Extended - Abstract ID# 271029 Submitted To COMPUTING AND SYSTEMS TECHNOLOGY DIVISION PDF

A Systematic Approach for Conceptual
Process Design:
Production of Methylamines from
Methanol and Ammonia
Seyed Soheil Mansouri, Muhammad Imran Bin Ismail, Karim Almoor

Department of Chemical and Biochemical Engineering, Technical University
of Denmark, DK-2800 Lyngby, Denmark
E-mail: seso@dtu.dk (SSM), s101298@student.dtu.dk (MIBI),
s030931@student.dtu.dk (KA)
Production of MMA, DMA & TMA from Methanol and Ammonia
Preface
This report is the result of the design project in the course “28350 Process Design: Principles
and Methods” a 10 ECTS point course offered by the Department of Chemical and Biochemical
Engineering at Technical University of Denmark (DTU). It was offered in spring 2012 and under
the supervision of Professor Rafiqul Gani. The project was executed by the undersigned with
equal distribution of the workload.
In connection with this project, we would like to thank Professor Rafiqul Gani for the help and
guidance he has provided throughout the process. We would also like to thank teaching
assistants of the course who were always available to help and give comments on individual
task, especially, Alessandra Pennati.
Since we are a multicultural group (Danish/Iranian/Malaysian) a lot of things were discussed

throughout the process, and it turned out to be advantageous that so many different viewpoints
could be taken into consideration.
Production of MMA, DMA & TMA from Methanol and Ammonia
Summary
Methylamines are very important chemicals as they are commonly used as intermediates for a
wide range of agricultural chemicals, animal nutrients, catalysts, electronics, explosives, fuel
additives as well as gas and oil treatments.
A systematic method is applied to design a sustainable and environmentally acceptable plant for
producing mono-methylamines, di-methylamines and tri-methylamines from methanol and
ammonia. The systematic method divides the process design work into 12 sequential tasks that
covers all stages of conceptual design, starting from the consideration of qualitative aspects of
the process flow sheet and preliminary calculations to the detailed process simulations,
equipment sizing, costing, an economic evaluation, and sustainability of the designed process. At
the end of task-9, the base case design is obtained, which is then further refined and improved
with respect to heat integration and process optimization. In the final task-12, a sustainability
analysis is performed to assess the environmental impact of the process design. In addition,
PRO/II is used for process simulation (for verification of design), ICAS for property prediction
and analysis of design options; ECON for cost and economic analysis.
The annual profit of base case is estimated to be about 6 million USD with a payback time of 2
years for production rates of 1200 kg/hr, 4150 kg/hr and 1100 kg/hr of mono-methylamine
(MMA), di-methylamine (DMA) and tri-methylamine (TMA), respectively. The capital and
operating costs are divided into the individual cost items. It is found that compressors are the
most expensive equipment and the steam utility is the main contributor to the total operating
cost. A new conceptual typical separation method using gas hydrate formation was also
proposed for the first time in this report and has not been reported elsewhere. This information
is then used as target for process improvement by heat integration and process optimization,
thus increasing the annual profit and reducing the payback time. The environmental impact
analysis identifies impact due to the release of chemicals.
Production of methylamines from methanol and ammonia m
CONTENTS
LIST OF TABLES
LIST OF FIGURES
Task 1: ................................................................................................................................................................................... 1
1 Product Background .............................................................................................................................................. 1
1.1 Mono-methyamine (MMA) ........................................................................................................................ 2
1.2 Di-methylamine (DMA) .............................................................................................................................. 2
1.3 Tri-methylamine (TMA) ............................................................................................................................. 2
1.4 Physical properties of products .............................................................................................................. 3
1.5 Production ........................................................................................................................................................ 3
1.6 Feasibility Study ............................................................................................................................................ 3
1.7 Global production of methylamines ...................................................................................................... 4
1.8 Largest producers ......................................................................................................................................... 5
1.9 Process constraints ...................................................................................................................................... 5
Task 2: ................................................................................................................................................................................... 6
2 Process Description ............................................................................................................................................... 6
2.1 Raw Materials ................................................................................................................................................. 6
2.2 Chemical reactions and catalysts ............................................................................................................ 8
2.3 Process Conditions .................................................................................................................................... 11
2.4 Economic Potential .................................................................................................................................... 13
Task 3: ................................................................................................................................................................................ 16
3 Process Synthesis Methods .............................................................................................................................. 16
3.1 Level 1: Decisions on Batch versus Continuous ............................................................................ 17
3.2 Level 2: Decisions on Input-Output Structure ................................................................................ 17
3.3 Level 3: Decisions on Recycle Structure and Reactor ................................................................. 18
3.4 Level 4: Decisions on Separation System ......................................................................................... 19
4 Mass Modelling ..................................................................................................................................................... 22
4.1 Preliminary Flow sheet ............................................................................................................................. 22
4.2 List of Specifications ................................................................................................................................... 23
4.3 Model Analysis ............................................................................................................................................ 26
4.4 Flow sheet Decomposition ....................................................................................................................... 28
Task 5: ................................................................................................................................................................................ 33
5 Process Conditions .............................................................................................................................................. 33
5.1 Thermodynamic Model Selection ........................................................................................................ 33
5.2 Reactor............................................................................................................................................................ 37
i
5.3 Flash Unit ....................................................................................................................................................... 38

5.4 Distillation ..................................................................................................................................................... 39
5.5 Absorber ........................................................................................................................................................ 41
Task 6: ................................................................................................................................................................................ 43
6 Mass and Energy Balance ................................................................................................................................. 43
6.1 ProII Simulation .......................................................................................................................................... 43
6.2 Mass Balance ................................................................................................................................................ 43
6.3 Energy Balance ............................................................................................................................................ 44
6.4 Heat Duties .................................................................................................................................................... 45
Task 7: ................................................................................................................................................................................ 48
7 Total Flow Sheet ................................................................................................................................................... 48
7.1 Mixers .............................................................................................................................................................. 48
7.2 Heat Exchangers ......................................................................................................................................... 49
7.3 Reactor............................................................................................................................................................ 52
7.4 Flash Unit ....................................................................................................................................................... 52
7.5 Distillation Columns .................................................................................................................................. 52
7.6 Absorber ........................................................................................................................................................ 55
7.7 Overall process performance ................................................................................................................ 55
Task 8: ................................................................................................................................................................................ 60
8 Sizing and Costing ................................................................................................................................................ 60
8.1 Equipment List ............................................................................................................................................ 60
8.2 Sizing of Equipment .................................................................................................................................. 61
8.3 Summary of Equipment Sizing .............................................................................................................. 70
Task 9: ................................................................................................................................................................................ 72
9 Cost Calculations .................................................................................................................................................. 72
9.1 Capital Cost ................................................................................................................................................... 72
9.2 Manufacturing cost .................................................................................................................................... 78
9.3 Economic Evaluation ................................................................................................................................ 79
Task 10: ............................................................................................................................................................................. 83
10 Process Flow sheet Optimization ............................................................................................................. 83
10.1 Operating profits as the objective function ..................................................................................... 84
10.2 Solvent Optimization ................................................................................................................................ 87
10.3 Purge minimization ................................................................................................................................... 92
10.4 Investigating the possibility for optimization of distillation columns ................................. 93
10.5 Compressors optimization ..................................................................................................................... 94
ii
10.6 Economical analysis of the process optimization ....................................................................... 101

Task 11: ........................................................................................................................................................................... 104
11 Heat Integration............................................................................................................................................. 104
11.1 Synthesis of Heat Exchanger Network (HEN) .............................................................................. 104
11.2 Stream identification .............................................................................................................................. 104
11.3 Methods of Pinch Analysis .................................................................................................................... 106
11.4 Heat exchanger network design......................................................................................................... 111
11.5 Comparison of Heat Utilization Efficiency ..................................................................................... 115
11.6 Summary of minimum utility required ........................................................................................... 116
Task 12: ........................................................................................................................................................................... 119
12 Sustainability Analysis ................................................................................................................................ 119
12.1 Environmental Impact Assessment (EIA) ...................................................................................... 119
12.2 Health and Safety Index ......................................................................................................................... 124
Conclusion…………………………………………………………………………………………………………………………126
Nomenclature
References
iii
LIST OF TABLES
Table 1.1 Physical properties of MMA, DMA and TMA ....................................................................... 3

Table 1.2 Methylamines demand ......................................................................................................... 4
Table 1.3 Largest producers of methylamines and their method of production ............................. 5
Table 2.1 Selected properties for the raw materials and solvent ...................................................... 6
Table 2.2 Solubility parameters for the compounds those are present in the process. .................. 8
Table 2.3 Typical properties of KDC-6 catalyst produced by Albemarle. ....................................... 11
Table 2.4 List of main unit operations in the process....................................................................... 11
Table 2.5 Cost of raw materials .......................................................................................................... 13
Table 2.6 Price for Selling Products ................................................................................................... 13
Table 3.1 Main properties of the compounds in the process for separation analysis ................... 19
Table 4.1 Number of system variables and systems equations. ...................................................... 27
Table 4.2 Determination of variables that need to be specified ...................................................... 27
Table 4.3 List of nodes and precursors for flow sheet decomposition ........................................... 29
Table 4.4 Incident Matrix .................................................................................................................... 31
Table 5.1 Specified conversion fraction and the result of Kg-Mol/hr from PRO/II ....................... 37
Table 5.2 Conversion in the reactor ................................................................................................... 38
Table 5.3 The mole fractions for the flash unit. ................................................................................ 38
Table 5.4 Properties of mixture’s components for determining the operating condition for flash.
.............................................................................................................................................................. 38
Table 5.5 The ratio and the temperature different based on Boiling point of the components ... 40
Table 5.6 Estimation temperature based on bubble point temperature for distillations ............. 41
Table 6.1 Inlet stream total mass rate ............................................................................................... 43
Table 6.2 Outlet stream total mass rate............................................................................................. 44
Table 6.3 The summary of the products ............................................................................................ 44
Table 6.4 Temperatures and the duty for reactor ............................................................................ 45
Table 6.5 Work duty from PRO II for main equipment ................................................................... 45
Table 6.6 Work duty from PRO/II for heat exchangers. ................................................................... 46
Table 7.1 Operating condition for mixers......................................................................................... 48
Table 7.2 Heat echanger stream data ................................................................................................ 50
Table 7.3 List of feeding location for distillation .............................................................................. 53
Table 7.4 Process performance .......................................................................................................... 56
Table 7.5 Stream Summary for total flow sheet ............................................................................... 59
Table 8.1 List of equipment for pressure vessel ............................................................................... 60
Table 8.2 Size of heat heat exchangers .............................................................................................. 69
Table 8.3 Summary of the compressor specifications as per result from PRO/II .......................... 70
Table 8.4 Summary of the equipment sizing for the production methylamines. ........................... 71
Table 9.1 CI data as per different year ............................................................................................... 73
Table 9.2 Overall total cost estimation .............................................................................................. 74
Table 9.3 Overall total utilities cost ................................................................................................... 75
Table 9.4 Total capital instalment ...................................................................................................... 77
Table 9.5 Total operating cost ............................................................................................................ 78
Table 9.6 The profitability evaluation result from ECON ................................................................. 80
Table 10.1 The maximum amount of available raw materials and their corresponding prices. .. 84
iv
Table 10.2 Reactant requirements, processing and selling costs for the products. ....................... 85
Table 10.3 Optimum production ratios found by solving the operating profits objective function.
.............................................................................................................................................................. 87
Table 10.4 Amount of money that will be saved by replacing n-heptane with water. .................. 88
Table 10.5 Cost of raw materials before and after purge minimization. ........................................ 93
Table 10.6 Comparison between driving force concept (DFC) and shortcut method in PRO/II
(SCM) to find the optimum feed location (NF)................................................................................... 94
Table 10.7 Summary of multistage compression for compressor C1. ............................................ 96
Table 10.8 Summary of multistage compression for compressor C2. ............................................ 99
Table 10.9 Analysis of the profit after optimization ....................................................................... 101
Table 10.10 Comparison for compressors before and after optimization in term of installation
cost ..................................................................................................................................................... 102
Table 11.1 Summary of hot and cold streams available for heat integration ............................... 105
Table 11.2 Temperature intervals tables ........................................................................................ 107
Table 11.3 Temperature intervals for LP transshipment method................................................. 108
Table 11.4 Comparison of the utility before and after HEN ........................................................... 116
Table 12.1 Components flow rates and operating condition for the streams entering and exiting
the system (based case) .................................................................................................................... 122
Table 12.2 The environmental impact of the base case design ..................................................... 123
Table 12.3 The environmental impact of optimized case design .................................................. 123
Table 12.4 Total Inherent Safety Index Analysis ............................................................................ 124
LIST OF FIGURES
Figure 1.1 Demand of methylamines products from 2001-2005 ................................................................. 4
Figure 2.1 Simple flow sheet for production of methylamines. ................................................................. 12
Figure 3.1 Process sythesis method....................................................................................................................... 16
Figure 3.2 Production of methylamines using continuous process.......................................................... 17
Figure 3.3 Input and Output in the methylamines process .......................................................................... 17
Figure 3.4 Production of methylamines process flow sheet at the end of Level 2 ............................. 18
Figure 3.5 Production of methylamines process flow sheet at the end of Level 3 ............................ 19
Figure 3.6 Production of methylamines process flow sheet at Level 4 ................................................... 19
Figure 3.7 Preliminary flow sheet of methylamines production ............................................................... 20
Figure 4.1 Flow sheet for methylamines process............................................................................................. 22
Figure 4.2 Model for mixing process ..................................................................................................................... 23
Figure 4.3 Model for reaction process .................................................................................................................. 23
Figure 4.4 Model for splitting process .................................................................................................................. 25
Figure 4.5 Signal flow diagram ................................................................................................................................ 29
Figure 4.6 PRO/II flow sheet and stream summary for linear mass balance model ......................... 32
Figure 5.1 Chemical structure of (a) mono-, (b) di- and (c) tri-methylamines .................................... 34
Figure 5.2 Chemical structure of (a) ammonia, (b) methanol and (c) water ........................................ 34
Figure 6.1 PRO/II flow sheet and stream summary for mass and energy balance model .............. 47
Figure 7.1 Operating condition in the Mix-1 ...................................................................................................... 49
v
Figure 7.4 Heat transfer process in HEX1 ........................................................................................................... 50

Figure 7.6 Heat transfer process in HEX3 .......................................................................................................... 51
Figure 7.8 Operating condition in reactor .......................................................................................................... 52
Figure 7.9 Condition in flash ..................................................................................................................................... 52
Figure 7.10 Distillation column one....................................................................................................................... 53
Figure 7.11 Distillation column two ...................................................................................................................... 54
Figure 7.12 Distillation column three ................................................................................................................... 54
Figure 7.13 Distillation column four...................................................................................................................... 55
Figure 7.14 Absorber ................................................................................................................................................... 55
Figure 7.15 Total flowsheet....................................................................................................................................... 58
Figure 9.1 Graph plot in determine the current CI value .............................................................................. 73
Figure 9.2 Percentage of equipment installation expenditure ................................................................... 75
Figure 9.3 Percentage of utility cost used by equipment .............................................................................. 76
Figure 9.4 Cumulative cash flow analysis based on 10 years project life time .................................... 80
Figure 9.5 Factors influence the profitability of the process (sensitivity analysis). .......................... 81
Figure 10.1Flow diagram of the plant with respect to the reactions…………………………………..….. 85
Figure 10.2Chemical structure of TMA semi-clathrate hydrate…………………………………………… 90
Figure 10.3 A typical schematic of a separation process by using gas hydrate formation…………91
Figure 10.4 Driving force for each distillation column………………………………………………………… .93
FIgure 10.5 Compression sequence with intercooling………………………………………………………… ..94
Figure 10.6 The number of stages with respect to actual compression work for compressor
C1…………………………………………………………………………………………………………………………………….. .97
FIgure 10.7 The optimum number of compression stages based on the annual utility costs…… 98
FIgure 10.8 The energy consumption using different compression stages for compressor C2..100
Figure 10.9 The optimum number of compression stages based on the annual utility cost for
compressor C2………………………………………………………………………………………………………………… 100
Figure 10.10 Comparison of compressor utilities cost for 1 stages and 3 stages for compressor
C1…………………………………………………………………………………………………………………………………… 102
Figure 10.11 Percentages of equipment cost after optimization…………………………………………..103
FIgure 10.12 Percentage of utilities cost for selected equipment after optimization……………..103
Figure 11.1 Grand composite curve plot…………………………………………………………………………….108
Figure 11.3 New flow sheet after heat integration……………………………………………………………….118
Figure 12.1 Input and Output stream considered in for WAR algorithm……………………………….121
vi
Task 1:
Product Information
Introduction
The objective of this project is to design a process to convert methanol into final products
streams of mono-methylamine (MMA), di-methylamine (DMA) and tri-methylamine (TMA),
while keeping the process economical, energy efficient, safe and environmental friendly. This
project was selected due to an ever increasing demand for the mentioned chemicals in different
applications.
This conceptual design project contains main elements of the report and analysis from
feasibility study, economical potential analysis and selecting a process flow sheet by process
synthesis method. Later, a simple mass balance and energy balance, detailed process simulation,
equipment sizing, costing as well as the economic evaluation will be performed. This is aimed at
designing a production plant which can produce approximately 1200 kg/hr MMA, 4500 kg/hr
DMA and 1200 kg/hr TMA. Production rate for the each product per year is given in the
following table:
Production rate of the products
Products Processing Capability Production Rate per year

MMA 1,200 kg/hr 10,000 MT/Year
DMA 4,500 kg/hr 39,000 MT/Year
TMA 1,200 kg/hr 9,000 MT/Year
1 Product Background
Methylamines (in this study MMA, DMA and TMA) are used to make intermediates for a
wide range of agricultural chemicals, animal nutrients, catalysts, electronics, explosives, fuel
additives as well as gas and oil treatments. In this part of the report the main applications of the
products and their physical properties will be discussed.
1
1.1 Mono-methyamine (MMA)
Mono-methylamine is the organic compound with the

chemical formula CH3NH2. This colorless gas is a derivative of
ammonia, but with one H atom replaced by a methyl group. It
is the simplest primary amine. It is sold as a solution in
methanol, ethanol, and water or as the anhydrous gas in
pressurized metal containers. Industrially methylamine is sold
in its anhydrous form in pressurized railcars and tank trailers. It has a strong odor similar to
fish. MMA is used as a building block for the synthesis of many other commercially available
compounds.
1.2 Di-methylamine (DMA)
Dimethylamine is an organic compound with the

chemical formula (CH3)2NH. This secondary amine is a
colorless, flammable liquefied gas with an ammonia-like
odor. Dimethylamine is generally encountered as a solution
in water at concentrations up to around 40%.
Dimethylamine is a precursor to several industrially
significant compounds [1] [2]. It reacts with carbon disulfide to give dimethyldithiocarbamate, a
precursor to a family of chemicals widely used in the vulcanization of rubber. The solvents
dimethylformamide and dimethylacetamide are derived from dimethylamine. It is raw material
for the production of many agrichemicals and pharmaceuticals, such as dimefox and
diphenhydramine, respectively. The chemical weapon tabun is derived from dimethylamine.
The surfactant lauryl dimethylamine oxide is found in soaps and cleaning compounds.
Unsymmetrical dimethylhydrazine, a rocket fuel, is prepared from dimethylamine [1].
1.3 Tri-methylamine (TMA)
Trimethylamine is an organic compound with the

chemical formula N(CH3)3. This colorless, hygroscopic, and
flammable tertiary amine has a strong "fishy" odor in low
concentrations and an ammonia-like odor at higher
concentrations. It is a gas at room temperature but is usually
sold in pressurized gas cylinders or as a 40% solution in
water. Tri-methylamine is used in the synthesis of choline,
tetramethylammonium hydroxide, plant growth regulators, strongly basic anion exchange
2
resins, dye leveling agents and a number of basic dyes [1]. Gas sensors to test for fish freshness
detect trimethylamine.
1.4 Physical properties of products
The physical properties of MMA, DMA and TMA are given in Table 1.1. As for any other
type of substance, some physical and chemical properties can be assigned (i.e. melting point,
boiling point, etc). These properties can be later used to design unit operations and separation
methods. It should be noted that in this part of the report only basic physical properties of the
products are given. Other properties such as Antoine parameters, thermophysical properties
and temperature dependent ones will be used depending on the process conditions and
production method.
Table 1.1 Physical properties of MMA, DMA and TMA1
Parameter MMA DMA TMA

CAS number 000074-89-5 000124-40-3 000075-50-3
Chemical formula CH5N C2H7N C3H9N
Molar mass (g/mol) 31.06 45.08 59.111
Boiling point (Tb, K) 266.82 280.03 276.02
Melting point (Tm, K) 179.67 180.96 156.08
Viscosity (cP) 0.23 at 273 K -- --
Density (g/mL) at 25oC 0.6650 0.6500 0.6290
Solubility in water (kg/dm3) -- 3.54 Miscible
1.5 Production
When ammonia is reacted with methanol, the products MMA, DMA and TMA are formed
in consecutive reactions [3].The most widely used method for the production of methylamines
is the reaction of methanol with ammonia at temperatures of about 400°C in the presence of
acidic solid catalysts. These catalysts are capable of dehydrating and aminating methanol. For
example, modified γ-alumina, aluminosilicate and thorium oxide catalysts [4] [5]. MMA and
TMA are less desirable than DMA. The demand for TMA is the lowest. DMA is of greatest
importance as a starting material in the production of solvents dimethyl formamide and
dimethyl acetamide.
1.6 Feasibility Study
Even if a great business idea is available, one still has to find the most cost-effective way
to market and sell the products which in this case are MMA, DMA and TMA. Methylamines have
1 The data has been acquired from ICAS database and Yaw’s Thermophysical Properties of Chemicals and Hydrocarbons
3
turned in a demand growth rate of 2.5% per year for the period 2000 to 2005 as shown in
Figure 1.1. Strong application sectors include mono-methylamine consumed for pesticides
(2.3% p.a.), and alkylalkanolamines (2.6% p.a.); and dimethylamine used for water treatment
polymers (4.8% p.a.); dimethylaminopropylamine (8.5% p.a.); and dimethylaminoethanol
(6.2% p.a.) [6].
500
400
Million of Pounds
300
200
100
0
2000 2001 2002 2003 2004 2005
Demand Imports Exports
Figure 1.1 Demand of methylamines products from 2001-20052
DMA is the most desirable methylamine product because of its greater usage
industrially as a chemical intermediate while dimethylamine and monomethylamine being next
most preferred. The demand for methylamines (106 lb) is summarized in Table 1.2 [7].
Table 1.2 Methylamines demand3
Mass ratio Mole ratio

Region MMA DMA TMA
(x106 lb) (x106 lb) (x106 lb) (MMA/DMA/TMA) (MMA/DMA/TMA)
US 62 143 46 25/57/18 34/53/13
Western Europe 59 191 62 19/61/20 26/59/15
Japan 10 79 10 10/80/10 14/78/8
Equilibrium -- -- -- 10/18/72 17/21/62
1.7 Global production of methylamines
Various agencies have reported an increasing trend for demand of MMA, DMA and TMA
by 4-5% annually. Over 1 million tones of methylamines are produced annually [8]. In 2005, an
estimated 270,000 tons of DMA and close to 100,000 tons of TMA were produced [1].
2 Based on ICIS.com, methylamines production profiles (2006)

3 The data has been acquired from CEH Market Research Report for Methylamines 1993
4
1.8 Largest producers
The largest producers of methylamines are given in Table 1.3. It can be seen that all the
large producers prefer to produce methylamines from methanol and ammonia.
Table 1.3 Largest producers of methylamines and their method of production
Producer Country Method of production

Air Products USA Methanol + Ammonia
AkzoNobel The Netherlands Methanol + Ammonia
BASF Germany Methanol + Ammonia
Nitto Japan Methanol + Ammonia
Davy Process UK Methanol + Ammonia
1.9 Process constraints
As a result of the increasing demand for DMA all major producers and researchers are
looking for a catalyst that increases the yield of DMA. Therefore, in many processes MMA and
TMA are converted into DMA by being recycled into the feedstock. There are also byproducts
that are produced during the catalytic reaction and they include ethanol, ethylamine,
dimethylether, methane and etc. Henceforward, major producers have focused to develop a
catalyst that reduces the amount of byproducts in the catalytic reaction for production of
methylamines. Thus, choosing an appropriate catalyst is a very important factor to the final
efficiency of the process.
5
Task 2:
Process Description
2 Process Description
In this section a general overview of the process will be provided. This includes the raw
materials and products with their corresponding physical/chemical properties, reactions
involved in the process and the catalyst being used, some general process conditions, and the
economical potential of the conceptual design.
2.1 Raw Materials
Methanol and ammonia are both produced in very large scales globally and that is due to
their various applications to produce a wide range of chemicals. Their very large production has
resulted in very low prices for these two chemicals which will be used as raw materials in this
project. The general properties for the raw materials (methanol and ammonia) as well as for
solvent (n-heptane) are shown in Table 2.1.
Table 2.1 Selected properties for the raw materials and solvent4
Property Methanol Ammonia n-heptane
CAS. No 000067-56-1 007664-41-7 000142-82-5

Formula CH3OH NH3 C7H16
Molecular weight (g/mol) 34.04 17.03 100.204
Boiling point (Tb, K) 337.85 239.72 371.58
Melting point (Tm, K) 175.47 195.41 182.57
Specific gravity 1.1 0.59 --
Flash point (K) 284 -- 269
Methanol
Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a
chemical with the formula CH3OH (often abbreviated MeOH). It is the simplest alcohol, and is a
light, volatile, colorless, flammable liquid with a distinctive odor very similar to, but slightly
sweeter than, ethanol (drinking alcohol) [9]. At room temperature, it is a polar liquid, and is
4 The data has been acquired from ICAS database and Perry’s Chemical Engineering Handbook
6
used as an antifreeze, solvent, fuel, and as a denaturant for ethanol. It is also used for producing
biodiesel via trans-esterification reaction.
Methanol is a common industrial chemical that has been used as an alternative blended
liquid transportation fuel and under consideration for wider use. In the USA its application
profile in 1998 was MTBE, 36%; formaldehyde, 24%; acetic acid, 10%; solvents, 6%;
chloromethanes, 4 %; methyl methacrylate, 3% and miscellaneous, including methylamines,
glycol methyl ethers, dimethyl terephthalate, antifreeze and fuels which all together count for
17%. In many countries, notably in Asia, methanol is almost exclusively used to produce the
intermediate chemical formaldehyde as input to urea formaldehyde composite wood adhesive.
Ammonia
Ammonia or azane is a compound of nitrogen and hydrogen with the formula NH3. It is a
colorless gas with a characteristic pungent odor. Ammonia contributes significantly to the
nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers.
Ammonia, either directly or indirectly, is also a building-block for the synthesis of many
pharmaceuticals or is used in many commercial cleaning products. Although in wide use,
ammonia is both caustic and hazardous. In 2006, worldwide production was estimated at 146.5
million tones [10].
Because of its many uses, ammonia is one of the most highly produced inorganic
chemicals. Dozens of chemical plants worldwide produce ammonia. The worldwide ammonia
production in 2004 was 109 million metric tons. China produced 28.4% of the worldwide
production (increasingly from coal as part of urea synthesis) followed by India with 8.6%,
Russia with 8.4%, and the United States with 8.2%. About 80% or more of the ammonia
produced is used for fertilizing agricultural crops [11].
n-Heptane
The properties of the solvent are closely related to the operation of a solvent based
separation technique that is employed to perform a specified separation task. The best feasible
solvent candidate is analyzed in terms of separation task, performance, environmental impact
and special considerations in order to determine the most appropriate solvent. In order to
separate TMA and DMA, n-heptane was selected to be used as the solvent for the separation of
these two components in an absorber.
TMA and DMA have very close boiling points. n-heptane is proven to be used as a good
solvent to separate the both components and does not have the environmental and health
7
concerns associated with the latter. Table 2.2 shows the solubility parameters for the
compounds considered in the process for producing methylamines. It can be seen that n-
heptane has a very similar solubility parameter to that of tri-methylamine. Therefore, n-heptane
can be a suitable candidate to be used as a solvent in the absorber to separate tri-methylamine
from di-methylamine.
Table 2.2 Solubility parameters for the compounds those are present in the process.
Compound Water Ammonia Methanol MMA DMA TMA n-heptane
Absolute Solubility 47.81 29.22 29.59 23.10 19.00 15.17 15.20
HansenD Solubility
-- -- 15.45 15.67 15.63 15.84 15.13
(MPa½)
HansenP Solubility
-- -- 7.74 8.99 5.33 4.02 3.06
(MPa½)
HansenH Solubility
-- -- 13.87 10.41 8.59 6.69 2.80
(MPa½)
2.2 Chemical reactions and catalysts
In this section the chemical reactions that will occur in the process for production of
methylamines will be introduced. It should be noted the reactions will happen on the surface of
catalyst; therefore a brief introduction to the potential catalysts will be given in this section.
Chemical reactions
The reaction of ammonia and methanol in the presence of a solid acid catalyst forms a
mixture of mono-, di- and trimethylamine (MMA, DMA and TMA, respectively). They are
important intermediates in the manufacture of various industrial chemicals.
The reactions in which methanol is consumed are as follows:
2.1
2.2
2.3
The reactions in which methylamines are consumed are as follows:
2.4
2.5
8
2.6
2.2.1 Catalyst
2.2.1.1 Non-zeolitic catalysts
Variety of catalysts for the vapor phase methanol-ammonia reaction has been reported
in the open literature, including aluminas, silicas, zirconia, thoria and phosphates. These data
include patent literature showing that many other materials that perform dehydration
chemistry have been used for methylamines synthesis; even crushed building tile was reported
[10]. Among the more exotic reports are a photocatalytic Pt/titania [12] system where at MeOH
conversion of <0.1% only TMA is produced and a heteropoly acid [13] catalyst that suppresses
TMA completely at 477°C and N/C=2. Interestingly, a 1935 patent to DuPont mentions zeolites
as possible supports for aluminas [14]. It was recognized early on that a high N/C ratio favored
MMA formation [15]. The temperature range employed was, as expected, large 250-500°C. The
first process using higher than atmospheric pressures was patented by Farben [16], with
pressures >50 atm being used. However, separation of methylamines by distillation under
pressure was already mentioned by Martin and Swallen [17].
Silica-alumina (SA) is currently the most widely used catalyst for methylamines
synthesis. It is usually made by coprecipitation [18]. Heinsohn [19] used SA with approximately
87 wt% silica. Leonard [20] has reported steamed, metal-doped with 85-90 wt% silica. Brake
[21] has found that reduced coking and improved rates are obtained by using a high alumina
(94 wt%) SA catalyst. When a SA (46.9 wt% SiOa) was compared to a boron phosphate and an
SA-boron phosphate hybrid [22], SA was found to be the preferred catalyst; it had a higher
selectivity to amines. Leaching of phosphate was observed from the phosphate-SA hybrid.
Schmitz [23] showed that at the same conditions, conversion and selectivity to amines increased
with increasing surface area and acidity.
A way to improve DMA selectivity of SA catalysts was found by Foley [24] who showed
that a carbon molecular sieve hybridized with a commercial SA exhibited enhanced selectivity
towards MMA and DMA, the molar ratio of (MMA+DMA)/TMA increased from 1.05 to 3.30 at a
MeOH conversion of ~95%. Comparing data on SA catalysts [25] to others based on silica and
alumina like boehmite/kaolin composites [26], clay [27] or straight alumina show clearly that
these kinds of equilibrium catalysts cannot meet the amine selectivity the world demands.
9
2.2.1.2 Zeolite catalysts
Zeolite molecular sieves represent a large fraction of the approximately 500 materials
listed in the Handbook of Molecular Sieves [28]. The primary building blocks of zeolites are
{SiO4}4- and {AlO4}5- tetrahedra. As a result of the difference in charge between these tetrahedra,
the total framework charge is negative and hence must be balanced by cations, typically
protons, alkali, or alkaline earth metal ions. Generally in the protonic or acid form, these
materials behave as solid acids and as such are excellent candidates as catalysts for
methylamines synthesis. In addition, the {SiO4}4- and {AlO4}5- tetrahedra are linked to form
channels and cages or cavities of discrete size.
The numbers of tetrahedra in the openings to these channels and cages determine the
dimensions of the zeolite pore openings. Generally, zeolites are classified by the size of the
largest pore opening. The pore openings to these channels and cages generally range from 3 to 9
Å and allow for molecular sieving. In catalysis this molecular sieving ability is referred to as size
or shape selectivity. At least three types of shape selectivity over zeolite catalysts have been
described [29]:
 Product selectivity: molecules smaller than the pore openings can exit from the framework
into the product stream while larger molecules are retained within the framework.
 Transition state selectivity: certain reactions are prevented because the corresponding
transition state requires more space than is available within the framework of the zeolites.
 Reactant selectivity: only those components of the feed stream that are small enough to
enter the pores can react while larger ones are excluded.
In this process, fresh methanol and ammonia feed are combined with recycled ammonia
and methylamines (mainly MMA and TMA) are fed to a reactor containing a solid acid catalyst.
The amorphous silica alumina catalysts produced by Albemarle are those most commonly used
in the methylamine production process. These catalysts are highly active and stable but have no
specific product selectivity. Various catalysts are available in the market under commercial
names such as LA-30, KDC-4 and KDC-6.
Albemarle’s KDC-6 catalyst is the state-of-the-art commercial choice used in many

methylamine production units around the world as well as the present study. Compared with its
predecessors, KDC-6 offers superior activity, stability, strength and overall productivity. Low
carbon formation on the catalyst prevents particle swelling, which, combined with the catalyst’s
high initial strength, means that slow pressure drop build-up over time during the catalyst cycle
10
is not seen. This gives KDC-6 its long cycle time and high productivity over the run. Typical
properties of KDC-6 catalyst are given in Table 2.3.
Table 2.3 Typical properties of KDC-6 catalyst produced by Albemarle.
Estimated
SiO2, Al2O3 Size Surfacearea
Packaging reactor density, Shape
(%db) (%db) (mm) (m2/g)
kg/m3
21 Balance 5 100 kg/drum 470–520 350 Pellet
2.3 Process Conditions

2.3.1 Feed conditions
The flow rate depends on the amount of production rate. In the most cases, the
temperature for inlet methanol is room temperature and while for ammonia it may be different
depending on the its source (in this case more than 8 ton/hr of methanol and 2 ton/hr of
ammonia will be used). In this process no water exists as the feed and therefore, all the water
present in the system is produced in the reactor as a byproduct of the catalytic reaction.
According to some patents [20] [21] [29], an excess ammonia (ammonia/methanol (N/C)=4)
has to be present and re-circulated in the process.
2.3.2 Process operating conditions for main units

The main unit operations in this process will be discussed briefly with some
specifications which will facilitate the process design in other stages. A list of main unit
operation in the process is given in Table 2.4.
Table 2.4 List of main unit operations in the process.

Type of Unit Operations Number of Unit
Reactor 1
Flash 1
Distillation column 4
Absorber 1
2.3.3 Reactor
A series of reactions take place in the reactor (Eqs. 2.1–2.6) while only the first 3
reactions in which methanol is consumed are considered. This is due to the fact the reaction
rates for the reactions in which ammonia is consumed are much smaller than those of the
methanol [24]. The reaction is conducted in an adiabatic, fixed bed reactor over an amorphous
silica-alumina catalyst at temperatures of 400–420oC and high pressures (>2000 kPa) to
produce an equilibrium mixture of MMA, DMA and TMA. The conventional process offers some
11
flexibility in production volumes of the three products as any undesired product can be recycled
over the catalyst and converted to the equilibrium mixture of methylamines.
2.3.4 Distillation columns
In this process, four distillation columns are used to separate the products, un-reacted
raw materials; solvent and water are shown in the general flow sheet for the methylamines
production in Figure 2.1.
 First column: The first column is to recover excess ammonia and to recycle it back into the
reactor. Recycling ammonia into the feed stream of the reactor will result in their lower
production. From the bottom of this column a mixture of MMA, DMA, TMA and MeOH will be
obtained. This column includes a re-boiler and a condenser and operates at pressures about
1000 kPa [30] [31].
Second column: The separation process in this column is to obtain MMA from the top of the
column and TMA and DMA from the bottom. This column includes a re-boiler and a
condenser and operates at pressures about 1770 kPa.
 Third column: The mixture of MeOH, TMA and MMA which were obtained from the bottom
of the second column will be used as the feed for this column. In this column methanol will
be obtained at the bottom of the column and DMA and TMA from the top. This column
includes a re-boiler and a condenser and operates at pressures about 330 kPa.
 Fourth column: In the final column the mixture of n-heptane and DMA will be used as the
feed from absorber. These mixtures will be obtained from the bottom of the absorber. From
the top TMA and from the bottom n-heptane will be separated respectively. This column
includes a re-boiler and a condenser and operates at pressures about 400 kPa.
MMA DMA
TMA
MeOH
NH3
MeOH recovery Column
Ammonia Column
Reactor
MMA Column
TMA Column
Absorber
Solvent
MeOH
Figure 2.1 Simple flow sheet for production of methylamines.
12
2.4 Economic Potential
In order to verify that this project is feasible, the economic potential (EP) concept can be
used to predict the profit estimation. However, these calculations will vary based on the current
price of raw materials and also the price of selling products. The maximum potential profit is
the difference in cost between the products and the least amount of raw materials needed to
produce it. The calculation of EP is as follows:
2.7
This is to show that if the plant will make a profit by calculating the cost of the raw
materials compared to the price that the main products and the other by-products could be sold
for. In this calculation, the cost of utilities, solvents, catalyst, labor are omitted. Besides the
operating cost and annual capital cost are also subtracted.
Table 2.5 Cost of raw materials
Cost of Raw Material USD/kg Remarks

Methanol $0.22 Price for Asia Pacific region. Price range from USD/MT 370-
400 based on ICIS price review report.
Ammonia $0.40 Ammonia price for Europe and Asia Pacific region. Price is
ranging from USD/MT 530 to USD/MT 600.
Table 2.6 Price for Selling Products

Average Products Price USD/kg Remarks
Mono-methyamine (MMA) $0.78 European region price from BASF
Di-methyamine (DMA) $1.04 European region price from BASF
Tri-methyamine (TMA) $1.17 European region price from BASF
Raw Material cost for a year is calculated in USD is shown as following:
2.8
Cost of Material 1: Methanol
2.9
13
Cost of Material 2: Ammonia
2.10
Total Cost of Materials
2.11
The selling prices of the products are based on the three main products which are MMA, DMA
and TMA. The selling price is calculated as following:
2.12
Product 1: MMA
2.13
Product 2: DMA
2.14
Product 3: TMA
2.15
2.16
14
Therefore the total rough estimation of the profit for a year of production is shown below:
2.17
The price of sources, methanol and ammonia is depending on the location of resources.
However, for purpose of rough estimation for the price of raw material is based on international
market price. With total revenue of products and the raw material cost, it is estimated that the
economic potential for methylamines processing plant is about $28 million per year. The
maximum potential profit indicates that the process will be economically feasible and it would
be favourable to continue with the design of the process.
15
Task 3:
Process Flow sheet
3 Process Synthesis Methods
In order to further guide the selection of process alternatives, a hierarchical decomposition

of the process synthesis, as formalized by Douglas (1988), will be conducted. The method is
classified according to the following process decision. At the present time (in Task 3), no
calculations on heat recovery network will be performed, while only level 1 through 4 are
examined. The heat recovery network will be determined once all of the other flow sheet
decisions have been made.
Figure 3.1 Process sythesis method
16
3.3 Level 1: Decisions on Batch versus Continuous
In the first level, we have to choose whether to operate a batch or continuous process. A
batch process is only considered if:
 The process must be operational with a few months.
 Only a few days of production per year are needed.
 We have little design information and the process in sensitive.
 The product life time is short.
 The value of the product over helms the manufacturing cost.
If none of the above cases are relevant, a continuous process should be considered.
In our case, none of the above criteria hold. Based on the information gathered in the Task
2, the products (methylamines) are known as commodity chemical that have a long product life
in an already established. Therefore, there is no rush to put the product on the market since it is
already part of long industry. Secondly, there is a continuous supply of methanol in large
amounts, why the production of methylamines can continue all year round at high production
rate. Finally, the cost of the product is set by the production cost, so we have to be cost-effective.
It is also cheaper to produce large amounts of methylamines through long expecting operating
time by using a continuous process. As a result, it is chosen to run the process continuously.
Continous
Raw Materials Products
Process
Figure 3.2 Production of methylamines using continuous process
3.4 Level 2: Decisions on Input-Output Structure
In the level 2, we have to consider decisions regarding the input and output of the process.
This involves impurities of the raw materials and the number of product streams. This process
uses methanol and ammonia as the raw material to produce methylamines. The final streams
are divided into 3 different specific products which are mono-methylamine (MMA), di-
methylamine (DMA) and tri-methylamine (TMA).
MeOH MMA
Continous
DMA
Process
NH3 TMA
Figure 3.3 Input and Output in the methylamines process
17
Additionally, in this level the purge stream lines are set for each recycle to recover
byproduct streams, and it depends on selectivity versus cost. The impurities have boiling points
lower than reactants and products. Therefore, a recycle streams is needed and it is necessary to
use a purge stream to avoid accumulation of impurities in the plant. In addition, the un-reacted
reactants (methanol and ammonia) and also solvent (n-heptane) will be recycled. The by-
product (water) which is non valuable will be removed as a waste for further treatment and can
be used in the utilities. In this case it is estimated that still can be achieved at high profits.
(water)
3.1
If it is assumed that the impurities in the outlet streams are valuable and the feed stream
is at a high flow rate, it is useful to recycle back to the process. Therefore, the decision in this
level is important and needs to be investigated in later stages.
Recovery
Purge
MeOH MMA
Reactor Separator DMA
NH3
TMA
Recycle
Figure 3.4 Production of methylamines process flow sheet at the end of Level 2
3.5 Level 3: Decisions on Recycle Structure and Reactor
In the level 3, the number of reactors is identified. Besides, the structure of the process
and the decision whether to recycle or recover byproducts is determined. In addition, the
component phases, reactor type, desired and undesired reaction kinetics, equilibrium, capital
and operational cost of the reactor are taken into consideration.
In producing methylamines, only one reactor is needed to get the desired product where
all the reactions take place simultaneously on the surface of a catalyst. Methylamine is formed
directly from methanol and ammonia from the reactions. The reaction is exothermic and the
reactor is isothermal where the temperature change is high and heating is needed. All the un-
reacted reactants will be recycled back to the process to increase the effectiveness and to get
higher yields of the products. Therefore, this process requires compressor for recycling vapor
phase stream compounds and pump is needed for liquid recycle.
18
Compressor
Purge
MeOH MMA
Reactor
Separator DMA
NH3 1
TMA
Pump
Figure 3.5 Production of methylamines process flow sheet at the end of Level 3
3.6 Level 4: Decisions on Separation Methods
For this level, the separation methods used in the system will be decided upon.
Separation system is necessary in order to divide the products, by-products as well as the un-
reacted raw material and impurities which are needed to be recycled. This is done by looking at
the properties of reactants, products and impurities, primarily the boiling points as they are
shown in Table 3.1. It is preferred to separate the condensable and the non-condensable
components in an early stage.
Table 3.1 Main properties of the compounds in the process for separation analysis5
Compound Tb (K) Tm (K) Molar Liquid density in

kmol/m3
NH3 239.72 195.41 0.025
MMA 266.82 179.67 0.045
TMA 276.02 156.08 0.090
DMA 280.03 180.96 0.067
MeOH 337.85 175.47 0.041
n-Heptane 371.58 182.57 0.147
H 2O 373.15 273.15 0.018
Purge
TMA
MeOH Vapor Recovery

Reactor MMA
1
NH3
Liquid Recovery DMA
1 Waste
1
Figure 3.6 Production of methylamines process flow sheet at Level 4
5 Properties from ICAS database
19
Purge stream is used in the vapor recovery to avoid accumulation of impurities. For the
product recovery, a series of distillations is chosen in order to produce three different final
products due to separation of vapor and liquid phase. The distillation columns sequence can be
determined by following rules as below:
 To recover the lightest components first
 To recover most plentiful component first
 To separate the most difficult component last
Besides, the separation mechanism can be identified based on the driving force
diagrams. The separation starts with the easiest component with the largest driving force. It is
due to the fact the higher the driving force is, the minimum energy is required. The summary of
the main objective of each separation is given below:
 1St Separation: Separating liquid (water) and vapor
 2nd Separation: Recover ammonia in the top product with purging line
 3rd Separation: MMA as the top product
 4th Separation: Recover methanol in the bottom product for recycle
 5th Separation: DMA as the bottom product
 6th Separation: TMA as the top product and solvent recovery at the bottom
product
Based on the separation task configuration and the hierarchal decomposition, a simple initial
flow sheet was developed for methylamines production as shown in Figure 3.7.
Purge
MeOH Split
Reactor Split
NH3 1 1 2
MMA
A
Water
DMA
Split Split
3 5
TMA
Split Split
4 6
Purge
Solvent
Figure 3.7 Preliminary flow sheet of methylamines production
20
The flash tank, absorber and distillation columns are represented by splitters (stream
calculators in PRO/II). It should be noted that the given preliminary flow sheet does not include
mixers, pumps, compressors and others.
21
Task 4:
Linear Mass Balance Model
4 Mass Modeling
The mass balance is an important part of the design process, because it is a fundamental
step for the energy balance, and it will give a clue whether the design process will be able to
produce the desired amount of product. There are approaches to perform mass balance for a
process system:
 Simultaneously using linear algebra
 Sequentially using a tear stream approach (iterative)
In this project, the second approached has been used. This method has been implemented
in PRO/II to calculate the mass balance.
4.1 Preliminary Flow Sheet
The preliminary process flow sheet in Figure 3.7 has been updated to a more detailed flow
sheet as shown in Figure 4.1.
Purge
S10 S9
SP-7
S7
S8
NH3 S2
S4 S5
M-1 R-1 SP-1 SP-2
S3
MeOH S1 S6
S11
M-2
S12 S23
MMA
A S20
M-3
DMA
SP-3 S14 S16
TMA
S13 SP-5
SP-4 S21
S18 S24
S17
S15 SP-6
SP-8
SP-9
S19
Purge Purge S25 S22
Figure 4.1 Flow sheet for methylamines process
22
The different units shown in the Figure 4.1 are analyzed separately and the mass balance
calculation for each unit is performed. There are 25 streams in the process with 7 components
which are MeOH, NH3, MMA, DMA, TMA, n-heptane and H2O.
4.2 List of Specifications

Mixing
MIX
Figure 4.2 Model for mixing process
The mass-balance for the mixer is given by the general equation:
4.1
Where;
= The total number of inlet streams
= The molar flow rate of component
= MeOH, NH3, MMA, DMA, TMA, H2O, n-heptane in stream
i = Number of unit
j = Output stream of unit i
In this project, there are three mixers were used and the mass balances are:
k=1,NC 4.2
k=1,NC 4.3
k=1,NC 4.4
Reaction
RXN
Figure 4.3 Model for reaction process
23
The mass-balance for the conversion reactor is given by the general equation:
4.5
Where;
= Equilibrium constants
= The normalized stoichiometry coefficient
In this project, there are three reactions taking place in the conversion reactor for this process.
Therefore, the calculation of reaction involves is divided in three theoretical reactors: RX1,
RXN2 and RXN3 for each reaction.
a) RXN1
As in equation (4.6), the first reaction (RXN1) is modeled. The conversion for this reaction is
η1= 0.13 and the limiting reactant is methanol. The stoichiometry is as following:
MeOH NH3 MMA DMA TMA H 20

-1 -1 1 0 0 1
The reaction is as following:
4.6
b) RXN2
As in equation (4.7), the second reaction (RXN2) is modeled. The conversion for this reaction
is η2= 0.62 and the limiting reactant is methanol.. The stoichiometry is as following:

-1 0 -1 1 0 1
4.7
c) RXN3
As in equation (4.8), the second reaction (RXN3) is modeled. The conversion for this reaction
is η3=0.18 and the limiting reactant is methanol. The stoichiometry is as following:

-1 0 0 -1 +1 +1
24
4.8
Splitting
SPLIT
Figure 4.4 Model for splitting process
The flash and component splitter (distillation column) can use the same model as divider.
The splitting operation can be formulated given by the general equation below:
with 4.9
= The total number in outlet streams (split streams)
= The split fraction between 0 and 1 for outlet stream .
a) SPLIT 1-Flash:1
The split mass balances are:
4.10
4.11
b) SPLIT 2-Distillation: 1
4.12
4.13
c) SPLIT 3- Distillation: 2
4.14
d) SPLIT 4-Distillation: 3
25
4.15
4.16
e) SPLIT 6-Distillation: 4
4.17
4.18
f) SPLIT 5-Absorber
4.19
4.20
g) SPLIT 7-Divider: 1
4.21
4.22
h) SPLIT 8-Divider: 2
4.23
4.24
h) SPLIT 9-Divider: 3
4.25
4.26
4.3 Model Analysis
Before setting up a mass balance it is useful to analyze the degrees of freedom of the
whole system. The degrees of freedom analysis allows the establishment of the maximum
amount of variables needed to be set to have a completely determined system.
Figure 4.1 shows that the system contains nine units (three mixers, one reactor, six
stream calculators and three dividers). To calculate the degrees of freedom, the total number of
system variables and the total number of system equations must be determined, since the
definition of the degrees of freedom (DOF) is:
DOF = Total no. of variables of the system (NV) – Total no. of system equations (NE) 4.27
26
Table 4.1 Number of system variables and systems equations.
Number of equations Equations Number of components

M-1 : Mixer 1 Eq. 4.2 NC
R-1: Reactor 1 Eq. 4.6, 4.7 and 4.8 3
SP-1: Flash Eq. 4.10 and Eq. 4.11 2*NC
SP-2: Distillation 1 Eq. 4.12 and Eq. 4.13 2*NC
SP-6: Absorber Eq. 4.18 and Eq. 4.19 2*NC
SP-7: Divider 1 Eq. 4.22 and Eq. 4.23 2*NC
Total number of equations NE 16*NC+3
Number of Variables Variables Number of components
Component flow rates fk 25*NC
(stoichiometric coefficients)
Reactors parameters 3*(NC + 1)
Kpr (Equilibrium constant)
ζs (recovery of each compound compared
Spliting parameters: 6*NC
to feed)
Divider parameters (divide fraction compared to feed) 3*NC
Total number of variables NV 37*NC+3
Degree of Freedom NV - NE 21*NC
It is shown in Table 4.1, the mixers, divider and reactor have three linear equations, while
each stream calculator has two linear equations. The degrees of freedom it would be DOF =
(37*NC+3-16*NC+3) = 21*NC, i.e. 147 variables.
Table 4.2 Determination of variables that need to be specified
Variables Type Specify Variables
Known Variables Process 3NC

(By decision-Fix by variables
system through
solving the problem) Equipment 6NC
parameters
Split 9NC
fractions
Sub-Total 21*NC
Unknown variables Process 22NC
(Algebraic-Explicit) variables
Sub-Total 22*NC
27
These variables must be specified in order to have a completely determined system. This is
done by utilizing what is known about the system.
 The molar rate of the feed stream, the production rate and the desired purity of the
product is known.
 The conversion of each reaction is known.
 The stoichiometric coefficients are specified according to the main reactions.
 The stoichiometric coefficients are specified according to the main reaction (1) and the
side reactions (2) and (3).
4.4 Flow Sheet Decomposition
Flow sheet decomposition can be solved with respect to mass balances. For this purpose,
each operation in the flow sheet is decomposed into three different elementary operations:
 Reaction: Single input, single output, single reaction
 Mixing: Multiple input, single output
 Splitting (and dividing): Single input, multiple output
The decomposed flow sheet can be seen in the signal flow graph as shown in Figure 4.5. As it
can be seen the decomposed flow sheet consists of three partitions with three recycle loops. The
first column lists all the nodes in the process. In the second precursors, nodes with single
precursor are eliminated. Based on the Table 4.3, the selected tear streams are the stream 4 and
11.
28
S10 S9 Purge
(Recycle Loop 1)
SP-7
S7
S8
NH3 S2
S4 S5
M-1 R-1 SP-1 SP-2
Partition 1 S3 S6
Partition 2 S11 Partition 3
MeOH S1 S12 MMA

S23 TMA
A S20
M-2 M-3
S14 S16
SP-3 DMA
SP-5
Solvent S21
S18 S13
S24
SP-4 S17
SP-6
(Recycle Loop 2)
SP-8 S15 SP-9
Purge S22
S19
Purge (Recycle Loop 3)
S25
Figure 4.5 Signal flow diagram
Table 4.3 List of nodes and precursors for flow sheet decomposition
Nodes Precursors (1) Precursers (2) Precursers (3) Precursers (4)

1 -
2 -
3 18
4 3,10 8,18 7,5 4
5 4
6 5
7 5
8 7
9 8
10 8
11 7
12 11
13 11
14 13
15 13
16 14,22 13,17 11,16 11
17 14
18 15
19 15
29
20 16
21 17
22 17
23 -
24 22
25 22
Incident Matrix Analysis
Incident matrix analysis can be performed based on all the model equations. To specify
variables are 2 process variables, 6 equipment parameters and 7 split fractions as shown in
Table 4.3. The unknown variables are all 17 process variables. The table of incident matrix
analysis is shown in Table 4.4.
Derivation of solution strategy can be analyzed based on Table 4.3 and the incident
matrix. Firstly, we solve all the equation in the reactor (Eqs 4.6-4.8) by using the guess value for
the recycle stream. Then equation for stream simulators (Eqs 4.9-4.27) can be calculated.
Finally equations in the mixers are solved and will result in a new value for recycle stream is
determined.
30
Table 4.4 Incident Matrix
Variables to specify
Unknown variables
Units Eqn (Decisions)
MIX1 (20) x x x (x)

MIX2 (21) x x
MIX3 (22)
(24) x x (x) x
RXN (25) x x (x) x
(26) x x (x) x
(28) x (x) x x
SP-1
(29) x x x
(30) x x
SP-2
(31) x x (x)
(32) x x
SP-3
(33) x x (x)
(34) x x
SP-4
(35) x x
(38) x x
SP-5
(39) x (x) x
(36) x (x) (x)
SP-6
(37) x
(40) x (x)
SP-7
(41) x (x)
(42) x (x)
SP-8
(43) x (x)
(44) x (x)
SP-9
(45) x (x) (x)
31
Figure 4.6 PRO/II flow sheet and stream summary for linear mass balance model
32
Task 5:
Process Conditions
5 Process Conditions
To proceed with energy balances calculation, it is important to determine the

temperature and pressure for all streams and the main equipments for every process unit. This
section deals with determination of temperature and pressure of each stream so that unit outlet
streams remain at saturated liquid or vapor. Here, other factors such as if the saturated stream
is below the critical point needs to be taken into account, as well as whether the specified
recovery is achieved or not and if the distillation columns run with partial or total condensers.
Also, selecting an appropriate thermodynamic model is crucial to the calculations since the
predicted values and phase behavior of compounds in the process may differ significantly in
case of choosing an in-appropriate thermodynamic model.
5.1 Thermodynamic Model Selection
Availability of the values of the thermophysical, physicochemical, and/or thermodynamic

properties of the involved components (or their relevant mixtures) as well as accurate
knowledge about the corresponding phase equilibrium data would finally lead to design
efficient chemical processes. However, the broad experimental efforts, since the past two
centuries, indicate that generating these kinds of data are intrinsically time-consuming, costly,
and with probable non-negligible uncertainties. Therefore, there have been considerable
numbers of theoretical studies to correlate/predict the experimental data for particular
conditions and for specific chemical compounds or mixtures. These correlations/models may be
later applied to predict the corresponding properties for other systems at specific conditions
within the domain of their applicability. Since the selection of the most suitable thermodynamic
model has generated numbers of discussions in the literature, it consists of a prominent section
of the conceptual process design. In this section, different criteria are discussed upon which a
thermodynamic model has been selected for the process of methylamines production.
Analysis of the chemical structures of the compound present in the process
In the first step, the chemical structures of compounds present in the process are
sketched and analyzed. The main objective of this task is to check the potential of the molecules
33
of the compounds to establish various chemical/physical bonds to the same molecules or

molecules of other chemicals e.g. hydrogen bonding which may lead to association, self-
association, cross association etc., or analysis of the active sites of the molecules. Enough
information about the chemical structures finally results in a clear point of view for selection of
the thermodynamic model (particularly regarding the non-idealities in the aqueous phase).
Figures 5.1 and 5.2 illustrate the chemical structures of the compound present in the process.
(a) (b) (c)
Figure 5.1 Chemical structure of (a) mono-, (b) di- and (c) tri-methylamines
(a) (b) (c)
Figure 5.2 Chemical structure of (a) ammonia, (b) methanol and (c) water
Investigation of process operating conditions (P, ρ, T)
The temperature and pressure ranges of the operational conditions of the whole process
are defined in this step. Since the majority of thermodynamic models are generally
recommended for particular range of applications, this step is one of the most vital ones in
selection of the thermodynamic model. For instance, low pressure phase equilibria can be
modeled using ideal gas law, especial equations of state (EoS) can be applied to deal with
cryogenic conditions, or meta-stable regions can be modeled by particular correlations.
Regarding the operating conditions of the conceptually designed process, we are dealing with
25 to 400oC temperature range and 1 to 20 atm pressure ranges. Furthermore, it is
34
recommended that the temperature and pressure ranges for each of the operating units are
defined separately.
Availability of experimental data (phase equilibrium and/or physico-chemical properties)
The accuracy and reliability of models for the representation and prediction of physical
properties as well as phase equilibria of various systems directly depend on the quality and
comprehensiveness of the applied data sets for their development. The aforementioned
characteristics of such models include both the diversity in the investigated chemical families
and the number of pure compounds available in the data set. However, as already mentioned,
reliable experimental datasets are not always available for different properties or phase
equilibria of systems of interest. Therefore, particular attentions should be paid in selection of
the models dealing with these kinds of systems. It is worth pointing out that the group
contribution models (like UNIFAC activity model or PSRK EoS) are generally preferred in the
case of the corresponding processes. To the best of our knowledge, enough experimental
information exist for each property of the involved systems in the designed process (in the
PRO/II and/or in open literature) except the binary phase equilibrium data of the MMA, DMA,
and TMA systems.
Availability of the thermodynamic models
Comprehensive works have been done so far to propose appropriate thermodynamic

models to evaluate the required phase behaviors/thermodynamic properties of pure
compounds/mixtures. Therefore, there is wide range of available thermodynamic models in
open literature. However, not all of the aforementioned models have been thus far implemented
in the simulation software. Moreover, especial properties of compounds are needed to apply
some of the thermodynamic models e.g. the SAFT. These facts assign some limitations for the
users to select the desired models. For instance, some of the chemicals present in the
conceptually designed process in this works are associating compounds. It is normally
recommended to use associating equations of state like the SAFT or the CPA EoS for modeling
the phase behavior of the systems containing these compounds. However, the following criteria
contributed not to select these models:
 The SAFT parameters including the associating energy, associating volume etc. are not
provided in PRO/II for the compounds of interest in this study.
 The CPA EoS has not been implemented in the equations of state package of PRO/II.
35
Taking advantage of recommended model selection procedures
Broad computational attempts show that particular instructions may result in selection
of the most suitable thermodynamic model for the processes of interest. For instance, ASPEN
Tech. has published a document entitled "Aspen Physical Property System" [32] in which
comprehensive guides have been provided leading the users (even non-experienced ones) to
have a clear view about selection of thermodynamic models. Another guidelines were provided
in the course "28350 Process Design: Principles and Methods" at DTU. However, these
guidelines should generally coupled with the users' experiences in the related fields to provide
the most efficient instructions. In this work, the aforementioned guidelines have been pursued
to select the appropriate thermodynamic model.
Selection of the most appropriate thermodynamic model
The selection of the appropriate thermodynamic model for this system is based on the
following points:
 The molecular structures present in the process reveals that they generally posses active
sites and consequently have the potential of forming hydrogen bonding (i.e. they can be
considered as associating compounds). Therefore, the non-idealities of the phases present
are non-negligible. Therefore, capable equations of state along with suitable activity models
should be applied for property estimations.
 The pressure-temperature operational conditions of the process show that the selected
thermodynamic model(s) should be able to predict the behaviors of the systems at wide
ranges of pressure and temperatures. For instance, the alpha function of the selected EoS is
supposed to be tuned over extended vapor pressure/liquid densities of pure compounds to
make it possible to account for high pressure predictions (the PRO/II is able to provide us
with this feature).
 To the best of our knowledge, enough experimental information exist for each properties of
the involved systems in the designed process (in the PRO/II and/or in open literature)
except the binary phase equilibrium data of the MMA, DMA, and TMA systems. Therefore, it
seems to be necessary that the equations of state with known binary interaction parameters
or the group contribution methods would be more suitable candidates for being selected as
the thermodynamic models.
 PRO/II software package allows us to select the thermodynamic model among the limited
numbers of models. As previously stated, the SAFT and the CPA EoSs cannot be selected
because of this reason.
36
 In this work, both of the guidelines described in section 1.5 have been followed to select the
thermodynamic model.
On the basis of the explained factors, the PR EoS and the Benedict–Webb–Rubin equation
(BWR) EoS have been selected as thermodynamic models. These models lead to the following
features:
i. The required binary interaction parameters of the PR and the BWR EoSs have been
already available in the PRO/II packages. Therefore, there is no need to tune these
parameters.
ii. The calculations (later performed in Task 7) show that the UNIQAC, UNIFAC, and
GEx/EoS (including the PR combination with the Modified Huron-Vidal (MVH1 and
MVH2) models do not contribute to the convergence of the simulations while this is not
the case for the PR and the BWR EoSs. In-appropriate UNIQUAC parameters for the
pressure-temperature-compositional (PTx-y) conditions of the process might be one of
the reasons of this drawback.
iii. The PR and the BWR EoS also consist the entropic term which allows their application in
calculation of thermal expansion coefficient in compressors.
iv. There seems to be only one drawback in the case of the BWR EoS that is its large
numbers of the adjustable and non-adjustable parameters.
5.2 Reactor
The process condition for reactor 1 is referring to the literature [31]. Therefore no
specific calculation is needed to be performed as the information found has been implemented.
There are three reaction involved in the reactor. The base component for the reaction is
methanol. The conversion fractions for each reaction are specified as follows:
Table 5.1 Specified conversion fraction and the result of Kg-Mol/hr from PRO/II
Kg of methanol converted
Reaction Fraction
(Kg-Mol/hr)
1 0.13 38.5794
2 0.62 183.9939
3 0.18 53.4176
The reactor mass balance with respect to individual components is given the table that
follows. It should be noted that the values in the table are at the reactor’s operating conditions
(i.e. 400oC and 20 atm).
37
Table 5.2 Conversion in the reactor
Component Feed (kg/hr) Change (kg/hr) Product (kg/hr) Conversion (%)

Ammonia 3709.9 –2525.1 1184.8 68
MMA 723.6 1197.3 1920.9 --
TMA 111.3 1051.7 1163.0 --
DMA 200.5 4144.5 4345.0 --
Methanol 9501.9 –8836.8 665.1 93
Water 11.1 4968.3 4979.5 --
5.3 Flash Unit
Base on the mass balance result, the recovery of water 1.0. The mole fractions for
the vapor and liquid stream calculated from PRO/II are given in the Table 5.3.
Table 5.3 The mole fractions for the flash unit.
Component Yk Xk
NH3 0.313 0.000
MMA 0.157 0.000
DMA 0.374 0.000
TMA 0.072 0.000
MeOH 0.084 0.000
n-heptane 0.000 0.000
H20 0.000 1.000
To develop the flash model, an overhead split fractions for each of the
components k. In this case, n is the key component which is water and k is all the components in
the process. The condition for temperature and pressure is specified. Table 5.4 shows the
mixture of the components, flow rates, boiling points and Antoine coefficients.
Table 5.4 Properties of mixture’s components for determining the operating condition for flash.
Comp., k Fk (kgmol/hr) Boiling Points (K) Ak Bk Ck
NH3 67.97 239.72 7.58857 1022.161 250.37
MMA 38.57 266.82 7.34551 1016.554 233.96
TMA 17.8059 276.02 7.11926 991.015 226.394
DMA 91.98 280.03 6.86567 954.761 226.394
MeOH 20.77 337.85 8.09058 1583.726 1239.162
n-heptane 0 371.58 7.096 1381.677 228.794
H 20 275.99 373.15 8.02927 1713.681 232.633
38
For the flash unit and distillation columns, the shortcut method by PRO/II was used to
estimate the operating temperature and pressure. Ideal performance of the shortcuts is
assumed, which leads to the following assumptions:
5.1
where is a vapor fugacity coefficient, is the liquid activity coefficient, is the pure
component fugacity and is the vapor pressure. This assumption leads to the following
equilibrium relation:
5.2
where Ak, Bk, and Ck are Antoine coefficients. The relative volatility can now be defined with
respect to the key component:
5.3
The relative volatility is independent of pressure for the ideal solution. For the flash unit, the
split fractions for component k can be defined in terms of the key component recovery:
k / n n 5.4
k 
1  ( k / n  1)  n
With the specification of the key component recovery, an additional specification is still
required in order to calculate the split fraction of component k. The split fraction is dependant
of the relative volatility. To calculate the relative volatility, the operating temperature shall be
specified. It is important to specify the right operating temperature for the flash unit to get the
best separation of water from the rest of the products in the flash unit. Therefore, the
temperature of the top and bottom product of the flash unit is 340 K.
5.4 Distillation
Distillation operations can be described as a cascade of equilibrium trays with each one
solved a flash unit [33]. The feed enters at a specific tray and counter current liquid vapor
streams are set up in the distillation column. At the bottom, liquid product is removed and a
39
reboiler will vaporized the liquid stream on the lowest stage. Table 5.5 is referred in order the
determined light and heavy key for each distillation.
Table 5.5 The ratio and the temperature different based on Boiling point of the components
Compound Boiling Point Ratio Temp. Different

NH3 239.72 K
0.898 27.1 K
MMA 266.82 K
0.967 9.2 K
TMA 276.02 K
0.985 4.01 K
DMA 280.03 K
0.828 57.82 K
MeOH 337.85 K
1.0998 33.73 K
n-heptane 371.58
1.004 1.57 K
H 20 373.15 K
The recovery of key components in the distillation columns is specified based on an

appropriate setting of condition for temperature and pressure which is needed to separate the
light and heaviest key components. By choosing the correct operation conditions for the
separation column there will be a vapor and liquid phase with the desired yield. In the bottom
end of the column there is a reboiler which deliver the necessary heating and after the vapor
leaves the column it has to be condensed.
Compressor type selection
There are two options are possible for condenser which are partial or total condenser.
The idea of a total condenser is that the vapor stream will be 100% condensed and then a liquid
stream will be obtained while a partial condenser will only cool the stream. The liquid stream is
then will be reflux in the reactor and a stream of saturated vapor product will be obtained at
bubble point. The choice of condenser depends on the lowest energy equipments as well as the
cascade of pressure between a series of distillation units.
The selection of condenser type will be effect the distillation column operation.
Basically, there are potential for saving energy with separation columns using partial
condenser, however the pressure cascade have to be taken into consideration. Therefore the
selection for both types condenser for split 1, 2, 3, 4 and 5, and the estimates temperatures and
pressures are determined.
40
Determination of operating conditions for distillations
In the first distillation, the separation process is aimed to recover excess ammonia from
the process. As shown in Table 5.6, ammonia has the lightest boiling point and therefore will be
recovered at the top of the column. Both total condenser and partial condenser are valued in
this separation unit. The condenser is assumed to be operated with cooling water at 30°C.
Since the bottom product will be sent to the next column, we prefer total condenser,
which allows us to operate the distillation column 1 and distillation column 2 at high pressures.
We assume a pressure drop 0.5 atm in the distillation columns. The reboiler temperature can be
calculated now. DMA is the most plentiful component in the bottom, which is 0.544. Therefore,
the temperature of the bottom product is the boiling point of DMA at 10 atm. The Antoine
equation (Eq. 5.2) is used to determine the temperature.
In the second columns the MMA product is recovered at the top of the column while the
mixture of TMA, DMA and also methanol is sentto the third column. Methanol is then recovered
at the bottom of the third column and recycles back to the feed stream. In the last column TMA
and n-heptane are separate at top and bottom product respectively. The entire initial guess for
the distillation is using bubble point temperature. The summary of the operating condition for
each distillation based on the stream calculator in the PRO/II is shown below.
Table 5.6 Estimation temperature based on bubble point temperature for distillations
Number of Distillation Estimated Temperature (oC) Estimated Temperature (oC)

Top product Bottom product
Distillation 1 39.23 75.37
5.5 Absorber
Absorption refers to the transfer of a gaseous component from the gas phase to a liquid
phase. Absorption occurs into liquid droplets dispersed in the gas stream, sheets of liquid
covering packing material, or jets of liquid within the vessel. The liquid surface area available
for mass transfer and the time available for diffusion of the gaseous molecules into the liquid
are important factors affecting performance. In this process an absorber is chosen to separate
tri-methylamine from di-methylamine by using n-heptane as the solvent.
The gaseous compound being absorbed (tri-methylamine) must be at least slightly soluble
in the scrubbing liquid (n-heptane). Mass transfer to the liquid continues until the liquid
41
approaches saturation. At saturation, equilibrium is established between the two phases. The
mass transfer rate of the tri-methylamine into the liquid is equal to the mass transfer rate of the
dissolved species back into the gas phase. Accordingly, the solubility of the tri-methylamine in
the liquid creates a limit to the amount of its recovery that can occur with a given quantity of
liquid.
In this process a packed-bed absorber is chosen which is shown by a stream calculator in

Pro/II. The absorbing liquid is dispersed over the packing material, which provides a large
surface area for gas-liquid contact. The gas (mixture of di- and tri-methylamine) stream enter
the bottom of the tower and flows upward through the packing material and exits from the top
after passing through a mist eliminator. Liquid (n-heptane) is introduced at the top of the
packed bed by sprays or weirs and flows downward over the packing. In this manner, the most
dilute gas contacts the least saturated absorbing liquid and the concentration difference
between the liquid and gas phases, which is necessary for mass transfer, is reasonably constant
through the column length.
The desired recovery for TMA is 99%, therefore, the absorption factor is calculated by
iteration by adjusting the solvent rate to satisfy a final recovery of 99% TMA. The absorption
factor is obtained by the following equation:
5.5
From the above equation an absorption factor (A) of 10 with is

obtained. By knowing this the absorption factor and a recovery of 99% TMA, the number of
theoretical stages is calculated buy employing Kremser equation as follows:
5.6
42
Task 6:
Mass and Energy Balance
6 Mass and Energy Balance
6.1 PRO/II Simulation
In order to calculate the energy balance, a few extra equipments were added in the flow
sheet. Pumps, heat exchangers, expansion valves as well as compressors are added to the
existing simple flow sheet that was built in PRO/II for Task 4. The splitting units are still
represented by simple models which are stream-calculators in the PRO/II. Pump is needed to
pumping the liquid stream while compressor is used to transferring the vapor phase to the
other unit. Both equipments will increase the pressure in the operation. Meanwhile, expansion
valve is installed to decrease the pressure. In addition, heat exchangers are implemented to
increase/decrease the temperature of certain streams.
6.2 Mass Balance
Now it is important to set up a new mass balance in order to check whether the design
process will be able to produce the desired amount of products. The mass balance has been
simulated in PRO/II and is used to calculate the mass balance iteratively. Tables 6.1 and 6.2
show the amount of reactants and products in the main unit operation.
Table 6.1 Inlet stream total mass rate
Inlet Stream
Stream Number Type of Material Total Mass Rate (Kg/hr)
S1 Methanol (Feed raw material) 8850
S2 Ammonia (Feed raw material) 2767
S13 n-heptane (Feed solvent) 17.035
Total Mass Rate 11634.04 Kg/hr
43
Table 6.2 Outlet stream total mass rate
Outlet Stream
Stream Number Type of Material l Total Mass Rate (Kg/hr)
S13 Product-MMA 1198.177
S15 Product-DMA 4147.621
S17 Product-TMA 1052.526
S8 Water 4972.053
S11 Purge line 1 255.373
S19 Purge Line 2 1.629
S23 Purge Line 3 6.656

Total Mass Rate 11634.04 Kg/hr
The global mass balance equation is:
6.1
6.2
Besides, from the mass balance results, the product obtained in the process also can be
summarized as the following:
Table 6.3 The summary of the products
Product Product (kmole/hr) Purity

MMA 38.5794 95%
DMA 91.9970 99%
TMA 17.8059 99%
This products value is slightly different compared to the value obtained in the preliminary
mole balance that was done in the previous sections in Task 4.
6.3 Energy Balance
In the previous sections the mass balances have been developed over the entire process
on the basis of a simplified flow sheet and temperatures and pressures are fixed in the feed and
output streams. When the flow rates, compositions, states and temperatures of the streams are
known, an energy balance can be performed for the whole process. The energy balances are
based on the first law of thermodynamic; the principle of conversion of energy. The enthalpy of
44
the various streams is provided by PRO/II using a shortcut model. The heat added or removed
from a process can be found from these. The conversation of energy says that for a steady state
operation the heat added can be found by:
6.3
The temperatures of the various streams were found in the previous section. Heat is
removed in steps of the process; where the heat value is negative heat is added when the heat
value is positive heat is removed. Heat is added in the reactor hence the conditions are kept
isothermal and the reaction is endothermic. Heat is removed after the reactor as a result of the
fact that the temperature is brought down from 673 K (the temperature in the reactor) to 340 K.
Table 6.4 Temperatures and the duty for reactor
Inlet Inlet Pressure Outlet Temp. Outlet Duty

Unit
Temp. (K) (kpa) (K) Pressure (kpa) (M*kJ/hr)
Reactor 673 1976 673 1976 -9.4534
6.4 Heat Duties
A heat exchanger is needed before the reactor, since the reactor operates at high
temperature about 650K. Table 6.5 shows the duty from the reactors and stream calculators.
Pressure is specified at both top and bottom of the stream calculators. Dew point is chosen for
the top product while bubble point is chosen for the bottom product. The heat duties of the
processing units are calculated by;
6.4
Table 6.5 Work duty from PRO II for main equipment
Equipments Duty (M*kW-Hr/Hr)
Reactor 1 -2.63586E-03
Flash Tank 1.3558E-03
Absorber -2.8882E-05
The heat duty for reactor is negative, which means that the reaction is exothermic. It also
means that about -9.4534 M*KJ/h of heat is available for energy integration in the rest of the
process. The recycle streams are at different pressures, therefore the pressure is need to be
increased up to the feed pressure before mixing by using compressor. Besides, pumps are
needed for feeding in liquid feed stream to the reactor. We assume the efficiency of pumps and
compressors to be at least 85%.
45
An evaluation of the heat contents of all heat exchangers is carried out in order to
determine heating and cooling duties. Besides, two expansion valves are needed, one after
reactor and another expansion valve before the third distillation column, to account for the
decrease in pressure.
Table 6.6 Work duty from PRO/II for heat exchangers.
Equipments Duty (M*kW-Hr/Hr)

Heat Exchanger 1 3.2112E-03
Based on the heat duties and the stream inlet and outlet summary, the global energy
balance can be performed using following equation.
6.5
46
Figure 6.1 PRO/II flow sheet and stream summary for mass and energy balance model
47
Task 7:
The Total Flow sheet
7 Total Flow Sheet
Like the previous section, in this section, the simulations were carried out in PRO/II as well.
It will be later shown that further process considerations regarding pressure, temperature,
heating and cooling must be taken into account. These new considerations call for further unit
operations in the flow sheet. Some of these unit operations have to deal with the recovery of
that part of the ammonia that is not condensed in the flash. Other new unit operations are heat
exchangers, compressors and expansion valves. The design process contains various unit
operations (i.e. three mixers, four heat exchangers, one reactor, one flash unit, four distillation
columns and an absorber). The description of the unit operations will be given in this section
when substituting the simple models with rigorous ones.
7.1 Mixers
Mixers are usually used when multiple feed streams have to be sent in one unit operation.
The mixing process plays a vital role with efficient mixing being a key to good production. In the
current process three mixers are used at different stages in the flow sheet. A description of
streams that enter and leave the mixers will be given. Some specifications about the mixers used
in the process are given below.
Table 7.1 Operating condition for mixers
Mixer Temperature (oC) Pressure (atm) Pressure drop (atm)

MIX 1 30.67 1 0.5
MIX 2 387.50 20 0.5
MIX 3 57.97 2.5 0.5
Mixer 1 (MIX1)
The first mixer that is used in this process is used to mix the methanol feed (S1) with a
recycle stream that comes from the bottom of the third distillation column (S10). Since both
streams contain methanol but with different concentration (i.e. stream S10 contains very low
concentrations of DMA and TMA), temperature and pressure; therefore, it is necessary to mix
both streams before being sent to the next unit operation.
48
Figure 7.1 Operating condition in the Mix-1
Mixer 2 (MIX2)
The second mixer in the flow sheet is responsible to mix three streams which all
together will form the feed stream of the reactor. The methanol feed stream (S15) is mixed with
ammonia which partly comes from the feed (S17) and partly comes from the top of the first
distillation column as a recycle stream (S19). The outlet stream of this mixer is sent to a heat
exchanger (HEX1) to reach a certain temperature before entering the reactor.
Mixer 3 (MIX3)
The third mixer in the process flow sheet is used to mix the n-heptane recovery feed that
enters the absorber with the n-heptane that is obtained from the bottom of the fourth
distillation column. The mixture that leaves the mixer will be sent to a heat exchanger to be
cooled down before being sent to the absorption unit.
7.2 Heat Exchangers
The simple heat exchanger unit operation is used to heat or cool a process stream, or
exchange heat between two streams. The heat exchanger unit can have one or two sides. One-
49
sided units exchange energy between a process stream and a theoretically infinite source or
sink. Two-sided units exchange heat between two process streams, or exchange heat between a
process stream and a utility stream.
The heat exchanger unit can have any number of processes feed stream for both Hot and
cold sides. Water, air, and refrigeration medium can be used as a cold utility stream, while steam
or any other heating medium can be selected as a hot utility stream. All heat exchangers and the
role that they play in the process will be discussed here. The pressure and as well as inlet and
outlet temperature of the heat exchangers present in the process are given in the following
table:
Table 7.2 Heat echanger stream data
Heat Exchanger Inlet temperature (oC) Outlet temperature (oC) Pressure

HEX1 32 171 20.5
HEX2 387 400 19.5
HEX3 400 67 9.3
HEX4 144 36 3.0
Heat Exchanger 1 (HEX1)
This simple heat exchanger is used to evaporate the methanol feed stream before being
mixed with anhydrous ammonia. To this end, steam at 10 atm pressure is used as the utility and
the stream that disembarks this heat exchanger is methanol vapor at 171oC.
Figure 7.4 Heat transfer process in HEX1
The second simple heat exchanger in the process is used to heat up the inlet feed of the
reactor up to 400oC. In practice it cannot be simply done with steam, even if possible, it would
be very costly to use steam as the heating medium. Therefore, using a fired heater instead of this
heat exchanger is highly suggested since using them would be economically more feasible than
very high pressure steam.
50
This heat exchanger is used to cool down the outlet of the reactor so that it can be sent
to the flash drum. The outlet temperature is set to be 66oC in which the water is in liquid form
while the other compounds in the inlet stream of the flash drum are vapor. Therefore, this heat
exchanger enables us to have a two phase mixture (i.e. liquid and vapor). The utility that is used
for purpose of cooling is water which enters the heat exchanger at ambient temperature of 25 oC
and leaves it at 30oC.
Since the solvent and the mixture that are send in the absorber need to be at the same
temperature using a heat exchanger to cool down the solvent that is mixed with the recycled
solvent is inevitable. Therefore, HEX4 is used to cool down the temperature of the solvent (n-
heptane) from 144oC down to to 36oC. The cooling utility that is used for this purpose is water at
25oC.
51
7.3 Reactor
This reactor is considered to be a plug flow reactor (PFR). In PRO/II by default, the
reactor operates isothermally at the feed temperature. The plug flow reactor simulates a tubular
chemical reactor by solving the heat and material balances based on supplied reaction
stoichiometry and kinetic data. In a PFR it is assumed that there is no mixing as the material
moves along the length of the tubes. The conversion
depends on the reaction rate and the residence time
of the reactants in the reactor. The reactor geometry
must be defined in order to determine the residence
time. The reactions as they were described in
previous sections take place over the surface a
catalyst (KDC-6). The products are in gaseous phase
at an elevated temperature and pressure. They will
pass an expansion valve in order to reduce their
pressure from 20 to 10 atm. The temperature of the
product stream is then reduced by using HEX4 which
functions as a cooler.
Figure 7.8 Operating condition in reactor
7.4 Flash Unit
The flash unit (i.e. vapor–liquid separator) which

operates at 67oC and 9.3 atm is a device used in several
industrial applications to separate a vapor–liquid mixture.
In the present process it is used to separate the water
content of the reactor outlet before being sent for further
processing. This is done due to several reasons such as
preventing excess costs operating costs, avoid external
space in equipments and corrosion.
Figure 7.9 Condition in flash
7.5 Distillation Columns
There are four distillation columns in this process. Different distillation columns have
therefore, different operating conditions. Each distillation column has a reboiler and condenser
and a number of trays. The reflux ratio, pressure and temperature of each distillation column
were set according to different constraints associated with it. In order to determine the number
52
of trays for each distillation column, stream calculators were replaced with temporary unit
operation in the PRO/II which is namely known as distillation shortcuts.
By using the results from the shortcuts, the estimated number of trays and the feed
location could be identified. Then, the data were used to simulate distillations in PRO/II. A brief
description of each distillation unit will be given afterwards in this section. In the following
table the number of trays, reflux ratio and the feed location of each distillation column is given:
Table 7.3 List of feeding location for distillation
Distillation Duty Reflux Ratio Number of Feed Location

(M*kW-Hr/Hr) Trays Tray
DC 1 6.6258 12 7
Condenser –0.0019
Reboiler 0.0012
DC 2 1.1592 44 8
Condenser –0.0057
Reboiler 0.0061
DC 3 0.3098 16 10
Condenser –0.0003
Reboiler 0.0006
DC 4 0.7865 8 4
Condenser 0.0000
Reboiler 0.0003
Distillation column 1 (T2)
The first distillation column is used to separate

ammonia from the other vapor products that leave the
flash unit. This column operates at 10 atm while the
temperature at the first tray is 39.2oC and at the last tray
(i.e. tray number 12) is 75.4oC. In the top of distillation
column (T2) ammonia and water come out where
ammonia will be sent back as recycle to the mixer (MIX2)
and water will be purged by a decant water stream that
leaves the condenser at the top of the column. The
bottom products will be sent to the second distillation
column. To simulate this column Sure method was used
in PRO/II.
Figure 7.10 Distillation column one
53
The second distillation column is used to separate

mono-methylamine (MMA) from the rest of the products.
This column operates at 17 atm and the temperature of the
product streams at the top and the bottom of the column are
82 and 110oC, respectively. The product stream at the top
consists of MMA with 95% purity while methanol, DMA and
TMA and very small amount of MMA are obtained from the
bottom and are sent to the third distillation unit (T3).
Although To simulate this column Sure method was used in
PRO/II, water super saturation was detected on 3 trays.
Therefore, Sure method with decant water stream was
enabled in the simulator (no water exists in the process at
this point and the decant water stream was used merely for
the purpose of simulation while no water goes into that
stream). Figure 7.11 Distillation column two

The third distillation column is used to separate
methanol from the mixture of two remaining methylamines
(i.e. DMA and TMA). This distillation unit operates at 3 atm
and the temperature of top and the bottom product streams
are 36 and 87oC, respectively. The product stream at the top
of the column contains a mixture of DMA and TMA is vapor
phase while methanol that leaves the column at the bottom
is liquid. The top stream will be sent to the absorption unit
and the bottom stream will be recycled back to the feed
stream through a mixer (MIX1). Inside/out method was
used to simulate this column in PRO/II. Water super
saturation was detected on 3 trays, therefore, inside/out
method with a decant water stream was enabled in the
simulator (no water exists in the process at this point and
the decant water stream was used merely for the purpose of
simulation while no water goes into that stream).
Figure 7.12 Distillation column three
54
Finally, in the fourth distillation column, TMA will be

obtained as a vapor from the top of the column and n-heptane
will be recovered in liquid phase at the bottom of the column
and will be recycled back to the absorber. This column
operates at 3 atm and the temperatures of the top and the
bottom poroduct stream are 44 and 146oC, respectively.
Inside/out method was used to simulate this column in
PRO/II.
Figure 7.13 Distillation column four
7.6 Absorber
Since separating tri-methylamine (TMA) and di-

methylamine (DMA) in a distillation column is very difficult due to
their very close boiling points; in this design it was decided to use
and absorption unit instead of a distillation column. In the
absorption unit, the vapor mixture of DMA and TMA enter the
column at the bottom while liquid solvent (n-heptane) is
introduced into the column from the top. TMA is a non-polar
amine that can be solved in n-heptane while DMA due to its
hydrogen binding has a very low solubility in n-heptane.
Therefore, pure DMA will be obtained from the top of the
absorption column and a mixture of n-heptane and TMA will be
obtained from the bottom of this column which will be sent to the
next unit operation in order to separate TMA from n-heptane.
Figure 7.14 Absorber
7.7 Overall Process Performance
At the end of this section which the base case flow sheet has been obtained. The process
performance will be briefly discussed. Table 7.4 presents the overall process performance in
55
terms of specific energy consumption (MJ/kg of product), yield of production and yield of
separation. It can be seen that yield of separation for mono-methylamine (MMA) is as low as
62% which implies the low efficiency of first column (ammonia column) for this purpose. It
should be noted that in course of this design project several approaches were tried to increase
this efficiency and the present percentage is the maximum that could be obtained. Therefore,
improving the separation efficiency of ammonia column is subject to further in vitro and in situ
investigations.
The yield of production has also remained quiet low and that can be improved by using
better catalysts with higher selectivity to methylamines. The yield of production which is the
percent of products obtained from the raw materials stands at 55%. A kinetic and dynamic
simulation of the reactor can be also beneficial were the reactor is not considered to be
isothermal. It is believed by the authors of this report that the performance of this reactor might
be higher at elevated temperatures though no evidence to the aforementioned statement could
be found and it can be verified by a dynamic and kinetic simulation of the reactor where
reactions rates available.
Table 7.4 Process performance
Specific
Energy Yield of Production Yield of separation
Consump.
Kg of
Kg of
product
Initial Process Yield of product Yield of
MJ / kg of obtained
Product Target Performance production obtained separation
products in the
(Kg/hr) (Kg/hr) (%) out of the (%)
outlet
reactor
streams
MMA 0.029 1200 1200 10.3% 1926 1200 62.3
DMA 0.102 4500 4150 35.6% 4346 4150 95.5
TMA 0.027 1200 1100 9.5% 1162 1100 94.7
Total 0.158 6900 6450 55.4% 7434 6450 --
In this process, the total wastes can be classified as the total of flow rate purge line and
the by-product line which is water removed from flash tank. As shown in the total flow sheet
(Figure 7.15), the purge lines are stream S11, S24 and S33 and the flow rate are 7kg/hr, 483
kg/hr and 5 kg/hr, respectively. Stream 26 is referring to the by product which has flow rate of
4864 kg/h resulted the total waste is 5359 kg/hr. The process produces 6450kg/hr of all
products. Therefore the calculated total waste per kg of product is 0.83 kg. This result is high
due to the impact of high volume of water discharged from flash tank. The purge line in stream
56
S24 is subject to optimization in Task 10 since its amount is relatively too high compared with
other purge streams. Considering the water consumption in the process, it should be noted that
no water is consumed in this process as raw material and it is only obtained as byproduct of the
catalytic reaction in the reactor as well as the amount being used for process utilities (i.e.
cooling water and steam).
57
Figure 7.15 Total flowsheet
58
Table 7.5 Stream Summary for total flow sheet
59
Task 8:
Sizing of Equipments
8 Sizing and Costing
8.1 Equipment List
The main units for the process are listed in the Table for pressure vessel and processing
equipments.
Table 8.1 List of equipment for pressure vessel
Unit Operation Equipment Label Equipment Type

Distillation column 1 Pressure vessel T-101 Vertical
- Reboiler Processing equipment rT-101 Shell and Tube
- Condenser Processing equipment cT-101 Shell and Tube
Distillation column 3 Pressure vessel T-103 Vertical l
Reactor Pressure vessel R101 Plug Flow Reactor
Absorber Pressure vessel A101 Vertical
Flash Pressure vessel F01 Vertical
Processing equipment C101 Motor driven and Adiabatic
Compressors
Processing equipment C102 Motor driven and Adiabatic
Processing equipment E-101 Shell and Tube
Heat Exchangers Processing equipment E-103 Shell and Tube
Processing equipment E-104 Shell and Tube
Processing equipment P-101 Centrifugal
Pump
Processing equipment P-102 Centrifugal
60
8.2 Sizing of Equipment
In this task a rough sizing will be performed for each of the units. The sizing parameters
will be case specific, e.g. the heat exchanger area will be a measure of its overall size and
proportionality between the area and the overall cost can be assumed. On the other hand, the
sizing parameter for the compressors will be the brake horsepower, since it is the most
representative measure of their performance. After all the sizing is completed, the equipment
cost estimation will be carried out in order to make an overall economic feasibility study of the
process.
8.2.1 Pressure vessels
a) Reactor
In this section, the focus will be on the reactor design for the methylamines production.
The production process capacity has been designed previously to produce for each component
around 8878 ton/year of MMA, 33048 ton/year of DMA, and 8682 ton/year TMA. It is desired to
produce methylamines at a rate of 1088 kg/hr, 4050 kg/hr and 1066 kg/hr for MMA, DMA and
TMA, respectively in a plug flow reactor.
The production of methylamines is an exothermic process. The reaction should be

thermally controlled to keep the reaction at an optimum temperature of 400oC at 20 atm. The
reaction is kinetically driven and has conversion of methanol by 93% and ammonia by 68%
under the given conditions. The reactant and product have to be kept on gaseous form.
In order to size the reactor volume it is necessary to assume the residence time to be
around 1 minute. The reactor inlet flow rate is known from the PRO/II as per Appendix and is
14245.13m3/hr. The reactor volume can now be calculated as:
8.1
It will be assumed that the reactor has an optimal L/D ratio, which is assumed to be 4 as
specified by Biegler et al [33]. The dimensions of the reactor therefore become:
8.2
8.3
8.4
61
The volume of the catalyst bed is calculated based on 50% void fraction which leads to
the following relation:
8.5
The volume of catalyst is then = 181.328 m3 = 666.66 ton. A commercial type of the
catalyst which is called ‘’KCD-6’’ has been used for methylamines synthesis and are typically
(SO4)4 and (AlO4)5 catalyst [34]. These catalysts have a life time of 5 years and for regeneration
of catalyst we estimate that for each ton of catalyst we will lose 10%. The cost of the catalyst is
estimated to be 360-405 $/ton.
In this case lifetime has been chosen to be 5 years and according to commercial price of
catalyst, which is provided by the supplier, the price of the catalyst will be calculated
considering its mass. Therefore, to proceed with calculations, Table 2.3 in this report is
considered. In this table it can be seen that KCD-6 consists of two compounds with different
compositions, 21% SiO2 and 79% Al2O3. The densities of SiO2 and Al2O3 are 2648 and 3950
kg/m3, respectively. Therefore, a series of calculations can be done to find the final price of the
catalyst. The calculations are given below:
The density of the catalyst can be calculated by using the following equation:
8.6
Where subscript and are the composition and density of component i in the
catalayst. Hence, the density of the catalyst is calculated as follows:
8.7
8.8
8.9
8.10
As it was previously mentioned, the world cost of catalyst is around 360–450 $/ton and
this price varies from time to time depending on the customer needs. Therefore in present
62
calculations we used the average price of the catalyst which was estimated to be around 400
$/ton. Thus, the total price of the catalyst is calculated as follows:
8.11
8.12
(considering 10% loss)
8.13
8.14
Total cost of catalyst including the cost for 10% loss annually would be:
8.15
b) Flash
The volume of the flash drum can be determined using the following equation:
8.16
FL is the liquid flow rate leaving the flash drum (S26). This value together with the
density of the liquid are obtained from the PRO/II. is the residence time which, as an
assumption, is set to the value of 5 minutes. The dimensions of the flash drum are constrained
by the L/D ratio that approximately equals to 4.
8.17
8.18
8.19
c) Distillation columns
In this section the sizing calculations related to the distillation columns are performed. As it
can be seen in the total flow sheet of the process (Figure 7.15), there exist four distillation
columns which all have their own specific constraints and operating conditions. Therefore, the
sizing of the distillation columns is a crucial part of the purification in the methylamines plant. It
63
is where the majority of the product from the reactor is sent to, and the dimensioning of the
distillation column is therefore what determines if the final product will meet customer
demands with respect to purity.
The data for the distillation columns and the number of theoretical equilibrium stages were
found in PRO/II. However, before focus being devoted to the actual value of the data a short
explanation will be given on how these data could have been obtained without the use of
computer programmes.
The feed stream is in this case of a known composition and quantity and the stage number
could therefore have been found quite easily with the McGabe-Thiele method. The only thing
needed for this method is a calculation of the minimum reflux-ratio and a decision on the reflux-
ratio that should be used in the column. With this and specified recoveries of the components
the stage number could be found by mass balance considerations. The McGabe-Thiele method
does not provide any inside into the properties of each stage. This is done by solving the MESH-
equations. These equations could be solved by using the Inside-Out algorithm as was used in
PRO/II and they provide component flow rates inside the column and also the pressures and the
temperatures of each stage.
i. Column 1 (Unit T2)
In this column ammonia is being separated from MMA, DMA, TMA and methanol. The
inlet mass flow rate of this column is 9380 kg/hr which enters the column at 66oC and 9.3 atm.
2417 Kg/hr of ammonia is obtained from the top of the column while MMA, DMA, TMA and
methanol are obtained at the bottom of this column. Therefore, 99% of the ammonia is
recovered in this column. This column has 12 stages which the first is the condenser and the last
is the reboiler, therefore, it contains 10 trays. The results of the tray diameter for each stage,
after convergence in PRO/II can be seen in the table below.
Tray no. 2 3 4 5 6 7 8 9 10 11
D (m) 0.914 0.914 0.914 0.914 0.914 0.914 1.067 0.914 0.762 0.762
Since the difference in the top and bottom diameter is not too large it was chosen to give
the entire column a diameter of 1.07 m. The values for the extra feed space, disengagement
height and the skirt height are taken from Biegler et al [33]. The tray spacing is chosen to be 0.6
m in correspondence with the information given in Biegler et al. The next step in the
dimensioning is to calculate the height of the column. This is can be done in the following way:
64
Therefore, considering the above values the total height of the column will be 12 meters.
ii. Column 2 (Unit T1)
In this column mono-methylamine (MMA) is separated as the pure product and in its
anhydrous form from the top of the column at purity of 97%. The inlet mass flow rate of this
column is 6861 kg/hr which enters the column at 47oC and 5 atm. 1088 kg/hr of MMA is
obtained from the top of the column and DMA, TMA and methanol are obtained as a mixture
from the bottom of this column. This column has 44 stages which the first is the condenser and
the last is the reboiler, therefore, it contains 42 trays. The results of the tray diameter for each
stage, after convergence in PRO/II can be seen in the table below.
Tray no. 2–5 6 – 12 13 – 19 20 – 22 23 – 28 29 – 34 35 – 40 41 – 43

D (m) 1.372 1.676 1.676 1.676 1.829 1.829 1.829 1.829
Since the difference in the top and bottom diameter is not too large it was chosen to give
the entire column a diameter of 1.83 m. The values for the extra feed space, disengagement
height and the skirt height are taken from Biegler et al [33]. The tray spacing is chosen to be 0.6
m in correspondence with the information given in Biegler et al. The next step in the
Therefore, considering the above values the total height of the column will be 31.2 meters.
iii. Column 3 (Unit T3)
In this column methanol is separated as the pure product in the liquid form from them
bottom of the column at purity of 99%. The inlet mass flow rate of this column is 5773 kg/hr at
110oC and 17 atm. 700 kg/hr of methanol is obtained at the bottom of this column and DMA and
TMA are sent to the next unit operation. This column has 16 stages which the first is the
65
condenser and the last is the reboiler, therefore, it contains 14 trays. The results of the tray
diameter for each stage, after convergence in PRO/II indicates that the trays number 2 – 14 have
a dimater of 0.762 meters while the last tray (i.e. tray number 15) has a diameter of 0.610
meters. Therefore, since the difference in the top and bottom diameter is not too large it was
chosen to give the entire column a diameter of 0.77 m. The values for the extra feed space,
disengagement height and the skirt height are taken from Biegler et al [33]. The tray spacing is
chosen to be 0.6 m in correspondence with the information given in Biegler et al [33]. The next
step in the dimensioning is to calculate the height of the column. This can be done in the
following way:
iv. Column 4 (Unit T4)
In this column TMA is separated as the pure component (99% recovery) from the top of
the column and n-heptane is obtained from the bottom (99% recovery). The inlet mass flowarte
of this column is 3138 kg/hr. 1064 kg/hr TMA and 2037 kg/hr n-heptane is recovered from the
top and the bottom of this column respectively. This column has 8 stages which the first is the
condenser and the last is the reboiler, therefore, it contains 6 trays. The results of the tray
diameter for each stage, after convergence in PRO/II indicate that the trays number 2 and 3
have a dimater of 0.475 meters while the 4 – 7 have a diameter of 0.610 meters.
Therefore, since the difference in the top and bottom diameter is not too large it was
chosen to give the entire column a diameter of 0.61 m. The values for the extra feed space,
disengagement height and the skirt height are taken from Biegler et al [33].The tray spacing is
chosen to be 0.6 m in correspondence with the information given in Biegler et al [33]. The next
step in the dimensioning is to calculate the height of the column. This is can be done in the
following way:
66
d) Absorption column (Unit SC1)
Tri-methylamine (TMA) is recovered by absorption using n-hepatne as the absorbant in

an absorption column. Based on the solubility parameters of TMA and n-heptane, it is assumed
that only ammonia is absorbed. From the mass balance carried out in PRO/II it is known that
the gaseous stream entering the absorption column has a TMA mole fraction of yTMA  0.15 .
The calculations in the previous sections indicated that the number of trays is approximately 2;
therefore, considering 20% efficiency for each tray as equilibrium on a tray is usually a very
poor assumption. This will result in an actual number of trays equal to 8. In order to calculate
the height of the column 0.6 m spacing between the trays is assumed. The diameter of the
column can be calculated by using the following equation:
8.20
In the above equation is the maximum allowable vapour velocity based on the total
column cross sectional area, l is spacing between the trays (0.6 m) and and are liquid and
vapour densities, respectively. Therefore, is defined by the following expression:
8.21
The values of and are obtained from PRO/II, therefore, performing the calculations
will reveal 1.5 m for the diameter of the column (D). The values for the extra feed space,
disengagement height and the skirt height are taken from Biegler et al [33].The next step in the
67
e) Heat Exchanger
The equation by which the sizing calculation for heat exchangers can be performed is
given below and Q is the heat duty and can be found from the energy balances performed in
Task 5, U is the overall heat transfer coefficient and A is the required area.
8.22
which is given by:
8.23
In the above equation, is the logarithmic mean temperature, T1 and t1 are the inlet
temperatures of the hot and cold streams, respectively while T2 and t2 are there corresponding
hot and cold outlet temperatures. The overall heat transfer coefficients depend on the medium
in the shell and tube side. In this production process, HEX1, HEX2 and HEX3 have a mixture of
vapor-liquid media. The required area is determined for both vapor media and condensing
media. For all heat exchangers, we assumed the design U = 200 Btu/ft2hr-oF (1136 W/m2K). The
value of U is referring to the tables in Biegler et al [33].
For vapor media;
8.24
For condensing media;
8.25
The total area is:
8.26
Table 34 shows the different heat exchangers used in our flow sheet along with the heat
duties needed to accomplish the desired cooling and heating. In the same figure the inlet and
outlet temperature and Tlm difference is shown. For each set of Q, U and Tlm the needed area
68
is calculated. If the calculated area had at any point exceeded a limit of 1000 m 2, multiple heat
exchangers will be needed; however this is not the case for any of the heat exchangers.
Based on the result form PRO/II, the size for heat exchangers are as following:
Table 8.2 Size of heat heat exchangers
Parameters HEX1 (E1) HEX2 (E2) HEX3 (E3) HEX4 (E4)

Feeds Stream S6 S3 S18 S14
Products stream S15 S16 S5 S39
Hot outlet
180.63 399.85 66.85 180.63
temperature (oC)
Cold outlet
171 - 130 36
temperature (oC)
Duty (M*KW-
45.108 1.5207E-04 4.9269E-03 1.829E-04
Hr/Hr)
U (kW/m2K) 1.135 - 1.135 1.135
(oC) 52 - 135.26 70.4918
Area (m2) 61.85 - 135.26 2.29
f) Pump
In this process, centrifugal pump was used which has basic configuration cast iron and
can be operated below 390K. Besides, centrifugal pump also has a suction pressure about 10
bars. The brake horse power for the pump can be calculated as following:
8.27
Where is the pump efficiency and is the motor efficiency. The efficiency for pump is
assumed to be 0.5 and the efficiency for the motor is assumed to be 0.9.
g.) Compressor
Two compressors are being used in this process. The brake horse power for the
compressor is calculated by the following equation:
8.28
In the above equation is the molar flowrate and is the gas enthalphy. In this process, we
assume as an ideal system and the equation can be written as the following:
69
8.29
Where the constant pressure heat capacity and R is is the gas constant (8.314 J/gmolK).
For an ideal system, is 0.4 and defined by . By assuming the compressor to be
isentropic and also adiabatic expansion, can be calculated from the pressure ratio by
using the following equation:
8.30
By substituting back above expressions, the following theoretical power expression for an ideal
system can be used:
8.31
For the efficiencies of compressors or turbines a typical number is chosen, , for both
compression and expansion. The driver can be either an electrical motor or a turbine. The
efficiency related to the driver is assumed to be 0.9 for the electrical motor and 0.8 for the
turbine. Thus the actual (or brake) horsepower for a compressor is:
8.32
Therefore, the electrically driven motor is chosen, thus .
Table 8.3 Summary of the compressor specifications as per result from PRO/II
Parameters C-101 C-102

Feed Stream S2 S23
Product stream S17 S19
Outlet Pressure (atm) 20 20
Pressure increase (atm) 19 10.62
Outlet temperature (oC) 296.26 97.64
Work, KW 553.68 51.61
Head, M 62417.45 9794.55
8.3 Summary of Equipment Sizing
In the table that follows a brief summary of the sizing calculations for the equipments
present in the process will be given. It should be noted that to design a plant, these values can be
70
considered as educated guess while further considerations have to be taken into account to find
the exact size and specifications of the equipments.
Table 8.4 Summary of the equipment sizing for the production methylamines.
Unit Operation Tag . No Sizes Details
Diameter, D =1.07 m Number of trays : 12

Distillation column 1 T-101
Height, L =12 m Feed Location : 7
Height, L =31.2 m Feed Location : 8
Height, L =14.4 m Feed Location : 10
Height, L=9.6 m Feed Location : 4
Diameter, D =4.865 m
Reactor R101
Height, L =19.5 m
Diameter, D =1.5 m
Absorber A101
Height, L =9.6 m
Diameter, D =0.52 m
Flash F01
Height, L =2.08 m
C101 553.68 kW
Compressors
C102 51.61 kW
HE101 Area, S = 61.85 m2
Heat Exchangers HE103 Area, S = 135.26 m2
HE104 Area, S = 2.29 m2
71
Task 9:
Economic Evaluation
9 Cost Calculations
In order to determine the cost for each operation the earlier sizing parameters were used.
All the calculations were performed in ECON.
9.1 Capital Cost
Fixed capital cost needs to be calculated for all equipment and this can be done by
summation of bare module cost, the contingency cost as well as the cost of building, services and
land.
a) Total Installed Cost
9.1
(i) For pressure vessel
A more specific version of the previously presented general equation is available for
cylindrical pressure vessels such as flash drums. The cost depends on their length (L) and
diameter (D) which together serve as a measure of capacity. The equation for vessel cost is:
9.2
Where L0 is the base length, D0 is the base diameter,  and  are economy of scale
exponents. Vessel cost is also influenced by their orientation, horizontal or vertical, and the
material of which they are made of.
(i) For process equipment
The cost of each unit processing unit can be found from correlations developed by Guthrie.
The general equation is:
9.3
Where C is the uninstalled equipment cost, C0 is base cost, S is the equipment capacity and
S0 is the base capacity.  is an exponent generally less than one that reflects an economy of
scale.
72
b) Bare module cost
A modular method is used to factor in additional direct and indirect costs where the
equipment cost that was previously found is multiplied by a module factor, and an update
factor. Costing information on all the above mentioned units are taken from K. Guthrie’s
research in 1969. Guthrie developed generic costing equations in 1969. Most of his equations
take the 1969 material cost into account and therefore they must be multiplied by an update
factor (UF) in order to express the current costs. The update factor is defined as:
9.4
To obtain the UF, the following data for CI was fitted as function of year to predict the CI
for 2012. For cost updating we will use the Chemical Engineering (CE) Plant Index reported in
Chemical Engineering magazine.
Table 9.1 CI data as per different year
Year 1957- 1968 1970 1983 1993 1995 2000 2001 2002 2003 2004
59
CI 100 115 126 316 359 381 394.1 394.3 395.6 402 444.2
500
450
400
350
300
250 y = 8,3501x - 16300
CI
200 R² = 0,9478
150
100
50
0
1965 1970 1975 1980 1985 1990 1995 2000 2005 2010
Year
Figure 9.1 Graph plot in determine the current CI value
A linear extrapolation of the values from 1957 to 2004 gives a 2012 cost index of 500.4.
Figure 9.1 shows the cost index trend from 1968–2004. Since the price correlations from
Biegler et al. [33] are from 1968 the update factor of 2012 is:
9.5
The module factor (MF) accounts for installation cost and depends on equipment cost.
The material and pressure correction factor (MPF) adjust the price from a carbon steel and
73
atmospheric pressure basis to the appropriate material and pressure. The update factor (UF)
updates the cost from the 1969 basis to the current year 2012. The total updated bare module
cost (BMC) is given by:
9.6
All the calculation is performed in ECON. The result for total cost for equipment
installation and the utilities cost for base case design are shown as following table:
Table 9.2 Overall total cost estimation
Unit Equipment Size Unit Material Purchase cost ($)

C-101 Compressor 470.63 kW Carbon Steel 397,029
C-102 Compressor 51.63 kW Carbon Steel 74,124
E-101 Heat Exchanger 61.85 sq.meter 316 Stainless Steel 171,280
M-101 Mixer 400 m3 Stainless Steel 56,957
R-101 Heat Exchanger 297 sq.meter SS shell & SS tube 94,188
V-101 Vessel 2 meters 316 Stainless Steel 33,607
rT-101 Heat Exchanger 4 sq.meter 316 Stainless Steel 48,889
cT-101 Heat Exchanger 4 sq.meter 316 Stainless Steel 48,889
T-101 Tower Unit 12 meters 316 Stainless Steel 135,208
P-101 Pump 0.0002 m3/s 316 Stainless Steel 55,782
P-102 Pump 0.003 m3/s 316 Stainless Steel 33,803
H-101 Fired Heater 152 kW 316 Stainless Steel 569,908
The total cost for purchasing the equipments is $ 21,160,430
Based on the overall total cost estimation as shown in Table 9.2, the percentage of main
equipment cost is illustrated in Figure 9.2. The pie chart shows that the highest capital cost for
74
this process is for compressors and distillation columns. It is due to the fact that the size of the
duty of the compressor is high and 44 trays are needed in distillation column 2.
C-102 C-101
4% 28%
E-102
E-101 2%
1% H-101
T-105
4% 3%
T-104 M-101
4% 3%
M-102
T-103 3%
M-103
7%
3%
R-101
4%
T-101
V-101
T-102 6%
2%
24%
Figure 9.2 Percentage of equipment installation expenditure
The result of total utilities cost calculations generated by ECON software is listed in Table
9.3 and the percentages are shown in Figure 9.3. As it was expected, compressor 1 uses the
highest amount of utilities as well as reactor because the reactor is operating at high
temperatures.
Table 9.3 Overall total utilities cost
Unit Equipment Utility Size Unit Price, $/gj Utility cost ($)
C-101 Compressor Electricity 470.63 kW 16.80 37,014
C-102 Compressor Electricity 51.63 kW 16.80 273,250
R-101 Heat Exchanger MP steam 700 kW 8.22 149,144
H-101 Fired heater Natural Gas 152 kW 6.00 26,791
75
C-101
59%
R-101
C-102 32%
8%
Figure 9.3 Percentage of utility cost used by equipment
c) Total Capital Investment
Capital investment costs are incurred initially at the start of the project. The total capital
investment (CI) is given by summation of the fixed and the working capital. The fixed capital (CF)
is the amount needed to build the physical process. It is divided into manufacturing and non-
manufacturing capital. Manufacturing capital is the sum of the updated bare module costs
(BMC) of each piece of equipment plus a 25% contingency value. Non-manufacturing capital,
such as real estate, is typically 40% of the manufacturing cost. Therefore the fixed capital is
given:
9.7
The Working capital (CW) covers the funds required to operate the plant due to delays in
payment and maintenance of inventories. An approximation for working capital is given in
Beigler et al.:
9.8
The total capital cost (CI) is then expressed as:
76
Table 9.4 Total capital instalment
Percent of Delivered-
Manufacturing Fixed-capital Investment equipment for Result
(Direct Cost)
Fluid Processing Plant
Purchased Equipment Delivered 1.1 $ 23,276,473
Purchased Equipment Installation 0.47 $ 10,939,942
Instrumentation and Controls (installed) 0.36 $ 8,379,530
Piping (Installed) 0.68 $ 15,828,001
Electrical Systems (Installed) 0.11 $ 2,560,412
Buildings (Including Services) 0.18 $ 4,189,765
Yard Improvement 0.1 $ 2,327,647
Service Facilities (Installed) 0.7 $ 16,293,531
Sum 2.6
Total Direct Cost $ 83,795,302
Nonmanufacturing Fixed-capital equipment for Result
Investment (Indirect Cost)
Engineering and Supervision 0.33 $ 7,681,236
Construction Expenses 0.41 $ 9,543,353
Legal Expenses 0.04 $ 931,058
Contractor's Fees 0.22 $ 120,824
Contingency 0.44 $ 10,241,648
Sum 1.44
Total indirect cost $ 33,518,121
Fixed-capital Investment equipment for Result
Fixed-Capital Investment (FCI) $ 117,313,423
Working Capital Investment equipment for Result
Working Capital Investmenst (WC) 0.89 $ 465,529
Total Capital Investment (TCI) $117,778,953
All the calculations were performed by ECON. The result from ECON is shown in Table
9.4. The total of capital installment is $ 117,778,953. The direct expenses such as maintenance
and supplies were assumed to be 6 and 2 % respectively of the fixed capital. The indirect
expenses include depreciation and insurance, they are assumed to be 8 and 2% respectively of
the fixed capital. The utilities expenses is the cost summation of cooling water steam needed in
the process. The prices of the steam and cooling water are taken from Beigler et al. and updated
to 2012 prices.
77
9.2 Manufacturing cost
Manufacturing costs involve expenses that are directly related to the day-to-day
operation of the plant as well as indirect expenses such as taxes, insurance, and depreciation.
However in this study taxes will not be considered.
A few assumptions were made in the estimation of the manufacturing cost. The
expenses for labour were calculated as 0.01% of capital cost. It was assumed that the operation
for this processing plant took place 340 days per year. The total running time,
The total operating cost is the sum of the following items.
Table 9.5 Total operating cost
Items of Operating Cost Factor Basis Cost, $/year

Raw Material 0 25,052,832
Operating Labor 0.01 Fixed Capital Investment 1,173,134
Operating Supervision 0.15 Operating Labor 175,970
Utilities 0 149,144
Maintenance and Repairs 0.06 Fixed Capital Investment 7,038,805
Operating Supplies 0.15 Maintenance and Supplies 1,055,820
Laboratory Charges 0.15 Operating Labor 175,970
Royalties 0.01 Total Product Cost 510,798
Variable Cost 35,332,475
Property Taxes 0.02 Fixed Capital Investment 2,346,268
Financing (interest) 0 Fixed Capital Investment --
Insurance 0.01 Fixed Capital Investment 1,173,134
Rent 0 Fixed Capital Investment --
Fixed Charges 3,519,402
Plant Overhead 0.6 Labor + Supervision + Maintenace 5,032,746
Manufacturing Cost 38,851,877
Administration 0.2 Labor + Supervision + Maintenace 1,677,582
Distribution & selling 0.04 Total Product Cost 2,043,192
Research & Development 0.04 Total Product Cost 2,043,192
General Expense 5,763,967
Total Product Cost with Out Depreciation 51,079,816
78
9.3 Economic Evaluation
The last step in the base case designing process is an overall economic evaluation, which in
turn reveals the economic potential of the relevant process. It is convenient to divide costs
related with the process can be into fixed and variable cost. Variable costs are raw material,
labour, utilities, and other costs that are dependent on operation. Here we are primarily
concerned with manufacturing costs, which are continuous expenses, given on an annual basis.
The fixed costs are direct investment as well as overhead and management associated with this
investment. In particular we are interested here in capital investment costs.
Operating Profit
The total capital investment is $ 117,778,953 mill. Subtracting the manufacturing costs
from the total revenue gives a profit of $6,020,447 mill as per result from ECON. This means
that the methylamine production is a profitable process.
NAME QUANTITY COST, ANNUAL NAME QUANTITY PRICE, ANNUAL

, KG/YR USD/KG PRICE ($) , KG/YR USD/KG PRICE ($)
MeOH 72,216,000 0.22 15,887,520 MMA 9,792,000 0.78 7,637,760
NH3 22,848,000 0.40 9,139,200 DMA 33,864,000 1.04 35,218,560
n- 16,320 1.60 26,112 TMA 8,976,000 1.17 10,501,9200

heptane
Total $ 25,052,832 Total $ 53,358,240
The next step in the economic analysis is to evaluate the profitability of a process. There
are different measures of how profitable a process is. Such a measure is the Net Present Value
(NPV) which uses a fixed rate of return to calculate how much the project is worth when
discounted to the present day. Another measure is the rate of return i*, which is the interest rate
when NPV is equal to zero. The NPV is defined as:
9.9
where n is the investment lifetime (pay back time), R is the gross profit and is equal to the gross
sales minus the manufacturing cost. The gross sales are found by multiplying the capacity of the
plant by the product price.
79
Table 9.6 The profitability evaluation result from ECON
Profitability
not include time value of money
Rate of Return 59%
Pay Back Period 1,31
Net Return $6,020,447
(include time value of money)
Annual End of Year cash flows and discounting
Net Present Worth $ 3,239,730
DCFR 0.15
Continuous cash flows and discounting
Net Present Worth $ 3,477,871
DCFR 0.14
Figure 9.4 show the cumulative cash flow for the process whereas Figure 9.5 illustrates
the factor that influences the profitability of the process. Based on the both graphs it shows that
the cumulative cash flow is about two years and profitability is influenced by the product price
and the raw material price.
$100.000.000,00
$80.000.000,00
Cumulative Cash Flow
Cumulative Cash Flow
$60.000.000,00
$40.000.000,00
$20.000.000,00
$-
-2 -1 0 1 2 3 4 5 6 7 8 9 10
$(20.000.000,00)
project life time (year)
Figure 9.4 Cumulative cash flow analysis based on 10 years project life time
80
$250.000.000,00
$200.000.000,00
$150.000.000,00
$100.000.000,00
NPV
$50.000.000,00
$-
-50% -40% -30% -20% -10% 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
$(50.000.000,00)
$(100.000.000,00)
percentage of change
Raw Material Product Price Labor Cost
Figure 9.5 Factors influence the profitability of the process (sensitivity analysis).
Annualized Cost Evaluation
a) Annualized cost per Kg of product

The total product cost based on the result from economic evaluation in ECON is
$54,2006,309. This is the value for the third year of production as the cumulative cash flow
is about 2 years with 17% depreciation cost. The annualized cost per Kg of product is
calculated for the entire main product and the results are given as follows:
Product Total Kg production per year Annualized cost per Kg of product

MMA 9,789,552 0.174
DMA 33,842,376 0.600
TMAN 9,000,072 0.160
The results show that the annualized cost per kg of DMA is high due to the fact the product
is the main target in the production as represent 63% of the total products.
b) Annualized cost per Kg of raw material

The main raw material for this process is methanol and ammonia. N-heptane which is only
solvent for the process is not taken into consideration for the calculation of annualized
cost per Kg of raw material. The results are as follows:
81
Product Total Kg consumption per year Annualized cost per Kg of product

Methanol 72,216,000 1.281
Ammonia 20,971,200 0.372
c) Water consumption cost per Kg of product
In this process water mainly use for utilities such as in the steam generation for heating the
process line, cooling water in the cooling towers for chilling process and as coolant in the
condensers. Besides, water also use for general cleaning. However, it is hardly to calculate the
total amount of water used in the boiler for steam. Therefore, for the purpose of water
consumption cost calculation, only water in the cooling water is considered and it assumed
that the total amount of water is fixed in the system and it is always re-circulated. That means
that this flow rate is equal to purchase cost/year assuming that the life time of the utility is 1
year. Cooling water 1 used 12,243kg/hr while cooling water 2 is used only about 2,420 kg/hr.
The total is 14,663kg/hr. Therefore the estimation of water consumption per kg of product is
as follows assuming 10% water evaporation per hour:
Product Water Consumption (Kg) per Kg of product

MMA
1.22
DMA
0.35
TMAN
1.33
82
Task 10:
Process Optimization
10 Process Flow sheet Optimization
The optimization process is carried out to determine the optimum operating condition and
physical design that could achieve best process performance. All the process of each unit
operation done without compromising all the constraints those are predetermined. The reason
for optimization is to reduce the capital cost and operating cost without violating the
constraints that are predetermined. Typical objectives for the optimization of the process
design include capital and operating cost, product yield, and overall profit.
However, the optimization does not necessarily mean that the process production will
increase or the plant will bring more profit after optimization. Optimization also can bring
changes that lead to reduction of plant cost, increase in management bring changes that lead to
reduction of plant cost, increase in management productivity and make the plant more safely to
work with.
The values of the objective function are determined by manipulation of the problem
variables. These variables can physically represent equipment sizes and operating conditions
such as pressures, temperatures and feed flow rates. Limit of process operation, product purity,
validity of the model, and relationships among the problem variables need to be considered as
constraints in the process. Similarly, the variable values must be adjusted to satisfy these
constraints [33].
It usually concerns with optimizing unit operations that will affect that particular unit
operation only. In this proposed plant, the following major equipments and general plant
optimization has been considered for optimization study;
a) Operating profits
b) Solvent
c) Compressors
d) Heat Exchanger Network
83
The heat exchanger network optimization is discussed in detail in Task 11. The optimization
problem can be written mathematically using a model for the system.
Max or Min Objective function 10.1

Subject to 10.2
10.3
Eq. 10.1 is the objective function and can be represent as to maximize the profit, to
minimimize the purge and to minimize the number of stages for compressors. Eq. 10.2 is
equality constraints and can represent the process conditions. Eq. 10.3 is equality constraints
that can be represented by material balance with lower bound upper bound.
10.1 Operating profits as the objective function
In the present process three products are being produced namely known as MMA, DMA and
TMA while two raw materials are being used which we consider them to be in limited supply
based on a daily basis. The reactions that take place in the process are given below:
10.4
(RXN1)
10.5
(RXN2)
10.6
(RXN3)
The maximum amount of raw materials and their corresponding prices are given in the
following table. This information will be later used to derive the profit objective function and
are therefore considered as part of the daily costs of the plant.
Table 10.1 The maximum amount of available raw materials and their corresponding prices.
Raw material Maximum available (kg/day) Cost ($/day)

Methanol 212,400 0.40
Ammonia 67,200 0.22
A flow diagram of the plant with respect to the reactions is given in Figure 10.1 (the separation
units are not a matter of concern at this point):
84
Methanol
RXN 1 MMA, Water
Ammonia RXN 2 DMA, Water
RXN 3 TMA, Water
Figure 10.1 Flow diagram of the plant with respect to the reactions.
The formulation of this optimization will be performed using the information given in
Table 10.1. The goal is to maximize the total profit by maximizing an objective function. The
general formulation for profit optimization is as follows:
Max = 10.7
s.t : 10.8
10.9
Where C is vector of cost, x is vector of flow rate and A and B is vector of material balance.
Table 10.2 Reactant requirements, processing and selling costs for the products.
Product Reactant requirements Processing cost Selling price

(kg/kg product) ($/kg) ($/kg)
MMA 0.13 Methanol, 0.87 Ammonia 0.12 0.78
DMA 0.62 Methanol, 0.38 MMA 0.40 1.04
TMA 0.18 Methanol, 0.82 DMA 0.11 1.17
The income in dollars per day from the plant can be found from the selling prices and that is:
10.10
The operating costs in USD per day include:
85
10.11
10.12
Therefore, considering the above equations, the total cost per day in USD can be given as
follows:
10.13
The daily profit can be found by subtracting daily operating costs from the daily income. The
daily profit function is the function which is intended to be maximized and is given below:
10.14
10.15
10.16
The five variables in the objective function are constrained through material balances
( ), namely:
10.17
10.18
10.19
10.20
Also,
10.21
10.22
The above optimization problem was solved using MS Excel LP solver. The results are
given in Table 10.3. It can be seen that the optimum production ratio to maximize the profit is
found. However, its utilization is subject to use/develop appropriate catalysts or a different
process approach. It should be also noted that a market analysis is beneficial in case the
mentioned results are going to be used. The ratio is the amount of a product over the total
amount of products that are produced.
86
Table 10.3 Optimum production ratios found by solving the operating profits objective function.
Prod. Ratio Prod. rate Optimum Prod. Ratio (Kg of Prod. rate
(Kg of product/ (Kg/hr) product/ (Kg/hr)
Kg total prod.) Kg total prod.)
MMA 19% 1200 15% 967
DMA 64% 4150 38% 2451
TMA 17 % 1100 47% 3031
Total 100% 6450 100% 6450
10.2 Solvent Optimization
Using an efficient solvent has utmost importance in separation processes. A process that
has minimal solvent loss together with easy recovery of the solvent is the most favorable. To
this end, several alternatives to the current solvent (i.e. n-heptane) that is being used in this
process are considered here. These alternatives include finding a solvent through molecular
design, gas hydrate formation and using ionic liquids as promising solvents.
Solvent selection
To find alternatives to the present solvent ProCAMD (which is a function of ICAS v.13)
was used. The specified solvent was set to be acyclic, completely miscible in TMA and DMA,
minimum normal boiling point of 300K. Unfortunately, no solvent could be selected using the
mentioned approach. Therefore, some alternatives will be considered using the following
factors regarding TMA and DMA.
 The boiling points of TMA and DMA are very close to each other.
 TMA is a non-polar molecule while DMA is a polar molecule.
 No VLE data are available in the literature presenting the solubility of either DMA or
TMA in n-heptane or similar organic solvents. Though, some data are available
regarding their solubility in water.
Therefore, in order to find a better solvent, a literature survey was performed. Al-Malah
[35] presented aqueous solubility of some organic compounds as a function of their size and
dipole moment. In his study the molecular dipole moment was chosen to represent the polar
character of a poly-atomic molecule. It was hypothesized that at a given pH, temperature, and
pressure, the solubility of an organic molecule in water will be a function of its polar character;
namely, dipole moment and of its molecular size. He found the aqueous solubility of
87
monomethylamine (MMA) and dimethylamine (DMA) to be very high almost 520 at 25oC and
atmospheric pressure ( ).
Therefore, based on the above evidence, water might be an alternative solvent in this
process. Using water in the process means that DMA will be dissolved in water and obtained at
the bottom of absorption column while TMA will be obtained from the top of the column at
vapor phase. The water for the absorption column can be supplied from the bottom of the flash
unit. The price of the fresh water is going to be considered negligible since it will be recovered
in the distillation column and its recovery is not also considered as an imposed cost due to its
very low quantity. Therefore, regardless of how much water is consumed, the amount of money
that will be saved by replacing the solvent is given in Table 10.4.
Table 10.4 Amount of money that will be saved by replacing n-heptane with water.
Solute Annual price ($/year)

Solvent
n-heptane Tri-methylamine 26,200
Water Di-methylamine (DMA) Free
It should be noted that replacing the solvent may cause an increase in the capital and
operating cost of the process since the fourth distillation column has to operate at a higher
capacity due to lager production of DMA which is four times greater than TMA. Henceforward,
using water instead on n-Heptane almost 26,200 $/year will be saved.
Gas hydrate formation process
Gas hydrates (clathrate hydrates) are crystalline solid structures consisting of water and
small molecules such as CO2, N2, CH4, H2, etc. which are formed under conditions of low
temperature and specified (generally high) pressure [36] [37]. A clathrate is a structure
composed of a molecule or molecules of one or several components (guest molecules) which are
enclosed within a cage built from molecules of another component (host molecules) [36] [37].
In the 1930s, Hammerschmidt [38] found that natural gas hydrates might result in
blockage of gas transmission lines. The formation of hydrates leads to a reduction in the
pipelines’ cross sectional area and consequently increases the pressure drop in the processing
of natural gases leading to higher production, processing, and transportation costs and the
corresponding lower flow rates. Inhibition of gas hydrate formation in pipelines has therefore
attracted the attention of engineers in the field over the past century [36] [38] [37].
88
There has been a dramatic increase in gas hydrate research over the last decade.
Interestingly, the research has not focused on only the inhibition of gas hydrate formation,
which is of particular relevance to the petroleum industry, but has evolved into investigations
on the promotion of hydrate formation as a potential novel separation technology [36]. Gas
hydrate formation as a separation technology shows tremendous potential, both from a physical
feasibility (in terms of effecting difficult separations) as well as an envisaged lower energy
utilization criterion. It is therefore a technology that should be considered as a future
sustainable technology and will find wide application, possibly replacing a number of current
commercial separation processes [36].
Gas hydrate formation, even though it is something that has negative connotations in the
petroleum and gas processing industry, also has the potential for numerous positive
applications, e.g. the use of clathrate hydrates as means of gas storage. Many positive
applications of clathrate hydrates such as in carbon dioxide capture and sequestration, gas
storage, air-conditioning systems in the form of hydrate slurry, water desalination/treatment
technology, concentration of dilute aqueous solutions, separation of different gases from flue
gas streams, and many other examples have been reported, especially in recent years [36] [37].
However, slow gas hydrate formation rates and high pressure/low temperature
conditions for industrial applications of clathrate hydrate storage processes are among the
factors that have been subjects of many studies recently. Gas hydrate promoters have been
generally considered as additives to the hydrate crystallization (formation) processes to greatly
reduce the required hydrate formation pressure and increase the formation rate and/or
temperature along with modification of the selectivity of hydrate cages for absorption of various
gas molecules in the water cages or increase in the storage capacity of these structures [39].
The common gas hydrate formation promoters can be categorized into two distinct
groups: (1) water “soluble” and (2) water “insoluble”. The first group can consist of mainly two
branches of substances including those that do not take part in the structures of the hydrate
cages, e.g., tetrahydrofuran (THF), 1,4-dioxane, 1,3-dioxalane, acetone, etc., which normally
form structure II of clathrate hydrates in the presence/ absence of gas moleculesand the ones
that take part in the structures of the hydrate cages such as tetra-n-butylammonium halides
(TBAX) especially tetra-n-butylammonium bromide (TBAB) and other halides like tetrabutyl
phosphonium bromide (TBPB), [39] which form semi-clathrate hydrates.
89
Some experimental investigations (crystallographic studies and X-ray structure analysis)

have demonstrated that alkylamine compounds can act as hydrate formers (like quaternary
ammonium salt hydrates) to form semi-clathrate hydrates e.g. tertiary amine and
trimethylamine (TMA) [40]. As a matter of fact, amine group forms a part of the bonded water
network and the alkyl may occupy the cavities for stabilization of the hydrate. The semi-
clathrate hydrate structure of the TMA is shown in Figure 10.2.
Figure 10.2 Chemical structure of TMA semi-clathrate hydrate [40].
A novel approach to separate gas components from gas mixtures is through gas hydrate
crystallization techniques, as mentioned earlier. Due to the difference in affinity between the
involved gases in the hydrate cages when hydrate crystals are formed from a mixture of these
gases, the hydrate phase is enriched in a particular gas while the concentration of other gases is
increased in the gas phase. The hydrate phase can be later dissociated by depressurization
and/or heating and consequently the component of interest can be recovered.
Since the mixture of TMA + DMA is considered as the input stream to the absorption
column in the base case design, the solvent + absorption processes can be replaced by the
aforementioned separation process utilizing gas hydrate formation technique. A typical
schematic diagram of this process is given in Figure 10.3. It should be noted that this gas
hydrate formation process is subject to further economical and feasibility investigations.
90
Figure 10.3 A typical schematic of a separation process by using gas hydrate formation.
Absorption by ionic liquids
Ionic liquids recently have attracted special attention from the scientific community, and
hundreds of studies that involve different aspects of ionic liquids have been presented in the
literature. Room-temperature ILs are organic salts that are generally liquid at room
temperatures [41]. They are normally composed of a large organic cation and organic or
inorganic anions. The applications of ILs have generated a large number of interests in the past
decade. This is mainly because of their tunable properties that can be controlled by a judicious
combination of cations and anions. This phenomenon allows researchers to design specific
solvents for the development of more efficient processes and products. Having a negligible
vapor pressure, no flammability, good thermal stability, a wide liquid range, and electrical
conductivity, and so forth are a few of the attributes, among others, that have made ILs an active
hub of research [42] [43]. The extractability of different amines (e.g. tri-methylamine) in ILs has
been previously described elsewhere [42] [43]. Several studies [42]- [44] have argued that both
1-hexyl-3-methylimidazolium hexafluorophosphate [C6MIM][PF6] can be used as an alternative
solvent to absorb TMA in the absorption column. However, their application in the
aforementioned process may not be economically beneficial due to high costs of the
corresponding ionic liquids production as well as costly and time consuming VLE, LLE and VLLE
phase equilibrium measurements.
91
It should be noted that a more appropriate ionic liquid solvent can be defined pursuing
the following steps:
1. Determine the desired properties of the solvent e.g. solubility parameters, normal
boiling point temperature, vapor pressure, transition temperature etc.
2. Develop/use a Group Contribution (GC) or Quantitative Structure Property
Relationship (QSPR) model for various ionic liquids to calculate/estimate the desired
property.
3. Utilize the functional groups and/or molecular descriptors found in the previous step
to design (or select) a variety of desired ionic liquids.
4. The aforementioned models can be further applied to select (or design) another IL (or
a group of ionic liquids e.g. immonim-based ones) taking into account the
corresponding process concerns.
Use of ionic liquids is seemed to be promising if they are provided at low prices.
Therefore, since the price for ionic liquids is very high they are not economically feasible,
though their application might become feasible in future.
Summary of solvent selection
Different approaches to select the appropriate solvent or alternative separations were

discussed in this part. From the discussion it can be concluded that the water can be a suitable
substitute to n-heptane. To the best of authors’ knowledge, there are not many information
available in the literature to fully support the rhetoric. However, for this conceptual design it
was decided to choose water as an alternative to the current solvent. It’s practical application
needs accurate and reliable LLE and VLE binary experimental data of the compounds present in
the process. The other approaches, i.e. a gas hydrate formation separation method for
methylamines and ionic liquids as solvents, need further investigations in which the latter is a
novel idea presented for the first time in this report.
10.3 Purge minimization
In the base case design given at the end of Task 7 there are three purge streams.
Minimizing the amount of purge will help reducing the cost of raw materials. In the base case
design a large amount of ammonia (230 kg/hr) is being purged in the splitter (SP1). Therefore,
it is necessary to minimize this purge since it mainly consists of the raw materials being used in
the process. Table 10.5 shows the amount of money that is being saved after purge
minimization and savings on the cost of raw materials per annum. This purge stream was
92
optimized and the amount of ammonia being purged per hour was reduced 5 kg/hr,
respectively. The total cost reduction per year is $323,522.
Table 10.5 Cost of raw materials before and after purge minimization.
Raw Before purge Annual cost After purge Annual cost Annual cost
materials optimization before optimization after reduction
(kg/year) optimization (kg/year) optimization ($/year)
($/year) ($/year)
Ammonia 72,134,400 15,869,568 70,641,120 15,541,046 323,522
Therefore, by minimizing the purge stream S24, the total waste per kg of product is reduced to
as low as 0.72 kg which equals to 15% reduction in the waste that is produced in the process.
10.4 Investigating the possibility for optimization of distillation columns
Commonly, parameters like number of trays and reflux ratio will be optimized to
minimize the condenser duty for cooling water or operating cost optimization. Besides that, it is
also important to minimize the capital cost for the number of trays. Then, the feed tray location
will be determined from this condition for the optimum distillate stream. The distillation
columns in this process were designed using the shortcut method (SCM) in the PRO/II.
However, comparison of the obtained results with the driving force concept (DFC) reveals that
the distillation columns are working at their optimum condition. The driving force diagram for
the distillation columns is given in Figure 10.4.
0,6000
0,5000 Distillation column 2
0,4000 Distillation column 4
0,3000
0,2000
0,1000
0,0000
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Figure 10.4 Driving force for each distillation column
93
The results of comparing both methods (i.e. driving force concept and shortcut in PRO/II)
show that the columns are working at their optimum since using the DFC to find the optimum
feed location not decreases the duties of reboilers and condensers but increases them.
Table 10.6 Comparison between driving force concept (DFC) and shortcut method in PRO/II (SCM) to
find the optimum feed location (NF).
Qr, SCM Qr, DFC Qc, SCM Qc, DFC

No. of NF NF R R
Column (M*KW (M*KW/ (M*KW/ (M*KW/
Trays (SCM) (DFC) (SCM) (DFC)
/hr) hr) hr) hr)
1 12 7 9 6.6258 0.8208 0.0012 0.0026 –0.0019 –0.0034
2 44 8 40 1.1592 0.2521 0.0061 0.2743 –0.0058 –0.2739
3 16 10 8 0.3098 0.9754 0.0006 0.0006 –0.0003 –0.0003
4 8 4 3 0.7865 1.0837 0.003 0.003 0.0000 0.0000
10.5 Optimization of Compressors
The thermal efficiency is affected not only by the clearance volume but also by rates of
pressure P0/PN. Thus, if the compression is carried out in two or more stages, the thermal
efficiency of multistage compression will be greater than that of a single stage compression of
the same clearance volume and total pressure range. Furthermore, it is possible to save
considerable power by using two or more stages by using an intercooler in order to lower the
gas temperature between stages. Moreover, using intercooler prevents the gas to gets very hot
when compressed to high pressures, therefore, avoids causing trouble with lubrication.
Staged compressors are useful to perform a given service (a desired increase in gas
pressure) with less work. This is accomplished by inter cooling after each compression stage.
The inter cooling is due to the fact that isothermal compression requires constant heat removal
to keep the system at its initial temperature (T0). Intercooling in staged compression requires
the configuration given in Figure 10.5.
Figure 10.5 Compression sequence with intercooling.
Moreover, for a fixed number of compressors, N, it can be shown that the minimum work
occurs when all compression ratios are equal, i.e:
94
10.1
and the required work is given by the following:
10.2
In the above equation, is the molar flowrate (gmol/s), which is equal to 1.4 for an
ideal system and . As , we can obtain the expression for isothermal
work:
10.3
Rather than finding the optimum number of stages which is case specific, a guideline
given by Biegler et al. for preliminary design will be followed; this states that a compression
ratio of can be applied to every stage of the compression.
However, the deficiency of the guideline given by [33] is that the gas is assumed to behave
ideally while in the real applications the gases that are being compressed behave non-ideally.
However, their method is suitable to obtain near optimum stages which can significantly reduce
the amount of calculations for discrete optimizations such as the present case.
Therefore, the objective is to find the minimum number of stages with minimum utility cost:
10.4
Optimization of compressor (C1)
For the first compressor in production of methylamines, anhydrous ammonia has to be

compressed from atmospheric pressure (1 atm) up to 20 atm which latter pressure is the
operating pressure of the reactor. To this end, the previously mentioned guideline will be
employed to find the number of stages for preliminary design as follows:
The total adiabatic work for one stage is obtained from PRO/II and it equals to 553.68 kW
where adiabatic and polytropic efficiencies are 85% and 88.51%, respectively. The isothermal
95
work will be calculated using Eq. 10.3. The molar flowrate is 45 gmol/s, initial temperature (T0)
is 300K and the final pressure and initial pressures are 20 atm ( ) and 1 atm ( ), respectively.
10.5
For the staged compression we choose compression ratio at 2.5. Thus, the near optimum
number of stages can be found by using Eq. 10.1 as follows:
10.6
Therefore,
4 and
However, different stages of compression were considered to find the configuration which
gives less amount of work with setting a maximum number of stages to be 7. Table 10.7
presents the results that were obtained from the calculations. It can be seen that as the
compression ratio decreases the total work done by the compressors decreases. This trend is
observed up to six compression stages whereas using seven compression stages the amount
work done by all stages increases.
Therefore, the minimum amount of work can be obtained using six compression stages
instead of single stage compression. In case of using six stages of compression 41.6% will be
saved in terms of energy consumption by the compressors. Nonetheless, the capital cost for
using six stages of compression instead of one single stage compression will be greater. It
should be noted that all compressors in all cases were assumed to have an adiabatic efficiency of
85%.
Table 10.7 Summary of multistage compression for compressor C1.
Stage Outlet pressure Actual work

Stage Inlet pressure (atm)
number (atm) (kW)
1 1 20.00 553.68
One stage
compression Total -- -- 553.68
1 1 4.47 233.83
Two stage 2 4.47 20.00 226.12
compression
Total -- -- 459.95
1 1 2.71 147.01
2 2.71 7.34 114.65
Three stage
compression 3 7.34 20.00 138.93
Total -- -- 424.87
96
1 1.00 2.11 106.98
Four stage 2 2.11 4.47 106.49

compression 3 4.47 9.46 104.01
4 9.46 20.00 98.73
Total -- -- 416.21
1 1.00 1.82 84.35
2 1.82 3.31 83.59
Five stage 3 3.31 6.02 82.47
compression 4 6.02 10.94 80.25
5 10.94 20.00 1.56
Total -- -- 331.98
1 1.00 1.64 68.85
2 1.64 2.62 64.60
3 2.62 4.18 63.85
Six stage
4 4.18 6.67 62.97
compression
5 6.67 10.64 61.44
6 10.64 20.00 1.61
Total -- -- 323.32
1 1.00 1.53 58.72
2 1.53 2.34 58.36
3 2.34 3.57 57.59
Seven stage 4 3.57 5.44 56.78
compression 5 5.44 8.28 55.63
6 8.28 12.60 54.07
7 12.60 20 1.27
Total -- -- 342.42
Figure 10.6 presents the results given in Table 10.7. It can be seen that the optimum
number of stages with respect to the actual compression work is found to be six compression
stages. However, the goal of this optimization is to find the number of stages at which the annual
utility cost is minimized. Therefore, economical analysis was performed using ECON for all
seven compression stages that were considered in optimizing compressor C1.
Figure 10.6 The number of stages with respect to actual compression work for
compressor C1
97
Figure 10.7 presents the optimum number of compression stages based on the annual
utility costs. It can be seen that, considering the annual utility cost which was the objective of
the optimization, three stage compressions is found to be the optimum number of compression
stages.
$300.000
$275.000
Utility cost ($/yr)
$250.000
$225.000
$200.000
$175.000
$150.000
1 2 3 4 5 6 7
Number of stages
Figure 10.7 The optimum number of compression stages based on the annual utility costs for
compressor 1.
Optimization of compressor (C2)
For the second compressor in production of methylamines, the top product of the first
distillation column (ammonia column) has to be compressed from approximately 9.3 atm up to
20 atm which latter pressure is the operating pressure of the reactor. To this end, the guideline
which was used for compressor C1 will be followed in order to find the number of stages for
preliminary design as follows:
The total adiabatic work for one stage is obtained from PRO/II and it equals to 51.61 kW
where adiabatic and polytropic efficiencies are 85% and 86.01%, respectively. The isothermal
work will be calculated using Eq. 10.3. The molar flowrate is 23.23 gmol/s, initial temperature
(T0) is 312K and the final pressure and initial pressures are 20 atm ( ) and 9.38 atm ( ),
respectively.
10.7
98
For the staged compression we initialy choose a compression ratio at 2.5. Thus, the near
optimum number of stages can be obtained by using Eq. 10.1 as follows:
10.8
Therefore,
and
Similar to what was done for the compressor C1, different stages of compression were
considered to find the configuration which gives less amount of work with setting a maximum
number of stages to be 4. Table 10.8 presents the results that were obtained from the
calculations. It can be seen that as the compression ratio decreases the total work done by the
compressors decreases. This trend is observed up to the fourth compression stage. Therefore,
the minimum amount of work can be obtained using four compression stages instead of single
stage compression. In case of using three stages of compression 66% will be saved in terms of
energy consumption by the compressors and since using four stages will increase this
percentage by less than 1%, the optimum number of stages was chosen to be three with respect
to actual compression work done by the compressors. Nonetheless, the capital cost for using
three stages of compression instead of single stage compression will be greater. It should be
noted that all compressors in all cases were assumed to have an adiabatic efficiency of 85%.
Table 10.8 Summary of multistage compression for compressor C2.
Stage Inlet pressure Outlet pressure Actual work

number (atm) (atm) (kW)
One stage 1 9.38 20.00 51.61
compression Total -- -- 51.61
1 9.38 13.60 24.60
Two stage 2 13.60 20.00 1.00
compression
Total -- -- 25.60
1 9.38 12.00 16.17
Three stage 2 12.00 15.35 0.5

compression 3 15.38 20.00 0.5
Total -- -- 17.17
1 9.38 11.26 11.94
2 11.26 13.51 3.21
Four stage 3 13.51 16.20 0.5
compression
4 16.20 20.00 0.5
Total -- -- 16.15
99
Figure 10.8 presents the results given in Table 10.8. It can be seen that, as it was
previously mentioned, the optimum number of stages is found to be three with respect to the
work done by the compressors. After the third stage a steady behavior in energy consumption is
observed from which adding more stages will merely induce more capital costs while the energy
consumption does not change considerably.
Figure 10.8 The energy consumption using different compression stages for compressor C2.
However, to proceed with the goal of this optimization which was to find the minimum
number of stages with respect to annual utility cost, economical analysis was performed for all
compression considered compression stages using ECON.
$160.000
$140.000
$120.000
Utility cost ($/yr)
$100.000
$80.000
$60.000
$40.000
$20.000
1 2 3 4
Number of stages
Figure 10.9 The optimum number of compression stages based on the annual utility costs for
compressor C2.
100
Figure 10.9 shows the annual utility costs based on the number of stages. It can be seen
that a linear trend is obtained which is probably due to the deficiency of ECON in calculating the
prices below its lower ranges. ECON analysis is taken as the reference for economical analyses
in this study. Therefore, single stage compression is chosen as the optimum number of stages
for the second compression.
Some insights into optimization of compressors
There are several ways to make better use of the work done by the compressors. Some of
the possible approaches will be only discussed here and their application is subject to further
investigations.
i. Using the compressed gas to generate electricity by implementing a generator in the

series of compressors. The generated electricity can be then used as an energy
source for the compressors and therefore, less electricity will consumed. However,
this idea is subject to further investigations both technically and economically.
ii. Using the hot gas that leaves the compressors as process utility in heat exchangers
can be beneficial specifically in cases that the prices for steam or other means of hot
utility are high.
10.6 Economical Analysis of the Process Optimization
In this section, the results of the process optimization from an economic point of view will
be given. It will be shown that how much could be saved in terms of costs by performing process
optimization. Table 10.9 presents an analysis for the profits that will be made after optimizing
solvent, purge and operating profits.
Table 10.9 Analysis of the profit after optimization
Annual cost before Annual cost after

Process optimization optimization Details
($/year) ($/year)
Profit increase
Profit maximization 28,343,445 30,881,887
$ 2,538,4426
Cost reduction
Solvent selection 26,112 0.00
$ 26,112
Cost reduction
Purge Minimization -- --
$ 323,522
6
The number is based on estimated economical potential using the optimum production ratios (obtained
through operating profits objective function).
101
Table 10.10 shows the savings in unit costs of compressors after optimization. It can be seen
that over a million USD will be saved in terms of the unit costs of the compression units.
Table 10.10 Comparison for compressors before and after optimization in term of installation cost
Base Case Optimized case Annual cost after optimization

Unit cost
design design ($/year)
C-101 $ 5,909,767 C-101A $1,759,150
C-101B $1,401,640
C-101C $1,670,580
C-102 $ 951,068 C-102A $ 951,068
Total $ 6,860,835 $5,782,435
Figure 10.10 shows the comparison between utility cost for compressor C1 before and
after optimization. It can be seen that close to $75,000 will be saved in case of using three stage
compressions. The utility cost for compressor C2 did not change after optimization since it was
found that it is at its optimum number of stages in the base case design.
$300.000 $273.250
$250.000
$197.698
Utilties cost ($/yr)
$200.000
$150.000
$100.000
$50.000
$-
C-101 C-101 (A,B,C)
Compressor C1 Configurations
Figure 10.10 Comparison of compressor utilities cost for 1 stages and 3 stages for compressor 1
To proceed with economical analysis, the percentage of equipment cost after optimization
was re-calculated using ECON software. The results are shown in form of a pie as they are
depicted in Figure 10.11.
102
E-102 H-101 C-101:A

C-101:B
2% E-101 3% 9%
7%
1% C-104
C-101:C
T-105 5%
8%
4% T-104
M-101
4% 3%
T-103 M-102
8% 3%
M-103
3%
T-102 T-101
7% V-101 R-101
26%
2% 5%
Figure 10.11 Percentage of equipment cost after optimization
Similar calculations were carried out in ECON to find the utility costs after optimization.
However, only the percentage of certain unit operations are given and depicted in Figure 10.12
as they were accounted for largest consumers of energy in the base case design. Compared with
the base case design the utility consumption has decreased by almost 20% after optimization.
C-101:C
17%
C-101:B
14%
C-104
9%
C-101:A
18%
H-101 R-101
7% 36%
Figure 10.12 Percentage of utilities cost for selected equipments after optimization
103
Task 11:
Heat Integration
11 Heat Integration
In the production of methylamines, several heat exchangers have been used to

achieve desired temperature. Normally, the consumption of the energy is a major part of
plant’s operating cost. Energy is used for heating and cooling purposes. The process of
maximizing the use of heating and cooling streams generated by the plant itself is called
heat integration. Heat integration can lead to a substantial reduction in the energy
requirements of a process, and consequently saves up the operating cost of the whole
plant.
In the heat integration of this plant, specific heat targets can be calculated and the
amount of energy that can be recovered from this plant can be determined by using heat
exchangers network (HEN) to transfer heat from one stream to another. Besides, this
heat integration method is also used to determine the pinch temperature, minimum
heating and cooling requirements of the plant and to achieve our targets of minimum
usage of utilities.
The pinch design targets are:
 Minimum heating requirement (usually the steam rate)

 Minimum cooling requirement (usually the cooling water rate)
 Minimum number of units
 Minimum heat exchanger network area
Several benefits of HEN have been identified and these benefits are:
 Energy saving
 Capital cost saving
 Improved flexibility
 New design and retrofit
104
11.1 Synthesis of Heat Exchanger Network (HEN)

Since the cooling and heating for the process streams was supplied through external utilities
like steam and cooling water, in methylamines production, there are 4 heat exchangers needed
for heating and cooling. The heat exchange network for energy recovery will minimize the
annualized cost of the equipment and also the annual cost of utilities. This is performed by the
sequential optimization strategies whereby considering the minimum utility cost, the number of
unit as well as the investment cost.
11.2 Stream identification
Analysis of the heat exchanger network begins with identification of hot streams (heat
source) and cold streams (heat sink) where hot stream refers to stream that needs cooling and
cold stream refers to stream that needs heating. The initial temperature for the process stream
is known as supply temperature, Tin and target temperature; Tout for the final temperature of the
stream.
Summary of the cold and hot streams in the plant is shown in Table 11.1. The data for
each unit are taken from PRO/II process simulator. The heat contents (Q) are calculated by
using following equation:
11.1
Where F is flow rate (kg/hr), CP is heat capacity (kW-hr/ kg.C) and T is temperature
differences of inlet (Tin) and out let (Tout) of streams in oC. In this case where, there are four, heat
exchangers have been used in process. Therefore, it would be necessary to calculate Q as
amount of heat in order to determine the required energy in the process.
Table 11.1 Summary of hot and cold streams available for heat integration
Equipment Stream Stream Type Tin Tout Flowrate Heat Heat

In Out (oC ) (oC ) (kg/ Hr) Capacities,CP Contents,
(kW Hr/kg C) Q (kW)
E-100 S6 S15 C1 31 171 9544 7.16E-04 –957
E-101 S3 S16 C2 388 400 14243 9.10E-04 –156
E-102 S18 S5 H1 400 67 14243 9.79E-04 4643
E-103 S14 S39 H2 144 36 2420 7.77E-04 203
105
11.3 Methods of Pinch Analysis
Heat integration is a systematic tool used to design heat recovery networks for maximum
energy recovery. The First Law of Thermodynamics provides the energy equation for
calculating the enthalpy changes ( H) in the streams passing through a heat exchanger. As per
Table 11.2, it can be calculated that 3734kW must be supplied from utilities (if there are no
restrictions on temperature driving force). Meanwhile, the Second Law determines the direction
of heat flow. That is, heat energy may only flow in the direction of hot to cold. This prohibits
‘temperature crossovers’ of the hot and cold stream profiles through the exchanger unit. The
two most common methods to calculate the amount of energy recovered using the heat
integration are:
i) Composite Curves Model
 Calculate the cumulative tprocess heat availability (Surplus).

 Calculate the heat requirement (Deficit).
ii) LP Transshipment Model
 Process heat surpluses and deficits within some specified temperature interval.
These two methods use different approaches in identifying the pinch point and the
minimum heating and cooling utilities. However, both techniques gave the same results for
cooling and heating requirement. For methylamines plant heat recovery, both methods were
performed for comparing and checking.
11.3.1 Composite curve
The temperature intervals table shows that the process consists of two cold and two hot
streams and the composite curve is constructed to determine the maximum heat recovery and
the minimum energy consumption for the process. Both of the hot composite curve and cold
composite curves represent the profile of heat availability and heat demands respectively for
methylamines plant.
106
Table 11.2 Temperature intervals tables
Composite Hot Temperature Composite Cold Grand Composite for Hot

Stream (oC) Stream and Cold
Adj.
Avail Cascaded Required Cascaded Net Cascaded
Hot Cold Cascade
heat Heat Heat Heat heat Heat
d heat
0 410 400 C2 0 0 130

0 7 130 -130
0 H1 400 390 130 -130 0
28 6 26 2
28 398 388 155 -128 2
3026 5 0 3026
3054 181 171 C1 155 2898 3028
516 4 253 263
3570 H2 144 134 408 3161 3291
1219 3 526 692
4788 67 57 935 3853 3983
49 2 178 -129
4837 41 31 1113 3724 3854
9 1 0 9
4846 36 26 1113 3734 3864
As shown in the Figure 11.1, the hot curve was shifted to the right as shown by dashed
line and just touches the cold curves with the minimum driving force of 10oC. The pinch points
exists at 400oC (Hot)/390oC (Cold). This represents that within the heat exchanger network,
there is heat that needs to be removed and/or added. Based on the grand composite table, the
minimum amounts of supplied heat must be 130 kW using hot utilities. In the meantime, 3864
kW is the minimum amount of heat that is needed to be removed using cold utilities.
107
400 Cold Composite Curve

350 Hot Compoiste Curve
Shifted Hot Composite Curve
Temperature (oC) 300
250
200
150
100
50
0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500
Cascaded Heat (kW)
Figure 11.1 Grand composite curve plot
11.3.2 LP Transshipment Model
The LP transshipment model is one of the energy targeting techniques using numerical
approach. The problem table was constructed based on initial Tmin value which is also 10oC. As
shown in Table 11.3, the heat contents of the processing streams at each temperature interval
are calculated. The intervals table is then converted to the heat cascade diagram.
Table 11.3 Temperature intervals for LP transshipment method.
Temperature Intervals
Heat Contents (kW)
(oC)
Hot Stream Hot Cold Cold Stream H1 H2 C1 C2
410 400 C2
int. 1 130
H1 400 390
int. 2 28 26
398 388
int. 3 3026
181 171 C1
int. 4 516 253
H2 144 134
int.5 1074 145 526
67 57
int. 6 49 178
41 31
int.7 9
36 26
4643 203 957 155
108
Based on the heat cascade diagram as shown in Figure 11.2, the energy balance equations
can be derived.
Figure 11.2 Heat cascade diagram
The energy balances for each interval are as follows:
Interval 1:
11.2
11.3
Interval 2:
11.4
11.5
Interval 3:
11.6
11.7
Interval 4:
11.8
109
11.9
Interval 5:
11.10
11.11
Interval 6:
11.12
11.13
Interval 7:
11.14
11.15
From the energy balance equation, the objective function is added to solve the LP
problem. In this method, the objective function is to minimize the utility cost by minimizing
utilities and . Besides, all the value for residuals (R) and also utilities and must be
greater than zero.
11.16
S.t. 11.17
11.18
11.19
11.20
11.21
11.22
11.23
11.24
LP optimization is solved by using Excel Solver to find the pinch point and the
corresponding minimum utilities. The initial guess are used for and
the set target is the . The results of the LP are as following;
110
Heat load of steam:
Heat load of cooling water:
Residuals:
Min utility, Z:
The zero residuals for represent that there is pinch point for this problem exists at
400oC (Hot)/390oC (Cold). The result of the minimum utilities and the pinch point location are
the same from the composite curve approach.
11.4 Heat exchanger network design
Based on the pinch point location, stream matching was performed. In the process of
matching between hot and cold stream, several considerations should be taken into account,
which include:
i) Flow rate (FCp) of outlet stream from the pinch should be always higher than flow
rate inlet stream approaching the pinch.
ii) Each matches should violent the rules of thermodynamics where the achieved
temperature profile of each streams have a minimum difference of .
iii) The matching should be start at the pinch since the pinch is the most constrained
part of the network.
For the above pinch design, the following rules must be fulfilled:
i) The stream can only be matched where the FCp of cold stream is greater than the
hot stream (FCp, cold > FCp, hot)
ii) There is only heater appear in the above pinch region, cooler is prohibited in the
above pinch region

iii) The temperature differences of the hot and cold stream must be greater or equal to
111
For the below pinch design, the following rules must be fulfilled:
i) The stream can only be matched where the FCp of hot stream is greater than the
cold stream (FCp, hot > FCp, cold)
ii) There is only cooler appear in the above pinch region, heater is prohibited in the
above pinch region
iii) The temperature differences of the hot and cold stream must be greater or equal to
In this case, the stream matching was performed at both above and below pinch point.
The result shows that there are 2 cooling utilities and 1 heating utilities needed as well as 2 heat
exchanger for the integration.
Figure 11.3 Heat exchanger network after heat integration.
Based on the Figure 11.3, we have embedded the following alternatives stream matching;
Match 1: Heater – C2 = 130kW
Match 2: H1 – C2 = 26 kW
Match 3: H1 – C1 = 957 kW
Match 4: H1 – Water = 3660 kW
Match 5: H2 – Water = 203 kW
The first and second stream matching is operated at about 400oC. Therefore the type of
utilities used is Hot Oil. This is due to the facts that hot oil is a good heat transfer fluid and can
contained heat which can be gained from other stream. Besides, the third stream is operated at
lower temperature, therefore low pressure steam can be used. In addition both of cooling
utilities are supply by cooling water.
112
Stream matching above the pinch
Matching of Heater – C2 (Heater 1)
Water
Steam HEX-1
957kW
The heat content for stream above the pinch point is determined as follows:
As shown in the Table 44, the total amount heat available in the cold stream is 156kW. So,
the balance heat in the stream is 26kW. Therefore, the flow rate can be determined by assuming
that the heat supply at above 10oC higher than 400 oC. As the temperature of heat supply is high,
hot oil is selected as the material for heating supply. The heat capacities of Hot Oil at 400oC is
2.725 kJ/kg.k. Since the heat transferred is occurred and assume that there is no heat loss, the
flow rate can be determined as following;
Stream matching below the pinch
a) Matching of H1 – C2 (HEX-1)
HEX-2
398 oC 400 oC
Tt
The heat contents for the stream is calculated as follows:
Since the heat transferred is occurred and assume that there is no heat loss, the temperature
can be determined as following;
113
b) Matching of H1 – C1 (HEX-2)
390 oC
390 oC 390 oC
400 oC
For this stream cooling water is used. By assuming the supply temperature is at 30 oC, the heat
capacities for cooling water is 4.1784J/g.k. Since the heat transferred is occurred and assume
that there is no heat loss, the temperature can be determined as with flow rate of the stream at
8544kg/hr;
c) Matching of H1 – Water ( Cooler 1: Cooling Water)
388 oC
Tt 171 oC
398 oC
The heat contents for the stream are calculated as follows:
For this stream, the cooler for the stream is water and not refrigerant is required. The flow rate
can be determined by assuming that the temperature required at 10oC below than 329.49 oC.
Therefore Tt is assumed at 319.49 oC. In addition it is assumed that the water is supply at
temperature is at 30oC, and the heat capacity for water is 4.1784J/g.k. Since the heat transferred
is occurred and assume that there is no heat loss, the flow rate can be determined as follows:
10869 Kg/hr
d) Matching of H2 – Water ( Cooler 1: Cooling Water)
114
31 oC
Tt Tt
329.49
o
C
For this stream, the cooler for the stream is water and not refrigerant is required. The flow rate
can be determined by assuming that the temperature required at 10oC below than 144 oC.
Therefore Tt is assumed at 134 oC. In addition it is assumed that the water is supply at
temperature is at 30oC, and the heat capacity for water is 4.1784J/g.k. Since the heat transferred
is occurred and assume that there is no heat loss, the flow rate can be determined as follows:
1681.73 Kg/hr
11.5 Comparison of Heat Utilization Efficiency
The heating and cooling utilities decrease after heat integration. The percentage of
heating and cooling utilities saved are calculated as following:
12.25
12.26
The calculation shows that 88.4% of the hot utility and 20.3% of cold utility can be save
from the HEN. From this outlook, it is important that heat integration must be imposed to avoid
unnecessary energy wastage.
115
Table 11.4 Comparison of the utility before and after HEN
Before Heat After Heat

Type of utilties Saving %
integration integration
Hot utility comsumption 1113 kW 130 kW 88.4
Cold utility consumption 4846 kW 3863 kW 20.30
a) Cost Before Intergration
Tin Tout
Type Quantity Type of Utilties Cost per unit Cost per year
(oC ) (oC )
C1 31 171 957 (kW) Steam $110/kW $ 105,270
14,243 (kg/
C2 388 400 Hot Oil $3.20/kg [45] $ 45,577
hr)
14,243 (kg/
H1 400 67 Cooling Water $1.09/m3 $ 126,682
Hr)
H2 144 36 2,420 (kg/ Hr) Cooling Water $1.09/m3 $21,524
The total utilities cost per year is $ 799,053
b) Cost After Integration
The total cost for each type of utilities is calculated based on the amount used per year
and the unit cost. However utility estimates are often complicated because they depend on both
inflation and energy cost [46].
Supply Temp. Flowrate 7

Type of Utilties Cost per unit Cost per year
(oC ) (kg/ Hr)
400 3,434 Hot Oil $3.20/kg [45] $ 10,988
30 10,869 Cooling Water $1.09/m3 $ 96,673
30 1,681 Cooling Water $1.09/m3 $ 14,951
The total cost of utilities after heat integration is $ 122, 611.
The total saving after implementing heat integration is $676,442 per year. Although this
heat integration require one more heat exchanger which increasing the capital cost, however it
worth for the money as we can make more saving.
11.6 Summary of minimum utility required
The total number of heat transfer unit required for the integrated process is 5 units where
2 units for cooler, 1 unit for heater and 2 units for heat exchanger. The integrated network has
successfully increased the efficiency of the plant in the aspect of energy utilization. Heat
integration has saved 84.65% of the utility cost.
7 This amount is assumed fixed in the system and it is always re-circulated. That means that this flow rate is equal to
purchase cost/year assuming that the life time of the utility is 1 year.
116
However, in practice (real plant) many sources must be taken care of. Maybe the utility
cost is lower but the cost of piping, pump and maintenance maybe higher. Another problem is
the pressure loss and heat loss from the piping. It’s because the network between the
exchangers maybe too far.
117
Cooling
Water
Cooling
HEX-2 Water
HEX-1
Hot oil
Figure 11.2 New flow sheet after heat integration
118
Task 12:
Sustainability Analysis
12 Sustainability Analysis
Sustainability analysis concept takes into consideration the environmental concerns associated
with a chemical process in the design stage. Historically, the economics, operating and capital
costs of the chemical process were predominant issues in design stage [47] [33] [48].
12.1 Environmental Impact Assessment (EIA)
The last thing to consider in the design of the process is the environmental impact of the
process. The purpose of an Environmental Impact Assessment (EIA) is to examine, analyse and
assess the plant in terms of impact on the environment. This is done according to the waste
reduction (WAR) algorithm.
In this study the regarded system will at first be the designed methylamines plant,
where the feed enters as a methanol stream and an ammonia stream. This system will be
regarded both for the base case design and the optimised design in order to determine what
effect the optimisation have had on the environmental impact of the process. For the optimised
design the system boundaries will be extended to evaluate the environmental impact of the
production of methylamines.
The system boundary for the environmental impact analysis could be extended even
further to take into account that the electric energy for the process is generated in a power
plant, where the energy probably is generated from the combustion of coal. In this work the
environmental impact analysis will however be limited to the methylamines plant itself.
As described above, the environmental impact of the design will be investigated for the
base case design and for the optimised design. For the optimised design it will also be
investigated whether or not burning the purge gas would increase of decrease the
environmental impact of the process.
The WAR Algorithm
The environmental impact will be calculated according to the WAR algorithm. The
principle of this method is that the environmental impact of the process is given as:
119
12.1
A stationary mass balance for the methylamine plant gives:
12.2
If this is applied to the environmental impact, I, one gets the fundamental equation of the WAR
algorithm at steady state:
12.3
The calculation of the potential impact related to a stream is done according to the following
expression
12.4
Where the weighting factor for impact is type i, is the mass flow rate of chemical j
(mass/time), and is the chemical and category specific impact (PEI/mass). The different
impact types that are evaluated are:
 Human Toxicity Potential by Ingestion (HTPI)

 Human Toxicity Potential by Exposure (HTPI)
 Aquatic Toxicity Potential (ATP)
 Terrestrial Toxicity Potential (TTP)
 Global Warming Potential (GWP)
 Ozone Depletion Potential (ODP)
 Photochemical Oxidation Potential (PCOP)
 Acidification Potential (AP)
The calculations are carried out in the computer program ICAS, which contains a database
of specific impact parameters. The impact parameters are calculated in ICAS according to a
group contribution method derived from experimental determinations of impact parameters.
120
36 oC
Figure 12.1 Input and Output stream considered in for WAR algorithm
Figure 12.1 shows the number of stream entering and exiting the process. Streams number
1 and 2 refer to the main raw material while stream 3 is the solvent. Stream 4 to 6 is the main
product for this process which is methylamine and the byproduct for this process is labeled as
stream 7. In addition stream 8 to 10 ilustrates the purge line involves in the processs. For base
case design, the flow rates for each compound as well as the operating condition are given in
Table 12.1. All of the these data were used and calculated in ICAS using WAR algorithm.
WAR algorithm also employed for optimized condition where only flow rate in stream 1,2
and 8 were changed. This is due to the changes of flowrate after solvent optimization. The result
for environmental impact for both cases shows in Table 12.2 and 12.3.
121
Table 12.1 Components flow rates and operating condition for the streams entering and exiting the system (based case)
Input Feed Output Product Purge
Compounds MeOH NH3 n-heptane MMA DMA TMA H20 Mixtures Mixtures Mixtures
Input/Output Input 1 Input 1 Input 1 Output 1 Output 1 Output 1 Output 1 Output 1 Output 1 Output 1
Stream No. S1 S2 S37 S20 S12 S36 S32 S24 S33 S11
Temperature (oC) 26.85 26.85 1.465.343 826.669 314.719 43.411 391.869 39,2303 146,9947 87,1483
Enthalpy Flow 0.5864 38.213 3.6 174.685 2.5 3 93.758 0,5214 0,00018 0,0014
Pressure (atm) 0.9998 0.9998 0.6829 0.9984 0.4284 0.4927 0.0165 9,3758 3,6 3,0138
METHANOL (Kg-mol/hr) 276,1986 0 0 0 0,2076 0 0 0 0 0,2076
NH3 (Kg-mol/hr) 0 162,4726 0 0,6827 0 0 0 13,5183 0 0
HEPTANE (Kg-mol/hr) 0 0 231.915 0 0,1919 0,19 0 0 0,0496 0
MAMN (Kg-mol/hr) 0 0 0 32,6467 0 0,0327 0 0,5874 0 0
DMAM (Kg-mol/hr) 0 0 0,0045 0,9193 89,2065 0,8966 0 0,8995 0 0,0091
TMA (Kg-mol/hr) 0 0 0,1712 0,357 0,0171 16,9518 0 0,4664 0,004 0,0002
H20 (Kg-mol/hr) 0 0 0 0 0 0 269,9373 0,1544 0 0
Total Mass Rate(Kg-mol/hr) 276,199 162.473 23.367 34,6057 89,6231 18,0711 0 15,4716 0,0536 0,2169
122
Table 12.2 The environmental impact of the base case design
Total
Stream HTPI HTPE ATP TTP GWP ODP PCOP AP
PEI
Input 1 3353.6 553.213 10.0435 0.2717 553.213 0 0 2236.86 0

Input 2 11015.3 2781.36 23.3275 356.794 2781.36 0 0 0 5072.48
Input 3 43690.3 3876.71 3.68061 10671.5 3876.71 0 0 25261.6 0
Output1 7298.43 3623.76 26.2269 3.37007 3623.76 0 0 0 21.3142
Output2
1 4167.22 2031.84 65.9619 14.996 2031.84 0 0 22.5842 0
Output3
2 2408.31 1175.34 25.3291 11.6024 1175.34 0 0 20.696 0
Output4
3 0 0 0 0 0 0 0 0 0
Output5
4 1150.9 347.63 3.73215 29.857 347.63 0 0 0 422.047
Output6
55 9.88739 1.09755 0.006547 2.28299 1.09755 0 0 5.40274 0
Output7
6 2.96901 0.636142 0.014565 0.000866 0.636142 0 0 1.68129 0
7 43021 30.99 –84.2194 10966.5 30.99 0 0 27448 4629
Table 12.3 The environmental impact of optimized case design
Total
Stream HTPI HTPE ATP TTP GWP ODP PCOP AP
PEI
Input1 3360.13 554.29 10.063 0.272229 554.29 0 0 2241.22 0

Input2 10269.6 2593.06 21.7481 332.638 2593.06 0 0 0 4729.0
Input3 43690.3 3876.71 3.68061 10671.5 3876.71 0 0 25261.6 0
Output1 7298.43 3623.76 26.2269 3.37007 3623.76 0 0 0 21.3
Output2
11 4167.22 2031.84 65.9619 14.996 2031.84 0 0 22.58 0
Output3
2 2408.31 1175.34 25.3291 11.6024 1175.34 0 0 20.69 0
Output4
3 0 0 0 0 0 0 0 0 0
Output5
4 254.323 121.246 1.83345 0.816374 121.246 0 0 0 9.18
Output6
5 9.88739 1.09755 0.006547 2.28299 1.09755 0 0 5.40 0
Output7
6 2.96901 0.636142 0.014565 0.000866 0.636142 0 0 1.68 0
7 43178 70.14 –83.8802 10971.0 7014 0 0 27452 4698
An interesting observation is that the environmental impact of the process is more

positive in the optimised case than in the base case. This is not caused by an increase in the
impact of the purge stream, which decreases from the base case to the optimised design. The
reason is that the impact of the Ammonia rich feed stream (input 2) used in the optimised
design doesn’t impact the environment as significantly as the larger feed stream used in the
base case. This causes the difference between impacts of ingoing and outgoing streams to
become slightly smaller in the optimised design.
123
The environmental impact analysis can also describe whether or not it would be
environmentally beneficial to burn the purge gas before it is released into the atmosphere. If
one regards the sum of the environmental impacts for the two subsystems in the methylamine
production it can be seen that the process roughly breaks even, when one balances the ingoing
feed streams and the outgoing purge stream and released NH3.
12.2 Health and Safety Index
Designing a safe process is an essential important and that can be provide more chance
for avoids hazards instead of controlling them, particularly by reducing the amount of
hazardous material and the number of hazardous operations in the plant. This issue can be done
by evaluating data analysis and the safety of a proposed design [47].
For this process, the Total Inherent Safety Index (ISI) Analysis was performed by
referring to the tables and article explained in the article on Inherent Safety in process plant
design [47] for each compounds involves in the process. The data properties as well as their
hazard and risk for all the compound was obtained in the Material Safety Data Sheet (MSDS) and
analyzed accordingly. The result analysis for the total ISI analysis for methylamines production
plants is shows in Table 12.4.
Table 12.4 Total Inherent Safety Index Analysis
Total Inherent Safety Index (ISI)

Chemical Inherent Process Inherent
Score Score
Safety Index Ici Safety Index Ici
Sub-indices for Produc Sub-indices for Reactant
Reactants Products
reactions hazards ts process conditions s
Heat of the
0 0 Inventory, Ii 2 3
main reaction, Im
Heat of the
0 0 Temperature, IT 3 3
side reactions, Irs
Chemical interactions, Iint 0 0 Pressure, Ip 4 4
Sub-indices for hazards substances Sub-indices for process conditions
Flammability, Ifl 3 4 Equipment, Ieq 1 1
Explosiveness, Iex 2 4 Ilsbl 1 1
Toxicity, Itox 4 3 IOsbl 1 1
Corrosivity, Icor 1 1 Process Structure, Ist 1 1
Maximum, Ici score 10 12 Maxium, Ipi score 13 14
Heikkila 1999 explained that the maximum of Chemical Inherent Safety Index (Ici ) and
Process Inherent Safety Index (Ipi) can be rated based on 0-4 score and the is maximum total
averages 27-28. In this case, the analysis were conducted for both of reactants and products and
124
the results as shown in Table 12.4 illustrated that the result for inherent in both chemical and
process index has the average about 10-12 for Ici and 13-14 Ici. By comparison to the references
Table [47], this process has lower maximum score. This is due to the fact that our process has
no high hazardous and process can be function as safe production process by installing
necessary safety control devices.
125
Conclusion
A conceptual design for producing methylamines (i.e. mono-, di- and tri-methylamines)
was performed. The simulations were carried out using PRO/II process simulator. Sizing,
costing and economical evaluation of the process were also performed and it was found to be
profitable. In order to improve the base case design compressors, solvent, purge were optimized
together with heat integration. However, the possibility for optimizing the feed location in the
distillation columns was investigated. The following table presents an overview of the process
in terms of raw material, energy and water consumption to produce the methylamines:
Total Kg
Energy
Total Kg Annualized consump. Annualized Water
consump.
production cost per Kg of raw cost per Kg consump. per
Product (MJ / kg of
per year of product material of product Kg of product
products)
per year
MMA 9,789,552 0.174 -- -- 0.029 1.22
DMA 33,842,376 0.600 -- -- 0.102 0.35
TMA 9,000,072 0.160 -- -- 0.027 1.33
Methanol -- -- 72,216,000 1.281 -- --
Ammonia -- -- 20,971,200 0.372 -- --
Total 0.158
Finally, some concluding remarks and future perspectives to the present design are given
below:
i. Conversion and selectivity of the reaction over KDC-6 catalyst can be improved by
introducing more efficient catalysts.
ii. The separation of mono-methylamine in the process can be improved.
iii. The role of thermodynamic model and availability of binary (V)LLE and VLE data is
significant in this process as the unit operations include associating compounds.
iv. A gas hydrate formation process may be beneficial but is subject to further technical and
economical investigations.
126
Nomenclature
List of Abbreviations
BWR Benedict–Webb–Rubin equation
BMC Bare Module Cost
CE Chemical Engineering
DFC Driving Force Concept
DMA Di-methylamine
EIA Environmental Impact Assessment
EP Economic Potential
Eq Equation
EoS Equations of State
HEN Heat Exchanger
ICAS Integrated Computer Aided System
MeOH Methanol
MF Module factor
MMA Mono-methylamine
NIOC National Iranian Oil Company
NV Number of Variable
TMA Tri-methylamine
UF Update Factor
USD United States Dollars
List of Symbols
Ak Antoine coefficients parameter
Å Angstrom (10-10 m)
Bk Antoine coefficients parameter
Cf Fixed capital
Ck Antoine coefficients parameter
Cp Capital investment
CP Heat capacity per (kW-hr/ kg.C)
Cw Working capital
C0 Base cost
OC Degree in Celsius
D Diameter (m)
fk0 Fugacity
Hv Gas enthalpy
K Kelvin
k Component
P Pressure
S0 Base capacity
Tin Inlet Temperature
Tout Out let Temperature
T Differences of Temperatures
(Rho) Density ( Kg / m3 )
Φk Vapor fugacity coefficient
ξ Mole fractions
ς Fraction
γk Liquid activity coefficient
v Velocity (m/s)
t Time (min)
127
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Production of MMA,DMA & TMA from Methanol and Ammonia
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A Systematic Approach for Conceptual

Seyed Soheil Mansouri, Muhammad Imran Bin Ismail, Karim Almoor

Since we are a multicultural group (Danish/Iranian/Malaysian) a lot of things were discussed

5.3 Flash Unit ....................................................................................................................................................... 38

10.6 Economical analysis of the process optimization ....................................................................... 101

Table 1.1 Physical properties of MMA, DMA and TMA ....................................................................... 3

Figure 7.4 Heat transfer process in HEX1 ........................................................................................................... 50

Production rate of the products

Products Processing Capability Production Rate per year

1.1 Mono-methyamine (MMA)

Mono-methylamine is the organic compound with the

1.2 Di-methylamine (DMA)

Dimethylamine is an organic compound with the

1.3 Tri-methylamine (TMA)

Trimethylamine is an organic compound with the

1.4 Physical properties of products

Table 1.1 Physical properties of MMA, DMA and TMA1

Parameter MMA DMA TMA

1.6 Feasibility Study

Demand Imports Exports

Figure 1.1 Demand of methylamines products from 2001-20052

Table 1.2 Methylamines demand3

Mass ratio Mole ratio

Western Europe 59 191 62 19/61/20 26/59/15

Japan 10 79 10 10/80/10 14/78/8

Equilibrium -- -- -- 10/18/72 17/21/62

1.7 Global production of methylamines

2 Based on ICIS.com, methylamines production profiles (2006)

1.8 Largest producers

Table 1.3 Largest producers of methylamines and their method of production

Producer Country Method of production

1.9 Process constraints

2.1 Raw Materials

Property Methanol Ammonia n-heptane

CAS. No 000067-56-1 007664-41-7 000142-82-5

Compound Water Ammonia Methanol MMA DMA TMA n-heptane

Absolute Solubility 47.81 29.22 29.59 23.10 19.00 15.17 15.20

2.2 Chemical reactions and catalysts

The reactions in which methanol is consumed are as follows:

The reactions in which methylamines are consumed are as follows:

2.2.1.1 Non-zeolitic catalysts

2.2.1.2 Zeolite catalysts

Albemarle’s KDC-6 catalyst is the state-of-the-art commercial choice used in many

Table 2.3 Typical properties of KDC-6 catalyst produced by Albemarle.

2.3 Process Conditions

2.3.2 Process operating conditions for main units

Table 2.4 List of main unit operations in the process.

2.3.4 Distillation columns

Figure 2.1 Simple flow sheet for production of methylamines.

2.4 Economic Potential

Table 2.5 Cost of raw materials

Cost of Raw Material USD/kg Remarks

Table 2.6 Price for Selling Products

Di-methyamine (DMA) $1.04 European region price from BASF

Tri-methyamine (TMA) $1.17 European region price from BASF

Raw Material cost for a year is calculated in USD is shown as following:

Cost of Material 1: Methanol

Cost of Material 2: Ammonia

Total Cost of Materials

In order to further guide the selection of process alternatives, a hierarchical decomposition

Figure 3.1 Process sythesis method

3.3 Level 1: Decisions on Batch versus Continuous