemma is the use of dendrimers to act simultaneously as monodisperse synthesis templates and stabilizers [36]. The decomposition of CO 2 also produces quantities of methane. Experiments with different ferrites (XFe 2O 4 ) have shown that with appropriate selection of X and particle size. also can be used in the preparation of carbon nanotubules. When combined with AFM. such as Pt. and Co ferrites and of varying particle sizes yielded dramatic results. on nanometer-scaled samples [34]. In a study of the thermal stability of supported silver catalysts. Polymeric supports show a marked increase in the stability of the catalysts. Comparisons of Zn. significant benefits are realized by polymer stabilization of nanocluster catalysts [35].Nanophase Materials in Chemical Process 163 nanostructure fabrication technologies of the semiconductor industry can be applied to create such engineered clusters and to provide viable model systems for industrial-supported catalysts [34]. However.

) to 200 nm [39]. synthesis of Pt nanoparticles within the hydroxyl-terminated dendrimer template. a . These common properties include a refined structure and concentrations of tetrapropylammonium species incorporated during the synthesis [40]. followed by immersion in a metal ion solution. the nanophase material exhibits a high concentration of defect sites. Between 12 and 60 Pt2 ions can be loaded into a single dendrimer and. The dendrimer-encapsulated Pt nanoparticles are electrocatalytically active. 11 Schematic illustration of fourth-generation (G4) PAMAM dendrimers having EOH and NH 2 terminal groups. (From Ref. 36. nanophase silicates have nondegenerate spectroscopic features such as the characteristic framework infrared (IR) vibration (550 cm 1 ) of the micrometer-sized crystal splitting into a doublet (at 555 cm 1 and 570 cm 1 ) in the nanophase material [40]. In addition. upon reduction with BH 4 . Alumina is removed by HF immersion [39]. Yet. A basic method used to synthesize metal-nanocluster-filled carbon nanotubes includes carbon deposition by CVD onto an alumina template membrane.164 Nanophase Materials in Chemical Process FIG. an entrapped cluster containing the same number of atoms results. Such tubules can be filled with metal catalyst nanoclusters of the types previously discussed to display interesting and potentially useful electrocatalytic properties [39]. Glass Silicates A physicochemical analysis of nanophase crystalline silicalite-1 shows that it has many properties in common with micrometer-sized crystalline silicalite-1 [40]. and attachment of the composite to an electrode surface. The mechanical and electrochemical properties displayed by metal-filled nanotubules hold promise for the fuel cell industry [39]. Air-drying and reduction by hydrogen gas completes the formation of the metal nanoclusters within the nanotubules.

An understanding of this powerlaw dependence can lead to very specific tailoring of physical and mechanical properties for various uses. and Young’s (E) moduli for bulk and nanophase a-SiO 2. (From Ref. where ρ-bar is the ratio of the sample density to the density of bulk silica glass [41].) strain in the crystallites along the a crystallographic direction. 12. with both structures consisting of corner-sharing Si(O 1/2 ) 4 tetrahedra [41]. as a function of the density relative to the bulk density. shear (G). 41. the elastic moduli of both the bulk and the nanophase a-SiO 2 clearly are density dependent [41]. along with high thermal stability. Transparent nanophase glass–ceramics achieve near-zero coefficients of thermal expansion. 12 Log-log plot of the bulk (K).Nanophase Materials in Chemical Process 165 FIG. The pore morphologies and mechanical behaviors of nanophase amorphous SiO 2. The requirements to achieve transparency have previously been recited [42]. In terms of mechanical properties. Glass–ceramics with these properties typically utilize lithium-stuffed β-quartz crystals to satisfy scientific and commercial applications. of course. However. providing an impressive uniformity of microstructure and the controlled mechanical properties not available in glass–ceramics of larger crystalline microstructures [42]. show that the bulk amorphous densities of the various nanophase a-SiO 2 glasses are characterized by different pore sizes and distributions. Nanophase microstructures composed of crystals 100 nm in size are achieved through efficient nucleation and slow crystal growth. is similar across various densities [41].5 0. which is controlled synthetically in the nanophase silica glass [41]. as well as a twostage dinitrogen physisorption in the low-pressure region [40]. Glass Ceramics Nanophase glass–ceramic technology also is a rapidly growing field with a wide variety of commercial applications. dependent on the density. yet the morphology of the pores. as shown in Fig. high thermal shock resistance. investigated by molecular-dynamics (MD) simulations.2. This consistent short-range order (SRO) of nanophase silica glass of various densities differs little from the SRO of bulk glass. transparency [42]. and. The solid lines are the best least-squares fits for each of the moduli. defined in terms of the fractal dimension of pores and the roughness exponents of pore–silica interfaces. analysis of the first sharp diffraction peak (FSDP) shows a significant difference in the intermediate-range order (IRO). . The moduli (M) scale as M (ρ-bar)3.

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Kluwer Academic. N. (ed. However. Figure 1 provides accident statistics for 1989 from the Accidental Release Information Program (ARIP) of the U. and natural disasters. 1997. Environmental Protection Agency [1]. it is clear that the number of accidents is large and many people. Wiley–VCH. E. Marcel Dekker. including human error. 1998. S. Komoreni. design flaws. USA. ARIP statistics cover catastrophic and unplanned releases of chemicals into the atmosphere. Fisher (eds. The danger posed to the employees of a chemical plant as well as the public is illustrated by the accidents that have occurred in onshore as well as offshore chemical process industries. and G. Weinheim. However. P. Dordrecht. The study found that from 1988 through 1992. The total number of process plant accidents cannot be estimated accurately because of underreporting. Handbook of Nanophase Materials. both workers and the public. C. J. C. MA. and lack of or disregard of operating and maintenance procedures. Nanophase and Nanocomposite Materials: Symposium held Dec. in 1991. A..S. AVERY N. The boardroom perspective on the cause of these accidents and what to do about them varies. and A.). Fendler. J. (ed. Computations for the Nano-scale.). 1993. the National Response Center received over 16.168 Nanophase Materials in Chemical Process Bibliography Bloechl.. H. Joachim. Thomas (eds. GOLDSTEIN DAVID M. For example.. wrong equipment specifications. Goldstein. FISHBACH Process Safety and Risk Management Regulations: Impact on Process Industry Introduction Chemical accidents have been caused by a number of reasons. 1993. 1–3. J.. Pittsburgh. I. lack of process and engineering knowledge. are affected adversely by these accidents. Characterization and Applications. New York. 1993. equipment failure. Boston. these statistics underline the fact that a large number of accidents and catastrophic releases occur because of design flaws.300 calls reporting the release or potential release of hazardous chemicals [3]. Material Research Society.). Another study [4] analyzed the EPA’s Emergency Response Notification System database of chemical accident notifications. Nanoparticles and Nanostructured Films: Preparation.). Inc. Parker. an average of 19 accidents .

. The causes behind the 1984 Bhopal accident. 2. which involved the release of methyl isocyanate and caused thousands of fatalities. Another shift not knowing the relief valve was missing. a number of highly publicized chemical plant incidents in the 1970s and 1980s focused attention on management systems and technologies. a pump relief valve was removed for overhaul and the open end blanked. (Reprinted with permission from Ref. The temporary piping was not properly designed and supported merely on scaffolding. According to the official report [8] following the 1988 Piper Alpha disaster in a North Sea offshore rig. Many process plant accidents in the 1970s and 1980s also exposed the need for management systems to ensure process and equipment integrity. the need for inherently safer design considerations is quite unanimous. 1 U. Change in population demographics. have been investigated quite extensively with varying conclusions. Bhopal and many other process plant incidents including the 1984 Mexico City disaster [7] also emphasize the need for application of structured management systems for hazard recognition and identification. In addition to the industry and government agencies. The promulgation of the Toxic Release Inventory Reporting requirements [5] as part of the Clean Air Act Amendments of 1990 led to the submittal of toxic release information which clearly delineated the number and extent of toxic chemical releases and their potential impact on the public and the environment.Process Safety/Risk Management Regulations 169 FIG. the university has a critical role in changing this situation. Environmental Protection Agency Statistics Accidental Release Information Program— 1989. Among other things. more than 34. the 1974 Flixborough accident occurred because a temporary pipe was used to replace a reactor which had been removed for repair [6]. this primary reason does not obviate the fact that a number of other factors contributed to the extensive damage.500 accidents involving toxic chemicals occurred over the 5-year period). the Phillips 1989 explosion [9] in the high-density polyethylene plant demonstrates the need to adhere to operating procedures and implementing appropriate management systems for contract workers. For example. In addition to statistics and the sheer number of facilities involved. increasing awareness of process plant . A management of change system could very well have prevented the incident. However.e. started up the pump. However.S.) occurred each day (i.

goods were manufactured by hand. EPA promulgated its risk management program regulation in 1996. This technological development. such as the Sedesol guidelines in Mexico for performing process risk audits and the post-Bhopal accident prevention law in India. The Impact of the Industrial Revolution The eighteenth century was the beginning of technological development. known as the industrial revolution. For example. The industrial revolution changed manufacturing by changing the way people worked. The World Bank has developed guidelines for identifying and controlling hazards. and environmental agencies to create regulations requiring companies to establish and practice specific programs to improve safety. in the later half of the eighteenth century has its roots in devices that were invented earlier in the era. was one of the main revolutions of this era. Without the industrial revolution. in single homes or cottages. The major advances in technology. In keeping with the congressional mandate given in Section 304 of the CAAA. Many other nations also have similar laws.170 Process Safety/Risk Management Regulations hazards. and the International Labor Organization has developed a code of practice for preventing major accidents. In the United States. In 1990. The CAAA directed the Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency (EPA) to develop regulations to reduce the frequency and severity of chemical plant accidents. the continuing threat of a chemical catastrophe continue to provide the impetus for governments to develop legislation for eliminating or minimizing the potential of such accidents. which affected society and commerce in ways that are felt even today. The industrial revolution has had far more impact on the world than the political revolutions of the era. it brought work out of the home and centralized it in the beginning to small and simple plant operations and increasingly to large and complex operations. Similarly. . the U. television. OSHA promulgated the Process Safety Management (PSM) regulation on February 24. because the Industrial Revolution effects on society are longer lasting. we would not have the technologies that we have today and neither would we have the standard of living that we enjoy. safety. This changed with the introduction of machines and mass production. For one thing. all made possible by this revolution. where the owner worked side by side with his employees. and computers. Congress enacted the Clean Air Act Amendments (CAAA) into law. today we have automobiles. and. as mandated by Section 301(r) of the CAAA.S. to protect the public and the environment. The PSM regulation is intended to protect workplace employees. Before the introduction of machines and the factory setting. International efforts include the Seveso Directive covering members of the European Community. 1992. above all. Several states have empowered their health. particularly in the use of steam. federal agencies are not the only government regulators active in the chemical accident prevention arena. The industrial revolution grew more powerful each year as new inventions and manufacturing processes added to the efficiency of machines and increased productivity.

the chemical hazards we strive to manage safely today did not exist because none of these chemicals were used.’’ The OSHAct allows OSHA to set and enforce standards that require employers to maintain safe and healthful workplaces. the Metal and Non-Metallic Mine Safety Act. Subsequent to the River and Harbor Act. so did the need for using increasingly complex processes and new and exotic chemicals at different operating conditions. In 1970. there has been a groundswell of opinions from various stakeholders for structured programs to improve safety. OSHA’s mission is to ‘‘Assure so far as possible every working man and woman in the nation safe and healthful working conditions. The Walsh–Healy Act led to early research into the identification and control of occupational diseases. The subject of risk-benefit analysis has been discussed to some extent but is not quite formalized. to the navigable capacity of any waters of the United States except on plans authorized by the Secretary of the Army. which impose environmental or safety regulations on businesses. Notwithstanding the benefits of the industrial revolution. The act was promulgated expressly to protect the nation’s waterways from excessive dumping. the Atomic Energy Act. the federal government enacted the Walsh–Healy Act to establish federal safety and health standards for activities relating to federal contracts. During the period between 1936 and 1970. these regulations were never sufficiently supported to carry out a satisfactory program. there has also been considerable dialogue about the risks posed by these industrial facilities. Congress has passed numerous laws. OSHA and the National Institute for Occupational Safety and Health (NIOSH) were established within the Department of Labor and the Department of Health and Human Services. NIOSH. Although some progress was made. In 1936. when the United States government issued the River & Harbor Act. Demographic changes and the unplanned growth of bedroom communities around industrial belts have also created a higher risk. This produced relatively inconsistent and ineffective results. but it is charged with the responsibility of training professionals and with the research and recommendation of new regulations to the Secretary of Labor. the Federal Water Pollution Control Act. . The ideas behind this act are the basis of many of today’s occupational health and safety regulations. Government Regulations The history of safety regulations in the United States can be traced back to 1899. This act prohibited the creation of any obstruction not authorized by Congress. a number of other regulations were promulgated. Before the industrial revolution.Process Safety/Risk Management Regulations 171 Each advancement in the industrial revolution has brought with it a certain amount of risk and hazardous activity. on the other hand. As global competition increased. Congress promulgated the Occupational Safety and Health Act (OSHAct). does not have any regulatory or enforcement authority. For example. and the Federal Coal Mine Health and Safety Act. respectively. As a result of this landmark legislation. Based somewhat on post-accident emotions and partly on a realization that industry can and should operate safely.

users. the release of 40 metric tons of methyl isocyanate from a pesticide manufacturing plant in Bhopal. EPCRA’s reporting requirements and emergency planning and notification provisions established a coordinated effort among EPA. The SERCs. are state organizations responsible for coordinating the local emergency response plans and administering state programs. SERCs and LEPCs. As a result. Congress in 1986 promulgated the Emergency Planning and Community Right-to-Know Act (EPCRA). the Environmental Protection Agency (EPA) was established in 1970 to protect the nation’s public health and environment. the EPA promulgated the Clean Air Act. The EPA is responsible ‘‘to find ways to clean up and prevent pollution. limit the use. The Toxic Substances Control Act (TSCA). Asbestos. the U. In 1977. followed by amendments to the act in 1977 and 1990. owners/operators of regulated facilities. require labeling. ensure compliance and enforcement of environmental laws. As a direct consequence of this incident. chlorofluorocarbons. or place other restrictions on chemicals that pose unreasonable risk. Subsequently. analyze the hazards. and storage facilities to keep records about quantity. In 1983. the Surface Transportation Assistance Act established protection from reprisal by employers for truckers and certain other employees in the trucking industry involved in activity related to interstate commercial motor vehicle safety and health. The TSCA is a federally enforced law and is not delegated to the states. state governors. assist states in environmental protection efforts.000 industrial chemicals produced or imported to the United States. and release of hazardous materials and make these records available for public record. gave the EPA the ability to track and study the 75.000 [10]. on the other hand.172 Process Safety/Risk Management Regulations Environmental issues affecting the public health and the environment also received widespread attention. and develop local emergency response plans. and polychlorinated biphenyls are some of the chemicals regulated by the EPA under TSCA. use. typically consisting of the following: . and scientific research and education to advance the nation’s understanding of environmental issues. India caused the deaths of over 2000 people and injuries to another 100. Under this act. In December 1984.’’ In 1970. public interest associations. and health agencies.S. and local fire departments. The LEPCs are voluntary organizations at the local level and are responsible for developing local emergency response plans in coordination and collaboration with local industry. The EPCRA provided pathways for better understanding of chemical hazards and called for community emergency response procedures at the local and state levels. the International Safe Container Act established uniform structural requirements for international cargo containers designed to be transported interchangeably by sea and land carriers. The LEPC’s makeup is specified by law. The LEPCs are responsible for disseminating this information to the public and serving as a focus for community awareness and action. The EPCRA requires manufacturers. The SERCs are appointed by the governors and consist of state emergency. LEPCs receive chemical inventory information. and others with emergency management experience. the EPCRA led to the formation of Local Emergency Planning Committees (LEPCs) and State Emergency Response Commissions (SERCs). the EPA has the authority to ban the manufacture or distribution in commerce. environmental. passed in 1976.

As a result. discharge less.Process Safety/Risk Management Regulations 173 • • • • • Representatives of elected state and local officials Law enforcement officials. as stringent as the federal regulation. and safety and health training. These are management commitment and employee involvement. and substitute less hazardous chemicals. health.S. be. hospital. OSHA fulfilled its mandate in 1992 by promulgating the process safety management regulation. EPA analyzed chemical incidents in the early to mid-1980s and compared them to the Bhopal incident. Twenty-three states and two U. respectively. OSHA published recommended Safety and Health Program Guidelines. The state implementation program must. in content and enforcement. and firefighters First aid. State and Local Government Roles During the late 1800s and early to mid-1900s. The state may request delegation from the federal government and submit a state implementation program. hazard prevention and control. promulgated the Risk Management Program regulation in 1996. By statute. The EPA. such as hospitals. LEPCs in many counties are marginally active or do not exist at all. In 1990. environmental. individual states have the option of seeking the delegation of most federal safety regulations. civil defense workers. In 1989. One major drawback of this initiative is the unfunded and voluntary nature of the LEPCs. worksite analysis. These voluntary guidelines identify four general elements that are critical to the development of a successful safety and health management program. These ‘‘State plan States’’ are integral partners in OSHA’s mission of assuring the safety and health of the nation’s workers. This information has stimulated communication between industries and communities and encouraged industries to store smaller inventories of hazardous substances. and small businesses The EPCRA extended right-to-know beyond the workplace and into the community. Thus. territories operate their own OSHA-approved occupational safety and health programs. They are not required to operate programs identical to those of the federal . The analysis concluded that 17 incidents released sufficient volumes of chemicals that could have been more severe than Bhopal if the weather conditions and plant location were different. the majority of worker-safety laws were enacted by the state and local governments and thus varied widely in their extent and enforcement. the Clean Air Act Amendments of 1990 contained specific mandates requiring OSHA and EPA to establish regulations to protect workplace employees and the public and the environment. at the minimum. The Clean Air Act Amendments of 1990 also established the Chemical Safety and Hazard Investigation Board. on the other hand. and transportation workers Representatives of community groups and the news media Owners and operators of industrial plants and other users of chemicals. farms.

The ultimate accreditation of a state’s plan is called ‘‘final approval. the rulemaking process followed by OSHA is discussed here. After at least 1 year following certification.’’ the first step in the state plan process. These elements include appropriate legislation.S. but they have the flexibility to operate programs that reflect their own statespecific issues and concerns. To gain OSHA approval for a ‘‘developmental plan. with some minor variations. and operate occupational safety and health training and education programs. federal agencies are developed in a similar manner. a state must assure OSHA that within 3 years. Certification renders no judgment as to actual state performance. States must set job safety and health standards that are ‘‘at least as effective as’’ comparable federal standards. it relinquishes its authority to cover occupational safety and health matters covered by the state. Such consultation may be provided either under the plan or through a special agreement under Section 21(d) of the act. worker protection ‘‘at least as effective’’ as the protection provided by the federal program. provided their programs are ‘‘at least as effective’’ as the federal OSHA program.’’ When OSHA grants final approval to a state under Section 18(e) of the act. At any time after initial plan approval. when it appears that the state is capable of independently enforcing standards. including the Secretary of Health and Human Services (HHS). Most states adopt standards identical to federal ones. A state must conduct inspections to enforce its standards. the state becomes eligible for final approval if OSHA determines that it is providing. cover public (state and local government) employees. Rulemaking Process Regulations by all U. The Occupational Safety and Health Administration can begin standards-setting procedures on its own initiative or in response to petitions from other parties. As an example. NIOSH. enforcement. most states provide free on-site consultation to help employers identify and correct workplace hazards. OSHA may enter into an ‘‘operational status agreement’’ with the state. state and . Once a state has completed and documented all its developmental steps.174 Process Safety/Risk Management Regulations OSHA. regulations and procedures for standards setting. but merely attests to the structural completeness of the plan. The state also must meet 100% of the established compliance staffing levels (benchmarks) and participate in OSHA’s computerized inspection data system before OSHA can grant final approval. in actual operation. it is eligible for certification. appeal of citations and penalties. This commits OSHA to suspend the exercise of discretionary federal enforcement in all or certain activities covered by the state plan. In addition. States have the option to promulgate standards covering hazards not addressed by federal standards. it will have in place all the structural elements necessary for an effective occupational safety and health program. and a sufficient number of qualified enforcement personnel.

All advisory committees. which advises the Secretary of Labor on formulation of construction safety and health standards and other regulations Recommendations for standards also may come from NIOSH. established by the act as an agency of the Department of HHS. and will publish. in advance. Interested parties who submit written arguments and pertinent evidence may request a public hearing on the proposal when none has been announced in the notice. employers and employees should be aware that. There are two standing committees. When such a hearing is requested. After the close of the comment period and public hearing. must have members representing management. OSHA will schedule one. just as they may petition . The Notice of Proposed Rulemaking will include the terms of the new rule and provide a specific time (at least 30 days from the date of publication. and state agencies. labor. they may be paid for by NIOSH rather than the employer. when necessary.Process Safety/Risk Management Regulations 175 local governments. amend. provides technical assistance to OSHA. any nationally recognized standards-producing organization. the time and place for it in the Federal Register. and recommends standards for OSHA’s adoption. NIOSH also may require employers to provide medical examinations and tests to determine the incidence of occupational illness among employees. The two standing advisory committees are as follows: • • National Advisory Committee on Occupational Safety and Health (NACOSH). While conducting its research. any of several advisory committees may be called upon to develop specific recommendations. along with an explanation of the standard and the reasons for implementing it. or any other interested person. employer or labor representatives.’’ An ‘‘Advance Notice’’ is used. Therefore. standing or ad hoc. and require that employers measure and report employee exposure to potentially hazardous materials. The National Institute for Occupational Safety and Health conducts research on various safety and health problems. it publishes these intentions in the Federal Register as a ‘‘Notice of Proposed Rulemaking’’ or often as an earlier ‘‘Advance Notice of Proposed Rulemaking. Once OSHA has developed plans to propose. gather testimony from employers and employees. or revoke a standard. consults with. If OSHA determines that a specific standard is needed. The Occupational Safety and Health Administration continually reviews its standards to keep pace with developing and changing industrial technology. OSHA must publish in the Federal Register the full. final text of any standard amended or adopted and the date it becomes effective. OSHA may also publish a determination that no standard or amendment needs to be issued. and makes recommendations to the Secretary of HHS and to the Secretary of Labor on matters regarding administration of the act Advisory Committee on Construction Safety and Health. which advises. NIOSH may make workplace investigations. as well as one or more designees of the Secretary of HHS. When such examinations and tests are required by NIOSH for research purposes. and ad hoc committees may be appointed to examine special areas of concern to OSHA. if one is held. usually 60 days or more) for the public to respond. to solicit information that can be used in drafting a proposal.

In 1984. injury. ATSDR is charged with assessing the presence and nature of health hazards at specific sites. Creating new ways to prevent workplace hazards is the job of NIOSH. to help prevent or reduce further exposure and the illnesses that result from such exposures. when requested by the EPA. ATSDR was also authorized to assist the EPA in determining which substances should be regulated and the levels at which substances may pose a threat to human health.176 Process Safety/Risk Management Regulations OSHA for the development of standards. In 1980. The Institute’s responsibilities include the following: • • • • • Investigating potentially hazardous working conditions as requested by employers or employees Evaluating hazards in the workplace. or individuals. and to expand the knowledge base about health effects from exposure to hazardous substances. Technology and Research Base The National Institute for Occupational Safety and Health was established by the Occupational Safety and Health Act of 1970.S. they also may petition OSHA for modification or revocation of standards. Congress created the Agency for Toxic Substances and Disease Registry (ATSDR) to implement the health-related sections of laws that protect the public from hazardous wastes and environmental spills of hazardous substances. With the passage of the Superfund Amendments and Reauthorization Act of . they are two distinct agencies with separate responsibilities. The National Institute for Occupational Safety and Health identifies the causes of work-related diseases and injuries and the potential hazards of new work technologies and practices. which provides for the management of legitimate hazardous waste storage or destruction facilities. NIOSH determines new and effective ways to protect workers from chemicals. machinery. and hazardous working conditions. amendments to the Resource Conservation and Recovery Act of 1976 (RCRA). OSHA is in the Department of Labor and is responsible for creating and enforcing workplace safety and health regulations. the U. With this information. states. and disability Conducting research and providing scientifically valid recommendations for protecting workers Providing education and training to individuals preparing for or actively working in the field of occupational safety and health Although NIOSH and OSHA were created by the same act of Congress. NIOSH is part of the Centers for Disease Control and Prevention (CDC) and is the only federal institute responsible for conducting research and making recommendations for the prevention of workrelated illnesses and injuries. NIOSH is in the Department of Health and Human Services and is a research agency. authorized ATSDR to conduct public health assessments at these sites. ranging from chemicals to machinery Creating and disseminating methods for preventing disease.

oil or gas well drilling or servicing operations. in quantities of 10. or explosive chemicals. or more (subject to few exceptions).119) were published in the Federal Register on February 24.Process Safety/Risk Management Regulations 177 1986 (SARA). the regulation does not apply to retail facilities. which may be excluded if used solely as a fuel. Hydrocarbon fuels. The performancebased approach does not prescribe specific methods and approaches. The Process Safety Management Program The 14 elements of the OSHA Process Safety Management (PSM) regulation (29 CFR 1910. establishment and maintenance of toxicological databases. thus giving facilities the flexibility for customizing the methods to best meet their needs and organizational structures. The management system required by OSHA’s process safety management regulation envisions a holistic program with checks and balances aimed at creating multiple barriers of protection. ATSDR received additional responsibilities in environmental public health. and medical education. or normally unoccupied remote facilities. and management practices. and processes which involve the manufacture of explosives and pyrotechnics. The process safety management regulation applies to processes which involve certain specified chemicals at or above threshold quantities. 1992 [11]. This act broadened ATSDR’s responsibilities in the areas of public health assessments. . The objective of the regulation is to prevent or minimize the consequences of catastrophic releases of toxic. 2. In addition. procedures. flammable. processes which involve flammable liquids or gases on-site in one location. This principle is shown in Fig. information dissemination. 2 Holistic implementation of the process safety management program. reactive. The regulation requires a comprehensive management program: a holistic approach that integrates technologies.000 lbs. are included if the fuel is part of a process covered by this regulation. The process hazard analysis (PHA) is the heart of the FIG.

Employee participation is important not only for the whole program but also provides critical information during the PHA. Process Safety Information This element of the PSM regulation requires employers to develop and maintain important information about the different processes involved. each process change should be evaluated by the management of change program. 5. and providing to employees and their representatives access to process hazard analyses and to all other information required to be developed under this regulation. if necessary.178 Process Safety/Risk Management Regulations program and impacts or interfaces with all of the other elements. The process safety information covers three different areas (i. and other impacted elements. accurate. A complete listing of the process safety information that must be compiled in these three areas is shown in Table 1. consulting with employees and their representatives on the conduct and development of other elements of process safety management required under the regulation. Results of the PHA should be used in modifying and or developing operating procedures. 2. an appropriate hazard analysis should be done. and up-to-date process knowledge is essential for safe and profitable operations. chemicals. Each element of the process safety program is discussed in more detail here and the interface with other elements of the process safety management is discussed. The information contained in the first column of Table 1 should be available from the Material Safety Data Sheets (MSDS) for the hazard- .. This information is intended to provide a foundation for identifying and understanding potential hazards involved in the process. and. Employee Participation This element of the regulation requires developing a written plan of action regarding employee participation. Pre-start-up safety review is an essential procedure for new or modified processes.. The process safety information and incident history are important inputs to the PHA and must be compiled before the PHA. 3. and equipment). reduce the frequency and severity of chemical plant accidents).e. The information in Table 1 is essential for developing and implementing an effective process safety management program.e. technology. 2 are as follows: 1. However. Some of the other concepts that are apparent from Fig. emergency response program. Irrespective of the PHA done earlier. The fundamental concept is that complete. mechanical integrity program. This information is intended to provide a foundation for identifying and understanding potential hazards involved in the process. 4. it must also be pointed out that all elements of the program must be implemented in their entirety to get the maximum benefit and accomplish the ultimate objective (i.

Process Safety/Risk Management Regulations TABLE 1 Process Safety Information Chemicals Toxicity Permissible exposure limit Physical data Reactivity data Thermal and chemical stability data Effects of mixing Technology Block flow diagram or process flow diagram Process chemistry Maximum intended inventory Safe limits for process parameters Consequence of deviations Equipment 179 Design codes employed Materials of construction Piping and instrumentation Diagrams Electrical classification Ventilation system design Material and energy balances Safety systems Relief system design and design basis ous chemicals. Processes must be operated and maintained within both the process parameter and equipment limits. process parameter safe limits are defined based on equipment design ratings. The safe limits for process parameters refer to the upper and lower bounds for the process parameters outside of which the process would be hazardous. in the case of a distillation process. the process parameters for which upper and lower bounds are to be specified are temperature. composition. In this example. process parameter safe limits are defined based on the process chemistry information or any restricted physical conditions for the reaction as well as the criteria used for nonreactive processes. In contrast. The maximum intended inventory refers to the maximum amount of any regulated chemical that may be expected to be present in the whole facility at any time. the upper and lower limits of the process parameters outside which the operation of the process could cause significant damage to the tower or other attached equipment would have to be stated. The information contained in the second column of Table 1 pertains to the technology of the process itself. . Safe upper and lower limits for process parameters and equipment are also necessary for calibrating instrumentation. which are used as primary or intermediate feedstocks or are produced as products at the plant. pressure. Safe upper and lower limits for process parameters can be defined as follows: • • For nonreactive processes. relief device set points. and upstream and downstream conditions of the process and/or equipment. The consequence of deviation from these stated bounds must also be compiled. The block flow diagram can be replaced by a process flow diagram. For reactive processes. The process chemistry information must contain the basic chemical reactions involved and a brief description of the chemistry involved. For example. equipment limits are specified by the manufacturer based on materials of construction and design basis. It is important to understand the distinction between process parameter limits and equipment limits. and flow rate.

Process Hazards Analysis This element of the PSM regulation requires facilities to perform a PHA. Many plants have therefore implemented or are in the process of implementing electronic data management systems to manage. the American Society of Testing and Materials (ASTM). human factors. The completion and accuracy of process safety information is crucial to the implementation of other PSM elements. and use these data. Information must also be compiled on any ventilation system. The PHA must address the hazards of the process. Accepted industry practices can be used to decide which standards apply. A simple plot plan showing the different areas of electrical classification would be considered to be in compliance with the regulation. compilation of the process safety information database represents a major challenge. including PHAs and mechanical integrity. installation. the consequences of the failure of engineering and administrative controls. equipment constructed in accordance with codes. Information should also be available on the location of these safety systems and the procedures to use these systems. This listing should include any and all equipment that is available for protection of the workers from any hazard or emergency. and all other connections shown. and an evaluation of effects of failure of controls on employees. previous hazardous incidents. It is therefore not only important to compile all equipment information but also to ensure that it complies with consensus standards. OSHA is recognizing that there are consensus standards for design and fabrication. or practices no longer in use should be evaluated to ensure that they are compatible with existing standards. maintenance procedures. Therefore. In cases where standards do not exist. The PSM regulation requires that process equipment should comply with generally accepted engineering practices.180 Process Safety/Risk Management Regulations The final type of information that must be compiled pertains to the equipment used in the process. For example. The different electrical classifications must also be compiled for different parts of the facility. and the National Fire Protection Association (NFPA). a multilayered vessel built years ago should be evaluated to ensure that it complies with today’s engineering standards. The intent is to assure that all equipment used in the process meets appropriate standards and codes such as those published by the American Society of Mechanical Engineers (ASME). valves. engineering and administrative controls. the American National Standards Institute (ANSI). the American Institute of Chemical Engineers (AIChE). A listing of all safety systems must also be compiled that are available to the workers. access. standards. and inspection and testing. generally acceptable engineering practices can be used. As is apparent from the foregoing discussion. The P& IDs must represent the facility exactly as it exists with flanges. The materials of construction for each equipment item and the design codes employed can be compiled as separate lists or may be listed in the Piping and Instrumentation Diagram (P&ID). This information would indicate the areas in the facility that are ventilated and the nature of ventilation. This element requires that the PHA be performed by one or more of the following methods or any other equivalent method: . This is complicated even more because the process safety information must also be kept up-to-date and accurate and made accessible to employees. the American Petroleum Institute (API).

Process hazard analyses and the results of PHAs can and will impact the development. and practice of other elements of the PSM regulation. in an ideal process safety management system. The losses complicated and prolonged the process of responding to the release. the PSM regulation requires that the process hazard analysis shall be updated and revalidated.. training and maintenance programs. Louisiana led to a partial loss of pressure. where an explosion led to the loss of all utilities. thereby increasing the damage caused by the release. PHAs may not be performed unless complete Process Safety Information is available for the process. and water lines were colocated with the lines carrying flammable gases [12].Process Safety/Risk Management Regulations 181 • • • • • • What If Checklist What If/checklist Hazard and operability (HAZOP) studies Failure modes and effects analysis (FMEA) Fault-tree analysis The regulation suggests a performance-oriented requirement with respect to the PHA so that the facility has the flexibility to choose the type of analysis that will best address a particular process. Similar problems occurred at a facility in Norco. Many other elements of the PSM program should flow from. Thus. A thorough and properly done PHA should identify these types of potential hazards and allow facilities to determine how to mitigate the problems. The intent of a PHA revalidation is to ensure that the PHA team evaluates the previous PHA. based on their completion date. Second. the results of the PHA. Philosophically.. implementation. and pre-start-up safety reviews may need to be revised to reflect changes in either practices or equipment that derive from the PHA. the whole PHA should not only be examined to verify that the PHA is consistent with the current process. examines the extent of any changes that might have occurred since the PHA was implemented (or last reviewed). For example.g. A PHA would help facilities identify hazards and ways to address them. It may also help a facility focus its emergency response programs on the most likely and most serious release scenarios. a 1989 explosion and fire at a facility in Baton Rouge. steam. The PHA may help define critical equipment that require preventive maintenance. or at least be revised based on. the PSM regulation requires that the updating and revalidating be done by a team similar in qualifications to the team that conducted the original PHA. The PSM regulation also requires that the PHAs be updated and revalidated.e. power. but it also should be analyzed to examine if the original analysis is valid. and testing programs. the following process safety concepts should work as checks and balances to accomplish the PSM program objectives (i. and fire water because the power. inspection. and decides what work is needed to make the PHA current. minimize the frequency and consequences of catastrophic releases): . PHAs also identify situations where major accidents due to control failure (e. pressure gauges. overfill alarms) could be prevented by redundant or backup control or by frequent maintenance and inspection practices. First. Louisiana. Existing standard operating procedures.

explain the facility’s emergency action plan. In addition. on or near covered processes. opening of process equipment or piping (i. Revalidation of process hazards analysis: Update and revalidate the PHAs to assure that the process hazard analysis is consistent with the current process.. and safe work practices. Training The regulation requires that facilities certify that employees responsible for operating the facility have successfully completed (including means to verify understanding) the required training. safety and health considerations. periodically evaluate contractor safety performance. Contractors The PSM regulation identifies responsibilities of the employer regarding contractors involved in maintenance. HAZOPed). Management of change: Assess the safety and health impacts of process changes and ensure that process changes are analyzed (e. Many incidents have resulted from inadequate safe work practices or a failure to follow procedures when they exist. Procedures must be readily accessible to employees.e.182 Process Safety/Risk Management Regulations • • • Initial process hazards analysis: Identify process hazards and develop mitigation techniques (technology. The host employer is required to consider safety records in selecting contractors. develop safe work practices for contractors in process areas. These safe work practices include lockout/tagout. Even though the operations department is involved with all of these practices. The employer must certify annually that the operating procedures are current and accurate. maintenance also plays a very vital role in ensuring that these procedures are followed during all maintenance tasks. Initial training must occur before assignment. and maintain an injury/illness log for contractors working in process areas. it is important to remember that operations and maintenance training should be coordinated.g. inform contractors of potential process hazards. repair. equipment. major renovation or specialty work. hot tapping). the contract employer is required to train their employees in safe work .. and procedures). and safety systems. must include steps for each operating phase. The synergism and commonality of operating procedures to maintenance procedures is in safe work practices. The training must cover specific safety and health hazards. and must cover special circumstances such as lockout/tagout and confined space entry. Refresher training must be provided at least every 3 years. turnaround. confined space entry. must be reviewed as often as necessary to assure they are up-to-date. Operating Procedures The operating procedures must be in writing and provide clear instructions for safely operating processes. operating limits. Even though this element of the PSM regulation pertains to operations staff only. emergency operations. and control of entrance into the battery limits.

therefore. quick turnarounds. piping systems. hot work permits are not required in cases where the employer or an individual to whom the employer has assigned the authority to grant hot work permits is present while the hot work is performed. Because welding shops authorized by the employer are locations specifically designated and suited for hot work operations. receive less training and often perform more hazardous tasks in process plants as compared to direct-hire workers [13]. and inspection and testing for process equipment. Modified facilities for this purpose are defined as those for which the modification required a change in the process safety information. Both the host employer and contract employer have specific responsibilities that they must fulfill. Maintenance should ensure that all necessary procedures have been completed prior to start-up. The purpose of this element of the regulation is to assure that the employer is aware of the hot work being performed and that appropriate safety precautions have been taken prior to beginning the work. and interlocks. Mechanical Integrity This element of the PSM regulation mandates written procedures. The need for flexibility. including pressure vessels and storage tanks. In the contractor paragraph. Pre-Start-up Safety Review This element of the PSM regulation requires a pre-start-up safety review of all new and modified facilities to confirm integrity of equipment. maintenance personnel should be well versed in pre-start-up safety review procedures. Contractors. alarms. PSM calls for correction of equipment deficiencies and assurance that new equipment and maintenance materials and spare parts are suitable for the process and properly installed. and to verify that a process hazard analysis has been performed. OSHA has used a belt and suspender approach.Process Safety/Risk Management Regulations 183 practices and document that training. Usually. assure that employees follow safety rules of facility. relief and vent systems and devices. training for process maintenance employees. Additionally. sensors. pumps. and specialized services is the main reason why process plants are contracting out increasingly significant portion of their daily work. to assure that appropriate safety. maintenance. in general. and advise host employer of hazards contract work itself poses or hazards identified by contract employees. Hot Work Permit This element of the PSM regulation mandates a permit system for hot work operations conducted on or near a covered process. operating. . and controls such as monitoring devices. particularly maintenance work to contractors. emergency shutdown systems. assure that employees know about potential process hazards and the host employer’s emergency action plan. the regulation does not require a permit for hot work in these locations. changes occur during maintenance and. and emergency procedures are in place.

time period necessary for the change.120(a). Emergency Planning and Response This element requires employers to develop and implement an emergency action plan according to the requirements of 29 CFR 1910. Employers must address and document their response to report findings and recommendations and review findings with affected employees and contractor employees. impact of the change on safety and health. technology. Compliance Audits This element of the regulation requires employers to certify that they have evaluated compliance with process safety requirements every 3 years and specifies retention of the audit report findings and the employer’s response. and (q). if appropriate). (p). including at least one person knowledgeable in the process (a contractor employee. equipment. the PSM regulation also requires information to be available to employees from the process hazard analyses and other documents required by the regulation. The regulation calls for an investigation team. As is apparent from the foregoing discussion. to develop a written report of the incident. Trade Secrets Similar to the trade secret provisions of the hazard communication regulation.38(a) and 29 CFR 1910. The regulation permits employers to enter into confidentiality agreements to prevent disclosure of trade secrets. and procedures which addresses the technical basis for the change. Reports must be retained for 5 years.184 Process Safety/Risk Management Regulations Management of Change This element of the regulation specifies a written program to manage changes in chemicals. and authorization requirements for the change. Segments of the hazardous chemicals industry have for sometime practiced some or all of the required programs. the process safety management regulation requires a systems approach for managing safety. modification to operating procedures. The regulation requires employers to notify and train affected employees and update process safety information and operating procedures as necessary. The promulgation of the regulation formalized the requirements and . The employer must retain the two most recent audits. Incident Investigation This element of the regulation requires employers to investigate as soon as possible (but no later than 48 hrs) incidents which did result or could have resulted in catastrophic releases of covered chemicals.

because of the same reason. The regulation requires regulated facilities to develop and implement appropriate risk management programs to minimize the frequency and severity of chemical plant accidents. This federal regulation was mandated by Section 112(r) of the Clean Air Act Amendments of 1990. facilities may take credit for both passive and active mitigation systems. The eligibility criteria and requirements for the three different program levels are given in Table 2. For alternative scenarios (note: the EPA used the term alternative scenario as compared to the term more-likely scenario used earlier in the proposed regulation). the EPA required a performance-based approach toward compliance with the risk management program regulation. subsequently. For gases.Process Safety/Risk Management Regulations 185 established minimum criteria. This is both good and bad. the scenario assumes an instantaneous spill and that the release rate to the air is the volatilization rate from a pool 1 cm deep unless passive mitigation systems contain the substance in a smaller area. and the local emergency planning committees and is communicated to the public. The EPA regulation also requires regulated facilities to develop a Risk Management Plan (RMP). Facilities submit the RMP to the EPA and. Impact on Process Industry In general. there is a tendency to look for ‘‘paper compliance’’ as compared to making real improvements in safety programs and technologies. However. the impact of any regulation on any part of the regulated community can be related to several factors which include. EPA promulgated the regulation for Risk Management Programs for Chemical Accident Release Prevention (40 CFR 68). The regulation now requires everyone to establish the management systems and apply the technologies needed to comply with the regulation. the worst-case release scenario assumes the quantity is released in 10 min. The toxic endpoints are based on ERPG-2 (Emergency Response Planning Guidelines—Level 2) or level of concern data compiled by EPA. In keeping with regulatory trends. including administrative controls and passive mitigation that limit the total quantity involved or release rate. Appendix A of the final regulation lists endpoints for toxic substances to be used in worst-case and alternative scenario assessment. and the emergency response program. The RMP regulation defines the worst-case release as the release of the largest quantity of a regulated substance from a vessel or process-line failure. the state emergency response commission. The Risk Management Program In 1996. prevention program. For flammables. the scenario assumes an instantaneous release and a vapor cloud explosion using a 10% yield factor. The flammable endpoints represent vapor cloud explosion distances based on overpressure of 1 psi or radiant heat distances based on exposure to 5 kW/m2 for 40 s. For liquids. The RMP includes a description of the hazard assessment. it is made available to governmental agencies. but are not limited to the following: .

2865. 2873. or 2911 Program Requirement Hazard Assessment Hazard Assessment Worst-case analysis Worst-case analysis Alternative releases Alternative releases 5-Year accident history 5-Year accident history Management Program Document management system Prevention Program Safety information Hazard review Operating procedures Training Maintenance Incident investigation Compliance audit Management Program Document management system Prevention Program Process safety information Process hazard analysis Operating procedures Training Mechanical integrity Incident investigation Compliance audit Management of change Pre-start-up safety review Contractors Employee participation Hot work permits Emergency Response Program Develop plan and program Hazard Assessment Worst-case analysis 5-Year accident history Certify no additional steps needed Emergency Response Program Develop plan and program • • • The degree to which a particular entity or entities is already attempting to reach a particular level of achievement The additional cost associated with regulatory overhead not directly associated with the goals of the program (e. 2879. 2821. 2869. 2812.. 2819.119) No public receptors in worst-case circle Emergency response coordinated with local responder Process is SIC code 2611. EPA’s Risk Management Program Regulation Program 1 No off-site accident history Program 2 Program 3 Program Eligibility Criteria Process not eligible for pro.g.186 Process Safety/Risk Management Regulations TABLE 2 Eligibility Criteria and Compliance Requirements for Different Program Levels. the cost of record keeping) The degree to which already successful programs are compromised by the regulation .Process is subject to OSHA gram 1 or 3 PSM (29 CFR 1910.

A positive result of regulatory action has been that companies who have not voluntarily invested in these kinds of programs are forced to make the investment.’’ Following the Texas City disaster in 1949. Safety programs for worker protection were in place years before OSHA. The one size fits all regulatory mentality caused those programs to be changed at great cost and effort. Responsible chemical companies have been responding to transportation emergencies involving their products for at least 50 years. Compliance Programs At first glance. many companies and industry groups have initiated voluntary programs which go further than regulations require. it would seem that ‘‘compliance’’ must imply compliance with regulations. . In some cases. dating back to the 1960s and 1970s. these efforts have been in partnership with government and nongovernment groups and in other cases they have been independent of government participation. For example. There were no regulatory drivers. The good news is that those same responsible companies extend their policies to their facilities wherever they may be. a one-size-fits-all approach to regulation and compliance may force a company to abandon a program that has proven successful over time simply to meet a regulation. For example. when compliance with regulation becomes the issue. Many companies had employed some form of lockout/tagout procedure for years that worked. Furthermore. Dow Chemical Company has had an excellent reactive chemicals program. The changed requirements also caused confusion in the case of some workers. Also.Process Safety/Risk Management Regulations 187 • • • • • • The technical feasibility of compliance The impact on compliance with other regulations The emphasis on compliance rather than impact The ability to maintain a profitable operation The ability to absorb the associated overhead cost when offshore competition does not have those costs The degree to which enforcement and other emphasis by the regulating authority promotes real improvement as opposed to ‘‘paperwork’’ compliance It must also be noted that painting all industry or even one segment of industry with one brush is very inappropriate. However. which might actually have increased the risk. It is very difficult to explain to management and workers that a highly successful. Many companies and/or groups of companies are and have been for many years investing considerable time and resources into process safety and risk management prior to any regulatory requirement to do so. Unfortunately. there are many examples of responsible industry doing something because it was ‘‘the right thing to do. popular program has to be changed or eliminated because of a rigidly written regulation. members of the American Chemistry Council apply the Responsible Care Code internationally. the industries on the Houston Ship Channel voluntarily formed Channel Industries Mutual Aid (CIMA) in order to help each other and the public during emergencies. It can be argued that the cost was not justified by the result. administrative overhead may increase significantly.

For example. As mentioned earlier. the availability of enforcement has probably had a positive impact on process safety and risk management. Overall. In many cases. Elimination of chlorofluorocarbons has caused a concurrent elimination of Halon-type fire-extinguishing systems. when the ultimate goal becomes compliance rather than results. was the goal. there is an obvious conflict between two competing interests. . and product yield. with both government and industry. one regulation may result in violation of another or an actual increase in emissions. regulations have had a net positive impact in that they have forced many companies not already committed to environmental and safety excellence to operate better. several persons both in and out of government during work on the National Response Team’s integrated contingency plan effort commented that in many cases facility and vessel owners hired contractors to produce response plans under the Oil Pollution Act of 1990 that were judged by government contractors to meet all planning requirements but were not useful for response. there has never been a catastrophic explosion of an underground fuel tank. It is very difficult to clear those tanks well enough to eliminate emissions during the inspection process. Very often.’’ At the same time. this improvement has actually been transferred to the bottom line. That is why many fire codes prohibit aboveground tanks at retail facilities. There is currently a great deal of concern that efforts to mix enforcement and response at the incident command level in oil spills may discourage the cooperative spirit necessary for an effective response. In this case. not planning and response. compliance issues can sometimes outweigh the issues of functionality or statutory and regulatory intent. that require procedures that may cause significant problems. These tests have a high likelihood of discharging some foam to the water—a violation of the Clean Water Act. compliance. Enforcement Enforcement can be a two-edged sword. morale. Operational Issues Operationally.188 Process Safety/Risk Management Regulations Finally. the issue becomes ‘‘did you meet the requirements’’ not ‘‘have you increased or reduced the risk. it is possible to be in technical compliance and not in functional compliance. however. Another example is the requirement to test marine facility foam systems by actually flowing foam. The underground storage tank regulations have made it very expensive to maintain and install underground tanks. however. For example. In other words. In this case. the threat of enforcement is the only leverage regulators have. The threat of enforcement has probably had a chilling effect on cooperative efforts that could possibly make an even larger impact. Sometimes. Some air regulations require inspection of the seals on floating roof tanks. the threat of enforcement may actually serve to increase overall risk. productivity. There are occasional situations. Improved operating discipline actually will increase quality. it must also be said that in some cases.

They may also apply to changes in operating procedures and other ‘‘soft’’ changes. This had the effect of creating a large number of unnecessary and wasteful emergency release reports from people who understood the regulations and in one sense made criminals out of almost everyone who had a radiator leak. Integrated Systems Versus Compartmentalized Systems Management systems for compliance must be integrated and cannot be compartmentalized. industry has learned that is not the most efficient or effective approach. Individuals in the organization must understand their respective roles. All of these issues also apply to modifications to existing facilities. the management system for compliance should be integrated vertically within the organization and horizontally across regulatory regimes. but more importantly safety and environmental excellence. Worker safety. should be an issue from the start. wastewater and stormwater handling. Under the reportable quantity (RQ) regulations of the Superfund Amendments and Reauthorization Act. including repetitive motion injuries.Process Safety/Risk Management Regulations 189 Management Systems for Compliance Management systems for regulatory compliance have evolved over a period of time. and other potential areas of concern. . First. a well-conceived management of change (MOC) system must be integrated into the culture. In the early stages. Only this approach can insure compliance. There are multiple regulations that impact every facet of a new process. Therefore. ethylene glycol defaulted to a 1-lb RQ. Only an integrated system could respond to that quirk. The real thrust of integrated management systems must be to include all safety and environmental concerns in the entire process from conception to design to construction and commissioning to start-up and operation to shutdown and demolition. The following provides a discussion of some example components of the management systems necessary for the effective implementation of process safety and risk management programs. waste handling. One example can be found in the list of chemicals regulated under the Clean Air Act Amendments that included ethylene glycol. safety must be integrated into the plant’s everyday activities through each phase of the plant’s life cycle. Process Design It is critical that companies have a system in place that assures compliance from the time of conception to eventual start-up of any process. For all of these reasons and for OSHA compliance. although statutes and the accompanying regulations are often conceived and written as separate entities. Toxic Substance Control Act implications. generation and reduction. In order to gain the most advantage. there was a tendency to manage process safety as a separate function. The process design must look at air emissions and permitting. Soft issues such as public perception must be considered. With experience. they often have impacts on other areas that may or may not be intentional. Risk Management Plan implications.

in recent years. or at least discourage. require opening processes to the atmosphere in order to make the equipment safe to work. Initiatives such as Responsible Care illustrate this recognition. a relatively small emission or environmental upset resulting from maintenance was avoided at the cost of an eventual catastrophic event. improve those systems. and if a molecule left the plant as waste to the environment. OPA90. responsible companies have had response systems in place for many years. RMP. one chemical company executive stated on the ‘‘Today’’ show that his company was in the business of making salable product out of raw materials. Many maintenance activities. this activity. Coast Guard will add still further requirements. Prevention and Reduction Responsible industry has always had prevention and reduction programs. the regulations created minimums that have been very effective. in most cases. As early as the 1960s. Response Mechanism Again. PSM. Because of this. often seemingly innocuous changes can have significant regulatory implications. Planning requirements under a multitude of federal and state regulations have. all companies have begun to recognize that they must be good neighbors by perception as well as by reality. Although experienced responders already had most of the required training and/or experience. Further. Equipment Maintenance For all of the reasons listed earlier. regulations have largely served to ‘‘level the playing field’’ between responsible and irresponsible industry. That operator may decide that the greatest risk occurs when changing the cylinder out. That change would then make the operator subject to the provisions of Section 112r of the Clean Air Act. however resulted in considerable duplication. As stated earlier. it represented lost profit. especially in older plants. equipment maintenance must be part of the management system. The OSHA PSM regulation and the Hazardous Waste Operations regulation (OSHA 1910. There is no way of quantifying how often needed maintenance is delayed or canceled because of environmental concerns. RCRA. The good news is that the effort of the National Response Team to publish the .120) have elevated the training requirements for responders. Air regulations may prohibit.190 Process Safety/Risk Management Regulations Very subtle. and others all mandate response planning. An operator of a water-treatment facility may have several 1-ton chlorine cylinders on site but never have more than one connected to the process. The obvious solution would be to manifold several cylinders together. It is possible that regulatory issues may actually discourage a good maintenance program. Several things have occurred to alter and. Community Right to Know. The vessel response plan requirements proposed by the U.S. This duplicative regulatory system resulted in numerous plans designed solely to meet compliance requirements and often had little to do with response.

We must remember that an accident from such a small facility has the likelihood of severe consequences and can damage the whole industry ‘‘license to operate’’ just like an accident in a plant operated by a large multinational company. information. reaction on the part of industry and government. The most lasting improvement has been in the response partnerships formed between industry and government at all levels. and other things. groups with hidden agendas have aggravated this process. zero negative impact is a vision for which industry and government must strive. Risk Communication For many years. training. . The challenge is creating an interactive dialogue with the public to a point where risk perception is based not only on emotion but also on some level of scientific reality. On the other hand. Zero risk is a myth. this is in spite of the record of Seveso in which there are still no documented longterm effects of the exposure. and equipment either to prevent the accident in the first place or respond to the consequences if it does occur. several things must happen. Very often. Preliminary investigations highlight the lack of reactive chemicals knowledge among the plant personnel. The challenge therefore is to develop collaborative efforts with government agencies (both state and federal). if not totally incorrect. and voluntary programs such as Responsible Care. All too often. the small facility probably lacks awareness. a significant portion of the economy consists of small and midsized companies. This has been significantly improved by Community Right to Know. Fears about dioxins that have not been scientifically confirmed have resulted in actions like Times Beach. training. However. A recent accident in the United States resulted in multiple fatalities and total destruction of a small plant. much of industry did a fairly poor job of telling people about potential risks. 112r of the Clean Air Act. and industry for safety programs aimed at improving safety in the small and mid-sized companies. Much remains to be done in this area. professional and trade organizations. Industry and government tend to respond to public perception of risk without doing a good job of education about true risk. the large facility probably has resources. uninformed public outcry has forced questionable.Process Safety/Risk Management Regulations 191 Integrated Contingency Planning Guidance has relieved much of that problem. Small Business Issues In the United States. In the case of OPA90 in particular. Future Developments In an increasingly global economy in which the developed nations will compete even more strongly with the less developed nations. oil spill response is much better than it was during the Exxon Valdez spill. However.

multinational companies must insist that the best practices of worker. . or the environment. procedures and practices were put in place to limit or eliminate the damage. Industries and governments not doing so should face sanctions in the international marketplace. Thus. It is imperative that those companies trying to do what is right are not penalized by unfair competition.192 Process Safety/Risk Management Regulations First. Partnerships between key players in this arena should be encouraged and rewarded. The industrial revolution brought prosperity along with the use of hazardous processes. a willingness to accept and work toward a vision in which no facility has a negative impact on its workers. the public. industrial programs and practices will have to keep pace with the changing clime and consensus standards and targeted safety goals. The public should be represented in these programs. Governments should also promote those best practices. Government programs and industry initiatives spurred improvements in the science and technology needed for the recognition of hazards and associated risks. but are not limited to the following: • • • • • Tort regimes that discourage sharing of lessons learned and near-miss information Regulations and requirements that are duplicative or not based on science Public policy that results in ‘‘knee-jerk’’ statutory and regulatory response to single events Companies and industry groups that are willing to conduct meaningful dialogue with stakeholders Most importantly. Examples include Integrated Contingency Planning and the OSHA Voluntary Protection Program. Summary and Conclusions Safety regulations in the United States have mirrored the industrial revolution. As our understanding of the hazards associated with these processes developed. Future developments in the United States with regard to process safety and risk management programs may quite likely be based on risk–benefit analyses. There is also number of efforts underway to develop stakeholder dialogue and arrive at consensus opinions regarding national safety goals and targeted improvements in safety performance. The regulatory regime and requirements will also keep changing as more information becomes available. Product stewardship is one effective method for ensuring the implementation of the same standards at small and medium-sized businesses in the United States as well as in facilities overseas. public. All of the stakeholders involved in these issues must work to identify and eliminate barriers to improvement. Management systems have been developed to implement safety programs and industry practices. and environmental protection be followed throughout the world. It is quite clear that the need to operate safely is recognized as a competitive advantage and a positive contributor to the bottom line. These barriers and issues include.

and K. Explosives and Blasting Agents. 1990. DC. 1992. 29 CFR Part 1910. it is also quite clear that profitability is directly related to safety and loss prevention. Department of Labor. DC. Eng. Community Right-to-Know. Department of Labor. W. P. It is also quite apparent that government regulations alone cannot accomplish our ultimate safety goals.’’ Chem. 8. Washington. R. 3. Risk Management Programs for Chemical Accidental Release Prevention. Environmental Protection Agency. 6. 12. Washington. Toxic Chemical Release Reporting. 58(201). DC. 4.S. 7. Cullen. Department of Labor. United States Public Interest Research Group. M. Accidental Release Information Program. Bleve—The Tragedy of San Juanico. Lessons from Disaster. the use of risk assessments and risk– benefit analysis will play a significant role in the future safety programs. G. TX. ‘‘Process Safety Management of Highly Hazardous Chemicals. 54. Ballinger.S. Kletz. Lamar University System. Accidents Do Happen: Toxic Chemical Accident Patterns in the United States.S. Reg. Shrivastava.. 11. 198–209 (1999). John Gray Institute.219 (1993). MA. M. A. 1993. FDA. DC. Skandia International. one of the main objectives of the management systems is to ensure compliance. References 1. SAM MANNAN JIM MAKRIS H. London. the management systems for safety are intricately tied into the operational management. U. 1991. Skandia International. Her Majesty’s Stationery Office. DC.Process Safety/Risk Management Regulations 193 Government regulations continue to be a significant driver for safety programs. Cambridge. 40 CFR Part 68. Thus. U. Environmental Protection Agency. Safety must be tied into profitability and business objectives. The Public Inquiry into the Piper Alpha Disaster. 2. U. R... Gulf Publishing Company. Reg. 1987. U. Also. Washington. Washington. JAMES OVERMAN . Final Rule. Bhopal—Anatomy of a Crisis. 13. T. Code of Federal Register. 1985. Mannan.190–54. However. John Gray Institute. Stockholm. R. DC. Anthony. As such. 1989. 57(36). Managing Workplace Safety and Health: The Case of Contract Labor in the U. 1993. 1993. Washington. EPA. Environmental Protection Agency.’’ Fed.S. 1994. Eubank. October 20. National Environmental Law Center and United States Public Interest Research Group. Darby. February 24. Akgerman. A. 33(3). 10. 1990. 1991. ‘‘New Challenges in Chemical Engineering: Integrating Process Safety into Chemical Engineering Education and Research. Environmental Protection Agency. A Review of Federal Authorities for Hazardous Materials Accident Safety: Report to Congress Section 112(r)(10) Clean Air Act As Amended. Petrochemical Industry. 40 CFR 372. Washington. Ed. DC. Hall. Proposed Rule. U. D. 5. 9.S. Occupational Safety and Health Administration. P. T. Houston. Washington. EPA. June 26.S. 6356–6417 (1992). Fed. The Phillips 66 Company Houston Chemical Complex Explosion and Fire.

These materials have had a tremendous impact on patients’ lives. The study of biomaterials is a multidisciplinary endeavor. With new materials and devices being developed to treat disease and injury. we will focus on new material development in three high-impact areas of biomaterials research: cell–biomaterial interactions.194 Recent Advances in Biomaterials Recent Advances in Biomaterials A vast number of materials (collectively termed biomaterials) are used in clinical applications. Here. they consist mainly of ‘‘off-the-shelf ’’ materials not originally designed for clinical use. hardening. metal. President Clinton signed the Biomaterials Access Assurance Act of 1998 to limit product liability in the biomaterials area. To help alleviate any future shortage of biomaterials. These materials are being designed using an advanced knowledge of cell biology and tissue–material interactions. . transdermal patches) to hip replacements to materials in hemodialysis machines to heart valves. chemistry. As one would imagine. The early use of cellulose in hemodialysis tubing resulted in anaphylactic shock and death in several patients. as many significant advances have also been made in other research areas that use biomaterials. or ceramic that is in intimate contact with a biological environment such as blood. this area has been an intensely researched for the last 20 years. a biomaterial can be classified as a material such as a polymer. This discussion is by no means exhaustive. complications have and continue to occur. the market for biomaterials is likely to increase significantly in the next decade. integrating knowledge from fields such as engineering. a blood contacting material should not cause thrombosis or complement activation. and medicine. and drug delivery. these biomaterials represent a significant health care cost. As a result. and pharmaceutical products using biomaterials in some capacity exceed $100 billion per year in the United States alone. device manufacturers have feared a shortage of materials. and rupture of silicone gel breast prostheses have lead to billions of dollars in litigation related to either real or perceived patient health problems attributed to the material. For example. research has focused on developing materials specifically designed for the clinic. Because of the high impact of these materials on patient care. or individual cells. from drug delivery (capsules. biology. Although current biomaterials have had a large impact in medicine. To eliminate many of the complications and expand the use of biomaterials in medicine. Many of these new materials represent chemical and physical modifications of existing materials or are entirely novel in their chemical structure. tissue engineering. tissue. The biocompatibility of a biomaterial is defined as the ability of a material to function with a specific host response. leakage. and a hip implant should be load-bearing and non destructive to the surrounding tissue. The annual sales of medical devices. many materials manufacturers no longer permit the clinical use of their materials. allowing many injured or ill people to lead a near-normal life in many instances. Specifically. thus. diagnostics. As a result of these incidents and numerous others. For example.

In the past few years. As the adherent cells grow and proliferate. G glycine. Via sulfhydryl interactions with a gold-coated substrate. Cells on these surfaces are sparse in number. In addition to integrin–cell adhesion. Stupp and colleagues [6–8] have developed a novel class of block copolymers that self-assemble into highly ordered supramolecular structures on surfaces.5]. have used the RAD (A alanine) sequence to promote cell adhesion to oligopeptides terminated with cysteine residues [3]. These proteins. these oligopeptides can form self-assembled monolayers (SAMs) on the surface of the substrate and thus create a good adhesion substrate for a variety of cell types. Materials modified with RGD peptide sequences alone are capable of integrin binding and thus permit cell attachment and growth [2]. Surfaces that minimize protein adsorption. specific for integrin binding. Hepatocytes readily adhered to these surfaces even though the ligand density was an order of magnitude lower than in similar galactose-modified polyacrylamide gels. that is. very loosely attached. Molecular modeling studies suggested that these aggregates were essentially supramolecular ‘‘mushrooms’’ with the ‘‘stem’’ consisting of . examples of which include laminin. The self-organization of the polymers on a surface was based on the crystallization of the biphenyl ester rod segments. even though the ligand density was low. such as RGD (R arginine. these polymers self-assembled to form identical nanometerscale clusters. When cast on surfaces. Adhesion to a surface is mediated by protein adsorption onto the surface. a large amount of research has been focused on understanding and controlling what happens at the cell–material and tissue–material interfaces. cells such as hepatocytes possess receptors for asialoglycoprotein receptors for β-d-galactose residues present in the ECM [4. Most mammalian cells are anchorage dependent. cell adhesion is strongly influenced by receptor–ligand interactions between integrins on the cell surface and ECM proteins adsorbed on the substrate. they added d-galactose moieties to the hydroxy terminus of PEG and cross-linked the gels using electron beam irradiation. In addition to purely thermodynamic considerations such as protein adsorption. fibronectin. contain peptide sequences. they must adhere to a substrate to grow and differentiate.Recent Advances in Biomaterials 195 Cell–Biomaterial Interactions Because the lack of biocompatibility of most conventional biomaterials can be attributed to adverse cell–material interactions. Zhang et al. and appear rounded. 2. as can be seen in the base of the structure depicted in Fig. and collagen. such as those modified with poly (ethylene glycol). they produce their own extracellular matrix (ECM) on which to adhere. followed by cell– receptor interactions with the adsorbed proteins. D aspartic acid). 1 and 2). The reason for this strong adhesion was that the flexibility of the PEG chains allowed necessary multiple ligand–receptor interactions to occur. Griffith and colleagues took advantage of these unique interactions to create an adhesion surface for hepatocytes. Starting with poly (ethylene glycol) or PEG star polymers (PEG chains radiating from a divinylbenzene core). also minimize cell adhesion and spreading [1]. These materials were diblock polymers termed ‘‘rod–coil’’ and are composed of a rigid rod segment of biphenyl esters and a flexible segment (the coil) composed of a block copolymer of polystyrene and polyisoprene (Figs.

6. for example. Researchers at Cornell. Others have shown that photolithography can define regions of cell adhesion. As described earlier.) the crystallized rod segments and the ‘‘head’’ comprised of the coil segments.) . 1 Structure of self-assembling rod–coil polymer. controlling both cell position and migration [9]. Whitesides and Lauffenberger used oligopeptide SAMs to create surfaces for cell adhesion [3]. (From Ref. resulting in the spatial control of cell adhesion and migration and creating unique geometries suitable for FIG. Such surfaces have had a profound influence on cell–material interactions. they hold great potential in the design of new biomaterials. These peptides can be patterned by µ-Cp. has received extensive attention as a method of both chemical patterning [10] and protein patterning surfaces [11] to control cell adhesion and migration. (Adapted from Ref. When annealed at high temperature.196 Recent Advances in Biomaterials FIG. a soft lithography technique. the isoprene segments cross-linked to form films stable in a variety of solvents. 2 Molecular graphics of a self-assembled rod–coil polymer structure containing nine layers or monomer units of isoprene. Microcontact printing or µ-Cp. have developed micromachined probes that show minimal adverse tissue response when implanted in the cerebral cortices of rats [2]. 6. Microfabrication techniques such as photolithography and microcontact printing have also been used to create surfaces with unique topographies and spatially defined chemistries. Because of the highly ordered and stable nature of these clusters.

have also used the low-mixing laminar-flow conditions in micromachined channels to pattern cocultures of eukaryotic cells on a single surface [15].) . 3). Cells seeded on patterned surfaces adhere and grow within the corrals. which promote cell adhesion. Earlier studies demonstrated that there are geometric limits to the extent cells can be confined without causing apoptosis (programmed cell death) [12–14]. a four-step soft lithographic process based on microcontact printing (µ-Cp) of organic monolayers. The corrals have hydrophobic. (From Ref. and walls consisting of hydrophilic poly(acrylic acid)/poly(ethylene glycol) (PAA/PEG) layered nanocomposites that inhibit cell growth. The functional units on these surfaces were three-dimensional cell ‘‘corrals’’ that have walls 50 nm in height and lateral dimensions on the order of 60 µm. 16. methyl-terminated n-alkanethiol bottoms. Cell viability studies indicate that cells remain viable FIG. and murine hepatocytes. Takayama et al.Recent Advances in Biomaterials 197 the study of cell–cell interactions on these surfaces. but they do not span the PAA/ PEG corral walls (Fig. hyperbranched polymer grafting. and subsequent polymer functionalization has resulted in polymer patterns that direct the grown of mammalian cells such as IC-21 murine peritoneal macrophages [16]. human umbilical vein endothelial cells. Besides µ-Cp. Going beyond SAMs. 3 Murine macrophages cultured on a micropatterned surface of poly(acrylic acid)/poly(ethylene glycol).

This capsule poses a difficult problem in the development of cell-based therapeutic devices and engineered tissues [17]. Prevascularization of polymer scaffolds for tissue engineering was attempted as a method to develop a vascular network in and around the implant and promote the survival of cells transplanted into the scaffold at a later date [22]. the natural tendency of the surrounding tissue is to degrade or extrude the implant. It presents a mass-transfer barrier and therefore limits the concentration of nutrients and oxygen reaching the transplanted cells. If the host cannot eliminate the foreign body. this is not true for all porous polymer membranes.. particularly in influencing the foreign-body response. a chronic inflammatory reaction results and the object is encapsulated in fibrous tissue. even those with similar porosities and chemistries. When islets were introduced. However. Materials that are microporous but contain large planar features prompted an avascular host response while the same material lacking these planar features and having a more . Other significant insights have been made in understanding tissue–material interactions. surface features greater than 10 µm appeared to attract foreign-body giant cells to the surface of the implant. 4). with results of these studies showing lower permeability for thicker capsules [19].20]. with round sutures resulting in less macrophage involvement than sutures with surface irregularities on the scale of 10–15 µm [24]. Studies by Padera and Colton [25] and Brauker et al. oxygen present inside these hollow fibers was also consumed by islets in minutes [20]. these cells frequently die from hypoxia or lack of nutrients. As a result. the anatomical site of implantation influences fibrosis. In another study. particularly cells that are highly metabolically active (e. Devices containing transplanted cells must therefore develop capillary networks with transcapillary mass-transfer rates high enough to ensure survival of the cells. When a foreign body such as a medical implant is introduced into a host. The presence of these inflammatory cells around the implanted material resulted in thickening of the fibrous capsule [23]. islets are very closely associated with capillaries [21]. pancreatic islets and hepatocytes) [18]. Increased distance from blood vessels also resulted in lower insulin production from transplanted islets [18]. In suture materials. In vivo studies of transplanted pancreatic islets showed that islet viability decreased dramatically with increasing distance between blood vessels and islets [17.198 Recent Advances in Biomaterials on the patterned surfaces for up to 21 days. In one early study. and microscopy studies demonstrate that cell growth and spreading does not occur outside of the corral boundaries. [26] have shown that certain microporous materials will allow blood vessels to grow and be maintained at the tissue–material interface and in some cases within the pores of the material (Fig. The ability of the capsule to limit mass transfer has been demonstrated in several studies. A number of studies have also shown that the microarchitecture of an implanted material has a great influence on its local tissue response [23]. What appears to be driving the host response is not necessarily the chemistry of the material.g. but the microstructure of individual features within the material onto which host cells can attach. In addition to implant topography. This result is not surprising because in a healthy pancreas. the topography of the surface affected macrophage involvement. fibrous capsules were generated by implanting materials in vivo followed by the harvesting of the capsule for permeability studies. Acrylic fibers implanted into the subcutaneous tissue of rats showed a higher degree of fibrosis than those implanted into the abdominal fat pad.

4 Top: Micrograph of a tissue section containing a PVDF membrane with a 0. Bottom: Micrograph of a tissue section containing a 5-µm PVDF membrane. Arrows indicate foreign-body giant cells at the tissue material interface. Arrows indicate blood vessels either at the tissue–material interface or within the material. . Note the lack of blood vessels near the tissue–material interface.22-µm pore size.Recent Advances in Biomaterials 199 FIG.

The ear began as cartilage cells (chondrocytes) cultured on a polymer scaffold in the shape of a human ear. it may then become possible to fabricate materials with a microstructure designed to promote specific levels of neovascularization. tissueengineered skin developed from biodegradable scaffolds are available from Advanced Tissue Sciences. The third approach. Other tissue-engineered products are currently in development. For example. tissue engineering has developed as a discipline with the goal of restoring. the polymer scaffold degrades and is eventually replaced by healthy and functioning liver tissue. uses cells from the desired tissue cultured in vitro on a three-dimensional biodegradable scaffold. The tissue– material construct is then implanted into the abdomen of the patient. Protein Polymer Technologies is developing silk/elastin gels that can be freeze-dried to form sponges for wound healing and organ-filler applications. For example. This approach has met with some success. in- . The second is the controlled release of growth factors and cytokines to promote tissue repair or regeneration using existing mechanisms within the body. They will then hopefully continue to grow and mature into the desired tissue. However. and liver failure. Many of these tissue substitutes take the form of cells from the tissue of interest cultured on biomaterials. To address this need. For some ailments such as burns. there exists a serious shortage in available donor tissue.000 people die each year waiting for a suitable liver for transplantation. which is addressed here. Tissue Engineering Tissue engineering is an interdisciplinary field combining fundamental principles from biology and engineering to understand the structure and function of tissue. maintaining. frequently microporous biodegradable polymer scaffolds. tissue-engineered products have moved outside the laboratory and into the marketplace. The first is the development of biohybrid artificial organs such as implantable islet-containing bioreactors or microencapsulated islets for the treatment of diabetes.200 Recent Advances in Biomaterials fibrous structure prompted neovascularization at the tissue–material interface. Tissue failure or loss due to disease or injury accounts for over $400 billion in total annual health care costs in the United States alone. If the mechanism of this response can be elucidated. the scaffold having degraded with time. Once these cells have reached a critical density on the scaffold. if one wished to form a tissue-engineered liver. Many readers may remember the television news image of a human ear growing on the back of a rat. hepatocytes (liver cells) are cultured in vitro on a polymer scaffold to a high cell density. For some types of tissue such as cartilage and skin. However. they are then transplanted into the subject at the desired location. Tissue engineering has taken on three basic forms. As an example. nearly 40. tissue transplantation is the conventional treatment. particularly for the generation of skin and cartilage. As the tissue continues to grow. there are several significant obstacles that must be overcome before it can be used for the repair or replacement of many types of tissue. kidney failure. an example of tissue engineering of cartilage. and improving the function of living tissue.

adverse tissue responses to the biodegradable polymer. This protein is a secreted cytokine that is specific for vascular endothelial cells and has been shown to have angiogenic activity in vivo [28–31]. 5) that. including poly(ethylene glycol) gels that can be interfacially polymerized to prevent intimal thickening following ballon angioplasty [35] and polymer solutions containing chondrocytes that can be polymerized transdermally [36. many challenges are present. new polymers. VEGF. both of these proteins are billion dollar drugs. VEGF bioactivity was retained and controlled-release sustained in excess of 30 days. when implanted in dogs. both degradable and nondegradable. Significant advances have also been made in the engineering of other tissues.37]. are being developed. Many of these materials can maintain a . and engineering tissue containing multiple cell types. Numerous studies have also shown that VEGF is secreted by macrophages and that VEGF expression is enhanced in macrophages under hypoxic conditions [31]. Anseth and colleagues have developed photo-cross-linkable polyanhydrides that have excellent mechanical properties and can be fabricated into complex shapes such as screws [33]. These materials are designed to control the mass transfer of drug to the surrounding tissue and to be biocompatible. Drug Delivery Drug delivery research in the controlled release of proteins has become increasingly important as many new drugs are either protein or peptide based. Most of these biomolecules are unstable in vivo and as a result must be administered by multiple injections. researchers such as David Mooney of the University of Michigan are developing polymer scaffolds prepared in supercritical carbon dioxide that release blood-vessel-promoting growth factors such as vascular endothelial growth factor (VEGF) [27]. Oberpenning and colleagues recently tested a tissueengineered bladder (Fig. also known as vascular permeability factor (VPF). For nervous tissue. including the integration of blood vessels and nerves. a number of systems have been developed for the in vivo polymerization of a matrix for tissue engineering. To promote blood vessel growth in engineered tissue. For other types of tissue such as liver and nervous tissue. was able to retain urine normally for up to 11 months [34]. Schmidt and colleagues found that electrically conducting polymers such as polypyrrole aid the reconnecting of severed nerves [32]. Two prime examples are human growth hormone and erythropoeitin for the treatment of anemia. This bladder. vascular grafts. and bone replacement. To stabilize these drugs in vivo and to control the rate at which they are delivered and the location of delivery. Other researchers such as Keith Gooch of the University of Pennsylvania are forming capillaries in vitro that connect to existing blood vessels when implanted. represents the first construction of a hollow organ by tissue engineering.Recent Advances in Biomaterials 201 cluding encapsulated cells and cell-based bioreactors for the treatment of Type I diabetes and liver failure. For bone. is a protein composed of two identical subunits which has a molecular weight of 45 kDa. based on smooth-muscle cells and urethelial cells cultured on a biodegradable poly (lactide-co-glycolide) scaffold. Finally.

After the brain tumor is surgically removed. As the polymer degrades over time.202 Recent Advances in Biomaterials FIG. the anticancer drug is released directly to the brain in concentrations that cannot be . and poly(ethylene glycol)–polyester copolymers.) constant release of drug over many days and months. (From Ref. These materials are chemically designed such that their degradation products are nontoxic. the first new FDA-approved treatment of gliabastoma (a deadly form of brain cancer) in 20 years [38]. This product is composed of a biodegradable polymer containing the anticancer drug carmustine. 34. Examples of such degradable materials include polyesters such as poly(glycolic acid) used in resorbable sutures. 5 Radiographic cystograms of a tissue-engineered bladder implanted in a dog. One example is Gliadel. the space formerly occupied by the tumor is lined with polymer wafers containing the drug. polyanhydrides.

cationic liposomes [43]. Discher and colleagues [46] described the formation of polymersomes. a novel system was described that may have significant applications in drug delivery. Although chloroquine and DEAE–dextran enhanced transfection. as determined from the expression of a luciferase gene in the vector. lymphoma. pH. In polyelectrolytic gels. Electrostatic complexes of DNA and dendrimers were shown to transfect a variety of cell lines. anemia. ionic strength. and cancer treatment are expected to be available shortly.000 to 40. have been of particular interest. including fibroblasts. and because equilibrium water content is directly proportional to biomolecule mass-transfer rates out of the gel. and hepatoblastoma [45]. Polycations investigated to date include polylysine [42].Recent Advances in Biomaterials 203 achieved by administering the drug via the bloodstream. Recently. Brannon-Peppas and Peppas describe research on the effects of comonomer composition and hydrophobicity on swelling [41]. In the Rat2 cell line. Rat2. occurred at levels easily measured. With the exception of swelling-controlled or osmotic delivery systems. Mikos and colleagues recently provided a comprehensive review of both nondegradable and degradable hydrogel systems for drug delivery [39]. Khare and Peppas have described the effects of copolymerization.000 times more efficient. extended release profiles can be achieved by increasing the hydrophobicity of the gel. This process is highly dependent on polymer chain mobility. As a result. and poly(amidoamine) (PAMAM) dendrimers [45]. they were not required and transfection. and buffer composition on the release of biomolecules [40]. vesicles made of amphiphilic diblock copolymers of poly(ethylene oxide) and poly(ethylethylene) (Fig. polyethylene imine [44]. the ionic character is pH dependent and can exhibit substantial changes in swelling caused by shifts in pH [41]. polymeric materials control drug release by limiting Fickian diffusion of the drug through the solvent-swollen network. Some specific examples are instructive. PAMAM dendrimers are unidispersed and have a high positive-charge density at their surface. Drug delivery products for vaccine delivery. These structures were found to be structurally . Hydrogels. 6). transfection was highly dependent on the generation of the dendrimer. These materials are highly swollen with water and can possess equilibrium water content in excess of 90% by weight. both degradable and nondegradable. reaching a plateau after the ninth generation of 20. Particularly in the case of anionic gels. which dictates the surface charge and size of the molecule. Network hydrophilicity controls swelling via water absorption. the reoccurrence of the disease is diminished and chemotherapy side effects are reduced because the drug is delivered only where it is needed. these factors influence the equilibrium water content of the polymer network and hence the mesh size in the gel. For example. Transfection efficiency as compared to simple exogenous DNA was found to increase exponentially with the generation of the dendrimer. Other research in drug delivery is currently focused on developing targeted polymer delivery systems (such as biodegradable microparticles to the lungs) and developing polymer delivery vehicles for gene therapy. DNA–polycation complexes have received extensive attention in recent years as an alternative to virus-mediated transfection of therapeutic gene therapy vectors into mammalian cells. CHO. Unless highly localized changes in pH occur. these pH-induced changes in swelling may not occur in vivo.

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’’ Science. 46.05. Won. Ege. which is defined as: α Y 1 /X 1 Y 2 /X 2 where X 1 and X 2 are the mole fraction of components 1 and 2. 4897–4902 (1996). Bates. In fact. . Kukowska-Latallo. such as extractive distillation (ED). Baker. The basis for ED is to increase α by introducing a high-boiling. J.95 α 1.’’ 93. respectively. α is one of the major economic factors for distillation. Hammer. and D. R. 284. Under this situation. Discher. Colburn and Schoenborn [1] gave the following generalized correlation for the approximate number of theoretical plates required for a separation of products each of 99% purity: Number of theoretical plates 4 α 1 In general. because a large number of plates requires very high capital investment and a large reflux ratio requires very high operating cost. J. The ease of separation is conveniently measured by the relative volatility (α) between the key components. The difference in boiling points between the key components to be separated is the means for separation. J. Lee. and operation of an extractive distillation column (EDC) have been thoroughly discussed in the literature [2–5]. polar solvent to the distillation column. Y. Spindler. A. PISHKO Recent Development of Extractive Distillation: A Distillation Alternative Introduction Distillation is the most commonly used method for recovering and purifying petrochemicals and chemicals in the industry. D. D. Tomalia. The characteristics. Johnson. 1143– 1146 (1999). a solvent-enhanced distillation. MICHAEL V. and J. F. D. ‘‘Polymersomes: Tough Vesicles Made from Diblock Copolymers. in the liquid phase and Y 1 and Y 2 are those in the vapor phase.Extractive Distillation 207 45. distillation becomes uneconomical when 0. B. becomes economically attractive and practical. ‘‘Efficient Transfer of Genetic Material into Mammalian Cells Using Starburst Polyamidoamine Dendrimers. design. Bielinska. Discher.

. so the EDC is normally operated using substantially higher amount of liquid (nonvolatile solvent) than the conventional distillation. extractive distillation is normally operated under significantly higher liquid to vapor ratios (L/V) as compared to conventional distillation. Also. Two types of packing were tested. the solvent-to-feed weight ratio (S/F) can vary from 3 to as high as 20. a certain portion of the EDC may have two liquid phases.208 Extractive Distillation Depending on applications. a random dumped packing [0. Hydrodynamic Behavior of a Packed EDC The presence of the nonvolatile solvent in the EDC not only substantially increases liquid flow (L) but also reduces the vapor flow (V) by preferentially absorbing the more polar components in the vapor stream. such information on packed columns used for ED operation was reported by Brown and Lee [6]. Therefore.63-cm protruded metal packing (Pro-Pak)] and a structured packing (Koch-Sulzer BX). the solvent-to-feed weight ratio (S/F) varies from 3/ 1 to as high as 20/1. Hydrodynamic behavior of a distillation operation with a highL/V condition has not been significantly reported in the literature. 1. 1 Schematic diagram of ED pilot plant for hydrodynamic study of packings. due the to difference in solubility of the key components in the polar solvent. Depending on applications. Nevertheless.15- FIG. the tests on Pro-Pak random packings were conducted in a 0. Significant progress has been made in the industry recently in terms of understanding and handling these special situations in the EDC. Shown in Fig.

1 1.0 99.0 Heptane recovery 95.9 100.1 72.1 4.3 59.4 93.6 99.0 100.3 99.3 94.8 100.6 4. All ratios and percents were measured by weight.1 88.1 3.5 6.7 3.0 99.3 100.7 99. 209 .8 99.5 99.0 100.2 2.5 10.7 100.2 Raffinate (%) Toluene purity 99.0 46.0 99. Packing code P S P S P S P S P S 174 174 182 182 182 182 193 193 172 172 protruded packing (ProPak).5 6.5 93.2 99.4 Run no.5 6.7 59.4 1.4 94.Extractive Distillation TABLE 1 ED Runs with Different Tower Packings Extract (%) Reflux ratio Toluene recovery 99. (°C) 6.0 Heptane purity 95.0 100.5 6.0 10.3 100.0 100.8 86.7 99.0 10.0 100. S Solventto-feed ratio Kettle temp.0 98.0 100.4 3.6 3.3 96.0 6.5 1 1 2 2 3 3 4 4 5 5 Notes: Packing codes: P structured packing (Koch–Sulzer BX).0 10.8 100.0 96.8 95.4 3.

The difference between the predicted and actual pressure drop for protruded packing are at least twice that of the structured packing under the same conditions. . It was also found that the height equivalent to a theoretical plate (HETP) on both packings was underpredicted by the vendor’s correlations [7. The feed (a mixture of 88/12 wt% toluene/heptane) was fed to the location at 55% above the bottom of the entire EDC. Then. To investigate the pressure drop in the EDC under high-L/V condition. A total of 31 elements with 5. using a rigorous computer algorithm capable of simulating distillation processes with multicomponents and multiphases. utilizing the composition of feed and products.3-m total packing height were fitted in the duo-column EDC. pipe distributors were installed at the top and at 40% above the bottom of each half-column. and the extractive solvent (N-methyl pyrrolidone) was fed at 88% above the bottom of the EDC. the difference in HETP for the structured packing and protruded packing are respectively 5 and 10 in. 3. Koch–Sulzer BX structured packing was also tested in the same EDC under the same condition as the Pro-Pak testings.015–0.022 m3 /h at a temperature slightly below the hydrocarbon bubble point and a pressure of 35 kPa. 2 Comparison of predicted and actual pressure drop. Distributors were placed only at the top of each half-column. hydrocarbon was introduced into the EDC at a rate of 0. Lean solvent was fed to the top of the upper half of ED tower at a subcooled temperature of 121°C. a plot of the difference between the measured pressure drop and the predicted pressure drop is given in Fig. The solvent-to-feed ratio (S/F) varied from 6. The actual HETP was roughly estimated by the Fenske– Underwood correlations. A summary of the selected runs is presented in Table 1. 2. and an average relative volatility.8]. computer simulations were run to determine the number of theoretical stages. It was found that the actual pressure drops measured in this study are significantly higher than the ones predicted by the packing vendor’s correlations [7.210 Extractive Distillation m-diameter EDC with 5.7-m total packed height loaded in a duo-column system: The top and bottom halves of the column were connected in series by insulted vapor and liquid lines.8]. As shown in Fig. During a normal run. Experimental activity coefficients FIG. During the operation.5 to 10 and the kettle temperature varied between 171°C and 193°C.

vapor–liquid equilibria. but protruded packing consistently shows a pressure drop three times FIG. . which was used to determine vapor–liquid equilibrium constants.Extractive Distillation 211 FIG. Figure 4 shows that the pressure drop for both packings increase with increasing F s. 4 Pressure drop versus gas capacity factor. A final solution was then made by convergence on the input specification values. 3 Comparison of predicted and actual HETP. an initial trial solution to the computer algorithm was made by assuming constant molal overflow and a guessed (assumed) columntemperature profile. The gas capacity factor (F s the superficial gas velocity times the square root of the gas density) is an important parameter in determining the loading on the column. A Newton–Raphson convergence technique was used. for N-methyl pyrrolidone/n-heptane/toluene were used as input to a Renon activity coefficient model. and heat and material balances. In the computer simulation.

FIG. higher than structured packing. 6 Pressure drop versus liquid loading.212 Extractive Distillation FIG. 5 HETP versus gas capacity factor. . and at 32–37% of flood. The HETP for protruded packing is slightly higher than that of structured packing (approximately 1–5 in higher). The pressure drop is plotted against the liquid loading (kg/h/m2 ) in Fig. using Koch–Sulzer BX structured packing [7]. It is estimated from vendor information that the column was at 12% of flood. The gas capacity factor is also plotted against HETP in Fig. Liquid loading in an EDC is much higher than the conventional distillation column. 6 for both packings. It appears that F s has no effect on HETP for both packings over the range tested. so it could be the limiting factor in the design of an EDC. 5. using the protruded packing [8].

Extractive Distillation


FIG. 7 HETP versus liquid loading.

Liquid loading shows a positive linear relationship with pressure drop for the protruded packing and shows a minimum pressure drop at liquid loading around 8070– 8310 kg/h/m2, but otherwise shows little correlation. Liquid loading is also plotted against HETP for both packings in Fig. 7. Although literature sources predict a decrease in HETP with increased liquid loading [9,10], the structured packing had a constant HETP and the protruded packing has little correlation over the liquid loading range investigated. The flow parameter, (L/V)(ρ v /ρ l )0.5, where ρ v and ρ l are the density of vapor and liquid, respectively, is an important parameter when considering the flood point or maximum loading on the column. Assuming the densities (ρ v and ρ l ) to be relatively constant in the range investigated, L/V is plotted against pressure drop and HETP. Figure 8 shows the pressure drop against the maximum L/V predicted in the computer simulation (normally at solvent feed stage). The column packed with the structured packing shows a constant pressure drop over a L/V range of 15–27, whereas the column packed with protruded packing shows a slight decrease in pressure drop with increasing L/V, although the data points were scattered. A very good linear correlation was found when L/V determined by the maximum liquid and vapor loadings in the column is plotted against the pressure drop, as shown in Fig. 9. Both packings show a pressure drop of about 0.1 in. of water per foot of packing for every 0.2 increase in L/V. This is consistent with established principles, as the stage with the maximum L/V plays the most important role in determining pressure drop in a column and will be used for sizing the column. The HETP is also plotted against L/V for the protruded packing in Figs. 10 and 11 for the solvent feed stage and for the stage with maximum vapor and liquid loadings, respectively. Both figures show an increase in HETP with increasing L/V. However, there was no change in HETP with L/V for the structured packing. It is concluded that both random and structured packings show a loss of effi-


Extractive Distillation

FIG. 8 Pressure drop versus maximum predicted L/V (on solvent feed tray).

ciency under ED operation (or under very high L/V) as compared to conventional distillation. Both pressure drop per foot of packing and HETP are underpredicted by vendor correlations for both types of packings, although the predicted results for the structured packing is closer to the actual results than those of the protruded packing. Also, compared to random packing, the structured packing appears to be less affected by the changes in gas capacity, liquid loading, and L/V. Further literature data are required to confirm the superiority of the structured packing for extractive distillation services.

FIG. 9 Pressure drop versus L/V determined by maximum liquid and vapor loadings.

Extractive Distillation


FIG. 10 HETP versus L/V (on solvent feed tray) for protruded packing.

Handling Two Liquid Phases in EDC
One of the considerations in ED technology is the handling of possible formation of two liquid phases in a certain portion of the EDC where the less soluble components are concentrated. The occurrence of a second liquid phase is caused by the fact that some of the less polar components have significantly lower solubility in the polar solvent than the more polar components. One way to solve the problem of two liquid phases in the ED tower is to select

FIG. 11 HETP versus L/V determined by maximum liquid and vapor loadings for protruded packing.


Extractive Distillation a polar solvent, which has enough solvency to dissolve all the components in the mixture under process condition. In general, however, solvents with a high selectivity for compounds to be separated will have a reduced solvency (capacity), and vice versa. Therefore, in order to eliminate two liquid phases, one may have to compromise the solvent selectivity, sometimes, to a great extent. A better way is to cope with two liquid phases in the EDC, without sacrificing the solvent selectivity, for following reasons: 1. Although two liquid phases normally reduce the solvent selectivity in a threephase equilibrium (vapor–liquid–liquid) condition in the EDC, it can be compensated by intrinsic selectivity of a highly selective solvent. For example, the performance of sulfolane (SULF) was compared with those of N-formyl morpholine (NFM), N-methyl pyrrolidone (NMP), 2-pyrrolidone (2PD), and dimethyl sulfoxide (DMSO). The rough comparison was made through their abilities to enhance the relative volatility of n-heptane over benzene (an aromatic and nonaromatic separation) in a one-stage equilibrium cell. Table 2 shows that although two liquid phases were observed using sulfolane as the solvent, it still gave a better performance than other solvents when a single liquid phase existed in the mixture. 2. Two liquid phases present no ill effects on the efficiency of small tray or packed towers with diameter from 0.08 to 0.46 m. However, in a larger tower, the heavy liquid phase tends to accumulate on the tray if the liquid phases are not well mixed. This problem can be eliminated by tray designs promoting gas agitation, causing the two liquid phases to behave as a homogeneous liquid that followed general correlations for pressure drop, liquid holdup, broth height, downcomer liquid level, and fractional entrainment. For larger packed

TABLE 2 Comparison of the ED Solvents for n-Heptane and Benzene Separation Phase composition† (wt%) Solvent SULF SULF NFM NFM NMP NMP DMSO DMSO 2PD 2PD S/F 1.0 3.0 1.0 3.0 1.0 3.0 1.0 3.0 1.0 3.0 X1 16.24 16.32 16.23 16.23 18.60 18.60 15.21 15.21 14.74 14.74 Y1 28.94 43.76 26.39 36.84 27.74 35.71 26.97 37.54 24.32 34.76 X2 83.76 83.68 83.77 83.77 81.40 81.40 84.79 84.79 85.26 85.26 Y2 71.06 56.24 73.61 63.16 72.26 64.29 73.03 62.46 75.68 65.24 α1/2 2.10 3.99 1.85 3.01 1.68 2.43 2.06 3.35 1.86 3.08 Liquid phases 2 2 1 1 1 1 1 1 1 1

Notes: SULF: sulfolane; NFM: N-formyl morpholine; NMP: N-methyl pyrrolidone; DMSO: dimethyl sulfoxide; 2PD: 2-pyrrolidone. † X1 and X2 are the liquid compositions of n-heptane and benzene, respectively, and Y1 and Y2 are the vapor compositions of n-heptane and benzene, respectively (all in weight% on solvent-free basis). (Y1 /X1)/(Y2 /X2), the relative volatility of n-heptane over benzene. α1/2

Extractive Distillation


columns, the liquid–liquid redistributor should be specially designed to allow separate distribution of the two liquid phases [11]. Computer simulations have been developed which are capable of accurately predicting the development of two liquid phases in the EDC and the summary was reported [12]. In one approach, the simulation algorithm starts from linearized pressure, temperature and concentration profiles, and feed conditions given by the program operator. New estimates of composition are solved using the material balance and equilibrium relationship for each tray. Then, the equilibrium constants are reestimated and a new temperature gradient is established to calculate a trayby-tray energy balance. Accumulated errors are calculated for the energy, material, and equilibrium balances. Appropriate column operation restraints are factored in at this point. A correction factor is found for the temperature, rate profiles, and liquid composition profile by inverting the accumulated error matrix. These correction factors are used to form new estimates of composition to start the process again until the correction factors are small enough to call the components converged. Multicomponent vapor–liquid and liquid–liquid equilibria solutions are required for the algorithm. Two activity coefficient models, NRTL and UNIQUAC, are readily extendable to multicomponent systems and capable of such solutions. Experimental activity coefficients, γ, at infinite dilution are used for calculating binary parameters for the NRTL equation. These parameters are then tested using experimental liquid–liquid ternary data, experimental vapor–liquid equilibrium data, and data from pilot plant or commercial plant. The NRTL equation is used in the algorithm to calculate activity coefficients and is given by the following equations: ln γ 1 x 2 τ 21 2 G 21 x 2G 21


τ 12G 12 (x 2 x 1G 12)2

ln γ 2

x 2 τ 12 1

(x 2

G 12 x 1G 12 )

(x 1

τ 21G 21 x 2G 21 )2

where ln G 12 τ 12 β 12 τ 12, η 12 S 12T , RT ln G 21 τ 21 β 21 τ 12 η 21 S 21T RT

where G ij , η ij , S ij, τ ij , and β ij are empirical constants, γ i is activity coefficient, R is the gas constant, T is the absolute temperature, and x i is the liquid-phase mole fraction of component i. A Newton–Raphson-based flash algorithm checks for two liquid phases by checking Gibbs free energies for possible second liquid-phase components. If two liquid phases are indeed present, regular solution theory provides a method of combining the liquid-phase activity coefficients.

and NMP. As shown in Table 3.15]. which has dominated the BTX aromatic recovery field for many years. none of the solvents listed in Table 3 have gained commercial importance for BTX aromatic recovery from the petroleum streams. proprietary cosolvents are added to the base solvents to enhance the solvent performance. The following is an example using the GT-BTX process to recover high-purity BTX aromatics from the full-range (C 6 –C 8 ) pyrolyTABLE 3 ED Solvents for Aromatics Recovery from Petroleum Streams Furfural Aniline Phenol-cresol Acetonyl acetone Dichloroethylether Nonanoic acid Nitrobenzene Phenyl cellosolve Sodium-o-xylene sulfonate H 2O Propylene glycol o-Chloroamine o-Phenyl phenol Dipheyloxide Nitrotoluene Cresol Phenol Phthalic anhydride Hexyleneglycol o-Chlorophenol Methyl salicylate 2-Ethylhexanol 2-Ethyl hexylamine o-Nitrophenol Dimethyl aniline–aniline o-Phenetidine . which contains 80% aromatics is one example. The modern state-of-the-art ED technologies for BTX aromatic recovery are based on several solvent systems: SULF. liquid–liquid extraction based on sulfolane. two of the leading ED processes for BTX aromatics recovery are offered by GTC Technology Corporation (GT-BTXSM process) and Krupp Koppers (Morphylane process) [14. Today. for example. Feeds with High Aromatic Content The recovery of BTX aromatics from pyrolysis gasoline. The modern ED processes can compete very favorably with. in the following cases. The high aromatic content tends to prevent the interface formation between the raffinate and the extract phases in the liquid–liquid extractor. a number of solvents selective for aromatic recovery from petroleum streams have been listed in the literature [13]. ED technology for recovering high-purity heavier petrochemicals from the petroleum streams has gained commercial importance only recently. In most cases. isoprene.218 Extractive Distillation Some Unique Applications of Extractive Distillation Extractive distillation technology has been practiced and continuously improved commercially since World War II when it gained commercial recognition in the recovery of high-purity butadiene. However. making the process inoperable. ED technology may be the preferred or the only choice. and C4 olefins from the C4 and C 5 petroleum streams. Many ED solvents have been studied during the past 50 years to determine their selectivity for purifying heavier hydrocarbons. NFM. However. However.

0%. were respectively 96.16 wt%) and the heavy portion of iso-octanes (0.50 49.87) of the heaviest nonaromatics in the feed.31 wt% heavy iso-octanes in the feed. and mixed xylenes (with 98. The lean solvent is then recycled to the top of the EDC.5 wt% purity) can be recovered from the extract product by distillation.90 0. a more detailed analysis was carried out to determine the nonaromatics in the feedstock.38 13. The pyrolysis gasoline feed is introduced to the middle portion of the EDC near its bubble point. Lean solvent is fed near the top of the EDC at about 10°C below the column temperature to generate internal reflux to improve the column performance. thus. which is necessary for LLE operation. In order to determine the purity of BTX aromatics produced without fractionating the extract product. The solvent preferentially extracts the more polar components in the mixture. and 99. According to material balances. According to Table 6. Table 6 shows the major components and their boiling points in Feed No. two different feedstocks were tested in a pilot plant consisting of a 60-tray extractive distillation column and a packed solvent stripper for solvent recovery.Extractive Distillation 219 sis gasoline.9 wt% purity).35 0. The bottoms of the column consist of the solvent and the aromatic components.31 wt%).00 Component (wt%) Nonaromatics Benzene Toluene C8-aromatics C9 -aromatics . because the aromatic content is so high that it prevents the formation of the interface between the extract and raffinate phases. A schematic diagram is presented in Fig. The solvent-to-feed ratio (weight) for both feeds was 3.0. The impurities in benzene and toluene products were the 0.83 29. 1 11. which contains around 90% aromatics. The analyses for the product streams are summarized in Table 5. commercial grade of benzene (with 99.54 wt%. The recovery for benzene. toluene (with 99.54 wt% 0.5–97.0 wt% purity).89 48.9% by weight. these nonaromatics were iso-nonanes (0. whereas the impurities in mixed xylenes were the 0. From Table 5.0%. To illustrate the application of ED technology to high aromatic containing feed.87. The nonaromatics in the extract is equivalent to 0. The simplified feed compositions are given in Table 4. the nonaromatics in the extract (product) stream was 0. 2 7. 1. A part of the raffinate stream from the LLE unit is often recycled to reduce the aromatic content in the feed stream (to ensure the interface formation) and. these are fed to a solvent stripper (containing 9. 12.47 wt% (0.79 11.08 Feed No. TABLE 4 Composition of Pyrolysis Gasoline for BTX Aromatics Recovery Feed No. toluene. allowing the nonaromatic components to rise as vapor to the top of the column as the raffinate product. reduces the efficiency of the process. 99. These experimental results demonstrate the effectiveness of a ED process (GT-BTX process) in recovering chemical grade BTX from a fullrange (C 6 –C8 ) pyrolysis gasoline containing high aromatics.28 27. This type of feed is unsuitable for liquid–liquid extraction (LLE).5 m of random packing) to separate the solvent from the extract products. and mixed xylenes. and the split of bottom (extract) to feed in the ED column was 0.16 wt% iso-nonanes in the feed.

22 32.69 3. such xylenes and C 9 -aromatics.87 0. To determine the performance of GT-BTX process. The latter compounds have relatively less solubility in the extractive solvents than the former compounds. which tend to stay the solvent at the bottom of the ED column.66 31. will provide higher recovery for the heavier aromatics.54 54. on the other hand.10 Feed No.04 0.84 13. Heavy Aromatics Recovery Liquid–liquid extraction is more effective to extract lighter aromatics. the solvent boiling point has to be high enough to allow a clean separation between the extract product and the solvent by stripping or distillation in the solvent recovery column.00 Extract 0. such as benzene and toleune.00 . 2 Raffinate 80.31 0. The performance of ED technology for recovering C 8 to C 9 aromatics has not been significantly reported in the literature.93 15.06 15. but less effective to extract heavier aromatics. However.44 52.66 13.220 Extractive Distillation FIG.30 1. 12 Schematic diagram of ED process.15 0.00 Extract 0. Extractive distillation. two heavy aromatic feeds with composition shown in Table 7 were investigated in a pilot plant consisting TABLE 5 Composition of Product Streams from the ED Unit for High Aromatic Feeds Component (wt%) Nonaromatics Benzene Toluene C8-Aromatics C9 -Aromatics Feed No. 1 Raffinate 84. due to their higher boiling points.11 0.23 0.

2 138.4 122–151 152–176 221 of a 60-tray extractive distillation column and a packed solvent stripper for solvent recovery.71 Feed No.0. 2.3-Dimethyl pentane 3-Methylhexane 1-cis-3-Dimethyl cyclopentane 1-tr-3-Dimethyl cyclopentane 1-tr-2-Dimethyl cyclopentane n-Heptane 2.3 63.8 80.50 0.51 0.7 71.87 for Feed No.91 14.2-Dimethylhexane Methyl cyclohexane 2. the kettle temperature and pressure of the ED column were adjusted to achieve the split of bottom-to-feed ratio of approximately 0.24 0.3 60.32 1. 1 and 0.32 0.52 27.07 1.22 0.52 59.17 Component (wt%) Nonaromatics Benzene Toluene C8-aromatics C9 -aromatics .6 125.12 0.9 109.31 2.47 0.8 91.4 110.8 90.36 1.7 90.21 0.8 100.42 3.4-Dimethylhexane Toluene n-Octane Iso-octane Ethylbenzene p-Xylene m-Xylene o-Xylene Iso-nonanes C9-aromatics Total Components and Their Boiling Points of Feed No.1 144. The solvent stripper (solvent recovery column) was operated TABLE 7 Composition of Heavy Aromatics Feeds for ED Study Feed No.7 91.38 100.21 3. 2 24.1 89. 1 Wt% 0.82 20.20 0.55 0.7 107–119 136.76 for Feed No.03 0.4 106.3 68. 1 12.07 0. The solvent-to-feed ratio (weight) for both feeds was 3.Extractive Distillation TABLE 6 Component Cyclopentane 2-Methylpentane 3-Methylpentane n-Hexane Methyl cyclopentane Benzene Cyclohexane 2-Methylhexane 2.26 Boiling point (°C) 49.36 6.8 91.57 49. Based on the feed analyses.9 98.40 1.3 139.16 0.19 0.30 0.1 80.66 63.18 0.65 1.38 0.29 0.

09 0. It is also observed that under similar operating conditions.38 96. 1 was 99.34 Raffinate 87.06 98. the overall aromatic recovery and purity have achieved the commercial requirements. Reformate containing BTX aromatics and the extractive solvent are fed into the LLE column according to the manner described in previous paragraph. 1 was 97. which is fed to the extractive stripping column. and for Feed No.76 with stripping gas under the proper level of vacuum to minimize the stripper temperature. This column strips the nonaromatics from the solvent and aromatics.16 23.81 Extract Recovery 0. The analyses of the production streams are presented in Table 8.02 8. BTX aromatics are recovered using LLE with sulfolane as the extractive solvent. which is recovered in a water-wash column. Revamping Existing LLE Processes Using the ED Method for BTX Recovery The ED method can be most effectively applied to revamping an existing LLE facility for recovering BTX aromatics from reformate or pyrolysis gasoline. 1 is indeed better than that of Feed No.59 73. Lean solvent from the solvent recovery column is recycled back to the LLE column. The raffinate stream from the top of LLE column contains some solvent.91 wt%.29 98. The solvent is introduced to the top of the column and flows downward through the column to preferentially extract the more polar components in the feed into the bottoms. and for Feed No.7 wt%.7 wt%. The bottoms from the extractive stripping column contain the aromatics and solvent are separated in a solvent recovery column. 1 (87.07 2.95 19. it was 98. The overall aromatic recovery for Feed No. This approach has been recently reported by Gentry and Kumar [16].10 1.89 wt%. The water is returned to the system in a closed-loop recycle.11 0. 2.05 Feed No. probably due to higher aromatic content in Feed No.00 1.0. A typical schematic diagram of this type of process is shown in Fig.33 8. 2. 1 Components (wt%) Nonaromatics Benzene Toluene C8-aromatics C9 -aromatics Raffinate 85.5 versus 76 wt%). 2.95 3. the feed is fed into the lower section of the LLE column and flows countercurrently against the solvent.91 98.00 2. In a typical LLE process where the solvent has higher density than the feed.31 78.51 2. and the overall aromatic purity for Feed No.75 0. . the process performance from Feed No. The bottoms stream is then fed to a solvent recovery column to recover the purified more polar components in the overhead and the lean solvent as the bottoms to be recycled to the LLE column.00 83. Shown in Table 8. The solvent extracts the aromatics and some nonaromatics into the bottoms.51 0. 2 Extract 1. for recycle to the LLE column.75 1.34 0. it was 95.00 63.15 Extract 0.222 TABLE 8 Extractive Distillation Composition of Product Streams from the ED Unit for Heavy Aromatic Feeds Feed No.03 Extract Recovery 3. under a solvent-to-feed ratio of 3. 13.

Extractive Distillation 223 FIG. Case A: Purifying By-product Benzene The xylene isomerization and toluene disproportionation units within the aromatic complex produce benzene as a by-product. but they should be the easiest to remove in the ED column due to their lower boiling point. Lighter nonaromatic impurities are more likely to be coextracted due to their solvent affinity in LLE column. A fundamental aspect of this process is that the solvent exhibits a selectivity favoring lower-boiling components more than the high-boiling components. The following are some examples. but the quality of benzene is low and requires reprocessing in the LLE unit to upgrade its purity. Adding just one ED column to the existing LLE process system can not only substantially increase the process throughput but also improve the performance in terms of product quality and purity. . 13 Schematic diagram of LLE process using sulfolane solvent. Figure 14 shows a new approach using a hybrid of the LLE process with ED that bypasses part of the feed around the original extraction section. The solvent selectivity favors the hydrocarbon species according to the following sequence: aromatics naphthenes/olefins paraffins.

whereas the LLE raffinate rich in paraffins could be blended into the feedstock for a naphtha cracker. 14 A hybrid of LLE and ED process purifying by-product benzene.g. The conventional LLE process can be retrofitted to use this hybrid process. If desired. Case B: Optimize the BTX Product Distribution Among the BTX aromatics. investment.. or shutdown time. the raffinate from the two can be segregated for optimum disposition. the petrochemical value of toluene . where the maximum aromatics limit in the feed charge is not a concern. In the hybrid scheme. the ED raffinate rich in cyclohexane may be recycled to the reformer unit. without requiring extensive modifications. toluene has historically contributed the least upgrade over its alternative value in motor fuel (e. the by-product (benzene-rich feedstock) is fed to the stand-alone ED column.224 Extractive Distillation FIG. The typical solvent-recovery column can usually manage the higher capacity or can be redesigned to do so. The primary changes are modifying the solvent system to be compatible with both LLE and ED operations and to make the appropriate tie-ins to the ED column. The original feed to the extraction section is not affected by this new ED operation. The rich solvent from both LLE and ED operations are combined into the existing solvent-recovery column.

As demonstrated in Fig. 15. As shown in Fig. (2) xylenes recovered should have higher purity because the majority of the C 8 –C 9 nonaromatics are purged with toluene in the ED column. toluene is inevitably extracted along with benzene and xylenes. (3) substantial increase in overall process capacity by adding only one ED column to the existing LLE system. Then. In a conventional LLE unit for BTX aromatics recovery. A number of benefits from this operation can be realized: (1) overall processing costs are reduced because the stream contains less toluene. Operation of the ED column is made to intentionally purge the majority of the toluene along with the nonaromatics to the column overhead. 16. 15 A hybrid of LLE and ED process for selective purge of toluene. Figure 15 shows a LLE and ED hybrid scheme where toluene is selectively purged from a BTX mixture to shift the product mix toward benzene and xylenes and to avoid some operating cost for toluene. it is not profitable to extract toluene. the toluene-lean ED column bottoms are combined with the benzene-rich solvent mixture from the extractive stripper bottoms as feed to the solvent-recovery column. thus. Case C: Capacity Increases Adding a new ED column to an existing LLE unit (as shown in Fig. the reformate splitter is retrofitted to include a side cut of the C 7 and C 8 components. which is fed to an ED column operated in parallel with the existing LLE unit. is only marginally above its fuel blending value). 13) can double the capacity of the unit. the new ED column takes .Extractive Distillation 225 FIG.

toxicity. corrosivity. Solvent is divided between the ED column and the raffinate extractor. a proprietary ED process was developed for the commercial application for recovering styrene directly from pyrolysis gasoline [17]. the fresh feed while the main liquid–liquid extractor takes the feed from the ED column overhead raffinate stream. to optimize the . freezing point. Using a single new ED column to retrofit the existing LLE unit can create significant increase in throughput and improvement in product quality with minimized capital costs. and. Styrene Recovery from Pyrolysis Gasoline One of the most difficult separations. a number of extractive solvent candidates were screened in the laboratory for selectivity. The selected solvent underwent an extensive pilot-plant test program to determine its performance in the ED process. and other important properties. and so forth. The method is based on the slightly higher polarity in styrene than the other C 8 aromatics. 16 A hybrid of LLE and ED for substantial increase of throughput. using the ED method. Recently. In developing this process. boiling point. is the purification of styrene from the close-boiling C 8 aromatic isomers. The original extractive stripper column is converted into a solvent-recovery column operating in parallel with the existing solvent-recovery column.226 Extractive Distillation FIG. solubility. due to the double bond in the side chain of the styrene molecule. such as thermal stability. consequently.

Extractive Distillation TABLE 9 Composition of Feed and Products of the ED Pilot Plant for Styrene Recovery Component Dicyclopentadiene Benzene Toluene Vinylnorbornenes Ethyl Benzene p-Xylene m-Xylene Cumene o-Xylene Styrene Allylbenzene Nonaromatics 2. were properly adjusted to yield styrene with 99.45 395 ppm 4. such as S/F. The bottom product (the rich solvent) was routed to the solvent stripper column. The main benefits for recovering styrene from pyrolysis gasoline generated from a naphtha cracking complex are as follows: .11 23 ppm 1 ppm 1 ppm 98.31 269 ppm 9.4 m from the column bottom.03 2. and the kettle temperature.37 Bottom (wt%) 1 ppm 1 ppm 1 ppm 1 ppm 1 ppm 1 ppm 1 ppm 1 ppm 1 ppm 1. The column was operated under reduced pressure to minimize the column operating temperature. In this operation. and a proprietary inhibitor was added in trace amounts to the feed to prevent styrene polymerization in the column. 12. The separation strategy for recovering styrene from pyrolysis gasoline is to remove the majority of the light and heavy components in pyrolysis gasoline by conventional distillation and to use ED to remove the remaining close-boiling components. The pilot-plant tests were conducted in a 7.80 431 ppm 5. and to decrease the solvent circulation by 20%.30 8. the reflux ratio.81 3. A schematic diagram of the pilot plant can be represented by Fig. a cosolvent was used as the key to improve the styrene purity from 95 to 99. where styrene was distilled overhead.88 227 key process variables to support the computer process simulation for scale-up and commercial design.52 23. which includes styrene recovery by ED.9 wt%.97 7.72 195 ppm 0.22 35.26 0.68 4. The key variables.79 10.08 172 ppm 0 Overhead (wt%) 0.82 390 ppm 9.3 m of knitted wire-mesh packing (Goodloe Style #773).73 12.47 3.3 m from the column bottom and the lean solvent was introduced at a location 6.5-Dimethylthiophene Solvent Feed (wt%) 0. to reduce the column temperature by 35°C. Figure 17 shows a possible scheme for processing pyrolysis gasoline. The composition of the column overhead and the bottom products are also given in Table 9.6-cm-diameter ED column packed with 7.25 13.9 wt% purity (on a solvent-free basis) in the column bottoms.23 43. and the lean solvent exited from the bottom of the column for recycle to the ED column. The C 8 cut of pyrolysis gasoline with the composition shown in Table 9 was fed at a location 4.40 0.

The potential debottleneck of the hydrotreating area can be avoided. 4. The economics of styrene recovery from pyrolysis gasoline depend to a great extent on the quantity of styrene available in this stream.000 metric tons per year of styrene in pyrolysis gasoline would be the candidate for this technology. The catalyst fouling and operating costs in the selective hydrotreater are reduced. it is impossible to recover high-purity cyclohexane from these streams by conventional distillation. 5. Table 10 shows that the economics for styrene recovery with a pretax return on investment (ROI) of 41% can be achieved. The xylenes can be upgraded from motor fuel value to the feedstock value to xylene isomer unit. The styrene component is upgraded from motor fuel value to petrochemical value. based on a 25.000 to 15. because of the close-boiling C 7 iso-paraffins in the streams. 1. 3. As shown in Table 11. The overall hydrogen consumption to convert styrene to ethylbenzene is reduced. Units produce at 10. 17 Schematic diagram for pyrolysis gasoline processing including styrene recovery. Because . it otherwise would be required for naphtha cracking expansion. Cyclohexane Recovery from Natural Gas Liquid or Naphtha Cyclohexane exists naturally in naphtha and natural gas liquid (NGL) streams and is an important raw material for the nylon industry.000-metric tons per year plant capacity.228 Extractive Distillation FIG. 2.

8 1.0 0. Because no effective single ED solvent has been found.4-Dimethylpentane 3.0 0. In fact.9 1.3-Dimethylpentane 2. Values on styrene product. Meanwhile.3 million per year 41% 229 Typical U.3-Trimethylbutane Dimethylcyclopentane n-Heptane .6 1. 18.1 1.3 wt% over the same composition range of the MIST solvent.4 86.3 Component Cyclohexane 2.7 79. a mixed solvent was developed commercially to recover high-purity cyclohexane directly from an NGL fraction containing 85% cyclohexane [18]. which has an average composition shown in Table 11.2-Dimethylpentane 2.1 0. The higher 2.6 98.1 0.3 4. The overall cyclohexane recovery changed from 100 to 56 wt% as the cosolvent concentration decreased from 30 to 10 wt% under a constant kettle temperature of the ED column.3-Dimethylpentane 2-Methylhexane 3-Methylhexane 2. At an 80% cyclohexane recovery.4-dimethylpentane in the raffinate stream (ED column overhead) increased from 87 to 96.7 89.1 Boiling point (°C) 80. processing cost. the cosolvent in MIST solvent played a major role in the success of this process [18]. the higher cyclohexane purity in the extract (product) stream. cyclohexane and the close-boiling components in the feed mixture have only a very small difference in polarity and are relatively insoluble in the selective solvents. the recovery of 2. Table 12 summarizes the results for 80% and 90% cyclohexane recoveries at various cosolvent concentrations.4-dimethylpentane in the raffinate stream. MIST solvent TABLE 11 Average Composition and Boiling Point of the Feedstock for Pilot-Plant Testing Weight% 89. As demonstrated in Fig.1 80.8 90.000 metric tons per year styrene capacity from a world-scale naphtha cracker. and capital investment were calculated based on the 1997 published information. Gulf Coast capital cost Styrene value in pyrolysis gasoline Styrene product sales value Processing cost Gross margin Pretax return on investment Note: Basis: 25. it also takes a very difficult ED process to do the separation.9 91.0 89. The proprietary mixed solvent (the MIST solvent) was developed through extensive test in the laboratory and the evaluation in a 150-mm-diameter ED pilot plant using a refinery NGL stream. feedstock.9 80.S.2.Extractive Distillation TABLE 10 Economics for Styrene Recovery from Pyrolysis Gasoline $ 20 million $ 180 per metric ton $ 550 per metric ton $ 40 per metric ton $ 8.

1 99.1 99. constructed and started up in 1991. At 90% cyclohexane recovery. MIST solvent having 25% cosolvent had similar performance to that with 10% cosolvent.0 Cosolvent (wt%) 25 20 10 30 25 10 25 10 . 18 Effect of cosolvent in MIST solvent on product purity and recovery.1 2. Finally.230 Extractive Distillation FIG.0 87.0 90.2 99.2 90.4Dimethylpentane Recovery (wt%) 89.9 99.8 92. Based on the successful pilot-plant testing on the MIST solvent.0 93.8 80.0 99.2 99. TABLE 12 Effect of Cosolvent Concentration on Cyclohexane Recovery and Purity Cyclohexane Recovery (wt%) 80 80 80 90 90 90 94 94 Cyclohexane Purity (wt%) 98.3 86. the MIST solvent with 25% cosolvent showed better performance than the one with 10% cosolvent. a commercial plant for purifying 100 metric tons per day cyclohexane was designed.2 99. containing 10% cosolvent appears to give the greatest cyclohexane purity.

6.(2). 15. K. Cannon Instrument Co. 83 (May 1991). Colburn and E. ‘‘Morphlane: Operational Experience and Results Obtained with New Plants. 11. 18. J. These can generally be grouped into six types: . C. 3. 16. and Applications of Polyolefins Produced by Single-Site Catalyst Technology Introduction Polyethylene is composed of only carbon and hydrogen (with some exceptions).. D. 617 (1952). G. M. 2. 34. Hydrocarbon Process.’’ AIChE Annual Meeting. ‘‘Two Liquid Phases in Extractive Distillation for Aromatic Recovery. p. Properties. 1992. (March 1998). ‘‘Effect of Packing on Distillation Columns with High Liquid to Vapor Ratios. Prog. F. Prog. Gentry. C. Prog. WA. T. 43. AIChE. B. G. Lee. Gentry and C. Kumar. Kruelskie. Chem. FU-MING LEE Structure. 69. M Lee.’’ AIChE Spring National Meeting. 62 (1998). Patent 3. McGraw-Hill. Cannon Instrument Co. Fair. ‘‘New Extractive Distillation Process for Aromatics Recovery. 7. S. C. C. AIChE J. 1995. 5. 553 (1949).Polyolefins Produced by Single-Site Catalyst 231 References 1. 47. which can be combined in number of various ways to make many different polyethylenes. A. Lee and J. p. Gentry and F. Department for Thermal Separation Processes. Boyer. 17. 1989. PA. 555 (1951). Distillation. J. M. 1989. P. et al. J. B.’’ NPRA Spring Meeting.. 8. Hydrocarbon Process. Herron. Hackmuth. 13. E. R. 43 (1991). M. Eng. E. 3(6). R... Lee. 41.783 (1963). TX. p. 12.’’ AIChE Summer National Meeting. Schoenborn. 45. Prog. R.’’ Bulletin 23. 1267 (1988). Kurtz. New York. Lee. Chem. R. and J. Chem. A. Hydrocarbon Eng. ‘‘Packed Column Analysis and Design. 14. 1995. 10. M. 1992. S. Brown and F. M. K. Butler and J. Eng. M. Emmrich. 48. U. 464. Eng. P. R. FL. Bichard. Van Winkle. Houston. A. Billet. Billet. M. State College.114. Miami Beach. Eng. R. Ruhr-University Bochum..(8).. Seattle. San Francisco. 1967.’’ Ruhr-University Bochum. 42 (1945). 4. C. M. 87. ‘‘Pro-Pak Protruded Metal Distillation Packing.. M. Jr. Brown and F.. Trans. Chambers. 9..’’ Department for Thermal Separation Processes.. H. ‘‘Packed Column Analysis and Design. Chem. Todd and F. 11. Atkins and C.

large parts such as storage tanks made by rotational molding process. crystallinities..232 Polyolefins Produced by Single-Site Catalyst • • • • • • LDPE. EPDM (NORDEL IP from DuPont Dow Elastomers. . and melting point available within each major type of polyethylene. VLDPE) Single-site polyethylenes (e. The total polyethylene consumption is expected to exceed 100 billion pounds by the year 2000. substantially linear homogeneous polyethylene) Polyethylene technology encompasses a range of crystallinity and melting points. and so forth.. slurry LLDPE (mPACT from Phillips Petroleum Company). Specialty ethylene copolymers such as acid copolymers and ionomers are not included. and melting points available within each major type of polyethylene. Several families of MTC.. Figure 1 illustrates the approximate range of densities. fibers. low-density polyethylene EVA. EXACT from Exxon Chemical Company). The use of these catalyst technologies has allowed a very rapid development of olefin copolymers with a wide range of structures and related properties. polyolefin plastomers (e. The most recent advance in polyethylene technology is the development and commercialization of polyethylenes produced by single-site-catalyst technology.g. wire and cable coatings. ultralow-density polyethylene (also known as Very low-density polyethylene. crystallinity. high-density polyethylene LLDPE. ethylene vinyl acetate copolymers HDPE. injection-molded and blowmolded parts. AFFINITY from The Dow Chemical Company. 1 The approximate range of density.and SSCtechnology-based polyolefin copolymers have been commercialized in the 1990s. and FIG. Two major classes of single-site catalyst (SSC) technology developed for the polymerization of ethylene and α-olefins are the metallocene catalyst (MTC) and the constrained-geometry catalyst (CGC) systems. enhanced polyethylene (ELITE from The Dow Chemical Company). ENGAGE from DuPont Dow Elastomers. This technology has initiated a major revolution for the polyolefin industry [1–4]. These include polyolefin elastomers (e. foams.g. LLC). extrusion coatings. LLC).g. gas-phase LLDPE (EXCEED from Exxon Chemical Company). Applications include films. linear low-density polyethylene ULDPE. adhesives.

properties.. The polymerization kinetics and the resulting polymer and copolymer structures can be modeled. under the trademark of INSITE by The Dow Chemical Company). Hence. 2. several other single-site-catalyst-related technologies that allow the copolymerization of α-olefins with polar comonomers are also under industrial and academic development [5.6]. they are called homogeneous copolymers and they behave much more like ideal polymers. 1-butene. These two catalyst systems are illustrated in Fig. rheology. The Zr in the Zr-based MTC used by many polymer producers has an FIG. This article will focus on the solid-state structure. 1-hexene. ethylene–α-olefin copolymers produced by SSC technologies have narrow composition distributions (narrow molecular-weight and comonomer distributions). This capability allows the polymer and material scientists to design new polymers using a molecular architecture approach and to develop new products with exceptional speed. 2 Structure of the Bis-Cp metallocene catalyst and the constrained geometry catalyst. This significantly advances the fundamental understanding of the structure–property relationships.Polyolefins Produced by Single-Site Catalyst 233 polypropylenes (ACHIEVE from Exxon Chemical Company). constrained-geometry mono-cyclopentadienyl single-site catalyst (known as constrained-geometry catalyst. . CGC. In addition to these commercial activities. Unlike conventional linear low-density polyethylenes (LLDPE) made by copolymerization of ethylene and α-olefins with Ziegler–Natta (Z-N) catalysts.g. 1-octene) using SSC technology. Preparation of Ethylene–α-Olefin Copolymers by SSC Technology Two major families of high-efficiency SSC are commercially used for the preparation of polyethylene copolymers. The major advantage of singlesite catalysts is its versatility in building well-defined molecular structures. These are a bis-cyclopentadienyl (Bis-Cp) single-site metallocene catalyst (also known as a Kaminsky catalyst) and a halfsandwich. and typical applications of homogeneous polyolefin copolymers made by copolymerization of ethylene and α-olefins (e.

Typical process conditions for making polyolefin copolymers in these processes are as follows: 1. Slurry Process: In the slurry process. The polymerization temperature usually exceeds 100°C. and slurry polymerization processes. Figure 3 compares gel permeation chromatography (GPC) traces of a conventional. Gas-Phase Process: In the gas-phase process. is the ratio Mw /Mn. 4. Solution Process: Stirred reactors are usually used for the polymerization of ethylene and ethylene–α-olefin copolymers in a solution phase. polymers are made in stirred or loop reactors with an organic liquid carrier (C 4 –C6 hydrocarbons). stirred autoclave and a tube reactor. The polymer powder is then converted into pellet form by an extrusion process. High-Pressure Process: Two types of commercial reactor. Products made in this process are in powder form and are converted into pellets using extrusion processes. The reactor pressure is usually set at 300 psi and the polymerization process is generally carried out at 90°C. 2. heterogeneous ethylene–octene copolymer versus a homogeneous copolymer.’’ On the other hand. Molecular Structure of Polyethylene Copolymers Made by Single-Site-Catalyst Technology Molecular-Weight Distribution Ethylene–α-olefin copolymers prepared by single-site-catalyst technologies exhibit a narrow molecular-weight distribution (MWD). or polydispersity. solution. are used for the polymerization of ethylene and ethylene– α-olefin copolymers at high pressure. Single-site-catalyst technology polyolefin copolymers can be produced by high pressure. the narrow MWD of a linear homogeneous co- . where Mw is the weight-average molecular weight and Mn is the number-average molecular weight.234 Polyolefins Produced by Single-Site Catalyst oxidation state of 4 and the Ti in the Ti-based CGC system has an oxidation state of 2. Ethylene and an α-olefin comonomer are usually compressed to at least 10. ethylene and α-olefin comonomers (1-butene and/or 1-hexene) are polymerized in the solid state in a fluidized-bed reactor into a powder form. In most cases. whereas the MWD of homogeneous polyolefins made by SSC technology is usually less than 2. Polymers with a narrow MWD in general have increased toughness and less ‘‘solvent extractables. C6 –C8 hydrocarbons are used as the solvent. Copolymers prepared by a conventional Zeigler–Natta catalyst have a MWD usually larger than 3. The polymerization process temperature is generally carried out at 90°C at a reactor pressure of 300 psi. MWD. 3. The reactors are operated under about 500 psi pressure and the polymerization is carried out at 60°C.5.000 psi when fed into the reactor. gas-phase.

etc. it is critical to understand and to measure the comonomer distribution . polymer also results in poor melt processability (low melt strength. Comonomer Distribution Because of the significant effect of the α-olefin comonomer on the properties of the polymer. thermal. is illustrated in Fig. and mechanical properties. 4. high extruder back-pressure. especially at lower densities.Polyolefins Produced by Single-Site Catalyst 235 FIG. made using a CGC catalyst. the crystallinity is measured and specified using density. 3 GPC MWD comparison of two ethylene–octene copolymers having a 0. Higher mole% butene is required to achieve the same density compared to octene.000 g/cm3.853 g/cm3 and 1. ρc ρ ρ ρc ρa ρa (1) The effect of comonomer content on the density of homogeneous ethylene–octene and ethylene–butene copolymers. Weight percent crystallinity can be obtained from the measured density (ρ) as follows: Wt% cryst. respectively. Crystallinity The comonomer content in the copolymer has a profound effect on the properties of the polymer. including crystallinity. The density of the amorphous phase (ρa) and crystalline phase (ρc) of ethylene–α-olefin copolymers at room temperature is about 0. The comonomer content was measured using nuclear magnetic resonance (NMR). high-energy consumption during extrusion.920-g/cm3 density.). In the case of ethylene–α-olefin copolymers.

among the polymer molecules (intermolecular distribution) and along the backbone (intramolecular distribution). this does not mean that the intramolecular comonomer distribution is uniform. The narrow intermolecular comonomer distribution for the homogeneous polymer arises from the single-site nature of the MTC and CGC. which is a mixture of polymer molecules having different levels of an α-olefin comonomer incorporated in the polymer backbone.g. however. although the intermolecular comonomer distribution for the homogeneous polymer is very narrow. structural characteristics for .236 Polyolefins Produced by Single-Site Catalyst FIG. The narrow TREF curve for the homogeneous copolymer signifies that the number of comonomer units per unit chain length between the copolymer molecules is very similar. the intermolecular comonomer distribution for a homogeneous ethylene–octene copolymer prepared by the CGC technology is much narrower than that of a conventional LLDPE. 4 Densities of homogeneous ethylene–octene and ethylene–butene copolymers as a function of mole% comonomer. is dictated by the reactivity ratio of the monomer and the comonomer. a heated solution of the polymer is placed in a column. and slowly cooled to room temperature. 5.). The temperature is then increased while solvent flows through the column to a detector that records the amount of polymer in the solvent at any given temperature. To address the issue of the effect of the intramolecular comonomer distribution on polymer properties of a homogeneous polymer.. However. Intermolecular comonomer distributions can be measured by the temperature rising elution fractionation (TREF) technique [7]. thermal properties. optics. Intramolecular comonomer distribution in homogeneous copolymers made by SSC technology can also have an effect on the solid-state structure and properties of the polymer (e. etc. As illustrated in Fig. In this procedure. The uniformity of the intramolecular comonomer distribution. packed with very small stainless-steel shot.

10. 5 Intermolecular comonomer distribution of ethylene–octene copolymers measured by TREF. in terms of ethylene block-length distribution between the short branches that are formed from the α-olefin comonomers.92 g/cm3). This is due to the fact that the lower-density FIG. Figure 6 illustrates the intramolecular comonomer distribution for three CGC copolymers. 6 Model prediction for intramolecular comonomer distribution of three CGC ethylene–octene copolymers: ethylene block-length distribution.Polyolefins Produced by Single-Site Catalyst 237 FIG.92 g/cm3 density. (From Ref. in terms of ethylene block length between the hexyl branches within a polymer molecule. As illustrated in Fig. is much broader than that of the lower-density copolymers. . the intramolecular comonomer distribution for the higher-density polymer (0. from 0.) CGC ethylene–octene copolymers were modeled using the Monte Carlo simulation [8].87 g/cm3 to 0. 6.

homogeneous copolymers made by MTC. or trans as shown in Fig. A few of the most significant features for the CGC-technology polymer are its melt fracture resistance and the control of shear-thinning behavior. (EXACT is a trademark of Exxon Chemical Company. Long-Chain Branching Homogeneous ethylene homopolymers and ethylene–α-olefin copolymers first made by CGC technology have one more unique molecular structural feature not found in the original MTC technology polymers. as illustrated in Figs. I2 is the melt index (MI) of the polymer (flow rate in grams per 10 min at 2. Homopolymers and copolymers made by the CGC technology at certain process conditions contain a controlled amount of long-chain branching. Thermal termination is one of the most effective ways to control molecular weight during the polymerization process. vinylidene. Depending on the last monomer or comonomer insertion.) . polymeric molecules with a vinyl chain end are formed due to a ‘‘β-hydride elimination’’ mechanism that is taking place in the thermal termination step (Fig.10].238 Polyolefins Produced by Single-Site Catalyst copolymers have more comonomer units along the polymer backbone. 9 and 10 respectively. and the distribution is also narrower. A polymer with LCBs made by the CGC technology has many unique rheological properties [9.16 kg weight. AFFINITY is a trademark of The Dow Chemical Company. In the thermal termination process. the unsaturation could be vinyl. The polymer with a vinyl chain end becomes one of the reactants (in addition to ethylene and α-olefin) that reacts with the catalyst site and forms long-chain branching. 7 Molecular structure comparison of three different ethylene–α-olefin copolymers. 10. This unique molecular structural feature is long-chain branching (LCB). 8). and substantially linear homogeneous copolymers made by CGC) are schematically illustrated in Fig. 7. To summarize this. 8. This results in a shorter ethylene block length between the short branches. These polymers are referred to as substantially linear homogeneous polyethylenes. One possible mechanism of LCB formation via CGC technology is as follows. at 190°C) and FIG. the molecular structure of three ethylene–α-olefin copolymers (conventional LLDPE made by a Z-N catalyst. In Fig.

Polyolefins Produced by Single-Site Catalyst


FIG. 8 Reactor sources of unsaturation in polyethylene during polymerization of ethylene and αolefin comonomers. (From Ref. 10.)

I10 is the flow rate in grams per 10 min at 10 kg weight, at 190°C. The I10 /I2 ratio is a measure of shear-thinning behavior of the polymer melt.

Solid-State Structure and Morphology of SSC-Technology Ethylene Homopolymers and Ethylene–α-Olefin Copolymers
The ethylene homopolymer and ethylene–α-olefin copolymers are semicrystalline polymers. Three major factors that affect the crystal morphology and crystallinity of ethylene polymers in the solid state are (1) the amount and size of α-olefin in the polymer, (2) the molecular weight of the polymer, and (3) the crystallization

FIG. 9 Extrudates of CGC polymer and LLDPE at 3.66 trademark of Ciba-Geigy Corporation.)

106 dyn/cm2 shear stress. (Irgafos is a


Polyolefins Produced by Single-Site Catalyst

FIG. 10 Rheology of CGC polymers measured at 190°C: effect of LCB on shear-thinning behavior of three 1 MI polymers with various amount of LCB. LCB/10,000°C was estimated using a kinetic model.

conditions (crystallization temperature at isothermal condition and/or cooling rate at nonisothermal crystallization conditions) [11]. A recent review article on polymer crystals was written by Phillips [12]. The most generally accepted crystal morphology for ethylene polymers is lamellae formed from a folded-chain conformation [13–15]. For very low-density SSC-technology ethylene–α-olefin copolymers (which contain a high percentage of comonomer), the crystal morphology can be very different from the conventional lamella model. For example, let us consider the morphological model of a 60/40 wt% ethylene–octene copolymer made by CGC technology. At this level of comonomer content, the polymer exhibits about 10% crystallinity, as measured by differential scanning calorimetry (DSC) and a density of approximately 0.87 g/cm3. The intramolecular comonomer sequence distribution of the hexyl branches from the octene comonomer, calculated from the reactive-ratio kinetic model (Fig. 6), illustrates that more than 90% of the octene units are less than 50 ethylene units apart. The regular ethylene block length between the octene units is, therefore, much less than the minimum length to form one ˚ folded unit to form the thinnest possible lamella (which is about 30 A thick). For a chain with this molecular structure, it is expected that the polymer has to crystallize in a crystalline form different from the conventional folded-chain lamella model. Figure 11 is a transmission electron micrograph of the crystal morphology of a higher-density (0.920 g/cm3) ethylene–octene copolymer made by CGC technology. At this density and octene level, the copolymer clearly shows a lamellar morphology. Figure 12 is a transmission electron micrograph of a very low-density ethylene–octene copolymer (0.87 g/cm3). It clearly shows that the major crystalline structure of this very low-density, low-crystallinity copolymer is ‘‘spotlike’’ fringed micelle crystals. Polymers having higher crystallinities with the lamella-

Polyolefins Produced by Single-Site Catalyst


FIG. 11 Transmission electron micrograph of a 0.920-g/cm3 ethylene–octene copolymer made by CGC technology.

FIG. 12

Transmission electron micrograph of a 0.87-g/cm3 ethylene–octene copolymer made by CGC technology.


Polyolefins Produced by Single-Site Catalyst

FIG. 13 Classification of SSC ethylene–α-olefin copolymer based on crystal morphology. (From Ref. 16.)

type crystal morphology are expected to have higher moduli and undergo yielding when deformed. Polymers having low crystallinities with the fringed micelle crystals, however, are expected to be more like elastomers and do not have well-defined yielding behavior. With these two different types of crystal structure, the SSCtechnology homogeneous ethylene–α-olefin copolymers can, therefore, be classified into four major domains [16], as illustrated in Fig. 13.

Thermal and Dynamic Mechanical Properties
Melting Behavior of SSC Polymers Differential scanning calorimetry is one of the most popular methods for studying the thermal properties (melting and crystallization) of semicrystalline polymers. Structural information can be uncovered by a careful interpretation of DSC thermograms generated at different conditions. Due to the narrow intermolecular comonomer distribution, SSC copolymers usually have a much narrower melting peak than their heterogeneous counterparts produced by multiple-site Z-N catalysts. Figure 14 shows the DSC melting curve of two ethylene–octene copolymers, both at similar density: one made by a conventional multiple-site Z-N catalyst and one by SSC technology. The heterogeneous LLDPE copolymer always has a peak melting point at around 120–130°C over a broad density range ( 0.89–0.95 g/cm3). This is because the conventional heterogeneous LLDPE copolymer is a reactor blend of molecules ranging from the un-

Polyolefins Produced by Single-Site Catalyst


FIG. 14

DSC melting curve of SSC and LLDPE ethylene–octene copolymers at about 0.903 g/cm3 density. Samples were cooled and heated at 10°C/min.

crystallizable and poorly crystallizable type to the HDPE type containing only of α-olefin [17]. These HDPE-type linear chains can, therefore, crystallize to a rather large size crystal that has a melting point in that temperature range. The shape of the melting peaks of all the homogenous copolymers still represents a single peak or a single peak with a shoulder, very different from that of the heterogeneous LLDPEs, as illustrated in Fig. 15. The peak melting point of the homogeneous copolymer, however, drops accordingly as the density/crystallinity of the polymer is lowered, as seen in Fig. 15. This characteristic has a very significant commercial value for heat-seal and oriented-shrink-film food-packaging applications. A plot of the melting points of LLDPE/VLDPE, LDPE, SSC ethylene–octene, and EVA resins as a function of density is shown in Fig. 16. All the samples were cooled and heated at 10°C/min using a Perkin-Elmer DSC-7. LDPE resins have slightly lower melting peak temperature compared to SSC ethylene–octene copolymers made using CGC technology at a given density. The density of EVA resins increases as the vinyl acetate content increases, even though the degree of crystallinity decreases. This is due to the bulky nature of the vinyl acetate group increasing the amorphous phase density. Hence, the density of EVA resins cannot be compared with the density of ethylene–α-olefin copolymer resins. A plot of melting points of LDPE, LLDPE/VLDPE, and SSC ethylene–octene and EVA resins as a function of resin crystallinity is shown in Fig. 17. Prior to 1990, EVAs were the only cost-effective polyethylenes widely available for packaging applications requiring low-temperature sealing, low-temperature shrinkage, and toughness properties. This is due to their lower crystallinity (typically less than about 40%) and lower melting point (typically less than about 100°C). Beginning in

Samples were cooled and heated at 10°C/min. and EVA resins versus polymer density. 15 DSC melting curve of SSC and LLDPE ethylene–octene copolymers at various densities. . LDPE. FIG. 16 Peak melting temperatures of heterogeneous and homogeneous ethylene–octene copolymers.244 Polyolefins Produced by Single-Site Catalyst FIG.

992 by Elston of DuPont. 18. Patent 3. Hence. early 1990. and EVA resins versus polymer crystallinity by DSC. The DSC melting curve of a polyolefin elastomer (POE) at 0. When plotted against resin crystallinity. polyolefin plastomers (POPs) and polyolefin elastomers (POEs).16. 17 Peak melting temperatures of heterogeneous and homogeneous ethylene–octene copolymers. the longer ethylene runs may form a larger lamella crystal with a higher melting point and the shorter one may form a small lamella crystal or even a fringe micelle crystal with a lower melting temperature. homogeneous ethylene–α-olefin copolymers.Polyolefins Produced by Single-Site Catalyst 245 FIG.87 g/cm3 density and one melt index is shown in Fig. For example. Two applications of SSC resins. Canada [19]. The broad melting range of the POE can be attributed primarily to the intramolecular comonomer distribution. LDPE. SSC resins can potentially be used in various film applications where EVAs are being used. the melting points of EVA resins lie very close to the curve for the SSC ethylene–octene resins (Fig.S. have been performed by many different institutes [11. made using a single-site catalyst. Many detailed studies of the thermal properties of SSC technology. The melting begins at temperatures as low as about 40°C. A substantial amount of crystallinity is molten by room temperature. 17). The glass transition temperature of the POE resin was about 54°C.645. sealants. .18]. and oriented shrink films where EVAs have been traditionally used will be discussed in detail later. The POE exhibited a very broad single melting peak with a shoulder and a peak melting temperature of 59°C. The first publication showing the effect of increasing comonomer content on the melting points of homogeneous copolymers was U. have become available over a wide range of crystallinity and melting points.

Dynamic Mechanical Properties Dynamic mechanical properties of the homogeneous copolymers as a function of density are illustrated in Figs. below the β-transition temperature. In some literature the γ peak was designated as the true glass transition temperature (Tg) of polyethylene. as shown in Fig. and for the 0. For example.87-g/cm3 elastomer is about 54°C. The β-transition peak for the polyolefin elastomer (0. For example. made using CGC technology. 18 DSC melting curve of ethylene–octene polyolefin elastomer at 0. The mechanical properties and deformation behavior of these homogeneous polymers will be discussed further in the next section. The storage modulus decreases sharply near the melting point. The storage modulus decreases with increasing temperature due to a decrease in crystallinity. 19 and 20. The 0. also at around 20°C. Therefore.87-g/cm3 elastomer. the glass transition temperature measured using DSC matches well with that of the β-transition temperature. The β-transition temperature of the 0. The β-transition temperature would be higher than the DSC Tg due to the high frequency (10 rad/s) used in the measurement. most polyethylene users usually report the β-transition temperature as the practical glass transition temperature. The γ-transition peak of all four copolymers and the homopolymer appear at about 120°C in the plot of tan δ versus temperature.87 g/cm3. it is about 20°C. the DSC Tg of the 0. Also. for the polyolefin plastomer (0. 18.246 Polyolefins Produced by Single-Site Catalyst FIG.920-g/cm3 copolymer.954-g/cm3 polymer has a broad β peak. the β-transition temperature can be related to the low-temperature performance of ethylene-based polymers and copolymers.87-g/cm3 elastomer is about 40°C. the α-transition is almost merged with the β-transition. For higher-density SSC polyethylene. In most cases. it is about 25°C. distinct α-transitions can also observed. . For the 0.898 g/cm3).870 g/cm3) appears at about 40°C. the polymer usually becomes brittle.

20 Tan δ of homogeneous ethylene–octene copolymers and a homopolymer as a function of temperature at 10 rad/s. . 19 Storage modulus of homogeneous ethylene–octene copolymers and a homopolymer as a function of temperature at 10 rad/s.Polyolefins Produced by Single-Site Catalyst 247 FIG. FIG.

the moduli were low and the deformation was essentially uniform (homogeneous) and elastomeric. At high densities.902. The yield region of copolymers is also enlarged in Fig. 22. 21 Engineering stress–strain properties of homogeneous ethylene–octene copolymers and a homopolymer. significant strain hardening was observed. The effect of increasing comonomer content on the tensile deformation behavior and the correlation between the structural classification and the large-scale deformation behavior have been studied and discussed in detail in many publications [16. For copolymers having medium densities (0. the deformation had characteristics common to many semicrystalline thermoplastics with localized yielding and cold drawing [16]. These polymers exhibited deformation behavior ranging from necking at room temperature (density greater than about 0. therefore.248 Polyolefins Produced by Single-Site Catalyst Deformation Behavior and Mechanical Properties of Homogeneous Ethylene– -Olefin Copolymers Made with SSC Technology Tensile Properties The stress–strain curves of homogeneous ethylene–octene copolymers and a homopolymer. 16. and 0. (From Ref. 21. The polymers were heated well above the melting point and cooled at 1°C/min.20–24] and. are shown in Fig. 21. measured at a strain rate of 0. will not be further discussed in this article. as evident by the broad spectrum of tensile properties. The density (crystallinity) of polymer profoundly affected the response to deformation.) .885 g/cm3). Differences in yield behavior of the four homogeneous polyethylenes at different densities are shown in the photographs in Fig. FIG.910 g/cm3). made using CGC technology. For copolymers having low densities (less than 0. 0. These photographs were taken at 150% engineering strain.918 g/cm3).91.04 s 1.910 g/ cm3) to uniform deformation (density less than about 0.

crystallite size distribution. 23. 16. it should be noted that it is very difficult to produce any ethylene copolymer having a density below about 0. and several conventional LLDPEs made by a Z-N catalyst over a range of polymer densities and comonomer content were measured for comparison purposes [25]. The slope of the stress–strain curve at very low strain (less than or equal to 2% strain) is measured as the modulus of the polymer.885 g/cm3 using Z-N catalysts.) Modulus and yield strength are important properties for ethylene homopolymers and copolymers for many commercial applications. Secant modulus at 1% or 2% strain and Young’s modulus are the ones most commonly used. the Young’s modulus of these polymers is simply a function of the polymer density. data for Z-N heterogeneous . There is also a direct relationship between initial modulus and crystallite size. which is related to a difference in crystallite size. The moduli of a series of homogeneous ethylene–octene copolymers made by CGC technology. injection molded containers. Therefore. These samples were prepared by compression molding at similar heating and cooling conditions to impart the same heat history on each of the samples. It seems that if the polymer samples are prepared under similarly controlled conditions. It has been shown [24] that two polyethylenes of the same degree of crystallinity can have very different moduli (up to 100% difference). The data are summarized in Fig. taken at 150% engineering strain. such as packaging film. it is generally true that the initial modulus increases with density (crystallinity) of the polymer.Polyolefins Produced by Single-Site Catalyst 249 FIG. For example. which results in orientation. several homogeneous ethylene–butene copolymers made by MTC technology. and so forth. However. and fabrication conditions. 22 Photographs of profiles of deformation behavior of Type I to IV homogeneous ethylene– octene copolymers. Even with this complexity. Moduli of the polyethylenes in the solid state are strongly controlled by polymer crystallinity. there are some ‘‘rules of thumb’’ which can be applied to the modulus. (From Ref.

Elastic Properties of Polyolefin Elastomers Polyolefin elastomers (POEs). 24. LLDPE at below 0. The elastic recovery (permanent set) of various polyethylenes is illustrated in Fig. The load/unload property under a tensile deformation mode for a representative octene-based POE (ENGAGE EG-8100. The small fringed micelle crystals dispersed in the soft. no matter how low the density is. amorphous matrix act as tie-points to anchor the amorphous chains during deformation and. may have a higher modulus than the homogeneous copolymer at similar densities. The sample was pulled . which may result in higher modulus than the homogeneous polymer at equivalent density. the very low-density heterogeneous polymer made by Z-N catalysts. The slow-cooled (15°C/min) 30-mil-thick compression-molded samples were pulled to desired elongation at 10 in. The sample was held at the desired elongation for 30 s. if one can make it. POEs are now commercially available from DuPont Dow Elastomers. 1 MI) is illustrated in Fig. The crosshead was brought back to the initial grip separation at 10 in. will always have some polymer chains that have a very low level of comonomer incorporated./min and held for 1 min.250 Polyolefins Produced by Single-Site Catalyst FIG. 23 Young’s modulus versus density of ethylene copolymers determined on compression-molded plaques. have a fringed micelle crystal morphology and exhibit a very different deformation behavior as compared to the higher-density copolymers having lamella crystal structures. 25.885 g/cm3 are not available for comparison purposes. Based on common knowledge of semicrystalline polymers. This is because the heterogeneous polymer. 0.870 g/cm3. result in an elastic recovery upon release of stress. These polymer chains will crystallize to form larger-sized crystals. therefore.)./min (gauge length 2 in. LLC (ENGAGE). very low-density (crystallinity) homogeneous ethylene–α-olefin copolymers.

24 Load/unload behavior of a representative octene-based polyolefin elastomer (ENGAGE EG8100. test was run at room temperature. the unrecovered strain became much higher beyond the 100% strain. specimens were compression molded and cooled at 15°C/min. The permanent set of homogeneous polyethylenes increased with increasing density.870 g/cm3. 2. Strain rate. 1 MI). 25 Permanent set of various polyethylenes as a function of elongation./min until the load rises above zero. 0. again at 10 in. . the percent set is low (less than about 20%) at elongations less than 100%.25 min 1. FIG.Polyolefins Produced by Single-Site Catalyst 251 FIG. At densities below 0. However.885 g/cm3. Percent permanent set is the percent elongation at which the load rises above zero.

The probability of tie-chain formation alone does not reflect the actual tie-chain concentration in semicrystalline poly- . The relative tie-molecule concentration has also been estimated from chain dimensions and the semicrystalline morphology (topology) of the polymers [28–33]. Unlike the heterogeneous ethylene copolymer made by conventional Z-N catalyst technology. In the past. A main cause for rejection of a polyethylene chain from a crystal is the presence of imperfections along the chain backbone. Beyond 100% strain. foams. and so forth are also controlled by the amorphous region. thus. which resulted in permanent deformation. 26. tear. The effect of density (crystallinity) on relative tie-chain formation probability and concentration is modeled [35] and the results are illustrated in Fig. New applications for this class of elastic materials were developed commercially for wire and cable insulation. Although crystalline domains control low-strain properties of semicrystalline polymers such as modulus and yield stress. which are usually branch points formed by the α-olefin comonomer.g. This will result in a polymer with very low mechanical strength. and chlorination of films [26].252 Polyolefins Produced by Single-Site Catalyst This phenomenon can hypothetically be explained by a slip-link theory in which the fringed micelle crystals are treated as slippage links. development of appropriate structure–property relationships in semicrystalline polymers has been perceived to be hindered by the inability to analytically measure relative tie-chain concentration.. A schematic diagram of the tie-molecule structure in an ethylene–α-olefin semicrystalline copolymer with a lamellar morphology is illustrated in Fig. shoe soles. particularly by tie-molecules. the amorphous chains that bridge adjacent lamellae [26– 33]. 27. elastic fiber and films. Without these branch points (e. Tie-Molecules in Ethylene– -Olefin Copolymers Made by SSC Technology Consideration of the crystalline domains has long dominated research to explain the properties of semicrystalline polymers such as linear low-density polyethylene (LLDPE). impact. impact. the major part of the polymer chain can possibly be incorporated into the same lamella crystal and. failure processes. it has clearly been established by many researchers that large-strain properties such as stretchability. infrared dichroism after deformation. HDPE). However. Tie-molecules in the semicrystalline polymer are critical for enhancing mechanical properties such as environmental stress crack resistance (ESCR). few tie-molecules can be formed. Probabilities for forming tie-molecules in a homogeneous ethylene–α-olefin copolymer made by SSC technology versus a heterogeneous copolymer were estimated [34]. tear. and so forth. these crystals started to slip. the SSC technology polymer has a homogeneous distribution of the α-olefin among the polymer chains. which results in a narrow crystallite size distribution. and tensile strength. A detailed discussion of the slip-link model and the use of this model to predict the overall elastic properties of POE has recently been published [22]. This allows all the polymer chains to crystallize similarly. relative tie-chain concentration has been semiquantitatively characterized using techniques such as measurement of the brittle fracture strength [27].

The relative tie-chain concentration would also depend on the concentration of ‘‘junction points.Polyolefins Produced by Single-Site Catalyst 253 FIG. . Intrinsic Elmendorf tear strengths on compression-molded 10-milthick films of various ethylene–α-olefin copolymers were measured [36] and the data are illustrated in Fig.’’ which would approximately depend on the volume fraction of the crystallinity. mers. 26 Schematic diagram of tie-molecule structure in an ethylene–α-olefin copolymer. The Huang–Brown model used to calculate probability of tie-chain formation does not take into account the effect of the type of α-olefin comonomer. The relative tie-chain concentration was obtained from the product of tie-chain probability and the volume fraction of the crystallinity. 27 Relative tie-molecule concentration in a SSC-technology ethylene–octene copolymer at various molecular weights. Figure 28 shows that higher α-olefin copolymers (octene and hexene) have much better intrinsic tear strength than butene and pen- FIG. 28. Figure 27 illustrates the optimum density range and the molecular weight effect on tie-molecule formation.

254 Polyolefins Produced by Single-Site Catalyst FIG. reduced blocking. whereas traditional Z-N ethylene–α-olefin copolymers typically are not available below about 0. Table 1 shows several examples of key properties of plastomers produced with SSC and the resulting packaging benefits. Indeed. and (3) a narrow MWD with a Mw /Mn of about 2. For example. the ability to control melting and crystallization behavior.885 g/cm3 are available from SSC. The narrow molecular-weight and comonomer distributions contribute to several unique properties. POEs with densities less than 0. one important commercial application for plastomers is use as a high-performance sealant in multilayer coextruded or laminated films. reduced extractables. three key distinctions have been noted between ethylene– α-olefin copolymers produced with single-site catalysts and ethylene–α-olefin copolymers produced with Ziegler–Natta catalysts: (1) an ability to incorporate higher levels of the α-olefin to achieve low polymer density or crystallinity. with octene being the highest of all.92 g/cm3. The unique characteristics of the homogeneous ethylene–α-olefin copolymers described make them useful for packaging applications.89 and 0. (2) a uniform comonomer distribution giving a lower melting point at a given density. the excellent optics. 28 Intrinsic tear strength of various SSC-technology ethylene–α-olefin copolymers.g. These experimental results are in good agreement with the tie-chain model.89 g/cm3 density. Applications In previous sections. excellent optics. . including controllable melting points. and excellent mechanical strength make POPs an ideal candidate to compete with the traditional high-performance sealants such as EVA copolymers containing 9–18% vinyl acetate and ionomers.. The ability to incorporate higher levels of comonomer has made possible new product families (e. and excellent mechanical properties. For example. POP and POE). The optimum tear strength for all polymers studied is found to be in the density range between 0. tene copolymers.

Other key attributes of a high-performance sealant are the hot-tack strength. One of the key attributes of a high-performance sealant is the low melting point. appearance. Many high-performance films are multilayer structures. Hence. permeability. coefficient of friction. and heat-seal strength.). caulkability. seal through contamination. tear. good moisture barrier Food-Packaging Film Applications The primary distinguishing feature of food packaging is the need to prevent contamination of the food and to maintain or extend the shelf-life. Beyond parameters like heat-seal-initiation temperature (HSIT).. and/or FDA compliance. and sales of the product. . oriented shrink films.g. The barrier of a flexible package can be compromised when (1) an hermetic seal of the package is not obtained during packaging. High-Performance Sealants Polyethylenes are widely used as sealants in various packaging applications.Polyolefins Produced by Single-Site Catalyst TABLE 1 Benefits of Plastomers in Flexible Packaging Polymer properties Toughness of a linear polyethylene Low sealing temperatures Low extractables Excellent optics High oxygen transmission Elasticity Hydrocarbon composition Thermal stability Moisture insensitivity Packaging benefits 255 Protection of goods. which facilitates the key performance requirement of a low seal-initiation temperature. plastomers can potentially be used in various films applications where low-melting-point polymers such as EVAs and ionomers are currently in use (e. 17). Seal performance. recently. consideration is given to parameters like processability during extrusion. and abuse resistance are some of the critical performance requirements for many. recycle friendly Processing flexibility Bulk handling. (2) the seal of the package is not maintained during the packaging. etc. The package acts as a barrier to the environment. ethylene acrylic acid (EAA) copolymers. and. sealants. cost. shrinkage. where the individual layers perform a specific function(s). Types of polyethylenes used as high-performance sealants include EVA. of the food packaging applications to be described. if not all. When plotted against resin crystallinity (Fig. or (3) the package itself fails due to inadequate puncture. ionomers. hot-tack window. or abrasion resistance. polyolefin plastomers. ULDPE. impact. placing constraints on the polymer design. gauge reduction Faster packaging line speeds Better taste and odor characteristics Package appeal Breathable films High recovery and flexibility Polyolefin compatibility. distribution. and hot-tack range. the melting points of EVA resins lie very close to the curve for plastomers produced via SSC technology. Barrier properties will vary depending on the specific type of food being packaged. High-performance sealants often must meet a number of performance requirements. machinability (stiffness.

29 Hot-tack strength of ethylene–octene plastomers made using CGC technology and EVA resins as a function of seal bar temperature.896-g/cm3 plastomer exhibited lower seal-initiation temperature. This may due to the high degree of LCB significantly lowering diffusion rates in EVA resins. in which the strength of the seal after it has just been made may be the rate-limiting step in this automated process. although the melting point of 0. the 0. an increase in melt index actually increases the hottack strength due to higher diffusion rates [37]. 29. One of the applications of high-performance sealants is the box inner liners FIG.5 mil)-blown coextrusion film was used. and seal (VFFS) equipment. . Interestingly. which significantly lowers diffusion rates across the molten interface. at the same melting point. Nylon–EAA–sealant (1/1/1. sharp melting points are thus well suited for high-performance sealants because the ultimate seal and hot-tack strengths of the polymer are achieved at low temperatures [38–41]. The ultimate hot-tack strength is the highest hot-tack strength achieved over a full range of sealing temperatures. The ethylene–octene plastomer resins exhibit slightly higher seal plateau strengths compared to EVA resins. Heat-seal strengths of ethylene–octene plastomers and EVA resins are compared in Fig.896-g/cm3 plastomer is about 94°C and the melting point of ELVAX 3165 (18% VA EVA) is about 86°C. For example. EVA resins exhibit somewhat higher heat-seal initiation temperatures compared to plastomer resins (at melt index of approximately 1 or less). EVA polymers exhibit much lower hot-tack strength compared to plastomers. Polyolefins plastomers with their low. This test is designed to predict the performance on vertical form. 30. High hot-tack strength reduces the likelihood that the food product will break through the seal when being dropped into the forming package. just-made seal.256 Polyolefins Produced by Single-Site Catalyst Hot-tack strength is a measure of the force required to separate a semimolten. fill. Hot-tack strengths of ethylene–octene plastomers and EVA resins are compared in Fig. In the case of EVA resins. This is due to the very high degree of long-chain branching present in EVA copolymers.

with a seal-initiation temperature of 84°C. Whereas a high-oxygen barrier is critical to preserve the freshness of meat and cheese. A typical plastic film structure for cereal and cake-mix inner liners is a coextrusion of HDPE with a sealant. A comparison of the other critical sealant performance requirements for a polyolefin plastomer (POP 2). hermetic seal is critical for maintaining the barrier of the package. such as cake mixes. because a strong.Polyolefins Produced by Single-Site Catalyst 257 FIG. an ionomer (Zn ionomer). 30 Heat-seal strength of ethylene–octene plastomers made using CGC technology and EVA resins as a function of seal bar temperature.e. The sealants typically used for these applications are ionomers or EVAs containing high levels of vinyl acetate (VA) (i. They are followed by the Zn ionomer.5 mil)-blown coextrusion film was used. The conventional blown shrink-film method involves extrusion of the molten polymer through an annular die at a certain drawdown ratio and a certain blowup ratio and then cooling the bubble via ambient or chilled air. Again. Note that the 18% VA copolymer provides very low ultimate hot-tack strength due to very high levels of long-chain branching retarding diffusion across the interface and is generally not suitable for the packaging of heavy products. POP 2 and EVA copolymers (18% VA) have comparable seal-initiation temperatures (69°C and 72°C.. Nylon–EAA–sealant (1/1/1. Orientation of the film takes place in a completely molten state and is . and crackers. respectively). cereal. and an EVA copolymer (18% VA) are discussed below and summarized in Table 2. Oriented Shrink Films Oriented shrink films can be differentiated from conventional hot-blown shrink films by their fabrication processes. Table 2 shows that POP 2 provides the highest ultimate hot-tack strength of the three products. followed by the Zn ionomer and the EVA copolymer. for dry foods such as cake mix. 18% VA). a high-moisture barrier is essential for preserving the freshness of dry products. POPs are another option for replacing ionomers or EVA copolymers (18% VA).

or below the peak melting temperature in the case of semicrystalline polymers.0 EVA (18% VA) 0. Fur- . to obtain shrinkage of the film around the meat [44]./in. Biaxially oriented films made via the ‘‘doublebubble’’ or ‘‘trapped-bubble’’ process are used to produce packages for very large. subprimal cuts of meat after slaughter. at a temperature below the melting point of the semicrystalline polyolefin). The first method is the tenter frame process and the second method is often referred to as the ‘‘double. the air evacuated.bubble’’ or ‘‘trapped-bubble’’ process.5 72 3. high-modulus films with high shrink and shrink tension.258 Polyolefins Produced by Single-Site Catalyst TABLE 2 High-Performance Sealants for Box Inner Liners Resin Melt index (dg/min) Density (g/cm3) 2. and a sealant layer.4 primarily in the machine direction. The broad comonomer distributions and melting ranges of LLDPEs and ULDPEs create a sufficiently broad orientation window for the double-bubble process.) POP 1.4 84 4..6 0. In contrast. More in-depth descriptions of these processes can be found elsewhere [42.5 Not available 6. as well as excellent clarity [42.43].2 day atm) 1.2 Zn Ionomer 1 5. usually via hot water. The package is then heated. The use of LLDPEs and ULDPEs alone or as blends with EVA copolymers in both the abuse and sealant layers have been taught in the patent literature [44. In addition. As a result.5-Mil HDPE/0.5 Not available 104 190 2. due to the drawdown ratio.8965 270 300 1. The packages are often referred to as barrier bags. The subprimal cuts of meat are inserted into a barrier bag that is generally sealed at one end.8 Not available 222 118 1. an oxygen barrier layer such as a poly(vinylidene chloride) (PVDC) or ethylene vinyl alcohol copolymer (EVOH).5-mil sealant.45]. blown coextrusion Heat-seal initiation (°C) Ultimate hot-tack strength (N/in. as a result of the blowup ratio.3) Tear Resistance (g) Haze (%) Odor intensity rating Water vapor transmission rate (g mil/100 in. adhesive layers may be used to tie the structure together. Orientation by these processes takes place in a semimolten state (i.2 2. These orientation processes produce high-tensile.e. and secondarily in the cross direction. the oriented shrinkfilm process can be described generically by the following steps: Extrusion–quenching–reheating–baxially stretching–cooling The reheating step involves temperatures just above the glass transition temperature in the case of amorphous polymers.9 2.7 Not available 69 7. Typical barrier bag structures range from three to five layers and minimally contain an abuse/shrink layer.0-Mil monolayer blown-film properties Puncture (ft-lb.3 1. and then the bag heat sealed.43]. a significantly higher degree of orientation is obtained compared to hot-blown shrink films. There are two basic methods to produce biaxially oriented films.

5 16. ULDPE resins offer improvements in shrinkage over higher-density LLDPE resins./s. * POP is an ethylene–octene copolymer having a melt index of 0. † LLDPE is an ethylene–octene copolymer having a melt index of 1.898 g/cm3. Further improvements in shrinkage can be obtained using POPs. the excellent toughness of these linear polymers provides the high level of abuse resistance needed to prevent punctures from the bones in subprimal meats and to sustain impact abuse during the distribution process. Both the POP and EVA have compaTABLE 3 Optics of Oriented Films EVA (12% VA)/ LLDPE Blend ratio Haze (%) Shrinkage at 90°C (%) 30%/70% 7.9 and density of 0.M. blends of EVA with ULDPE or LLDPE have been taught for use in barrier bag structures. A particular disadvantage of these blends is the poor optics and reduced abuse resistance.920 g/cm3. As shown in Table 3.6 16 POP*/LLDPE † 30%/70% 0.5 4.908 g/cm3 [46].5 Note: Films oriented on T.5 draw ratio at 5 in. Long stretcher under isothermal conditions at a 4. 31 Hot-water shrinkage at 90°C of films oriented on a T. As mentioned earlier. Long stretcher under isothermal conditions at a 4.0 dg/ min and density of 0. . Figure 31 illustrates the improved shrinkage at 90°C for POPs at a density below about 0./s.5 draw rate at 5 in.M. due to their reduced crystallinity. it is assumed that the improved sealability and abuse-resistance properties for POPs in conventional blown films also translate to improvements in oriented shrink films. the POP/LLDPE blend provides significantly better optics and potentially better toughness in an oriented shrink film than the EVA/LLDPE blend.Polyolefins Produced by Single-Site Catalyst 259 FIG. POPs can offer low-temperature shrinkage improvements over ULDPEs at the same density because of their lower melting points. thermore. In addition.5 4.

This allows the materials scientists to design products by a molecular-architecture approach. These resins may be fabricated into packaging films or containers via blown. In packaging applications. References 1. and injection molding.59]. the resins based on CGC technology have successfully replaced and/or upgraded EVA. B. Proceedings of Metcon ’93. p. and impact modification of polypropylenes [60–65].57]. W. and ULDPE.and cast-film methods. Swogger. W. extrusion coating [58. Kalyan Sehanobish of The Dow Chemical Company. biaxial oriented film processes. and heat-seal properties. building a model to predict properties for these polymers became feasible. They provided many useful data in this article. 1993. The poor optics of the EVA/LLDPE blend are believed to be due to the partial immiscibility of these two polymers [47]. These homogeneous polymers have narrow molecular-weight and composition distributions. optical. extrusion coating. Homogeneous polyolefins provide excellent utility in numerous packaging applications. Acknowledgments The authors of this article would like to express their sincere appreciation to Professor Eric Baer. Professor Anne Hiltner of Case Western Reserve University. Conclusion and Summary Development and implementation of SSC technology have greatly expanded the product range of polyolefins. p. ranging from retail meat packages to industrial stretch films. . 112. Story and G. K. Because of the simple and predictable molecular structure of this class of polyolefin copolymers. 1992. resulting in enhanced mechanical.260 Polyolefins Produced by Single-Site Catalyst rable melting points and crystallinity. 2. lamination. LLDPE. Knight. batch inclusion bags [55]. 115. and Pradeep Jain. ionomer. the authors expect the polyolefin industry can take great advantage of this technology to design unique polymers and fulfill their customer needs in the future. Other important applications of homogeneous polyethylenes made using SSC technology include fresh-cut produce packaging [48–50]. using property and performance requirements as guidelines. Proceedings of the 1992 Int’l Business Forum on Special Polyolefins. LDPE. A. With the advancement of the SSC technology for the production of polyolefin copolymers with well-defined molecular structures. high-performance films [51–54]. SPO ’92. cling layer in stretch films [56.

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