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Water Requirements

of the Petroleum
Refining Industry
By LOUIS E. OTTS, JR.

WATER REQUIREMENTS OF SELECTED INDUSTRIES

GEOLOGICAL

SURVEY

WATER-SUPPLY

PAPER

1330-G

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1963

UNITED STATES DEPARTMENT OF THE INTERIOR
STEWART L. UDALL, Secretary

GEOLOGICAL SURVEY
Thomas B. Nolan, Director

For sale by the Superintendent of Documents, U.S. Government Printing Office
Washington, D.C. 20402

CONTENTS
Abstract____________________________________________________
Introduction. _____________________________________________________
Purpose and scope_______________________-________________.____
How water is used-------_-------------------__-------_----_-_Quantitative requirements.-____--___-____-_______________-_-_-_-____
Published information________________________________________
Findings of the survey..._______________________________________
Sources of water___-__-------__-----______-------_-_------Total requirements.________________________________________
Cooling-water requirements._____--_-______-__-___-_____--__
Requirements for selected operations.________________________
Water-quality requirements_________--___---___-_____-_______-___-__
Cooling water.________________________________________________
Published information______________________________________
Findings of this survey___________-_____-____-_____________Boiler-feed water makeup__--___--_--_----_---__----_---___-_-_Published information____________________________-_________
Findings of this survey________________--_____-__-_____-___Process and sanitary water_-________________-___--___-_-__--_-__
Factors affecting water use_______________________________________
Availability of water___-_-_--_-_-_-__----_----_----_-_-__------Size ofrefinery_---___---__----_----_----_---------_----_----__
Types of processes,.___________________________________________
Operating procedures.._____-___________-____________---_----__Quality and physical characteristics of water______________________
Refinery waste water_____________________________________________
Future water requirements.----------------------------------------Location of refineries.--____--_________-_-_---__----_----__-___Growth of industry_______-_________--___-___--___---__-----Trends in petroleum refining in the United States.._._-__-________Summary. ________________________________________________________
Quantitative water requirements.----.---------------------..-----Qualitative water requirements--____-_--___-______-__--__-_----Trends in water requirements_...________________________________
Selected references____________-___-______-_____-_----_--------_--

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1955. ______________--______--_-_-----_6. Graphs showing frequency distribution of selected chemical constituents in untreated: 44.__________-. Map showing location of refineries surveyed. Water requirements of selected operations. Gross circulating cooling water. Water requirements of crude distillation units. Water requirements and disposition by type of use and type of refinery. ______________________________________ 2.products in the United States. 1955. _______ 301 44 48. Crude runs by petroleum refineries in the United States and the free world. by type of cooling system____ 5. Sanitary and service water_----__--__---___-____ 323 49-51. Crude oil runs by refineries and demand for petroleum . by type of cooling system and by type of refinery.IV CONTENTS ILLUSTKATIONS PLATE 3. Undesirable effects and methods of correction for common constituents in water__ _ _______-___________----_-_12.with curves extended to 1966____________ 336 TABLES Page TABLE 1... Flowsheet of a hypothetical refinery. Consumptive cooling water.---. Diagram showing source and use of water intake. Water for recirculated cooling. by type of cooling system and by type of refinery.. Water for once-through cooling__________________ 314 45. 192060. Cooling-water makeup. Quality tolerances of cooling water suggested by American Water Works Association___________-__--_---_- 295 296 298 299 302 304 305 306 307 308 309 311 311 .________________ 315 46. Makeup water for boiler feed-__________-_______ 319 47. _. Published unit water requirements of selected processes.__ 13.---------------------8.___________ 333 50. Published total unit water requirements of selected refineries._________ ___________ 7... Quality characteristics of untreated water for all uses. Process water______--___-----____-_-_---______ 322 48.__ In pocket Page FIGURE 42. 3. Total water intake. 1955. .----------11. Graphs showing: 49. 1950-60-___________ 334 51. Source and amount of water intake of the refineries 4. by type of cooling system and by type of refinery. Demand for major refinery products in the United States and the free world.________ 10. 1955.. 1950-60. _________-___------_ 9.-_________ 289 43.

Treatment of makeup for process water. Treatment of makeup for boiler-feed water____________ 19. Quality characteristics of untreated boiler-free water makeup-..______________ 21. Treatment of makeup water for cooling_______________ 16.____________--_-_-_---__ 23._______-______-_____--________--___-_-__ 20.__ 17._. Quality characteristics of untreated cooling water. Suggested water-quality tolerances for boiler-feed water_ 18.. Summary of the median of selected quality characteristics of untreated water used for various refinery purposes_ ______________________________________ V Page 313 317 320 320 321 324 325 325 329 337 . Waste-water treatment._____ 15.-_.-___-____________-_-_____-_-__--___-_. Treatment of makeup for sanitary water_______________ 22.CONTENTS TABLE 14. Quality characteristics of untreated process and sanitary water..

.

287 .1 ABSTRACT About 3. OTTS. University of Maryland.WATER REQUIREMENTS OF SELECTED INDUSTRIES WATER REQUIREMENTS OF THE PETROLEUM REFINING INDUSTRY By Louis E. they consumed about 24 times more water per barrel of charge than refineries using once-through cooling systems. Ninety-one percent of the water requirements of the petroleum refineries surveyed was for cooling.240 gallons per barrel. Refinery-owned sources of water supplied 95 percent of the makeup-water requirements. Less than 1 percent of the makeup water was obtained from reprocessed municipal sewage. which is less than the 471-gallon average of refineries with cracking facilities. An average of 468 gallons of water was required to refine a barrel of crude oil. Md. One-third of the refineries reused their cooling water from 10 to more than 50 times. Only 17 refineries used once-through cooling systems. JR. The average noncracking refinery used about 375 gallons of water per barrel of crude.5 to 3. Refineries are composed of various processing units. Refineries with recirculating cooling systems circulated about twice as much cooling water but needed about 25 times less makeup . Surface-water sources provided 86 percent of the makeup-water demand. withdrawals ranged from 6. however. INTRODUCTION PURPOSE AND SCOPE This report presents the results of a survey of water used in the manufacture of petroleum products from crude oil and is one of a series describing the water requirements of selected industries that are of i Professor of Civil Engineering. and the water requirements of such units varied .5 gallons per barrel for distillation units. median makeup needs ranged from about 125 gallons per barrel for polymerization and alkylation units to 15.500 million gallons of water was withdrawn daily in 1955 for use by petroleum refineries in the United States. College Park. This was about 3 percent of the estimated daily withdrawal of industrial water in the United States in 1955. and the median was 95 gallons of water per barrel of crude charge.

Refineries were selected to give a wide range in size. The literature was carefully reviewed to obtain information on the water requirements of the industry and to obtain an understanding of the water-supply problems of the industry. Information was obtained on the source of water. They processed 30 percent of the crude oil refined in the country during 1955. D. processing and sanitary. (See fig 42. J.) The refineries surveyed included no natural-gasoline plants. The author is indebted to his colleague. boiler feed.288 WATER REQUIREMENTS OF SELECTED INDUSTRIES national importance. This information will be helpful in planning the location of new refineries and the expansion of existing ones. who made the survey of the petroleum refineries in western Pennsylvania.S. Information was obtained on use of water for cooling. or 21 percent. Special acknowledgment is given to the officials and management of the petroleum refineries who permitted the author to visit their refineries and who supplied information on water use at their refineries. O. Searcy (written communication) of the U. geographic location. Data on the amounts of gross and makeup water required. Information for 48 of the petroleum refineries were incorporated in this report where applicable. the quality and treatment of the water. and the disposal of waste. exploration for and production of crude oil. Mussey. Sixty-one. and marketing of petroleum products. The report is designed to serve the dual purpose of providing basic information for national defense planning and of providing assistance to business and industry. of the refineries operating in 1955 were visited. Information on the crude charge and production of the refineries was also obtained in order to compute unit water use. and processes used. . but he did not obtain details on the use of water within the refineries. data for 1955 were collected so that information for an entire year would be available. and the amount of effluent were obtained for the complete refineries and for their component units. the amount used consumptively. Early in 1951. and no attempt was made to obtain information on the water requirements of the other divisions of the oil industry namely. transportation of crude oil or refinery products. the amount reused. the adequacy of the supply. A field survey of 1955 refinery operations was made in the summer and fall of 1956. K. A knowledge of the water requirements of industry is needed for planning the most effective use of the water resources of specific areas. Geological Survey obtained information on the water intake of 63 petroleum refineries and 29 natural gasoline plants in the United States.

Location of refineries surveyed.Refineries with cracking facilities A Refineries without cracking facilities FIGURE 42. to 00 . 1956.

Allowing for other water uses and assuming a 30 °F temperature rise in the cooling water. cracking. other fractions are drawn from the tower as side streams. A skimming or topping refinery separates crude oil by distillation into gasoline. In petroleum refining. refineries save both heat and water by cooling high-temperature products with raw charging stocks and other cooler liquid streams. by steam distillation. The crude oil is generally warmed by heat exchange with a fluid to be cooled. Atmospheric distillation is generally the first step in refining crude oil. The quantity and the quality of water required by the entire refinery and in individual operations are affected by the type of refinery process. however. Detailed descriptions of petroleum refining and refining equipment can be found in the literature. Ohio. fire protection. and coolers are used to lower the temperature of liquid products to permit safe handling.290 WATER REQUIREMENTS OF SELECTED INDUSTRIES HOW WATER IS USED The major use of water in a petroleum refinery is for cooling. and the uses of water were as simple as the refining process. The reduced crude from atmospheric distillation may be further processed by vacuum distillation. and reduced crude. Water is the normal cooling medium used in these units. alkylation. kerosene. Water-cooled heat exchangers condense overhead streams and cool tower side streams.000 million Btu. processing. per hr and that about 50 percent of this heat is removed by water. . sanitary services. Relatively small quantities of water are used for boiler feed. gas oil. In contrast. vapors are reduced to liquids in condensers. or by a combination of both to provide lubricating oil fractions or asphalt base stocks. Simonsen (1952) noted that a typical 50. The use of the crude oil as a cooling medium reduces the amount of cooling water required. polymerization. he estimated the refinery would require about 40. and treating and finishing. and miscellaneous purposes. Water was needed only for cooling and for generating sufficient steam for the pumps. This quantity of water would have supplied the domestic requirements of the city of Toledo. Water requirements of early refineries were small. The lightest vapors are drawn off at the top of the tower and are condensed as gasoline.000-barrels-per-day refinery generates more than 1. in 1952. both the modern refining process and the use of water are varied and complicated. as the oil is distilled at temperatures lower than those in atmospheric units.000 gpm (gallons per minute) to remove this amount of heat. The hot oil partially vaporizes as it enters the fractionating tower. The principal processes used are distillation. The heavier fractions of the crude oil may be fractionated without danger of decomposition or cracking in these units. fuel oil.

as it is a process that combines two or more molecules to form a larger molecule. Thermal cracking units operate at temperatures ranging from 800° to 1200°F and at pressures ranging from 600 to 1. In the alkylation process. Water is used for making brine solutions in refrigeration units of lubricating-oil plants. Polymerization could be considered to be the reverse of cracking. because it not only gives an increase in the gasoline yield to 70 to 85 percent of the charge but also improves the quality of the yield. or stability or to remove sulfur. Cracking processes may be thermal or catalytic. or other corrosive substances before the product . but thermal polymerization is not used extensively today. Steam is also used for pumping and heating.PETROLEUM REFINING INDUSTRY 291 A vacuum distillation unit consists of a pipe still and a distillation tower operated at a reduced pressure that is maintained by the use of a barometric condenser and steam jets or vacuum pumps. gums. Cracking is the breaking down of large molecules into smaller molecules. pumping. Products must be treated to improve color. They use steam for regenerating catalysts. The process is used largely to change the byproduct petroleum gases that are produced in cracking into high-grade motor fuel and aviation fuel. polymerization. complex saturated molecules are formed by the combination of a saturated and an unsaturated molecule. but most commercial applications are catalytic. In the manufacture of lubricants. Alkylate is the product of the process and is the principal component of many high-octane motor fuels and aviation gasolines. Catalytic cracking units utilize a catalyst to hasten the change in molecular structure of the material being cracked and operate at temperatures and pressures generally lower than those of thermal cracking units. and thermal cracking may be either liquid phase or vapor phase. a thermal-catalytic. and alkylation units use water for cooling and for other heat transfer operations. auxiliary towers known as stripping columns. Cracking. This equipment requires both water and steam. and heating. Because the separations obtained in distillation towers are not perfect. and heating. About 50 percent of the gasoline produced in this country is obtained by cracking. the undesirable fractions in side streams are vaporized and are removed by steam stripping in short. or a catalytic process. Cracking is an important process. the lubricating-oil base stock is prepared by vacuum distillation or by propane deasphalting. Steam is used for cleaning filter clays. pumping. or by solvent dewaxing.000 pounds per square inch. Alkylation can be a thermal. odor. The base stock is then dewaxed by chilling and cold filtering or pressing. Polymerization can be a thermal or a catalytic process.

The manner in which cooling water is used varies with local conditions. A diagrammatic flowsheet of a refinery is shown plate 3. A quantity of water equivalent to the evaporation and windage losses and to the withdrawal for mineral concentration control is added to the recircu- . The rate at which water is pumped into the cooling tower is known as the gross circulating rate. where water is in short supply and its cost is high. spray or cooling ponds. It merely illustrates how several of the more important processes may be utilized by a refinery to provide the products desired. Evaporation and windage losses occur as water passes through the cooling tower. makeup water requirements are kept to a minimum by reusing the cooling water many times. In the recirculating type of cooling system. On the other hand. Brines are generally removed from crude oils by scrubbing with water. oxidation sweetening. The water remaining is returned to the cooling system to be reused and is known as recirculated water. copper sweetening. The heat acquired by the water is removed by evaporative cooling in cooling towers. One type of reuse system uses water as a coolant for operations with low-temperature demands and then reuses the warmed water to satisfy cooling requirements of higher temperature operations. by contact with or percolation through clay. and some water is drained from the system to prevent excessive mineral concentrations. The designation of the type of a refinery will be determined by the combinations of processes used. Both steam and water are used to recover solvents and to clean filter clays in lubricant treating operations. Water is used for caustic and acid solutions and for product washing. Brines associated with many crude oils should be removed before the oils are distilled to prevent serious corrosion of refining equipment. and solvent extraction are some of the methods used to remove or alter the impurities in light distillates. A refinery is composed of a combination of several unit processes.292 WATER REQUIREMENTS OF SELECTED INDUSTRIES is marketable. and the cooled water is reused. Generally water will be used once in areas where it is plentiful and cheap. or by solvent extraction methods. nor is it a recommended refinery design. but no two refineries will use exactly the same process. The conventional recirculating cooling system in a modern petroleum refinery uses cooling towers to transfer the heat absorbed by the water to the atmosphere. Caustic treating. clay treating. or evaporative condensers. Most refineries use once-through cooling for some operations and several types of water reuse for other operations. It is not a flowsheet of any specific refinery. water absorbs heat as it flows through condensers and coolers. Lubricating oils are treated with acids. acid treating.

It is the same quantity as the makeup water if water is used only once and discharged to waste. for pumping. The second largest use of water in a refinery is makeup for boiler feed. and vacuum distillation. Smaller amounts of water are generally needed for process operations. Water Works Assoc. Evaporation and windage losses in a cooling tower and the discharge of process steam into the atmosphere are examples o. 1953). fire protection. whereas water that was used in one process or operation and is being reused in another as makeup is known as reused makeup water. and generally the steam condensate is so highly contaminated that it cannot be reused for boiler feed or for other purposes. and discharge to waste of the condensate from a steam trap or examples of effluents and not of consumptive uses. Some refineries also require water for company housing. The chief uses of steam are for stripping. The gross circulating water is the actual quantity of water circulating in a system.f consumptive use. The sum of new makeup water for all refining operations for a day is equivalent to the daily water intake of the refinery. Makeup water may be new or reused. and. for generating electric power. . in some refineries. The sum of consumptive uses and effluents equals the makeup water. Water is used both consumptively and nonconsumptively by the petroleum refining industry. If water is recirculated. as the increased water needs during a fire must be entirely or partially offset by a decrease in water uses in the refining process. and refineries with dock facilities may supply the water needs of oil tankers. The steam comes in contact with the products in these operations.PETROLEUM REFINING INDUSTRY 293 lated water to maintain the gross circulating rate. sanitary and plant services. Consumptive use is water that is discharged to the atmosphere or that is incorporated in the products of the process (Am. but the average requirements for fire protection during -a year will be negligible. This replacement is known as makeup water. and other uses. Water that is used for the first time is new makeup water. The water requirements during a fire will be large. Task Group. The latter method is less desirable. steam distillation. cooling-tower blowdown. The discharge of once-through cooling water. Some refineries use separate fire-protection systems. whereas others use water from the cooling or other water systems of the refinery to fight fires. it is the sum of the makeup and the recirculated water. Steam is also used for process heating. The condensate from the condensers and traps of these systems is usually reused as boilerfeed water or as makeup for other water needs.

and public facilities supplied about 5 percent. and 0.) Company-owned facilities supplied about 95 percent of the daily water intake. even though more heat and treatment for each gallon of crude are required owing to cracking and other intensive refining processes. Published water requirements of selected refineries are given in table 1. and catalytic cracking. The gallons of water used per barrel of feed stock for selected refinery processes are given in table 2. although some obtained water from only one source. . coking. Another example of water conservation is the reduction in water requirements of the Baton Rouge refinery of the Esso Standard Oil Co. FINDINGS OF THIS SUB-VET A typical (median) petroleum refinery of today has a daily capacity of about 16. One of these refineries that had a once-through water system used 1. Now. in its early days the Baton Rouge refinery used about 100 gallons of water for each gallon of crude processed. The possible reduction in water requirements by many refineries is suggested by this example of water conservation.5 million galons of water circulate daily in the several water systems within the refinery.294 WATER REQUIREMENTS OF SELECTED INDUSTRIES QUANTITATIVE REQUIREMENTS PUBLISHED INFORMATION Most descriptions of petroleum refining and processing given in the literature do not include data on water requirements.000 barrels of crude oil. and nine used saline ground water or saline surface water to supply part of their requirements. reforming. of Ohio refineries reported in the table. (See table 3. Those that do give such information usually show the total water requirements and do not subdivide the water needs by process or by type of use. nearly 14 percent was from wells. According to Miller and others (1953). whereas another that recirculated all cooling water required only 73 gallons per barrel. The wide variation between maximum and minimum water requirements is shown by the four Standard Oil Co.1 percent was sewage effluent.870 gallons of water to refine a barrel of crude oil. The literature shows that refinery processes have wide ranges of water requirements. One refinery used sewage effluent. Processes with large water requirements are deasphalting. To maintain this circulation rate the refinery needs a source of water capable of providing 2 mgd (million gallons per day). Approximately 22. SOURCES OF WATER Most of the 61 refineries surveyed obtained water from both surface sources and wells. About 86 percent of the total daily intake was from surface sources. the use of water has been reduced to 23 gallons per gallon of crude.

Besselievre (1952). refinery __ Esso Standard Oil Co.: Baton Rouge. of Ohio: Toledo. Unit water use is expressed in gallons per barrel of crude charge except where otherwise noted] Size Refinery or product Unit use Source of information Refinery Lubricating _ _ (') _ _ __ Do____-_____-____________ Do____.. 8 Average of a number of plants. Bell (1959). re- Cooling water. 4 Gallons per gallon ot product. 900 982 953 Do.__ 440 (') (') 540 630 1. __ Petroleum Processing (1957b). 120. Product Do Aviation gasoline (2) (2) _ 1 Data not given in source. Do. Do.____ Do. Kentucky. 000 44 Do.060 Latonia... 924 134. Do. 000-28. Ohio. 000 47-52 Aeschliman and others (1957.020 1.850 910 250 210 3770 800 0)0) 0) (') 0) (') (') 35. Virginia _ ___ Sea water (for cooling) _ ___ Torrance Refinery. _. _ _ Oil refining ___ __________ .870 311 144 73 Simonsen (1952). Do.PETROLEUM REFINING INDUSTRY 295 TABLE 1. 1. German (1943). Do. 55 420 Do. _ _ ___ _. 110. Do. General Watson Refinery. National Cooperative Refinery Association __ __ ___ __ 25. Complete refinery _ _ _ _ Amoco. Richfield Oil Corp. Jordan (1946). _ _ (') 357 4 7-10 *25 3 Gallons per barrel of product. 966 Standard Oil Co. 000 000 000 000 232. Louisiana. 39. 000 34 Partin (1953). Do.__. refinery __ __ Cleveland. Do. 000 Standard Oil Co. Ohio. Union Oil Co_ __ ___ _ _ ___ _ Fresh water. Do. . 000 43 3._. 44. __. (1950)._ Skimming and cracking ________ Half skimming. refinery____ Bell (1959). Published total unit water requirements of selected refineries [Size of refinery is expressed in barrels of crude charge per day. 000 McPherson refinery._________. Do. Yorktown. Do. 15. Do.____. __ __ ____ ___ Wilmington Refinery. Do. 114.__. Do. half lubricating __ Topping only 25 percent. 21. Youngquist (1942).____.

Do. 000 Thermofor: Boiler water to kiln _ _ _ _ 4.. Read (1946).840 Water. Do. ____ ___ __ ___ 10. Oil and Gas Journal (1955a).082 12 536 7 Petroleum Processing (1956c). 000 Water. 2 165 Do. 410 Do. __ Refinery 2: Refinery 3: Cooling water. Do. 000 Fluid: 2. 0) 3 1 (0 3 68 (') 22 (') Cooling water _ . 637 Do. Do. . Do. CATALYTIC HYDROGENATION Autofining: Steam.000 Fluid: Steam ___ __________ ___ 10.500 27 Oil and Gas Journal (1955b).500 Net steam consumed.. _ _ _ _____ (') (') 2 12. 4.296 WATER REQUIREMENTS OF SELECTED INDUSTRIES TABLE 2. Do. __ HF: Process (Phillips): Steam. _____________________ 10.500 1. Kimball and Scott (1948). Kimball and Scott (1948). 000 Thermofor: Steam. 800 Petroleum Processing (1956a). Do. Published unit water requirements of selected processes [Size of refinery unit is expressed in barrels of crude charge per day. Do. Do. __ ___ _______ _ Cooling water __ ___ _ _____ See footnotes at end of table. ALKYLATION Sulfuric acid (Kellogg) : Refinery 1: 0) 374 (0 3 3. CATALYTIC CRACKING Thermofor continuous percolation: 3 6 360 12 9 1.350 Cooling water. Unit water use expressed in gallons per barrel of crude charge except where otherwise noted] Process Size Source of information Unit use ANHYDROUS AMMONIA Service water..000 Cooling water _ --_-___-___ 2. __ _____ Petroleum Processing (1957a). _ _ __ _________ 10. Do.500 4 3.333 Water_ _____________________ 10. _ Houdry: Steam ____ __ _____ 10. 841 (') 0) 3 83 3 4.500 4. 3. 000 1.. . Do. 000 1. Do. Do. _ _ 0) (') 3 111 3 4. Pfarr (1948)..

PETROLEUM REFINING INDUSTRY

297

TABLE 2 Published unit water requirements of selected processes Continued
Size

Process
CATALYTIC HYDBOGENATION

Source of information

Unit use

Con.

Hydrodesulfurization :
Standard Oil Co. of Indiana:
Cooling water.
Gulf HDS process:
West Texas crude oil, fixed bed :
Cooling water __ __
Modified fixed-bed 4 :
Cooling waterHydrogen treating:
Cooling water _____

_

8,500

1

8,500

315

20, 000

1,460

20, 000

10

20, 000
20, 000

3,750
20

10, 000

432

10, 000

7

(')

82

(l)
0)

45
1,500

Petroleum Processing
(1956f).
Do.
McAfee and others
(1955).
Do.
Do.
Do.
Petroleum Processing
(1956e).
Do.

ISOMERIZATION

Catalytic (Phillips Petroleum Co.) :

Water, gross circulating
Pentafining (Atlantic Refining) :
Total:
Steam
__ _ __ __
Pentafiner:
Pentane splitter:
Steam ______
Once-through plant:
Steam ___
_

Petroleum Refiner
(1956b) and Oil
and Gas Journal
(1956b).
Do.
Do.
Petroleum Processing
(1956d).
Do.

2,000

2

2,000

114

1,783
1,783

2
22

Do.
Do.
Do.
Do.

_

__

3,758
3, 758

0
92

_

___

4,000

10

4,000

396

4,000
4,000

80
2,520

10, 000
10, 000

821
10

Murphree (1951).
Do.

1, 100

344

Petroleum Processing
(1955).

10, 000

1

10, 000

533

Petroleum Processing
(1957c).
Do.

Plant recycling hydrocarbon:
Steam ___
___ __
Cooling water

Nordburg and Arnold
(1956).
Do.
Do.
Do.

CATALYTIC REFORMER

Hydroforming:
Cooling water

_

Hyperforming:
Cooling water

___

_

Powerforming for octanes:
Steam _____
_____
Cooling water _____ __
See footnotes at end of table.

690-234 O 63

3

_ _

298

WATER REQUIREMENTS OF SELECTED INDUSTRIES

TABLE 2. Published unit water requirements of selected processes Continued
Process

Size

Source of information

Unit use

S02 EXTRACTION PROCESS

Straight SO2 refineries:
Refinery 1:
Steam..-. ______________

0)

Cooling water________
Refinery 2:
Steam_.______________
Cooling water__________
Refinery 3:
Steam________________
Cooling water.___________
Modified refinery:
Steam..._________________
Cooling water______________

Wilkinson and others
(1953).
Do.

8
750

0)

9
830

Do.
Do.

0)

10
930

Do.
Do.

0)
0)

13
1,600

Do.
Do.

THERMAL CRACKING

Thermal cracking refinery:
Steam____-_________..... 10, 000
Water....__________________ 10, 000
Fluid coking:
Steam______________________ 10, 000

392

Cooling water______________ 10, 000
Visbreaking:
Steam______________________ 16, 240

864

Cooling water______________ 16, 240

266

1 Size not given.
2 Gallons of water per ton of ammonia produced.

Kimball and Scott
(1948).
Do.

5

Petroleum Processing
(1956b).
Do.

6

Boone and Ferguson
(1954).
Do.

7

' Gallons of water per barrel of product.
4 Kuwait vacuum bottoms light catalytic furnace
oil distillate blend.

TABLE 3. Source and amount of water intake of the refineries visited, in million
gallons per day
Source

Public... -_
Self-supplied.
Public and self
supplied-.-._-All sources.
Percent of total
intake..._

Number
of
refineries

Surface water
Fresh

Saline

6.1
157
321
484

308
308

53

33

All Percent
water of total
intake
and

Ground water

Total

Fresh

Saline

Total

6.1
157

0.6
85

2.4
.7

3.0
86

629
792

37
122

3.1
.4

37
126

1.3

10. '
243

1.3

666
919

.1

100

100

TOTAL REQUIREMENTS

The average unit water intake of the refineries surveyed by the
author and by Searcy was 468 gallons per barrel. The U.S. Bureau
of Mines (White and others, 1959) showed that 2.54 billion barrels
of crude oil was refined in 1954. The U.S. Bureau of the Census
(1957) reported a total water intake of 1,220 billion gallons for pe-

299

PETROLEUM REFINING INDUSTRY

troleum refineries in the same year. These values indicate an average
water intake of 480 gallons per barrel of crude refined in 1954. The
close agreement between the two averages indicates that the refineries
surveyed were representative.
Although the average water intake was 468 gallons per barrel of
crude oil, most refineries used less than average amounts.' The median
water intake was 95 gallons per barrel of crude charge. (See table
4.) The water intake for 109 refineries ranged from 6.5 to 3,240
gallons per barrel of crude charge and depended on the type of refinery, variations in the refining process, and whether or not water
was recirculated. The median water intake for refineries that recirculated water was only 57 gallons per barrel of charge as compared
to 700 gallons for those that used the once-through system. Refineries
without cracking units used less makeup water than those with cracking units; the median water intake for the former was 75 gallons per
barrel of charge as compared to 100 gallons for the latter.
TABLE 4. Total water intake, 1955, by type of cooling system, in gallons per barrel
of crude charge
[Data from 61 refineries surveyed in 1966 and 48 in 1951]
Type of cooling system
Type of refinery

r

Reuse

Oncethrough

Combined

All
systems

62
6.5
35
57
86
403
81

17
133
300
700
1,200
3,240
1,360

30
46
108
240
800
1,950
571

109
6.5
49
95
285
3,240
468

52
17
42
63
92
403
80

12
133
300
700
1,300
2,210
1,450

27
46
105
280
850
1,950
574

91
17
54
100
280
2,210
471

5
186

3

ALL REFINERIES

Number of refineries. _ ___
____.
Minimum _ _
_
______
Lower quartile_ ________
_
___
Median ____
___
__
____
Upper quartile__ ___
__ _ ___
Maximum _____
_
__ ___
REFINERIES WITH CRACKING

Number of refineries. __ _____
_ __
Minimum _
_____
_______
Lower quartile ____ _
____
___
Median___ ____
__ __
Upper quartile __ _ L ____
_______
Maximum __ ______ ______ _______
Average. _
_
___________
REFINERIES WITHOUT CRACKING

Number of refineries. _
_
_ _
Minimum. _ _ _ _
Lower quartile.. _ _ _ _ _______
Median ___
__
_
_____
Upper quartile___ _
___ ____
Maximum.- _
_
______
Average. ._
_
_____

10
6.5
15
27
50
249
112

550
3,240
720

128

18
6.5
26
75
260
3,240
374

and consumed about 24 times as much water per barrel of crude charge as those with once-through systems. The corresponding cooling-water values were larger for refineries without cracking units. of refineries with cracking units exceeded the values given for those with no cracking units. The median gross circulation was 1. and quantities of effluents were obtained where available. their median requirement was 500 gallons per barrel of charge as compared to 1.600 gallons per barrel for cracking refineries. The balance was used as shown in figure 43. REQUIREMENTS FOR SELECTED OPERATIONS Petroleum is refined by subjecting crude oil or other petroleum materials to a series of processes. except cooling. The median and average makeup-water uses for total and for all types of water use. the makeup. and 8 show the gross circulation. Tables 6. Median values also indicate that refineries with cracking units consume more water than those without cracking units: 38 gallons per barrel of charge as compared to 24 gallons per barrel.ter per barrel than those without cracking units. Information on the water uses of individual processing units may therefore be useful in analyzing the water requirements of petroleum refineries. used about 25 times less makeup. as the amount for each of the several individual uses was negligible. This is because refineries with cracking units generally circulate more wi. data for the total makeup water used by the processing units and the amounts used by each for cooling. consumptive uses. and other miscellaneous uses were obtained during the survey. which has correspondingly larger makeup-water needs. The amount of water used for purposes other than for cooling and for boiler-feed water makeup is shown as one value. Where available. COOLING-WATER REQUIREMENTS About 91 percent of the water intake of the refineries surveyed in 1956 was used for cooling. boiler feed.300 WATER REQUIREMENTS OF SELECTED INDUSTRIES The total gross circulation was considerably greater than intake or new makeup. this difference was due to the greater use by refineries without cracking units of once-through cooling. Refineries with recirculating cooling systems circulated approximately twice as much cooling water. and the consumption of cooling water by type of cooling system and by type of refinery. Because data on the quantities and types of charges to the various process units were not avail- . Kefineries without cracking units required less gross circulation. 7. because some water was used more than once by most refineries.400 gallons per barrel of charge as compared to 95 gallons of new makeup per barrel and ranged from 14 gallons to 7.290 gallons (table 5). Similar data for gross circulation.

Sanitary and other \ Ground water ^ 14 percent FIOUEE 43. Source and use of water Intake. CO O .

050 7.6 2.3 14 .5 o *] OB H B o U o 2 o 3 6. __ __________ 17 376 20 Consumption : Number of refineries __ 61 61 61 0 0 0 Lower quartile _ _ 12 2. 418 16 .8 19 70 31 400 3.7 0 Upper quartile _ -----36 20 .4 9.6 30 56 175 1.5 11 25 166 19 47 88 1.2 .__ 94 125 13 Averaee __ .100 1.3 1.Sanitary feed and water other water Total water Cooling water Boiler.670 47 39 1. 120 483 44 644 47 0 14 19 25 60 20 47 0 3.4 ._________ 28 1.600 2.8 13 1.2 10 Refineries without cracking units Refineries with cracking units Cooling water 61 14 850 1.290 1. .550 2.4 0 12 6. 1 10 39 11 14 0 18 6.5 0 Median -_ ___________ 25 8.5 5.120 125. _________ Lower quartile _ ______ Cooling water Boiler. 5 14 145 400 23 42 900 3.880 374 61 0 24 36 55 304 39 47 0 18 26 36 94 29 Boiler.710 14 14 7.0 8.8 9.0 24 57 125 16 S g H . in gallons per barrel of crude charge All refineries Water requirements and disposition Gross circulation : Number of refineries _ _ Minimum.4 10 20 34 10 47 0 0 0 47 0 27 38 53 304 40 14 14 0 0 1.200 1.900 35 483 7.2 750 25 1.5 22 Upper quartile _ ______ 1.240 468 47 2.Sanitary and feed other water water 14 0 "" jj5 Total water 3 *° » Hrl H 14 14 190 500 960 3.0 60 20 Upper quartile _ -----250 26 Maximum.290 1.CO o to TABLE 5.Sanitary and Total water feed other water water 61 61 61 5.5 7.0 19 8.000 7.350 8.660 109 6. 240 699 § w H § | 3 47 12 22 27 34 141 28 47 0 3.2 .620 New makeup: 61 Number of refineries__ 61 61 Minimum. _ _________ 3. 100 7.120 125 79 Average.3 17 79 17 91 17 54 100 280 2.8 3.210 471 14 14 5. Water requirements and disposition by type of use and type of refinery.220 1.5 0 20 2.220 166 29 19 1.5 49 95 285 3.0 11 39 11 26 75 260 3.6 0 0 25 Lower quartile _ --__-_ 13 2.8 14 0 0 0 .3 Maximum __ ____ _.0 24 27 52 125 6.. _ ____________ 2. 240 374 47 0 3.8 3.400 2.

9 21 18 80 121 1. whereas the median for some other type of water use or for the total may be that of the same or another refinery. maximum and average water-use values for various types of water may not always equal the corresponding total water value.8 7.5 4. _ _ __ _ 23 5. The median water-use value for cooling may be that of one refinery.0 60 400 3.Effluent: Number of refineries __ 61 61 0 0 Lower quartile _ ______ 1.860 343 12 47 0 2. 120 429 NOTE. 120 121 Average __ --_______12 345 61 0 1.940 371 14 1.8 8. quartile.4 6. 6 9.0 110 17 Maximum ____________ 3.5 Median. 8 19 79 17 47 0 24 45 150 1.0 Q 6 39 10 14 4.0 5. The summation of the median. 1 5. minimum.120 374 47 47 0 0 1.7 1.8 12 48 11 14 0 .9 38 330 3.9 3.120 407 14 0 .2 16 79 17 61 0 20 51 200 3. O CO O CO .

250 1. Similarly.030 7.) Consumption of cooling water in distillation units is also less than in cracking units.900 7.630 61 7.900 3.620 2 21 819 1.030 606 3.220 1.650 5 161 3 ALL REFINERIES Number of refineries _ ______ _ ___ Minimum _________ Upper quartile ___ _ _ ______ Maximum _ ________ Average __________ ______ 30 7. _ ______ ___ Minimum _ _____ Lower quartile.980 3.740 REFINERIES WITHOUT CRACKING Number of refineries. Distillation units. by type of cooling system and type of refinery. total water requirements were divided by the capacities of the process units given in the Oil and Gas Journal (1956c) to obtain the unit water-use values in gallons of water per barrel of capacity. 120 804 24 189 1. 120 64 . in gallons per barrel of crude charge Type of cooling system Type of refinery Reuse All systems Once through Combined 7 161 410 700 1. 120 693 14 7.5 145 400 900 3. new makeup for and consumption of boiler-feed water by distillation units is less than for cracking units. either vacuum or crude. 5 140 520 1.5 750 1.640 47 39 1. require less makeup and gross circulation per barrel of crude charge than cracking units owing to the much lower temperature in the distillation processes as compared to the cracking processes. 100 1.680 1.304 WATER REQUIREMENTS OF SELECTED INDUSTRIES able. (See tables 9 and 10. Gross circulating cooling water. 200 1.500 2. _ _ Lower quartile. 5 520 1.590 1. TABLE 6.400 1. 1955.050 7.350 1.300 1.750 7.220 1.250 1.220 1.220 1.700 REFINERIES WITH CRACKING Number of refineries .290 3.__ _ _ ___ ___ Median _ _ _ _ _____ __ _ Upper quartile _ _ _ _ _ Maximum _ __ _ _ __ _ _ ______ Average 24 39 880 1.550 2. _____ Upper quartile ______ Maximum __ ______ Average________ __ _ ______ ___ 6 7. .

6 15 30 48 178 45 7 161 370 740 1.305 PETROLEUM REFINING INDUSTRY TABLE 7. 4 5 161 3 14 5.880 374 6 5. 6 30 56 175 1. 6 20 34 52 178 46 2 21 25 68 150 620 1.500 3.880 515 47 2. Minimum __ ___ _ Upper quartile _ Maximum _ _ ___ _ _ ___ __ ___ REFINERIES WITH CRACKING Lower quartile __ _ _ _ Median _________ Maximum _ _ _ _____ Average __ _______ ___ __ ___ ___ __ REFINERIES WITHOUT CRACKING Minimum. 120 418 Reuse ALL REFINERIES Number of refineries. in gallons per barrel of crude charge Type of cooling system Type of refinery All systems Once through Combined 30 2. ___ ___ Upper quartile ______ __ Maximum ___ _____ ___ Average _ _______ __ 690-234 O 63 11 520 31 23 3. 120 693 . by type of cooling system and by type of refinery. 6 25 60 250 3. 120 784 24 25 61 140 500 1. Cooling-water makeup. 1955.880 511 61 2. 4 12 70 400 3. 120 376 24 2.

5 . 3 9.. in gallons per barrel of crude charge Type of cooling system Type of refinery Reuse Once through Combined All systems ALL REFINERIES Number of refineries _ _ _______ _ Minimum. 1955. 6 23 30 16 5 0 3 14 0 REFINERIES WITHOUT CRACKING Number of refineries _ ____ _ ____ Minimum ______ __ ___ Lower quartile. ____ _____ ___ Maximum _ ______________ Average. ______ ___ ___ _ _____ ____ 30 . _________ ____ Median __ _ ___ _ ___ _ __ __ Maximum _ _ ____ ___ _ _ _ __ Average.306 WATER REQUIREMENTS OF SELECTED INDUSTRIES TABLE 8. 3 24 0 22 33 48 74 29 61 0 12 25 36 94 28 REFINERIES WITH CRACKING Number of refineries ____ _ ___ __ Minimum _ __________ _ _ Upper quartile __ _____ ___ 24 .8 12 24 29 94 31 7 0 0 48 1... 4 3. ___ _____ ___ ___ __ __ 0 48 2._ ___ ___ ______ Upper quartile.6 9.8 16 25 34 94 31 2 21 0 23 28 39 74 29 47 0 18 26 36 94 29 6 1. Consumptive cooling water..8 . by type of cooling system and by type of refinery.0 27 52 9.

3 '4.- ______ Average. _ -___ ___ .7 0 .6 8.__ __ __ ________ ________ __ Lower quartile.0 31 6.----.4 70 5. 9 44 3. 5 6.4 13 725 55 12 21 26 4. ________--_--______--------Maximum.05 .7 5. Water requirements of crude distillation units. 8 3.6 160 300 470 905 356 Total 34 63 340 690 905 512 0 .7 5.5 6.9 44 7.2 19 2. 2 . 7 12 1.__ Upper quartile__ -_--__ ___ ____________ __ Minimum __.7 12.4 4.9 7.4 2.7 660 461 00 K 21 51 Q 916 560 fiQ 440 7QO 300 445 748 352 44 IQft io Cracking Noncracking Total water TABLE 9. 8 7.5 Total 0 .4 4 6 8.2 .--.9 3..0 49 725 78 0 2. 5 43 210 652 451 Consumption 0 4. 1 0.6 175 290 430 725 347 Gross circulation Cracking Noncracking Cooling water .8 12 29 435 46 Cracking Noncracking Boiler-feed water 0 2.8 0.2 59 745 81 0 3. 9 2._ __ - Upper quartile.6 6. ___--_-_----_---_--_-------Maximum.0 3.8 ..9 18 44 9.-----------.6 2.0 8.8 10 62 725 85 8... 9 44 2.__ __ Water requirements and disposition 0 1.5 17 745 58 0 4. 1 0 0 1. 5 11 435 7.7 3.7 10 42 7.9 12 3._--___---------.8 6.9 4. 7 16 74 725 90 13 175 310 510 916 365 Total 0 2.9 2.3 0 0 1.1 31 6.__ __ Lower quartile_-_ -__ ___-___---.5 4. ________ _____ ___ __ Upper quartile.2 0 0 1. 1 11 35 725 67 I 3 Q 27 125 660 453 0 0 1. 5 0 0 3.05 .0 15 31 2. ________-----_----__ ____ __ Median. 1 0 4.3 4.----. 5 0 .3 31 1.________--___---.2 6.-.2 1.3 1.0 4.4 7.3 3.9 26 725 63 New make-up 8.2 .7 17 170 652 444 Effluent 0 2..8 5.0 7.8 7 Q 12 52 7.7 3. £ 20 34 52 6.9 2. in gallons of water per barrel of crude charge [Computed from data obtained from 9 refineries without cracking and 25 refineries with cracking] o .

.200 18 396 10 0 3.Boiler Total Cool._____ 49 2..0 11 20 671 85 23 0 16 19 26 50 20 23 13 27 38 53 707 109 20 23 1.470 348 16 22 3.2 6.4 6.240 1.5 2.0 5.5 81 Upper quartile _______ Lower quartile.8 3..3 31 31 6.8 76 66 14 0 .340 3.0 1.330 37 81 16 .7 20 0 .5 1.400 177 12..0 1.180 232 9 19 4.060 884 New makeup 24 ...1 25 7.3 1.01 1.01 .9 725 44 85 3.2 64 47 1..3 .0 950 1.350 4.Boiler Total Cool.7 4.8 13 96 4.010 26 2.7 160 3..4 4.7 4.400 2..240 16 1..6 8.2 9.4 270 8..0 .2 20 2.5 470 11 905 435 356 7.290 10 9 1.400 51 3. in gallons of water per barrel of crude charge B H QQ 3 H » H £> » ^ 00 .7 21 0 520 2.Boiler Total ing feed ing feed ing feed ing feed ing feed ing feed ing feed 34 34 34 0 0 0 1.0 31 8.6 5.4 299 8.2 100 7...8 140 5.6 73 23 19 294 520 1.8 3.0 670 11 1.3 500 15 950 i278 2.2 21 23 0 5.040 1.1 15 22 31 98 23 15 19 24 8.2 8.2 42 133 12 15 16 39 0 4.250 1. Water requirements of selected operations.3 17 0 17 0 1.3 6.200 11.5 299 14 0 0 2.100 10 961 ..5 62 6. Lower quartile .8 230 11 4SO 17 954 5.07 .Minimum ..Boiler Total Cool.2 13 0 .300 68 4.5 64 123 235 562 254 10 10 4..1 1.Boiler Total Cool.6 9.2 18 2.000 1.2 24 59 127 349 133 46 9 1.8 .5 2.7 13 26 38 80 29 .9 7.2 27 34 4.5 Gross circulation ..9 5.480 7.4 41 91 477 173 10 1.4 24 5..4 88 4.0 14 22 11 17 0 17 4..05 2.0 .1 25 108 20 16 0 4.3 7.8 1.6 1.2 700 840 5.5 17 0 0 .000 2...2 1.7 300 5.7 14 34 2. .6 5.. 010 7.2 1.2 Upper quartile .2 1.6 11 6.2 19 31 43 294 45 22 23 0 0 5.400 35 2.8 88 3..1 1.Boiler Total Cool.3 1.6 .1 14 0 22 23 260 500 950 2.470 14 0 20 37 67 238 37 14 19 0 0 1..0 96 23 5.900 882 8.440 2.0 11 93 6.8 1.7 16 74 725 90 34 34 0 0 4.3 14 806 1..6 15 25 40 14 19 0 2.150 12 1.3 8.9 3.000 16 1.9 82 22 125 54 390 150 1.230 158 2.0 52 46 7.6 19 1.8 13 19 118 215 345 655 223 34 13 175 310 510 916 365 34 34 8.3 35 79 116 221 77 10 2.5 20 35 53 15 10 9 0 0 2.8 10 3.0 12 294 27 Effluent 24 0 3.500 4.4 23 57 108 37 140 49 1.1 10 17 24 80 18 17 6.180 781 322 116 17 17 19 9.7 12 9.200 20 3.9 0 12 12 19 21 34 43 623 1.4 334 14 15 14 ..600 92 3.0 26 16 69 28 165 50 429 127 195 61 14 16 9 21 840 0 4.6 102 1..350 2.080 78 3.8 36 2.0 12 36 7...4 32 23 16 22 23 24 0 0 0 0 1..9 17 6. Water requirements and disposition Crude distillation units TABLE 10.8 3.5 28 115 17 744 1.2 .9 5.3 12 4.5 2.7 3.4 19 0 7.0 .8 12 19 103 6.6 20 0 .0 7.1 874 16 0 25 44 64 282 48 16 14 0 0 16 0 33 2.400 39 2.5 .840 2.2 19 60 92 168 60 10 0 4.08 12 1.2 34 34 0 0 2.4 8..2 15 21 10 20 6.4 Consumption 24 .3 5.790 133 7.9 5.5 2.0 1..3 50 23 1.Boiler Total Cool.3 15 6...0 4..3 8.7 5.9 60 725 44 745 78 2.3 1.940 Cool.. Thermal cracking units Catalytic cracking units Catalytic reforming units [Charge as reported in Oil and Gas Journal (1956c)] Vacuum distillation units Polymerization units Alkylation units 13 34 0 0 3.

1 ppm (7 ppm max). Although water quality is less important than quantity for petroleum refineries. Coalecing followed by skimming. Odor. and chlorine demand. corrosion. Kelly. Corrosion if alkalinity is low. Oxygen. undesirable effects. <5 Plus coagulant chemicals where necessary. a water of good quality is desirable. and methods of removal of the undesirable constituents in water as suggested by Forbes (1954a and b) and Betz (1950) are given in table 11. <5 ppm.007 ppm in boilers and economizers.3 5 <1 . retard heat transfer. Hot deaeration. aid corrosion. Carbon dioxide Aeration.PETROLEUM REFINING INDUSTRY 309 WATER-QUALITY REQUIREMENTS The various uses of water within a refinery have different waterquality requirements. Technical literature contains many references to methods of treating the intake water of petroleum refineries (Forbes. Absorption with preformed floe followed by filtration. Alkalinity Corrosion and pitting. Most sources of water provide both sufficient quantities and suitable qualities for all water needs. neutralization with alkalies. Undesirable effects and methods of correction for common constituents in water [Data modified from Forbes (1954a) and Betz (1950)] Impurity Undesirable effects Usual limit or tolerance Method of correction Residual after treatment. quality is a problem of economics. TABLE 11. Suspended solids. Chlorination. Brooke (1954) showed that complete treating and softening of all cooling water became profitable in less than 4 years and provided many intangible benefits. 1946). and Filtration. 1954a and b. In some refineries special equipment is installed to permit low-quality water to be used without treatment for some processes. Impede water flow. As cost is the deciding factor in choosing between the treatment of water of poor quality and the installation of special equipment for its use. Cold vacuum deaeration. <1 Hydrogen sulfide. Carbon dioxide. <0. <1 Causes sludges to bake on in form of scale. For example. and acid treatment of boiler-feed wastes.007 0. Most refineries use sources that will yield sufficient water and will satisfy the quality requirements by treatment.5 ppm. Sedimentation and filters. in a gulf coast refinery described by Resen (1957) salty water is used for once-through cooling. Usual tolerances. and high-quality demineralized water is used for high-pressure boilers. <0. (ppm) Aeration.1-0. Causes boiler foaming. Oil. 5-10 <0.

Iron and manganese. the source and quality of untreated water. deionization. causes boiler embrittlement. Adsorption on Fe(OH)aorMg(OH) 2. Of these analyses. Undesirable effects Usual limit or tolerance Method of correction Residual after treatment. 47 were furnished by the refineries and 35 were obtained from U. anion exchanged with or without fluoride addition. Any desired residual. forms COz in steam causing condensate corrosion. Anion exchange. (PPm) Promotes boiler foaming. 0-5 Chemical analyses were obtained of untreated water from 82 sources used by 56 of the refineries visited in 1956. lime with or without gypsum. 25-35 Hot lime soda. 12-15 Cation exchange (sodium or hydrogen cycle) . For each use of water. Generally 60-80 ppm max. For drinking. Cation exchange (hydrogen cycle) . 100-300 ppm max where possible. Boiler foaming corrosion. Geological Survey publications.1-0. <3 17-25 0-3 Silica. interferes with pH control. requirements for each use are discussed separately. 30 Magnesium. Low as possible.3 ppm. and sanitary water are different.310 WATER REQUIREMENTS OF SELECTED INDUSTRIES TABLE 11. . 10-0.S. Cold lime soda. 30-50 ppm. Scale formation. depending on boiler pressure. Generally 100-300 ppm max where possible. Undesirable effects and methods of correction for common constituents in water Continued [Data modified from Forbes (1954a) and Betz (1950)] Impurity Alkalinity. process. Because the minimum water-quality requirements for cooling. 0-10 ppm max. and the watertreatment methods for each type of water used. Scale formation. Cation exchange (hydrogen cycle). Scale. a brief discussion is given of the desired characteristics and suggested tolerances. Sulfate. 0. boilerfeed. 0-5 0. Same as Ca. Anion exchange. Sulfuric acid addition. The chemical and physical characteristics of un d water for all uses are given in table 12. Generally 60-80 ppm for process use and boilers. 0. Corrosion and scale. Scale formation. 0-5 Sodium. For boilers. Analyses of water supplied by private water companies or municipalities were of the water delivered t^ the refineries. <300 ppm. 300 ppm. Aeration followed by filtration (pH control may be required) .3 Calcium. 3-20 ppm. Concentration ratio: For ice. Barium treatment. Boiler foaming and corrosion. ^60 Chlorides.

.1 1.2 8..4 4. ___ ... organic slimes. especially where oncethrough cooling is used.1 COOLING WATER Water for cooling.57 . Quality tolerances of cooling water suggested by American Water Works Association [Data modified from Am.PETROLEUM REFINING INDUSTRY 311 TABLE 12...00 2. __ .1 3500 850 550 22 9. cooling water should be of sufficiently good quality to keep corrosion.8 60 14 220 83 266 484 565 1600 1. temperatures.)_ Fluoride (F)-_.0 17 .2 Median 12 42 12 19 167 59 28 .0 . Nitrate (NO3)-.5 520 275 56 10 7. (I960)] Constituent or property Limiting values (ppm) Hardness as CaCO3________________________________________________ 50 Iron (Fe)___.8 1....8 76 17 15 ._________________________________________________ .. and deposits of sediment to a minimum.4 146 76 63 10 0 19 74 67 0 1 6. ..10 . and velocities were high. the largest use in refineries.0 . Quality tolerances of water for cooling as suggested by the American Water Works Association are given in table 13. Water Works Assoc.4 7.4 . 5 Iron plus manganese__-----_-__--________-_-___-__-_-_---------_-_. specific conductance. 5 Turbidity______________________________________ 50 Corrosiveness._ Hardness as COs: Total pH__ . Temperature is a major consideration in the selection of a source.5 Manganese (Mn)__________________________________________________ . TABLE 13.7 1. _ Sodium and potassium (Na+K) . Their survey in- . In general.. These data are based on individual observations available and are not balanced analyses] Number of samples Constituent Silica (SiOs) Calcium (Ca)-.6 Upper Maximum quart ile 18 69 25 54 270 152 66 .. Quality characteristics of untreated water for all uses [Data expressed in parts per million unless otherwise indicated. They noted that where dissolved solids. Concentration Minimum Lower quart ile 52 38 64 63 34 69 64 75 28 28 50 2. _ _ _.____________________________________________________ None Slime formation ___________________________________________________ None PUBIJSHED INFORMATION In an extensive survey of refinery cooling-water systems.8 ..6 .0 .. Sulfate (SOO ~_ Chloride (C. Helwig and McConomy (1957) reported that fouling and corrosion occurred in all cooling-water systems when no treatment was provided. scale formation.5 265 144 20 5 7..04 18 4. ranges in quality from sea water for once-through systems to high-quality water for circulating systems. corrosion was accelerated.0 3 7.0 46 6.

the cost of treating sewage effluent is only slightly higher than the cost of treating chemically comparable natural water. (1950) is described in "The Lamp. and maximum values are given for each constituent and characteristic of once-through and circulating water for which there are a sufficient number of samples. The chemical analysis of one treated sewage effluent as delivered to the refinery was obtained. corrosion increased in circulating-water systems if the pH dropped below 7. The most prevalent treatment method^ reported were (a) pH adjustment with sulfuric acid or soda ash. median. Minimum. is reported by McCormick and Wetzel (1954). always be equal to the total number of analyses of water from all sources. An average use of 128.5 mgd of sea water for most cooling in the Bay way refinery of the Standard Oil Co.0. Helwig and McConomy also reported on the effectiveness and cost of the various types of chemical treatment. cathodic protection. (b) control of slime and algae growth with chlorine and other algicides. and silicates. but no analyses of sea water were included. lower quartile. Several refineries use the same source of water for once-through and circulating cooling systems. Miller (1951) also discussed the objectives and techniques of cooling-water treatment. In coastal areas low-quality water. .312 WATER REQUIREMENTS OF SELECTED INDUSTRIES dicated that. Sewage effluent created such problems as foaming in boilers and excessive slime growth in cooling systems. with the exception of the additional expense due to increased chlorine demand." The successful utilization of sewage effluent for cooling and for boiler-feed water by the Big Spring refinery of the Cosden Petroleum Corp. He noted that when open-circulating cooling-water systems were used. upper quartile. FINDINGS OF THIS SURVEY In the 1956 survey data were obtained on the chemical and physical characteristics of the untreated cooling water used by 68 petroleum refineries. whereas corrosion was mild if the pH was above 8. chromates. The authors noted that.5. treatment problems increased owing to concentration effects. and the use of special construction materials. and (c) control of corrosion and fouling with polyphosphates. in general. Table 14 shows the chemical and physical characteristics of untreated water that was supplied to the circulating cooling systems of 48 refineries and to the once-through systems of 26 others. The sum of the number of analyses of cooling water will not therefore. such as sea water. but these problems were corrected by modifications of standard treatment procedures. Refineries were actively and effectively combating fouling and corrosion by chemical treatment. is used by refineries for cooling.

0 17 .0 228 52 248 145 58 .8 .0 . 12 51 13 Concentration Upper quartile 14 72 24 .4 .1 . ------ Number of samples -------- Magnesium (Mg) __________ Sodium and potassium (Na+K)_____.6 13 7. 7 Lower quartile Median 5. 15 5 7.2 68 14 12 .TABLE 14.0 . 71 Number Maxof imum samples Minimum 46 14 204 83 34 23 41 40 2. 6 629 17 45 40 52 14 12 32 1.8 .0 .0 . These are based on individual observations available and are not balanced analyses] Once-through Constituent or property Silica (SiOs) Iron (Fe).0 83 27 60 8.5 1.02 18 4.6 1.8 .8 22 8.0 . 1 6.4 Lower quartile 7.170 160 10 319 56 45 13 .7 97 13 142 38 26 .0 22 .3 193 68 0 3 7.2 7. Bicarbonate (HC03) ___--_.04 16 4.0 46 33 27 12 0 52 5 160 22 326 58 850 550 51 40 10 0 10 31 1 6.0 . -____ _.00 19 30 30 32 15 14 21 1.2 113 18 19 .2 Median 12 Upper quartile Maximum 22 1.0 3 7.) Chloride (01) ___________ Fluoride (F)______ _ _ __ Nitrate (N03 )----_-------Hardness as CaC03 : Total ____ __ __-_-_ Color_____ T->HT pH __ _ ____________________ 24 19 28 28 Circulated Concentration Minimum 2.2 9.1 00 I1 00 .0 8 7.2 .8 1.5 624 266 484 558 900 1.2 .9 850 550 14 9. 1 2.0 46 6.4 . 9 7 49 1 6. Sulfate (SO.9 296 146 332 156 64 .7 204 83 52 198 68 30 .4 14 7. Quality characteristics of untreated cooling water [Results expressed in parts per million unless otherwise indicated.6 442 102 484 536 900 1.00 4.8 1.7 2.2 5.2 2.

C O Ui I INDICATED J 30 santples L V\ E2 100 200 300 400 500 SULFATE (SO4 ).314 WATER REQUIREMENTS OF SELECTED INDUSTRIES Additional information on dissolved solids. IN PARTS PER MILLION 33 samples 100 E3 200 300 400 500 600 700 TOTAL HARDNESS AS CaCO 3 . IN PARTS PER MILLION m 6C 30 samples 100 200 300 400 500 600 BICARBONATE (HCO. Frequency distribution of selected chemical constituents in untreated water for once-through cooling. Waters used for once-through and for circulating cooling were similar in quality. bicarbonates. however.). IN PARTS PER MILLION 800 0 200 400 600 800 DISSOLVED SOLIDS. IN PARTS PER MILLION FIGURE 44. water used for once-through cooling was of slightly higher quality. The use of higher quality water for oncethrough cooling is not due to higher requirements but is probably due to the availability of better quality water in areas of plentiful supply where recirculation is not necessary. . and sulfates is shown in figures 44 and 45. total hardness.

Frequency distribution of selected chemical constituents in untreated water for recirculated cooling. IN PARTS PER MILLION 1400 FIGURE 45. .315 PETROLEUM REFINING INDUSTRY 40 samples 600 100 200 300 400 500 SULFATE (SO4 ). IN PARTS PER MILLION 32 samples 200 400 600 800 1000 1200 DISSOLVED SOLIDS. IN PARTS PER MILLION I 5 1 45 samples 600 100 200 300 400 500 BICARBONATE (HCO 3 ). IN PARTS PER MILLION I 51 samples <r 0 UJ ffi 5 100 200 300 4OO 500 600 700 800 TOTAL HARDNESS AS CaCO3 .

which varied from screening to sedimentation and filtration. water from 52 of the 69 sources of circulating water was given some type of treatment. one on standby. and the boilers could be operated for as long as 2 months between cleanings. Table 15 shows the methods used for treating once-through and circulating cooling water at the refineries visited. 1954). and one being cleaned.316 WATER REQUIREMENTS OF SELECTED INDUSTRIES Most refinery intake water is treated to provide the desired quality of cooling water. . During World War I the plant had three boilerhouses: one on steam.and high-pressure steam. The boiler-feed water was not treated. BOILER-FEED WATER MAKEUP Large amounts of high-quality water are used by petroleum refineries to produce low. which operate on softened and internally treated waters. Modern boilers. and the average on-stream time for a boiler was 2 to 3 weeks. may never need cleaning and will be opened only for annual inspection (Brooks. Untreated water is generally not satisfactory for this use. Later the feed water was given internal treatment. therefore. careful consideration is given to the selection and treatment of makeup water for boiler-feed to prevent excessive corrosion. Although water from only 10 of the 39 sources of once-through cooling water was given treatment. Experience at a gulf coast industrial plant indicates the importance of high-quality boiler feed. scale formation and embrittlement.

Prior treatment of purchased water is not considered] Once-through cooling water Self-supplied Public supplied Type of treatment Ground water Screening. _.TABLE 15. ______ Surface water Saline Fresh Saline Fresh 12 1 8 1 4 5 1 3 - Dianodic_____--_pH adjustments. Other. _ __ __ Surface water Fresh Sedimentation _ _____ Filtration. ________ Softening: Disinfection and algae control: Chlorination.--. _______ Circulating cooling water 1 1 2 Self-supplied Total Ground water 1 Surface water Ground water Surface water Sewage Total effluent Fresh 30 1 Saline Fresh 4 1 3 1 4 4 3 1 5 1 3 1 3 12 7 5 8 2 Public supplied 3 6 12 2 15 6 1 1 Saline Fresh Saline Fresh 1 1 4 10 1 1 1 1 6 5 5 1 1 2 1 1 2 2 3 2 2 3 1 3 1 10 3 1 20 1 9 13 4 1 4 10 21 3 27 8 1 1 1 ._.. Treatment of makeup water for cooling [Figures refer to frequency of use of various types of water treatment.. _____ Organic compounds--------Other_-__------Corrosion and scale control: Chromates..

McCormick and Wetzell (1954) described the use of sewage effluent instead of hard ground water for boiler-feed water makeup. The boiler-feed water problems of petroleum refineries. are usually individual problems and require specialized treatments for satisfactory solutions. and water treatment experts could not provide a practical solvent for the scale. and the Permutit Co. Cosden contracted for use of the sewage effluent from the city of Big Spring.01 ppm. refinery of the Gulf Oil Corp. however. Tex. anthracite filtration. by the use of special treatment. 1950. This treatment was not entirely satisfactory as foaming and priming resulted.318 WATER REQUIREMENTS OF SELECTED INDUSTRIES PUBLISHED INFORMATION There are many textbooks and manuals on industrial water conditioning (for example: Nordell. Two samples from company wells could be classified as slightly to . In early 1944 the refinery was using water with hardness ranging from 700 to 1. Betz. 1954. 1951. and zeolite softening. gravity filtration. Analyses were obtained of water from 55 sources: 40 were company wells or surface water. At first the effluent used for boiler-feed water makeup was treated by the hot-lime process.300 ppm. Tex. and 1 was sewage effluent. Steam turbines obtained to drive centrifugal compressors and other equipment required the use of high-pressure steam. In July 1944. which lowers the mineral content to less than 6 ppm of dissolved solids and the silica content to less than . and internal phosphate treatment in the boiler drums.. The desired high-quality water for the high-pressure boilers was obtained by passing the gravity-filtered makeup water through an ion-exchange demineralization unit. Powell. This steam must be free of silica to prevent the deposition of silica on the turbines. McCormick and Wetzel reported. however. which causes reduced efficiencies and early maintenance shutdowns. that satisfactory operation was attained by changing to a hot-phosphate treatment in an external treater followed by the injection of a foam suppressing agent into the boiler drum. 14 were public supplies. Scaling was a serious problem in boilers and in other heat exchange equipment... at the Port Arthur. Eesen (1957) described the solution of a makeup-water problem for high-pressure boilers. 1947) that discuss the general problems caused by impurities in boiler-feed water and the treatments used to remove undesirable impurities. FINDINGS OF THIS SURVEY Chemical analyses of the untreated makeup waters for boiler feed used by the refineries surveyed were obtained where possible. The surface water used for boiler-feed makeup in the generation of low pressure steam had been treated by coagulation.

to interpret these analyses. IN PARTS PER MILLION 1200 FiotJEB 46. IN PARTS PER MILLION 200 300 400 500 60 70 600 BICARBONATE (HCO 3). IN PARTS PER MILLION 45 samples 100 200 300 400 500 600 700 TOTAL HARDNESS AS CaCO3 . frequency distribution for some important chemical constituents in boiler-feed makeup water. Figure 46 shows the 5 36 samples 10 0 100 20 30 40 50 SILICA (SiO2 ).000 ppm. A comparison of the quality characteristics of the untreated water with the suggested tolerances indicates a need for treatment by most refineries. Many of the refineries employed industrial water consultants to make water analyses. None of the refineries surveyed used sea water for boiler-feed makeup. The quality characteristics of untreated makeup water for boiler feed used at 54 refineries are given in table 16. Frequency distribution of selected chemical constituents in untreated makeup water for boiler feed. and to recommend .PETROLEUM REFINING INDUSTRY 319 moderately saline (Krieger and others. 1957). IN PARTS PER MILLION 800 32 samples ^^1 0 200 400 600 800 1000 DISSOLVED SOLIDS. as the dissolved solids content of both were over 1. Water-quality tolerances for boiler-feed water makeup suggested by Moore (1940) are shown in table 17.

..8 1.1 14 7....... . not to original water supply. . Concentration Number of samples Minimum Upper quartile Maximum 19 68 25 69 270 148 74 .00 2.6 water-quality tolerance for boiler-feed water [Data from Moore (1940)] Constituent Suggested water-quality tolerance (ppm..01 1 Limits applicable only to feed water entering boiler...__ __. was the most common method (table 18).-Silica (SiOi)__________..8 .0 . In other refineries consideration of problems of water quality and treatment ranged from giving no thought to the problems to assigning several full-time staff members to the work..__..10 39 14 24 186 62 33 .. ______ Bicarbonate (HCO3) 1 ______ _ Carbonate (CO3)__ ____ _ _ Hydroxide (OH)______ ___ __ Total solids 3 __ ___ _ _ ___ 15 1... _____ _____ _______ pH value (minimum) ___ Turbidity..2 7. External treatment of makeup water for boiler feed. 0 20 40 8..9 . 500 1 0 20 15 50 .____ ...8 5 7.1 ..4 .) at pressure (psi) indicated 0-150 150-250 250-400 10 4 >400 Oxygen consumed _ __ _ Dissolved oxygen 1 Hydrogen sulfide (H2S) Total hardness as CaCO3 _____ Aluminum oxide (AljOs).5 4. .320 WATER REQUIREMENTS OF SELECTED INDUSTRIES TABLE 16. 6 1 1:1 2:1 8:1 3:1 .. treatment of the boiler-feed water. ..0 . 14 23 40 .. 500 3 .0 86 18 18 . Nitrate (NO3). _ _ _ ______ Sulfate-carbonate ratio 4 (Na.4 10 51 _. either by the lime-soda or by the zeolite process...1 6.03 18 4...4 10 5 9.5 286 55 44 10 0 Silica (SiOj).. 5 20 30 100 40 500-2..__ Sodium and potassium (Na+K)-___ Sulfate (S)*..... 2 Except when odor in live steam would be objectionable.. Iron (Fe).0 22 .SO4 :Na..2 1...58 60 7... Of the 137 sources of makeup water for boiler feed.._-.7 1..2 173 56 266 484 558 465 1.... 4 25 80 5 40 50 200 50 500-3.... 000 Color.... DH... 4 American Society of Mechanical Engineer standards...___.... TABLE 17...0 46 6. 3 Depends on design of boiler.._ . .05 5 5 40 30 100-1..2 .CO3)__ - 80 8...Chloride (Cl). Internal treatment with chemicals for scale and corrosion control was second in frequency of use. 2 were municipal supplies and 1 was a company well. Hardness as CaCOs: Total.7 151 12 ..6 1170 644 416 22 9... .. These are based on individual observations available and are not balanced analyses] Constituent or property Lower quartile Median 36 24 43 43 21 49 45 54 15 15 33 2.... 3 received no treatment by the refinery....0 5 2 9..0 .0 622 272 52 142 14 66 0 3 7. Quality characteristics of untreated boiler-feed makeup water [Results expressed in parts per million unless otherwise indicated.... _ 1 6... ..0 0 10 0 2 .

Sanitary and service water may also vary in quality. whereas water for general refinery cleanup may be much lower in quality.. ____ _ _____ _ Sedimentation. Water for drinking usually satisfies sanitary quality standards suggested by local or State health departments. but some of this water is of necessity the highest quality used by the refinery. Prior treatment of purchased water is not considered] Public supplied Self-supplied Type of treatment Ground water Fresh No treatment. Water for product washing may need to be equivalent to drinking water or of a higher quality.S. These standards are generally equivalent to those of the U. _ __ ____ __ _ Saline Surface Ground Surface water water water Sewage effuent Fresh Fresh 2 4 4 2 1 2 2 4 7 2 10 3 2 1 2 16 10 1 1 1 Fresh 3 3 6 8 4 1 1 2 1 2 2 10 28 27 1 6 4 2 4 2 11 Total 1 2 1 2 2 2 1 1 2 2 1 1 18 1 2 1 5 5 15 PROCESS AND SANITARY WATER The quantity of water used for process and sanitary services is negligible compared to that for other refinery uses. _____ Other _ ____ ____ _ __ Corrosion and scale control: Phosphates __ ___ _ _ Dianodic___ ____ ___ _ Deaeration __ _ _ Embrittlement protectors __ _ pH adjustment. Usually the same quality of water and very often the same water is used in washhouses and sanitary fixtures. _ ___ _ _ Zeolite.321 PETROLEUM REFINING INDUSTRY TABLE 18. _____ _ ___ _ Softening: Lime-soda. process waters should be clear. __ _ ____ Other. Fifty quality analyses of water used for sanitary purposes and 49 analyses of process water were obtained in the survey. _ _ _ _ __ Coagulation. ________ Distillation _ ___ _____ Other _ ___ ___ _ ___ Disinfection and algae control: Organic compounds. Water from . _______ Filtration. Quality tolerances for process water vary widely with the purpose for which it is used. Water used in washhouses may be of lower quality than that for drinking. In general. and free from iron. hydrogen sulfide. manganese. ___ _ _ Antifoam. colorless. and organic growths (Nordell. 1951). Treatment of makeup for boiler-feed water [Figures refer to frequency of use of various types of water treatment. Public Health Service (1956).

distribution charts showing the occurrence of dissolved solids. Water for these needs received less treatment at the refinery than water used for other purposes because public supplies that had received previous treatment .322 WATER REQUIREMENTS OF SELECTED INDUSTRIES three sources (two rivers and one well) was saline. Extensive. and sulf ates in untreated process and sanitary water. IN PARTS PER MILLION 900 800 D Z 32 samples 200 400 600 800 1000 1200 DISSOLVED SOLIDS. Figures 47 and 48 are frequency 10 41 samples 155 V////A 100 200 300 400 500 SULFATE (SO 4). IN PARTS PER MILLION 100 200 300 400 500 BICARBONATE (HCO 3). or no treatment of refinery intake water may be necessary to provide the desired water quality for process and sanitary needs. IN PARTS PER MILLION 3200 3600 FIGURE 47. bicarbonates. minimum. and quartile values of the chemical and physical constituents of these waters. total hardness. Frequency distribution of selected chemical constituents in untreated process water. Part of the process needs of one refinery was supplied by sea water. Table 19 shows median. maximum. Tables 20 and 21 list the methods used to treat process and sanitary water at the refineries surveyed. but no chemical analysis of this water was obtained. IN PARTS PER MILLION 600 600 45 samples UJ CD J 5553 01 0 100 5 200 300 400 500 600 700 TOTAL HARDNESS AS CaCO 3. partial.

and the high-quality needs were obtained from sources receiving previous treatment. . were the source of process water for a quarter of the refineries and the source of sanitary water for half of the refineries. Frequency distribution of selected chemical constituents in untreated sanitary and service water. IN PARTS PER MILLION 33 samples 200 400 600 800 1000 1200 DISSOLVED SOLIDS. Process water from only 18 of the 58 sources and sanitary water from only 13 of the 65 sources received treatment at the refinery. IN PARTS PER MILLION 42 samples 0 100 200 300 400 500 600 BICARBONATE (HCO3 ). IN PARTS PER MILLION h-" O 46 samples 100 200 300 400 500 600 700 TOTAL HARDNESS AS CaCO3 . IN PARTS PER MILLION FIGURE 48. Several refineries had multiple sources of water. the low-quality needs were supplied from sources receiving no treatment.323 PETROLEUM REFINING INDUSTRY 15 10 39 samples O 0 100 200 300 400 500 600 SULFATE (SO4 ).

-i GO (M (M .-H ' CO ^HiO ' (MO COI> (M i-l ^H .-H ^5 (M C^ ^2" 03 ^* CO Ho ^3^ C^l ^f ^* ^^ i 1 i~H CO W CO G- __^ M1 s^x S S S o3 *^ -*^ "C *C ~£* 'X ^ E^ ^ x_xfij Q ^ d "T" O Q ^ ^ QJ ^.-H (M <* O ^H ^H~ 'OOO I> CO ^ ^ CO TJ( i-H OS i-H C3 ^ lO ^ ^* 00 ' C? Tt< 1>lO <MT^ ' .324 >.-H GO I> GO * i-H ' GO -^ CO 'cO ^H i-H OS COI> CO COI> ^ COI> 00 ^HCO ' OO °i-< GO CD CD CD CD i-il> ' CO 1C '(M ^^ CIS GO !> (M COO * * Oi 1 *-O !> CO O(M O (M (M OO GO CD ^5 c5 2 C3 a . ^AoS^^slolisw .a -S a ?? S C3 S o- os "d 1-1 s « g « 3 is r^ '§ H g a O S3 " 3 J O Cj ^ k^lTd r^ o3 'i^ Q O fcn tW j^. (S IS co CO 2 PH a w 03 s| && t> ^ o- 0) i3 ^ « EH si aa S| <3 M |«1 g g C9 a | S lO i-H O 'cOO CO ^H TH ' O 1C CO C3 (M CO O * CO CO CO 1> 1C lO ! ' 1-1 .-H CO ^^ <M COCOCOIO CO CO CO CO lO-^OlM CO CO OS CO (M OOOOS (M CO Tt«M . O O O g o a *c--26ogg ° §_ ^ ^ vS_^3 CO C^l CO CO C^l ^<OGOI> OC) Tt<0 3 § &=§ ^^M 1-3 o1 a 3 a § xf-a §°S g « 'S a WATER REQUIREMENTS OF SELECTED INDUSTRIES II ss C3 OB ^3 SS C3 o &< 5 <S -^ .-H oM 0 a o fcn OS lO COCO o cot^ (M iCt^ CO ot-^ GO <MO(5 (N OS CO (M OS lO i-l (M CO (M * CO Tt< (N (M CO co" O lO (MCO i-T CO ' Os 1C i-l OS ' 1-1 'i-ii-l OS (M (MlO 'COO CO lO (MI>COO C^^iOCO GOr^^l^1 >-O i^ !> CO CO i-l OOlOOSIM i-l i-l GO CO (M -* 1-1 i*^ GO O O (M I> i-( O CO i-H CO i-l O i*^ t^* iCiO GOiO lOGOOOOS CO (M CO CO '(M-* lO i ' (M i-l 'lOGO !> C^l i-i CO i-( (M GO C^l CO C^l |s o* ag _C9 * i-l (M " .

_ _-_. Treatment of makeup for sanitary water [Figures refer to frequency of use of various types of water treatment. Prior treatment of purchased water is not considered] Public supplied Self-supplied Type of treatment Ground water Ground Surface water water Surface water Fresh Saline Fresh Saline Fresh Fresh 17 1 4 1 1 1 3 3 2 10 1 1 1 Coagulation _ __. size of refinery.325 PETROLEUM REFINING INDUSTRY TABLE 20. Disinfection and algae control: Corrosion and scale control : Deaeration__ ___ Other _ _ __ __ Ground water Surface w ater Ground water Fresh Saline Fresh Saline Fresh Saline 17 1 1 1 2 2 1 32 1 1 1 1 1 1 53 2 2 4 3 3 1 1 2 Total Fresh 1 3 2 1 5 Surface water 1 9 1 1 FACTORS AFFECTING WATER USE The results of the current survey were studied to find an explanation for the wide variation in water use. type of process.. _ Other. _ _ _ _ Filtration.. _--_____ 1 Softening: Other. ___ ______ Softening: Lime-ash. _ _____ Zeolite _ .. Prior treatment of purchased water is not considered] Public supplied Self-supplied Type of treatment No treatment _______ Coagulation _ _ _ __ Sedimentation. and temperature and quality of the water upon the water use was investigated.. The effect of availability of water. Treatment of makeup for process water [Figures refer to frequency of use of various types of water treatment.. operating procedures..... . _ _____ Disinfection and algae con- Total 37 1 2 1 6 2 2 2 1 1 1 1 1 1 1 1 Corrosion and scale control: pH adjustment __ _____ Other_-----_-__----_-_ 1 2 1 1 1 3 1 1 3 I 1 TABLE 21...

000 and 100. owing to the large proportion of once-through cooling water used.600 and 100 gallons .000 barrels per day and those with capacities less than 10. The unit makeup-water requirements of the refineries surveyed varied with the runoff of the area in which the refinery was located. Therefore. Four of the five refineries required more than average amounts of makeup water. whereas the median for high-runoff areas was about 250 gallons per barrel. Five refineries with capacities of more than 100. There was a negligible difference in the average makeup-water needs of refineries with capacities between 10. Even though the large refineries had greater makeup-water requirements than smaller refineries.326 WATER REQUIREMENTS OF SELECTED INDUSTRIES AVAILABILITY OF WATER Location seems to affect water use. The median makeup-water use in arid locations was about 75 gallons per barrel of charge. and each was located in an area with an abundant supply of water. The makeup-water requirements of 20 refineries in high-runoff areas exceeded 100 gallons per barrel of charge.000. TYPES OF PROCESSES The type of refinery and processing units and the operating procedures affect the water requirements. the greater requirements were due to factors other than size. The water uses of refineries in arid areas in which the runoff was 1 inch or less were compared with the uses in areas in which the runoff was more than 10 inches. The negligible effect of size on water requirements is further illustrated by the small variation in the average unit gross circulatingwater needs among the three size groups. whereas only 4 refineries in arid locations had makeup requirements this high. the greater amounts of makeup water used were due to the favorable water situations at the refinery locations rather than to their sizes.000 barrels per day were visited during the 1956 survey. The average makeup requirements of both size groups were less than those of refineries with capacities in excess of 100. but its effect is actually due to the variation of availability of water. SIZE OF REFINERY Analyses of the data indicate that the unit makeup-water requirements of the refineries surveyed were not directly affected by size. The water requirements of refineries with cracking units were considerably larger than the requirements of those without cracking units. Table 5 shows that the median gross circulating-water requirements and the makeup-water requirements for refineries with cracking facilities were 1.000 barrels.

PETROLEUM REFINING INDUSTRY 327 per barrel of charge. circulating. The corresponding values for refineries without cracking were 500 and 75 gallons per barrel. The quality requirements of feed water become more exacting as operating pressures and temperatures increase. If a circulating cooling-water system were used for the same refinery. Other refineries continued using the river supply but increased the withdrawal for cooling as the river temperature increased. Conservation measures should also be used where low-quality water must be treated before use or where high-priced city water must be used. only 6 refineries in high-runoff areas reused their water this many times. Most refineries have several processing units. Several refineries that used water from rivers for cooling had auxiliary groundwater supplies for use in summer when the river temperatures were too high for effective cooling. Although 16 of the 21 refineries in arid locations reused their water more than 10 times.000 barrel-per-day refinery with cracking facilities and a oncethrough cooling system would require a source of makeup-water of 7 million gallons per day. and combined cooling systems (table 4) show the decrease in makeup-water requirements when water is reused. The data for average and median unit-makeup-water use by lefineries with once-through.5 gallons per barrel for distillation units. . OPERATING PROCEDURES Makeup-water requirements of refineries can be substantially reduced by recirculating as much cooling and other water as possible. It is essential to use such systems in arid and other water-short areas. based upon the median water-use value shown in table 4. QUALITY AND PHYSICAL CHARACTERISTICS OF WATER Water temperature affects the use of water by refineries. probably no more than 630. Unit water requirements of processing units are shown in tables 9 and 10. respectively. A 10. Suggested water-quality tolerance in concentrations of some chemical constituents in boiler-feed water at certain operating pressures are given in table 17. Median makeup-water needs for the processes ranged from about 125 gallons per barrel for polymerization and alkylation units to 15.000 gallons of makeup water would be required daily. The operating temperatures and pressures of boilers affect the quality of water that must be supplied for boiler-feed makeup. and the combination of the units affects the water use of the refinery.

The initial treatment of refinery wastes commonly is to remove oils by an API gravity-type separator. because low-quality water will become concentrated and require dilution sooner than high-quality water. and washhouses. boiler and cooling tower blowdowns. releases during shutdown or startup of equipment. equipment cleaning. Most modern refineries segregate their wastes so that similar wastes are collected for treatment in one plant. In a recirculating cooling system. primary settling tanks. and others collect all wastes for treatment in a single plant. Some refineries treat each waste stream at its source. Therefore. The solids content of the recirculating water is reduced by discarding a part of the circulating water (tower blowdown) and by the addition of new makeup water which contains less dissolved solids. waste water from crude oil desalters and from storage tanks. REFINERY WASTE WATER Waste products from refineries consist of oils. Waste treatment is different for each refinery. lavatories. Spent clays from clay treating units and bottom sediments from separators and traps are examples of waste solids in refineries. condensate from steam-stripping operations. Some chemical wastes from petroleum refineries must receive individual treatment. Sanitary waste water at most refineries is collected in a separate sewer system and treated in septic tanks. and phenols). Spent clays are usually disposed of by dumping. regeneration of ion-exchange units. alkalies. Sulfides in waste water are neutralized and stripped in an absorption tower. sulfides. the quantity of makeup water required for a recirculating system increases with a decrease in water quality. Phenols in waste water have been treated by aerobic biological processes and in trickling niters.328 WATER REQUIREMENTS OF SELECTED INDUSTRIES Low-quality water may require substantial treatment before it can be used. and suspended solids. Waste-water treatment methods used by the refineries surveyed are . oxidation ponds. and the waste streams that require special treatment are treated at the source. the solids content of the water increases owing to evaporation. The major sources of these wastes are equipment leakages and spills. The remaining oil is treated to break the emulsion. Acid and alkaline waste waters are neutralized by mixing with each other. and cooling towers. Treated water is usually used in a recirculating cooling system rather than discharged to waste from a once-through system. chemicals (especially acids. and oxidation ponds. storm water. whereas the other waste solids are withdrawn as slurry and pumped to settling ponds. or discharged into city sewers. backwashing of filters.

Factors other than water will probably -continue to control selection of future sites. __ ___ Sedimentation ___ _ _ _ _ __ Coagulation __ __ __ ___ Filtration _____ Skimming _ _ pH adjustment. which was used for treating 41 waste-water streams. proximity to a market for the refinery output. but water conservation within refineries will become more important. . An analysis of current refinery locations should be useful since areas in which refineries are currently located are areas of possible future expansion.329 PETROLEUM REFINING INDUSTRY shown in table 22. but five of these were discharged into city sewers. Eleven waste-water streams received no treatment at the refinery. whereas the effect of others can be more accurately determined. The necessary utilities and labor supply available and their cost are other factors of less importance. LOCATION OF REFINERIES Important factors that must be considered in selecting sites for petroleum refineries are sources of crude oil. Waste-water treatment Frequency of occurrence Treatment Refineries without cracking facilities API separator _ _ _ _ _ Ponding __ __ . The effect of some factors on water needs are rather uncertain. _ _ Chlorination__ __ ____ Septic tank or cesspool (sanitary sewage) _ No treatment. Analysis of some of these factors is necessary to make a reasonably accurate estimate of the future water requirements of the petroleum refining industry and of the areas of the United States in which new refineries will probably be located._ __ _ _ _ Refineries with cracking facilities 7 2 1 2 1 4 34 14 6 2 I 3 1 1 2 7 Total 41 16 6 2 2 5 1 I 3 11 FUTURE WATER REQUIREMENTS As noted previously (p. The most common method of waste treatment was the API separator. 325). Water has been a minor factor in site selection. and the transportation facilities available. but in water-short areas refinery operations have been adapted to conserve water. many factors affect the total and the unit water requirements of petroleum refineries.. TABLE 22.

and the cheap and abundant supply of natural gas available for fuel are factors that make the gulf coast areas of Texas and Louisiana an excellent location for petroleum refineries and account for the large number of refineries located in this area. Reuse of water is the general practice in this area. New Jersey. The tidewater location. and Boston.380. New York City. Indiana. East coast refineries are usually market oriented and are located near large population centers. and excellent transportation facilities. such as Philadelphia. the nearness to a crude-oil supply. Although California is the second largest crude-producing State in the Nation. a large source of crude. Reuse of cooling water is not as general in this area. Kansas. Pennsylvania.330 WATER REQUIREMENTS OF SELECTED INDUSTRIES There were 294 operating refineries in the United States with an average total operating capacity of 8. Michigan. a large market for refined products. One-fourth of the total operating capacity was located in Texas. and the Middle East is imported to supply the deficit. Most west coast refineries are located near such population centers as Los Angeles. or the gulf coast. the Middle East. and the refining capacity of Texas combined with that of California and Louisiana accounted for more than one-half of the operating capacity of the Nation. Approximately three-fourths of the operating refineries 90 percent of the national capacity were located within the 12 States of Texas. Sumatra. San Francisco. An additional condition favoring the area for refinery location is the natural gas that is available for use as fuel. Many east coast refineries have long used sea water for cooling. it does not produce sufficient crude oil to meet all west coast demands. Oklahoma. Most of the crude oil used by the refineries in this area is transported by pipelines from inland Texas and Louisiana oil fields. and the Puget Sound area. and crude from Canada.801 barrels per day in 1955 (Kirby. California. The Los Angeles area is one of the few places in the country that has all the important conditions for a favorable refinery location namely. The larger refineries are at tidewater. and the major part of the refinery output is transported by tanker to east coast markets. because these centers provide a large market for the refinery output. South America. The . because most of the crude-oil supply is delivered by tankers from South America. and Wyoming. and air-cooled heat exchangers are also used to supplement water cooling. 1956). several new tidewater refineries are using sea water for cooling. Some industrial plants are using sea water successfully for cooling. Illinois. Ohio. Louisiana. These refineries were scattered through 37 States from coast to coast.

Possible refinery locations have been increased manyfold with the advent of the transcontinental pipeline.PETROLEUM REFINING INDUSTRY 331 single deterrent to refinery expansion in this area is the water shortage. and therefore most refineries recirculate cooling water. Refineries in the Puget Sound area are connected to Canadian oil fields by pipeline. Kansas City. Recirculation of cooling water is also a common practice in refineries in the Central Valley area. Eefineries could be located in areas with favorable water supplies. and many . and St. Most midwestern refineries are located near markets and are supplied primarily from midcontinent oil fields. Kier constructed a small refinery in Pittsburgh. but pipelines are used extensively by most refineries in the Midwest to transport crude oil to the refinery and finished products to market. The expansion of the industry was limited by the small supply of crude oil that could be reclaimed from creeks. Some refineries located on navigable rivers and in the Great Lakes area use water transportation. and refineries reduce their water requirements by recirculating cooling water. Pa. Other parts of this area have water-shortage problems. and pipelines could carry crude supplies to refineries and deliver finished petroleum products to market areas. Sea water has been used for cooling by refineries in the Los Angeles and San Francisco areas. Thereafter. Pa. The source of crude supply can be extended from the oil field to any point along or to the terminus of a pipeline. Large refining centers in this area are Chicago. Many refineries in this area are located adjacent to large rivers or lakes and have sufficient water to use once-through cooling systems. The first oil well in the United States was successfully completed by Colonel Edwin L. springs. 1859. on August 27. Drake in Titusville. many additional wells were drilled in the area. In addition to these tidewater refineries. Conservation of water is essential in the water-short Los Angeles area. The refinery distilled 5 barrels of crude oil per day and produced a cheap illuminating oil similar to coal oil. Pipelines will possibly affect the selection of future refinery locations by allowing more consideration to be given to water availability. Louis. and salt wells in the Oil Creek area of Pennsylvania. and refinery markets can be expanded to include any territory connected to the refinery by a pipeline. GROWTH OF INDUSTRY The petroleum refining industry began in 1854 when Samuel W. supply-oriented refineries are located in or near oil fields in the Central Valley of California.. and expansion in this area to supply the west coast demands is probable.

and agriculture. The advent of the automobile in the early 1900's created a demand for gasoline and lubricating oils which soon exceeded the quantities that could be supplied by simple distillation and forced the development of secondary operations. The Burton cracking process was introduced in 1913. alkylation.480. public utilities.000 barrels of crude oil per day in 1955. 1941). and complexity of refineries increased. Early refining operations were very simple. 300 quarts of motor oil. Many new refining processes such as catalytic cracking. in just slightly over 100 years the petroleum industry has grown from a simple beginning to one of the largest industries in the world which ranks with transportation. . Estimates of the future growth of the petroleum refining industry should serve as a guide for making a reasonably accurate appraisal of the future water requirements. polymerization. 900 gallons of home heating oil. size. and poor quality lubricants were manufactured from crude oil as early as 1865. Although total water needs have increased. This was the first commercial cracking process to be operated successfully in the United States (Kraemer. Thus. and hundreds of other products in 1 minute. Increased water requirements have accompanied the growth of the refining industry. it is a thermal cracking process for converting high-boiling fractions of petroleum into hydrocarbons of low boiling points for use as gasoline. The quality of lubricants and other products continued to improve as refining methods improved. In these early refineries the lighter and more volatile gasoline and the heavy residue remaining after the kerosene was obtained were considered worthless and were either discarded or burned. This residue was soon being used as fuel. because the refineries were operated mainly to obtain illuminating oil (kerosene) by simple distillation. This decrease was caused by improved water-conservation practices that generally accompany additional water needs resulting from refinery growth. the unit water requirements have decreased as the industry grew. and reforming have been developed and are used by refineries to meet the continuing demand for more and better gasoline for automobiles.850 gallons of motor gasoline. Large modern refineries have increased in complexity and size to include single refineries capable of producing about 3.332 WATER REQUIREMENTS OF SELECTED INDUSTRIES refineries were constructed to keep pace with the rapidly increasing oil production. Refining has grown from Kier's single 5-barrel-per-day refinery to an industry consisting of 294 refineries processing an average of 7. As the number. the total water requirements of the industry increased.

9 percent per year. 1950-60. At the end of World War II the demand for refinery products was 2. Hammer.333 PETROLEUM REFINING INDUSTRY Figure 49 traces the increases in demand for major petroleum products in the United States and in the free world from 1950 through 1960 and indicates the percentage distribution of the total demand between the United States and the free world. The annual rate of increase was about 6 percent in both of these periods in the United States. Hill. Demand for major refinery products in the United States and the free world by (A) quantity and (B) percent.792 million barrels per year in the United States.588 million barrels per year for the free world.3 percent during the 1920-56. and Winger (1957) noted that demand for major refinery products in the free world increased at an average annual rate of 6. . and the demand accelerated in the post-World War II period to an average of 7. including 1. The demand in the United CO 1958 1960 1958 1960 100 1950 1952 1954 1956 FIGURE 49.

329 million barrels in 1955. 1950-60.334 WATER REQUIREMENTS OF SELECTED INDUSTRIES States increased to 2. Crude runs to petroleum refineries in the United States and the free world by (A) quantity and (B) percent. The free-world demand increased at a faster rate to 4.042 million barrels in 1960. . The quantities and percentages of crude runs to refineries in the United States and the free world from 1950 through 1960 are shown in figurfe 50.634 million barrels per year in 1955 and to 3. Average increases in yearly rates of crude runs to refineries in the free world slightly exceeded the average percentage increase 1950 1952 1954 1956 1958 1960 1952 1954 1956 1958 1960 100 1950 FIGURE 50. Annual percentage increases in crude charges to refineries in the United States approximately paralleled the yearly increases in demand for major refinery products in the period 1950 through 1960.

Hammer. TRENDS IN PETROLEUM REFINING IN THE UNITED STATES The President's Materials Policy Commission (1952) estimated that the 1975 consumption of petroleum products in the United States would amount to about 5 billion barrels per year. or 13.746 million barrels per year.730 million barrels in 1955 and to 2. the domestic demand for 1966 would amount to 10. On this basis. This extension indicates a probable domestic demand of 4. I have extended the curves to show the probable demand and crude runs in 1966. The lower rate of demand for crude will be due to part of the demand for petroleum products being satisfied by increased production of natural-gas liquids and increased yield of additional lighter products from a barrel of crude oil.4 million barrels per day calculated for 1966 from data published by the President's Materials Policy Commission (1952) but lower than the 14.5 percent per year for the same period. and Winger (1957). This value is somewhat higher than the demand of 10. He assumed that the total demand for crude oil would increase by only 1.730 million barrels per year in 1946 and increased to 2.945 million barrels in 1955. Crude runs to refineries in the United States amounted to 1. Figure 51 shows the total domestic demand for petroleum products and the crude oil runs to refineries in the United States from 1920 through 1960. or 13. Assuming the same annual rates of growth. An increase in the demand for petroleum products in the United States at an average rate of 2.4 million barrels per day. The extension of the crude-run curve indicates probable runs of . and 6.PETROLEUM REFINING INDUSTRY 335 in demand for refinery products during the same period.3 million barrels per day by 1966. Hammer.475 million barrels in 1946.953 million barrels in 1960.528 million barrels in 1960.0 million barrels per day in 1966. 4.7 million barrels per day. and Winger (1957) noted a slackening in the rate of growth in demand for petroleum products in the United States and to a lesser degree in the free world. Since 1946 the domestic demand has grown at an average rate of 5 percent per year. This would be an average increase in domestic demand of about 3 percent per year between 1950 and 1975. however. these authors predict that the domestic demand for petroleum products in the United States will increase at an annual rate of 5 percent between 1956 and 1966 and provide a domestic demand of 14.0 to 2. Crude runs to free world refineries were 2.3 million barrels per day estimated for 1966 by Hill.0 to 1. and refinery runs have increased at 4 percent per year. Hill.5 percent per year from 1960 to 1965 is estimated by Jameson (1960).

In 1955 the estimated average total water requirements for the petroleum refining industry was 3. SUMMARY QUANTITATIVE WATER REQUIREMENTS This survey was not conducted to determine the minimum amounts of water used by refineries.400 gallons per barrel. The average water intake of the refineries surveyed in 1951 and 1956 was 468 gallons per barrel of crude charge.1. The corresponding values for refineries without cracking units were 75 gallons and 500 gallons per barrel. and the gross circulation was 1. Crude oil runs by refineries and demand for petroleum products in the United States.336 WATER REQUIREMENTS OF SELECTED INDUSTRIES i i r T i i i i i r i i i i j3.0 Domestic demand u. Median water-use values for refineries with cracking facilities were greater than those for refineries without cracking facilities.8 i 1920 ' ' i 1924 1928 i ' i ' i i I I I I I 1932 1936 1940 1944 1948 1952 1956 ' ' ' 1960 1964 FIGURE 51.736 million barrels per year. The median intake for refineries with cracking facilities was 100 gallons per barrel of crude. or 10. On the basis of this value and the average unit water-requirement value of the 1956 survey.770 million gallons per day will be needed by petroleum refineries in the United States in 1966. 3. the median for the refineries surveyed was 36 gallons per barrel.0 O "Crude oil runs </> . The median intake and gross circulation was 95 gallons and 1. or about 3 percent of the estimated daily withdrawal of industrial water in the United States. a probable water intake of 4.2 million barrels per day in 1966. The high consumptive use is mainly due . or 40 percent of the intake. 1920-60 with curves extended to 1966.500 mgd. Consumptive use of water in the petroleum refining industry is high. but it was primarily concerned with the current water requirements of the petroleum refining industry.0 a-2.600 gallons per barrel. respectively.

TABLE 23. Water used for once-through cooling by the refineries surveyed was of slightly higher quality than that used for circulating cooling. especially cooling water. The quality needed will differ with the use within the refinery. and embrittlement. but most refineries provide the necessary quality by treatment. and sanitary purposes are summarized in table 23.10 39 14 62 52 14 89 36 10 40 142 200 126 5 7. 10 . 6 5 7. _. QUALITATIVE WATER REQUIREMENTS Water of good quality is desirable for the petroleum refining industry. boiler feed makeup. with a resulting . the quantity available is of more importance than the quality. 12 . and careful selection and treatment of makeup for boiler-feed water was necessary to prevent scale formation. Median values of selected chemical constituents and physical characteristics of untreated once-through and recirculated water used for cooling..6 3 7. Summary of the median of selected quality characteristics of untreated water used for various refinery purposes [Results expressed in parts per million unless otherwise indicated. These data are based on individual observations available and are not balanced analyses] Constituent or property Silica (SiO2).. 12 51 13 38 160 8 7.6 Sanitary purposes 11 . Petroleum refineries used large amounts of high-quality water to produce steam. The industry is quick to adopt new refining methods and equipment that increase the operating efficiency of the refinery. Untreated water was generally not satisfactory for this use.__ Iron (Fe)__ ___ ____ Calcium (Ca) Magnesium (Mg) __ Sulfate (SOO -Total hardness as CaCO3 --------Color__-___________ pH__ ___________ Cooling water oiice-through 9.4 Circulated Boiler-feed makeup Process operations 12 12 14 45 13 68 . process operations.6 TRENDS IN WATER REQUIREMENTS The petroleum-refining industry is a relatively new industry that is accustomed to change.15 160 5 7. excessive corrosion. however. There is a tendency for petroleum refineries to reuse an increasing amount of water.337 PETROLEUM REFINING INDUSTRY to the accumulative evaporation and to windage losses in cooling towers. The use of higher quality water for once-through cooling was probably not due to higher quality requirements but resulted from the favorable water situation at the refinery location.8 .

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2. of Am. The SO2 extraction process for aroinatics recovery: Chem. W. The "H-oil" process: Oil and Gas Jour. 1956f. 61. Catalytic isomerization : v. Powell. no. 5. 55. no. 135-137. 1956d. How four oil refineries use water: Sewage and Indus. R.. The Lamp. no. A fluid-catalytic cracking unit for the smaller refiner: Petroleum Refiner. 106-110. p. 24-26. N. 113. The outlook for key commodities: Washington. v. 14 p. p. Sze. Crude petroleum and petroleum products in Minerals Yearbook. Boiler-water conditioning at Talco Refinery: Petroleum Refiner. 1194-1195. Water conditioning for industry: New York.. Census Bull. C. p. U. G. 3950.. 1956a.S. v. Sta. 109-111. 1942. 9. Prog. J. 1957a. 548 p. 1. p. Pichler. Coumbe. D. Hydrogen treating: v. (1954 Census of Manufactures separate). S. Fuels: U. The chemical process industries: New York.. McGraw-Hill Book Co. R. Simonsen.. M. 25. 5. N. 1956e. p. v. SBK catalytic reforming: v. 11. 35. o . 7. C. no. 1959. Water for oil: New York. Bur. and Wolf. p. 11. Bureau of the Census. p. 21-24. 35. 12. 214 and 253.. 1004 p. Refinery tools for producing high-octane gasoline discussion: Proceedings 13th Midyear Mtg. 371-384. v. Hydrodesulfurization: v. 119-122. Industrial water use: U. no. in Resources for freedom.F. U. 2. Wilkinson. 87-89. How Gulf purifies its boiler water: Oil and Gas Jour. 97-148. 117-119. and Seeley. Youngquist. 11. 12.. The Permutit Co. 133-136. Standard Oil Co. 39. 1957.S. v. 12. 101-103. Powerforming for octanes : v. no.. 1050-1059. 25. Resen. 9. Larry. Eng. Colby. The. E. 1957. 9. H. 11. 462 p. 3. p. A.. reissued March 1956 as Repr.S. no. Unzelman. 51 p. 1952. Sulfuric acid alkylation: v. J. Lube oil improvement by Thermofor continuous percolation: v. and Campagnolo. no. Coke and lighter products: v... no. no. 6. 12. MC-209 Supp. p. no. 1956. no. v. Water conditioning handbook: New York. 1946. no. 1956a. 216-219. 8. Printing Office. Govt. M.. Petroleum Institute's Div. no. S. H. 28M. p. 11. no. McGraw-Hill Book Co. Water and war production: Ohio Eng. and Obergfell. J. C. A. p. 1954. 4. 131. 1953. Permutit Company. 1956b. no. 32. 1958. no. 313-430. p. 1952. V. p. F. 1948. Johnson..340 WATER REQUIREMENTS OF SELECTED INDUSTRIES Partin. Davis.. 1946. U. 25.. 1956c. 1949. (New Jersey).... no. v. p. 1955. 253. p. Isomerization of normal paraffins: v. Hyperforming. 1957b. S. 129. p. G. Refining process glossary (descriptions of processes) . Chervenak. 4. 257-262. C. 1957c.. no.S. 1956b. no.. 14. p. Amoco's latest built for high yields: v.. Petroleum Processing. p. 55. M.. v. G. p. 129. Public Health Service. Water conservation a byproduct of industrial waste control : Sewage and Industrial Wastes.. White. 11. 11. 1956. p. 12. Wastes. no. Ghublikian. P. v. Petroleum Processing... p. Projection of 1975 materials demand. 137-139. 10. 2697. no. v. President's Materials Policy Commission. 1957. of Mines. v. Bur. Petroleum Refiner. 5. Expt. Read. 1946. 1953. no.S. p. p. T. 5. Refining.. Public Health Service drinking water standards : Public Health Repts. A. Rook. 6. 107-109. v. p. C. T. 49.. Pfarr. News. 24. Anhydrous ammonia: v. 1. 11. R.. Shreve. 11. p. v. 130. 1957. 11. J. v. J. 10. L. v. Jr.