DESIGN OF METHANOL PLANT

EURECHA Student Contest Problem Competition 2013

Chan Wei Nian, chanweinian@gmail.com

Fang You, fang.you@gmail.com

Department of Chemical & Biomolecular Engineering, National University of Singapore, Engineering

Drive 4, Singapore 117576, Republic of Singapore

EXECUTIVE SUMMARY
This report presents a techno-economic analysis of setting up a methanol plant with a capacity of
50,000 MT/yr from natural gas feedstock of 31,000 MT/yr and 90% methane. This is performed in the
European context with due considerations for environmental sustainability. The plant is designed
assuming 10-year plant life and 8000 hours of operation per annum.
The methanol process was developed according to open literature and industry standard, as described in
Section 2; it consists of 5 units/sections: steam methane reformer, compression trains, methanol
synthesis reactor, hydrogen separation and methanol distillation. These were grouped into two main
segments of steam methane reforming and methanol synthesis, and were independently optimized in
Sections 3.1 and 3.2 using Aspen HYSYS v7.2 by varying important process parameters within
reported ranges. This is followed by a plant-wide heat integration study with Aspen Energy Analyzer
v7.2, described in Sections 3.3 and 4.3. Operating conditions favouring better overall process profit of
the order of USD$106 are reported in Sections 4.1 and 4.2 for the ideal case ignoring operating
constraints, and the base case for economic analysis was chosen based on practical industry constraints;
the reforming section utilizes an excess steam to carbon ratio of 2.7, inlet pressure of 2000 kPa and
furnace outlet temperature of 900C and while the methanol synthesis loop employs a reactor
temperature of 255C, compressor discharge pressure of 8010 kPa and a stoichiometric ratio of 9.035,
as summarized in Section 4.4.
The fixed capital investment, cost of manufacturing and revenue for the base case is 31,562,300,
29,520,600 and 43,952,670 respectively. The payback period is 3.2 years and the net present value
(NPV) of the investment is 32,840,270. The breakeven price for methanol is 0.3285/kg and the
discounted cash flow rate of return is 26.02%. The former is most sensitive to natural gas, hydrogen
and methanol prices, as shown in Section 4.5. In Section 4.6, Monte Carlo simulations performed
according to expected price fluctuations of natural gas and methanol obtained in the past 10 years
reported a 7.5% probability of making an overall investment loss.
The feasibility of substituting biogas for natural gas was analyzed for the given feedstocks in Section
4.7. Several options were explored, and the highest savings in net present value of 1,299,770 as well
as reduction of 2074 MT/yr of CO2 emissions were obtained for the case of utilizing the non-liquid
feeds. Options to capture carbon emissions from the plant as well as other carbon sources were
explored, and the most suitable technology for the plant was found to be absorption using mono-
ethanol amines, as elaborated in Section 4.8.

1
1. INTRODUCTION
Methanol demand in the global market is burgeoning with a 23% increase from 2010 to 2012 to 61
million tons and an expected increase to 137 million tons in 2022 [1]. However, its raw material:
natural gas faces both supply limitation and volatility; as a non-renewable resource, natural gas is
expected to deplete as early as 37 years depending on the level of conservativeness [2] while gas
infrastructure in Europe is fragmented and inconsistent [3]. At the same time, environmental concerns
for carbon emissions necessitate the integration of carbon capturing technologies. These usher a new
age of sustainable design in this age-old process, and it will be reviewed in this report. A base case for
the methanol synthesis was developed and optimized, followed by case studies on biogas substitution
and alternative carbon capture opportunities.
2. PROCESS DESCRIPTION
For the base case, the methanol synthesis is generally split into steam reforming, methanol synthesis,
hydrogen separation and methanol purification, which are described in this section.
Steam reforming: This is an overall endothermic reaction involving catalytic conversion of methane
and steam into syngas at high temperatures above 800oC [4], medium pressures of 15-30 bar [5] and
steam to carbon (S/C) ratio of 2 to 4 using nickel catalysts. Steam reforming is limited by equilibrium
[6], and higher conversion is achieved by increasing temperature, lowering pressure and higher S/C
ratio. It usually occurs in nickel catalyst-packed tubes located in the radiant section of a furnace.
Steam Reforming: (H25C = 206kJ/mol) ----------------- (1)
Water Gas Shift: (H25C = -41kJ/mol) ----------------- (2)
Methanol Synthesis: Syngas can be catalytically converted to methanol via an overall exothermic
reaction at medium temperatures of 210-270C and high pressures of 50-100 bar [7], over copper-
alumina catalysts. The presence of the water-gas shift reaction necessitates the use of a modified
stoichiometric ratio defined below, and it is typically in the range of 9-10 [4].
Methanol Synthesis: (H25C = -91kJ/mol) --------------- (3)
Modified Stoichiometric Ratio: -------------------------------------------------------- (4)

Methanol synthesis reactors are designed to remove reaction heat via cooling service fluids such as
unheated reactants or boiler feed water as well as feed quenching [8]. Isothermal cooling in shell and
reactor tube setups was modeled under conditions known to approach equilibrium [4], and it can
achieve higher conversions with lower temperatures, higher pressures and stoichiometric ratios.
Methanol Purification: Methanol synthesis products containing methanol and syngas are flashed to
separate unconverted light ends and crude methanol. Crude methanol is distilled to separate remaining
light-ends, methanol at 98%wt and water, in an atmospheric column with a partial condenser.
Hydrogen Separation: The flashed light-ends contain excess hydrogen; to avoid recycle
accumulation, these must be purged for furnace fueling or purified for hydrogen credit via pressure
swing adsorption, cryogenic distillation or membrane separation [9] with the latter being cheaper at the
low recoveries and purities required [10]. For this, polyimide membranes are fabricated as hollow fiber
tubes in a shell, and separation is achieved by partial pressure differences.
2
3. METHODOLOGY
The process was simulated using Aspen HYSYS v7.2, and individual units were designed to sufficient
detail for costing based on the module factor approach [11]. Expected revenue from methanol
(0.413/kg [12]) and hydrogen (8.04/kg [13]) sales was factored in for a plant-wide optimization. The
methodology for design and costing for each unit for the optimization is elaborated below.
3.1 Steam Reforming Section Optimization
This section focuses on the reformer furnace with the reaction modeled to reach equilibrium and the
costing based on energy used. This is independent of downstream synthesis and is optimized
separately. The variables affecting this section are the pressure, furnace temperatures (i.e., pre-heat and
outlet temperatures) and S/C ratio; these affect costs of individual sections/units, and their expected
effect on profit is shown in Table 1.
Table 1: Expected effect of increase in design variables on profit due to costs of individual sections/units
Design Variable Energy Recovery Convection Radiant
Compression Conversion
from Natural Gas Section Section
Pressure Uncertain Uncertain
Pre-heat Temperature NA Uncertain
Outlet Temperature NA NA Uncertain
S/C Ratio NA
Energy Recovery: Natural gas is expected to be delivered at 75 bar within European pipelines [3] and
must be expanded via a valve or turbine for energy recovery to the desired pressure; the latter can be
achieved with radial gas turbines at 75-88% efficiency [14] together with a minimum motor generator
efficiency of 95% mandated by EU Directive 640/2009 [15]. The turbine was priced based on energy
recovery rate and capital costs.
Steam Reformer Furnace: Natural gas is mixed with steam and preheated in the convection section
before reaction in the radiant section. The duties are summed, and used for furnace capital and energy
costs. Catalyst life is assumed to be within industrial norm, and is priced based on USD$0.55 per kilo
mole of natural gas processed [16]. A 95% approach to equilibrium was found to best match industrial
data from [17], and this was used in the reactor simulations
Water Let-Down Vessel: Excess steam is condensed and removed from the reformer products, in a
knock-out vessel to ensure dryness for the compression train. The design is based on the water
throughput to allow for 7.5 min of residence time, and the vessel volume is used for capital costing.
The condensate is pumped up to process pressure and reheated as recycle steam to the reformer.
Make-up Compressor: A separate compression train for syngas products (i.e., fresh feed) is designed
because it has less variability than the recycle compressor and so requires less capacity allowance. For
the discharge pressure of 50-100 bar and required flow of about 0.410 m3/s, reciprocating compressors
are suitable and are used for costing at 75% efficiency. To avoid adiabatic temperature rise beyond the
maximum temperature of 480 K [14], two-stage compression is used with inter-stage cooling. This
cooler is designed using heat transfer area obtained using typical overall heat transfer coefficients and
log mean temperature difference for cooling water service [18].

3
3.2 Methanol Synthesis Section Optimization
Due to low equilibrium conversion to
methanol, recycle of syngas is necessary. The
effect of reactor temperature, pressure and
stoichiometric ratio of reactants on
profitability of this section is shown in Figure
1. For modeling and optimization purposes,
common reaction conditions of 210-270C and
5-10 MPa were used. Costs involved for
cooling reactant products in the crude
methanol flash, pre-heating for distillation and
column duties are calculated based on a
preliminary setup, and optimized later using Figure 1: Schematic for inter-linked effects of varying
pinch analysis together with the steam parameters independent variables (black), parameters
reforming heat exchangers. affecting cost (shaded pink), calculated parameters (blue)

Methanol Synthesis Reactor: The recycle and fresh syngas streams are heated to the reaction
temperature with reaction heat and an optional pre-heating or cooling; this is possible in shell and tube
reactors [19]. The reactor was sized based on heat transfer area [20]. Catalyst cost, based on its
replacement norms, is USD$0.0513 per kilo mole methanol, for isothermal reactors [4].
Methanol Purification: The crude methanol flash vessel was sized similar to the water let-down
vessel, and the distillation column was optimized based on typical feed of 78-80%mol methanol at
70oC. Trade-off between reflux ratio and number of stages was analysed by costing the column,
condenser, reboiler, reflux drum and reflux pump, and the optimum number stages was found to be 27
for reflux ratio from 0.4 to 0.6 (Figure 2). This design is deemed optimal and used for all runs in the
optimization study.
1.56
Annualized Costs (USD$mil)

1.55
1.54
1.53
1.52
1.51
20 25 30 35 40 45 50
Number of Stages

Figure 3: Hollow Fiber Membrane Separation Module

Figure 2: Local optimization for distillation
Source: [21]
column
Hollow Fiber Membrane Module: Hydrogen separation is as shown in Figure 3 to recover hydrogen
from the purge stream. Feed to permeate pressure ratio of 6 was used to minimize recompression of
hydrogen [9], and this sets the limit for hydrogen recovery to 95%. The annualized capital cost increase
is calculated to be in the range of USD$2,442.9 for a 0.01 fraction increase in recovery, whereas the
gain in revenue was USD$365,600 for the same increase. As such, hydrogen recovery was maximized
at 95% for each optimization run. With the hydrogen flux constant, only the membrane cost will vary

4
according to required membrane area (USD$21/m2 [22]) obtained from changes in log mean pressure
difference as a result of changing reactor pressure levels for each run.
Recycle Compressor: The recycle compressor was designed for approximately 0.495 m3/s of flow with
reciprocating compressors as the suitable choice [14]. Due to a smaller pressure difference, single stage
compression is sufficient, and the compressor was priced using duty and 75% efficiency.
3.3 Heat Integration
In order to improve the energy efficiency of the methanol plant, heat integration is performed to
recover process heat, using Aspen Energy Analyzer (AEA) v7.2 coupled with the Aspen HYSYS v7.2
simulation of the methanol process. The Utility Composite Curve from pinch analysis is shown in
Figure 4 with minimum approach temperature (dTmin) contribution for various streams listed in Table
2. From Figure 4, the shifted process pinch temperature is 135.3C and the overall heating and cooling
targets are 15.9 MW and 13.3 MW respectively. The area target returned by AEA is 2345 m2 for 1 shell
pass and 2-tube pass heat exchangers.
Due to the lower price of natural gas compared to steam, AEA program recommends generating high
amounts of steam from the fired heater as seen in Figure 4. However, the credit from exporting steam
may be diminished if there is lack of demand for steam. Hence, the plant will not generate excess steam
from natural gas.

Figure 4: Utility Composite Curve for Methanol Plant Process

Table 2: dTmin Contribution for Each of the Stream Types

Stream Type dTmin contribution (K)
Condensing/vaporizing 2.5
Liquid 5.0
Gas 7.5

Subsequently, a Heat Exchanger Network (HEN) is designed with the following operating constraints:
(1) HP steam for SMR is to be generated in the furnace to ensure a steady supply of feed for the
process; (2) the reforming heat of reaction must be supplied by a furnace to maintain optimal reaction
temperature as process heat exchange potentially introduces fluctuations; and (3) crude methanol
distillation column condenser and reboiler are to be serviced by utilities to ensure controllability of
column operations.

5
 4. RESULTS AND DISCUSSION
Simulations were run for variations in operating parameters beyond the practical constraints applied in
industry; this was to explore the potential cost savings from surpassing operating constraints. Data was
extracted and costed according to Section 3 with detailed calculations in Section A4.2. The optimal
process was then chosen after applying the appropriate constraints and the heat integration study was
conducted to obtain the base case.
4.1 Optimization of Steam Methane Reforming
Methanol profit excluding methanol synthesis costs was found to increase with higher temperature,
lower S/C ratio and pressure while pre-heat temperature was found to have negligible impact (Figure
5). The results show that significant savings are possible in the magnitude of USD 106/yr if equilibrium
conversion can be achieved at the extreme ends of the optimization range. Constraints of temperature at
900oC due to mechanical strength limits of tubes [5], pressure at 20 bar and S/C at 2.7 to prevent
excessive coking [4] constrains the reforming section to operate at these limits and these are chosen as
the base case conditions.

Figure 5: Variation of expected profit with S/C
and temperature
4.2 Optimization of Methanol Synthesis Loop
Figure 6 shows that optimal methanol profit
Figure 6: Variation of methanol profit with pressure and
R: Red surface plot for reaction temperature of 211oC;
Green dots for 222oC, Red for 233oC, Magenta for 244oC
and multi-colour surface plot for 255oC
$3,400.00
Annualized Profit per
Methanol, USD$/kg

without reforming cost increases with lower $3,390.00

temperature and higher S/C ratio. However, to $3,380.00
ensure that the equilibrium can be achieved, $3,370.00
temperature was constrained to 255oC [23] and $3,360.00
S/C from 9 to 10 [4]. At these conditions, effect of 6500 7000 7500 8000 8500 9000 9500
pressure on cost reaches a plateau at 8900 kPa, as Pressure, kPa

shown in Figure 7, and this is chosen as the

Figure 7: Variation of expected profit with Pressure
operating pressure. at reactor temperature of 255C and R=9.063

6
4.3 Heat Integration Results
Following the practical considerations for heat integration, the HEN shown in Appendix A1.1 is
proposed. The heat recovered from the hot syngas is used to preheat methanol reactor feed as well as to
vaporize recycled water/condensate for steam reforming reaction. However, natural gas preheating for
the SMR reactor is not subjected to process heat exchange as this will cause difficulty in achieving
steady state during start up; hence the duty will be provided by LPS. Crude methanol feed to the
distillation column is preheated using LPS as the methanol reactor effluent stream is used to generate
MPS and LPS for plant-wide heating purposes and there are no other hot process streams in close
proximity for process heat exchange. The performance of the proposed HEN is summarized in Table 3.
The targets are not fully met due to the operating constraints stated in Section 3.3 as well as practical
considerations for process heat exchange due to the physical location of the streams, in which case
utility steam is generated for energy recovery.
Table 3: HEN Performance Summary
Overall targets Target Current
Heating (MW) 15.9 26.8
Cooling (MW) 13.3 24.2
Total area (m2) 2345 2078
Utility targets
Fired Heater (MW) 32.7 23.4
HPS (MW) 0 0
MPS (MW) 0 3.5
LPS (MW) 0 0.3
HPS generation (MW) 7.3 0
MPS generation (MW) 8.1 7.1
LPS generation (MW) 1.3 0.9
Cooling Water (MW) 13.3 16.2

4.4 Base Case Plant

The integrated results from the process optimization and pinch analysis are summarized in Table 4 and
the equipment schedule is shown in Section A4 with the PFD and stream data for the base case in
Appendix A1.1.
Table 4: Base Case Conditions for Methanol Plant
Steam Methane Reforming Methanol Synthesis Loop
Temperature 900C 255C
8010kPa
Pressure 2000kPa
(adjusted after heat integration)
S/C Ratio / R Value 2.7 9.035
MPS Generation: 3,672kW
Furnace Duty: 22,998kW
Utilities Cooling Water: 10,732kW
Cooling Water: 5493.5kW
Compression Duty: 4,128kW
Conversion 85.0% Methane Conversion 93.7% Syngas Conversion

With the capital and utility costs, additional direct, general and fixed manufacturing costs were factored
using multiplication factors on the process data [24]. Grassroots cost were used to account for off-site
and auxiliary costs. A straight line depreciation method typical of Europe [25] was used in generating
the cash flow diagram. Detailed calculations can be found in Section A4.2.

7
 40 0.7

Cumulative Discounted Cash Flow (in

0.65

Natural Gas Price, EURO/kg

30
0.6
Million EUROs) 20 0.55
10 0.5
0.45
0 0.4
0 1 2 3 4 5 6 7 8 9 10 11 12 0.35
-10
0.3
-20 0.25
-30 0.2
0.1 0.2 0.3 0.4 0.5 0.6
-40
Year Methanol Price, EURO/kg

Figure 8: Cumulative discounted cash flow for 10% Figure 9: Breakeven methanol price for different
discount, 30% tax and 10 years plant life price of natural gas
The fixed capital investment required is 31,562,300, and cost of manufacturing is 29,520,590 for
natural gas price of 0.361/kg [26]. Taking methanol price to be 0.413/kg and hydrogen price
8.04/kg, the revenue is 43,952,670. The payback period for the base case is 3.2 years from the time
of plant start-up after 2 years of allocated construction time. The net present value (NPV) of the
investment is 32,840,270, as shown in the cash flow diagram in Figure 8. The breakeven price for
methanol is 0.3285/kg holding other prices constant and discount rate at 10%.
4.5 Sensitivity Analysis
To understand the susceptibility of profits to the various parameters affecting the plant costs, a
sensitivity analysis was conducted. 10% changes in key parameters were made, and the change in NPV
was measured as a percentage of the NPV reported above; these results are reported in Table 5.
Table 5: Sensitivity of NPV to 10% changes in key parameters
10% Change in % Change in NPV
Methanol Price 25.8
Natural Gas Price -24.3
Hydrogen Price 27.2
Boiler Feed Water Price -0.6
Capital Cost -7.98

As observed, the production costs are most susceptible to changes in the methanol, hydrogen and
natural gas prices as expected. It is much less sensitive to the raw material price of boiler feed water
since it represents a smaller portion of overall costs, and capital cost changes have a smaller effect
because of its diluted effect over the plant life.
4.6 Economic Analysis
From cost calculations of the base case, a range of breakeven prices for the given discount rate can be
calculated for each variation in natural gas price. This is summarized in Figure 9. To understand the
impact of market volatility in natural gas and methanol, price trends were obtained from BP and
Methanex market surveys for the past 10 years [27] [28]. The price fluctuations were quantified by
performing a polynomial regression on the data points and determining the deviations from the
expected trend. Figure 10 and Figure 11 show the regression data:

8
 14 600
12
500
10
400

Euro/MT
USD$/GJ

8
300
6
y= -0.0691x2 + 1.7619x + 0.7863 200
4 R = 0.841
100
2 y = 0.0005x3 - 0.1022x2 + 7.0285x + 120.99
0 R = 0.3264
0
0 2 4 6 8 10 12 0 50 100 150

Index Time Index Time

Figure 10: Natural gas prices for 2001 to 2011 from Figure 11: Methanol prices for 2002 to 2013 from
BP Report Methanex Report

Although, price estimation involves a more complex interaction of supply and demand, these plots
provide a statistical estimate for the expected volatility for initial projections. From these, natural gas
was determined to fluctuate from 16.6% to -19.7%; for methanol, 17% to -22%. To estimate the range
of variation in sales volume, the world methanol capacity was taken as an index to obtain a fluctuation
of 40% in production volume [29]. Using these
40 120% variations, Monte Carlo simulations were conducted
35 100%
30 assuming triangular distribution of parameters
80%
Frequency

25 within the assumed fluctuations, to calculate NPV

20 60%
15
for each random permutation. Figure 12 displays the
40%
10 plot of NPV frequency distribution. It can be seen
5 20%
0 0%
that, despite the price and volume fluctuations, there
is only a 7.5% chance of making a negative NPV.
102
111
120
3
12
21
30
39
48
57
66
75
84
93
-15
-6

NPV, Million Euros
Figure 12: Frequency Distribution of NPVs
generated from random permutations of volatile
parameters
This indicates that the cash position of the plant is
safe from the volatility of the market for the given
price fluctuations. Standard deviation of the
distribution in Figure 12 is 22.8mil.

4.7 Case 1: Biogas substitution

To investigate the impact of biogas, yield, productivity and throughput data for the available food
waste were obtained from the literature, and these are summarized in Table 6:
Table 6: Biogas Kinetic Data
Productivity, Throughput of
Organic Load Methane Yield Reference
m3.CH4/m3/day Organic Waste
Corn Silage 181 L/kg.TS 0.73 5400 MT/yr [30]
Corn Grain 300 L/kg.TS 5.4 2600 MT/yr [31]
Wastewater 150,000 m3/yr
240 L/kg.COD 0.72 [32]
(Slaughterhouse) 5000 mg.COD/L
Animal Waste 30,000 MT/yr
207 L/kg.VS 0.37 [33]
(Chicken Dropping) 40% TS, 85% VS
Pre-treated Wheat 1257.8 MT/yr
349L/kg.TS 3.11 [34]
Straw 40% TS, 85% VS

9
These data represent an average of the relative crop rates; actual values are scattered about these
estimates [34] [35]. Corn grain is clearly more productive, which allows the reactor size to be smaller.
This effect on capital cost was calculated with costing exponential factor of 0.7 taken from [36] for the
reactor and auxiliary facility costs as well as compression requirements and storage. The operating cost
would vary with the amount of load transported and the travel duration [37] while heating costs were
neglected due to surplus heat streams from the main process. The costs were annualized across the
plant life and an average cost for each kg of biomethane is calculated. From this, it was concluded that
wastewater is unprofitable to use in isolation because the transportation of the dilute organic load is
uneconomical; the final cost of biomethane from such production is 3 times the natural gas price
(10.09/kg vs 0.361/kg). For solid waste, the savings in transportation allows biogas to be produced at
a lowest possible productivity value of 0.118 m3 of CH4/m3/day while maintaining biogas cost to be
comparable to natural gas price; this productivity is easily achieved in industry and literature.
Economic Analysis: From Table 6, several options to utilize the available waste for biogas production
were analysed to maintain positive NPV as shown in Table 7. Option 1 is the base case without any
biogas, Option 2 maximizes NPV by only utilizing the corn grain, Option 3 maximizes the production
of biogas, Option 4 maximizes NPV with a substitute for corn of plant origin, and Option 5 is the
scenario where all solid waste was processed to take advantage of the cheaper transport. The effect of
each biogas substitution option on the Monte Carlo simulated probability of earning a negative NPV is
also reported. This was done by reducing the variability and price of natural gas as a result of partial
substitution by biogas and assuming biogas does not fluctuate in price. As seen in Table 2, the biogas
substitution is economically justified, and the best improvement in NPV is from Option 5.
Table 7: Biogas Production Scenarios
Description Option 1 Option 2 Option 3 Option 4 Option 5
Biomethane Produced, KT/yr 0 0.439 2.027 0.439 1.995
Biomethane Cost, USD$/kg 0.4689 0.0981 0.4689 0.0900 0.2714
kg.CO2eq/kg.methanol 0.6587 0.6504 0.6174 0.6180 0.6173
NPV Change, USD$ 0.00 259,732.00 0.00 28,153.00 1,688,303.00
% of -ve NPV 7.52 7.33 7.99 7.72 6.53
Environmental Analysis: The carbon emissions data for each of the above options was also analyzed
to consider their environmental impact. This was developed by defining the system boundary to include
the natural gas production facility from fossil fuels, the treatment facilities of the respective organic
wastes, the alternative biogas production facilities for each respective organic wastes and the effect of
transportation. The effect of post-digestion sludge as well as the methanol plant was deemed to stay
constant for all scenarios. Greenhouse gas emission data were adapted from life cycle assessment
studies from [38] and [39] with global warming potential equivalency taken from [40]. Appendix A1.3
provides an elaborate write-up on the environmental analysis. As seen in Table 7, Options 3 and 5 are
the scenarios with the most carbon reduction.
Choice of Biogas Substitution Option: The best option is clearly Option 5. It yields the highest NPV
increase, has a lower probability of making a loss and has superior levels of carbon reduction. This is
because the transportation of solid wastes is both economical and environmentally sustainable, and
hence it should be capitalized.
10
Food for Energy: Corn has the best productivity and yield, and maximizing its use in biogas
production for Option 2 also yields some carbon reduction. However, its competition for arable land
may cause overall poorer performance in other life cycle parameters such as human health, ecosystem
quality and resource depletion [41]. This also spills over to market pressures to increase food price.
This should and can be avoided with readily available alternatives such as straw, fruits and vegetable
waste or plant residues [42]. For example, wheat straw pre-treated with alkaline can achieve very high
productivity similar to that of corn [34]; accordingly, Options 2 and 4 clearly show a similar
performance to the high productivity of corn grain. Alternatively, co-digestion of fruits and vegetable
waste with manure or slaughterhouse wastewater can yield up to 51.5% increase in biogas yield [43].
Co-digestion of wheat straw and chicken manure is also possible [44]. Therefore, these options of
direct substitution and co-digestion are viable alternatives.
4.8 Case 2: Carbon Capture Technology
The methanol production process leads to carbon dioxide effluents from its purge stream (which can be
routed to flare systems or into the furnace for additional fuel) and from furnace flue gas stream. These
must be effectively captured to the desired flow of 200 MT/day required for the production rate
enhancement. Table 8 summarizes the effluents specifications for re-use.
Table 8: Flue Gas and Target Composition
Available Flue Gas Composition Target Feed Composition
Mass Flow 138 MT/day 200 MT/day
Pressure ~ 1 bar 22.2 bar
Temperature ~ 200 C ~ 200 C
Composition in Mole Fraction unless otherwise stated
Water 0.171 < 600 ppm
CO2 0.0893 > 0.95
Oxygen 0.0175 < 10 ppm
Nitrogen 0.723 < 0.04
An additional 62 MT/day of CO2 is necessary, and this can be obtained from fossil-fuel firing units;
these include power plants or other chemical plants in neighbouring complexes depending on transport
constraints. The CO2 effluent stream would need to be purified to prevent introducing excess inert
gases such as nitrogen that would strain the recycle loop; to conform to certain standards, the IPCC
standard will be used [45]. The purification can be setup as a pre-combustion, post-combustion or oxy-
recycle [46]. The post-combustion method was chosen due to its flexibility of installation, suitability
over the oxy-recycle method specifically for natural gas fuels in the furnace as well as the need to
preserve carbon within the syngas flow for process purposes. For this method, CO2 is removed after it
leaves the furnace and options for performing the purification can be chosen as shown in Table 9.
Table 9: Summary of Different Carbon Dioxide Purification Technologies; See Text for References
Absorption Adsorption Membrane Cryogenic
(MEA) Separation Distillation
Energy Usage, GJ/kg.CO2 3.5 3.23 0.605 High Vacuum
Cost, /kg.CO2 28 44 80 High
Plant Life and Discount Rate 20 yrs, 10% 25 yrs, 7% 25 yrs, 5% Refrigeration

11
Cryogenic distillation is generally taken to be too expensive due to its extreme conditions [46]. Data for
membrane separation from [47] reports the lowest energy, unlike the excessive heating or re-
compression in liquid absorption and pressure swing adsorption (PSA); however, it is most expensive
due to the need for multi-stage membrane modules and compression for the low pressure carbon
dioxide feed. PSA energy usage reported in [48] is slightly better than that from absorption via mono-
ethanol amine (MEA) [49] despite the reported cost for the latter [50] to be cheaper than the former as
shown by [51]. From this, it is evident that there is a trade-off between profitability and energy use.
In consideration of economics and environmental energy concerns, liquid absorption with MEA is
ideal. This is due to it being the cheapest technology and most convenient to integrate in terms of
energy use; it only requires once-through compression as opposed to cycles in adsorption, and its
heating duty can be easily provided from the excess heat in the plant, hence mitigating its energy
penalty. In addition, membrane operation is inherently more prone to aging and poisoning issues such
as membrane wetting or plugging [52], therefore it is also superior in technical robustness. With this in
mind, the liquid absorption method was chosen.

Figure 13 shows the schematic representation of the

chosen carbon dioxide purification system. Flue gas is
pressurized as required, CO2 is absorbed by lean MEA
solvent, and then it is boiled off in the regenerator column
to release the high pressure CO2 as feed to the steam
reforming section. Steam required for regeneration/
reboiler is readily available from the main process steam
facilities.
Figure 13: Liquid Absorption via MEA
System

5. CONCLUSIONS
As shown in this preliminary process development, the base case for methanol production is profitable
to a company setting up operations within the European context. Furthermore, the traditional process of
methanol production holds potential for increased cost savings if operating constraints in reactor design
can be overcome to achieve equilibrium at more extreme conditions. In the context of sustainable
development, options to substitute the traditional natural gas feed with renewable biogas as well as
carbon capture were evaluated and shown to be economically justified while reducing carbon emissions
for the plant. This supports the relevance of the traditional methanol production process in a modern
technical, economic and environmental perspective.
In this study on methanol process development and design, steam methane reforming, methanol
synthesis, distillation and absorption of carbon dioxide are well-established technologies that can be
designed and implemented readily. On the other hand, hydrogen separation using membrane
technology is a relatively newer technology, and biogas generation requires further testing on the
specific feedstock to affirm the suitability of the feed. Further work on these is recommended before
implementing the proposed methanol process with biogas substitution for part of the natural gas feed.

12
A1. APPENDICES
A1.1 Appendix A: Process Flow Diagram and Stream Data Table
A1.2 Appendix B: HYSYS Simulation and Optimization Details
A1.3 Appendix C: Biogas Life Cycle System Boundary and Details
A2. METHANOL PLANT SIMULATION FILE

A3. AEA HEAT INTEGRATION FILE

A4. MS EXCEL SPREADSHEETS

A4.1 Optimization Spreadsheet
A4.2 Cost Spreadsheet

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15
A1.1 APPENDIX A
Stream Number 1 2 3 4 5 6 7 8 9 10
Temperature, C 41.369 76.831 11.995 219.137 218.284 219.951 900.000 484.962 136.754 35.000
Pressure, kPa 7500.000 6750.000 2222.000 2222.000 2222.000 2222.000 1799.820 1619.838 1457.854 956.498
Molar Flow, kmol/h 222.222 222.222 222.222 540.039 263.500 276.539 1177.615 1177.615 1177.615 1177.615
Mass Flow, kg/hr 3876.800 3876.800 3876.800 9730.254 4746.979 4983.275 13607.224 13607.224 13607.224 13607.224
Composition, mol fraction
Methane 9.000E-01 9.000E-01 9.000E-01 1.915E-09 1.915E-09 3.739E-09 3.122E-02 3.122E-02 3.122E-02 3.122E-02
Ethane 1.000E-01 1.000E-01 1.000E-01 1.214E-15 1.214E-15 2.370E-15 7.889E-07 7.889E-07 7.889E-07 7.889E-07
Water 0.000E+00 0.000E+00 0.000E+00 9.999E-01 9.999E-01 9.998E-01 2.395E-01 2.395E-01 2.395E-01 2.395E-01
Hydrogen 0.000E+00 0.000E+00 0.000E+00 5.156E-06 5.156E-06 1.007E-05 5.529E-01 5.529E-01 5.529E-01 5.529E-01
Carbon Monoxide 0.000E+00 0.000E+00 0.000E+00 1.580E-06 1.580E-06 3.086E-06 1.337E-01 1.337E-01 1.337E-01 1.337E-01
Carbon Dioxide 0.000E+00 0.000E+00 0.000E+00 1.026E-04 1.026E-04 2.003E-04 4.273E-02 4.273E-02 4.273E-02 4.273E-02
Methanol 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00
Ethanol 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00

Stream Number 11 12 13 14 15 16 17 18 19 20
Temperature, C 35.000 206.850 53.000 187.445 105.530 35.000 35.122 255.000 255.000 195.024
Pressure, kPa 956.498 3359.884 3023.896 8010.000 8010.000 956.498 2282.000 7209.000 6488.100 5839.290
Molar Flow, kmol/h 901.077 901.077 901.077 901.077 3253.539 276.539 276.539 4154.626 3765.392 3765.392
Mass Flow, kg/hr 8623.949 8623.949 8623.949 8623.949 18420.662 4983.275 4983.275 27044.836 27044.661 27044.661
Composition, mol fraction
Methane 4.080E-02 4.080E-02 4.080E-02 4.080E-02 1.347E-01 3.739E-09 3.739E-09 1.143E-01 1.261E-01 1.261E-01
Ethane 1.031E-06 1.031E-06 1.031E-06 1.031E-06 3.350E-06 2.370E-15 2.370E-15 2.847E-06 3.142E-06 3.142E-06
Water 6.164E-03 6.164E-03 6.164E-03 6.164E-03 2.563E-04 9.998E-01 9.998E-01 1.538E-03 1.293E-02 1.293E-02
Hydrogen 7.226E-01 7.226E-01 7.226E-01 7.226E-01 8.141E-01 1.007E-05 1.007E-05 7.943E-01 7.618E-01 7.618E-01
Carbon Monoxide 1.747E-01 1.747E-01 1.747E-01 1.747E-01 1.893E-02 3.086E-06 3.086E-06 5.272E-02 1.772E-02 1.772E-02
Carbon Dioxide 5.579E-02 5.579E-02 5.579E-02 5.579E-02 2.501E-02 2.003E-04 2.003E-04 3.168E-02 2.373E-02 2.373E-02
Methanol 0.000E+00 0.000E+00 0.000E+00 0.000E+00 6.986E-03 0.000E+00 0.000E+00 5.472E-03 5.772E-02 5.772E-02
Ethanol 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00
Stream Number 21 22 23 24 25 26 27 28 29 30
Temperature, C 169.832 40.000 40.000 40.000 70.000 134.053 64.607 45.923 48.978 42.273
Pressure, kPa 5255.361 4729.825 4729.825 4729.825 365.000 304.955 101.325 101.325 5416.000 5400.000
Molar Flow, kmol/h 3765.392 3765.392 243.102 3522.290 243.102 40.989 198.034 4.079 175.036 93.715
Mass Flow, kg/hr 27044.661 27044.661 7102.405 19942.256 7102.405 738.424 6250.544 113.437 352.873 1168.721
Composition, mol fraction
Methane 1.261E-01 1.261E-01 2.330E-03 1.347E-01 2.330E-03 1.203E-30 4.174E-05 1.369E-01 0.000E+00 3.863E-01
Ethane 3.142E-06 3.142E-06 1.179E-07 3.350E-06 1.179E-07 1.656E-73 5.156E-10 7.001E-06 0.000E+00 9.608E-06
Water 1.293E-02 1.293E-02 1.966E-01 2.563E-04 1.966E-01 1.000E+00 3.421E-02 5.244E-03 0.000E+00 7.351E-04
Hydrogen 7.618E-01 7.618E-01 3.064E-03 8.141E-01 3.064E-03 1.433E-30 2.901E-05 1.812E-01 1.000E+00 4.669E-01
Carbon Monoxide 1.772E-02 1.772E-02 1.070E-04 1.893E-02 1.070E-04 3.262E-50 2.260E-06 6.265E-03 0.000E+00 5.429E-02
Carbon Dioxide 2.373E-02 2.373E-02 5.079E-03 2.501E-02 5.079E-03 1.633E-30 2.138E-04 2.923E-01 0.000E+00 7.173E-02
Methanol 5.772E-02 5.772E-02 7.929E-01 6.986E-03 7.929E-01 2.198E-06 9.655E-01 3.781E-01 0.000E+00 2.003E-02
Ethanol 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00
A1.2 APPENDIX B
This appendix provides additional details and assumptions of the simulations in Section A2 to support
the main features discussed in the main report regarding process development and optimization
procedures in Sections 3.1, 3.2, 4.1 and 4.2.
General Simulation and Optimization Assumptions
For the simulations, HYSYS files used were developed according to a generic heat exchange network.
The core assumption is that the effect of heat integration presents a similar effect to all simulations. In
addition, HYSYS files used for optimization in each segment were separately developed to minimize
convergence errors across segments. The core assumption in this was that minor process parameters,
apart from the main factors discussed in Section 3, have marginal effect on the overall process
performance.
In the process development, pressure drops across heat exchangers and reactors was taken to be 10% of
inlet pressure for gases, 60 kPa for liquids of viscosity 1-10 mN.s/m2 and 35 kPa for <1 mN.s/m2. For
the distillation column, a pressure drop of 0.007 bar per tray was estimated together with expected
pressure drop from height differences according to the general formula of P = gh. The reflux
pump for the column was sized to make-up for this pressure loss in the reflux stream.
Costing Conventions for Optimization
As mentioned, the objective function of each run was characterized by profit. The optimization for
steam methane reforming uses the following objective function:
= + + + +
Where,
Cexp Annualized Capital and Operating Cost of Expander Turbine, US$
Ccomp Annualized Capital and Operating Cost of Make-up Compression Train, US$
Cfurnace Annualized Capital and Operating Cost of Furnace, US$
CVessel Annualized Capital and Operating Cost of Water Let Down Vessel, US$
Rmethanol Revenue for expected methanol conversion from syngas produced, US$

The optimization for the methanol synthesis loop utilizes the following objective function:

= + + + + + + 2
Where,
Creactor Annualized Capital and Operating Cost of Methanol Reactor, US$
Cexchangers Annualized Capital and Operating Cost of Heat Exchangers in Methanol Synthesis, US$
Ccompressors Annualized Capital and Operating Cost of Recycle Compressor, US$
CDistillation Annualized Capital and Operating Cost of Methanol Distillation including knock-out vessel, US$
Rmethanol Revenue for expected methanol conversion from syngas produced, US$
Rhydrogen Revenue for expected hydrogen recovered from syngas produced, US$
The formulas used for each cost term consists of a summation of annualized capital costs over 10 years
using a discount rate of 10% and annual operating costs. The operating costs are proportional to the
respective utility stream used while the capital costs depend on the characteristic parameter used in the
modular costing method.
Operating Costs: The utilities used are cooling water, boiler feed water, medium pressure steam,
natural gas and electricity. The costs and streams used are shown in A4.2 Cost Spreadsheet.xlsx .
Capital Costs: The general formula for capital costing is as such:
2
= 10^ 1 + 2 lg(A) + 3 lg(A) ------------------------------- (1)
1 = 1 + 2 ---------------------------------------------- (2)

2 = --------------------------------------------------------- (3)

= -------------------------- (4)
(P+1)D
+CA
29440.91.2(P+1)
, = tmin
------------------------------------------------------------- (5)
Where,
K1, K2, K3 Cost correlation factors FP,vessel Pressure Factor for Vessels
B1, B2 Bare module correlation factors P Operating pressure, barg
FM Material Factor CA Corrosion Allowance (assumed to be 0.00315), m
FP Pressure Factor D Vessel Diameter, m
A Dependent variable

Pressure factors for all units except vessels are calculated with a formula of similar form in Equation
(1) for the case of high pressures and using pressure in barg as the dependent variable; the value is
assumed to be 1 for low pressures or vacuum conditions. For vessels, the pressure factor used is
described in Equation (5) using a L/D ratio of 3 and assuming an ellipsoidal head of 2:1 ratio;
horizontal vessels are used for volumes larger than 3.8m3. Raw material factors are chosen based on
process requirement. Stainless steel is used for any stream containing methanol, alloy steel is used for
the furnace, while carbon steel is used for the make-up compressor and steam generation streams.
Other constants are obtained from [25] and are summarized in the costing spreadsheet of Section A4.
The factor used for annualization of capital costs is:

(1+)
= (1+)1 ----------------------------------------------- (5)
Where,
r Discount rate n Plant life in number of years
A1.3 APPENDIX C
This appendix provides a clarification for the system boundaries of the options in the biogas
substitution case study. These are shown in the diagrams below. The annotation and superscript notes
used in these figures are summarized in Table 1.
Table 1: Summary of Annotation and Notes
Superscript Number Description
1 Expressed in terms of potential methane that can be produced from reported kinetics
2 Proportion of feed converted to edible substance
3 Mass of waste
4 Proportion of waste converted to sludge

Figure 1: Option 1 System Boundary

In the base case of Option 1 without biogas substitution, the methanol plant procures natural gas from
fossil fuel sources while the potential feedstock for biogas remains in its default treatment procedures.
Corn is taken to be used for animal feed and ultimately converted to food; wheat straw and the other
organic waste of wastewater and animal waste are assumed to be treated in nearby facilities. The
emissions for corn used in animal feed is ignored while the rest were calculated from [39] for the case
of energy generation from anaerobic digestion. Methanol production and sludge treatment are ignored
as they remain constant across the different options.
 Figure 2: Option 2 System Boundary
Accordingly, routing corn from its default option of animal feed usage to maximize NPV from the high
productivity of corn grains would substitute part of the natural gas feedstock from fossil fuels. This
results in reduced emissions from fossil fuels, but results in increased emission from transportation of
the feedstocks and the biogas treatment procedures. The magnitude of the change in emissions are
summed and compared across the options. The subsequent figures elaborate on the last three options.
Figure 3: Option 3 System Boundary
Figure 4: Option 4 System Boundary
Figure 5: Option 5 System Boundary