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In general the group worked effectively as a team. Most members attended the group meetings.
However, the group was faced with an unforeseen challenge. Indeed, James Finlayson was not present
for the majority of the project for personal reasons. In addition, he insisted on taking on work with
the promise to deliver. Nevertheless, after a few weeks no work was sent back to the group and
communication was difficult and mainly one-sided. This sequence of events was repeated several
times as James reappeared periodically (every few months) for 1-3 days. A lot of group effort went
into redistributing his work to other group members which led to major delays.
This information was added as per Dr. Ahns request as it largely influenced the group dynamics over
the course of the project. We were unaware of the severity of James conditions. However, we are
sympathetic and wish him a speedy recovery.
Group 1:
Jennifer Coyle - s1227207
Jack Mercer - s1240259
Elissa Mui s1219617
Qi-Shaun Wong s1302249
Aidan Cairnie - s1102723
Yongjun (John) Chen - s1105812
Astrid Stroobants - s1202301
James Finlayson
Table of Contents
1
5.3.1
5.3.2
10
11
List of Figures
Figure 1-1: Hydrogen Market Distribution [2] .................................................................................................................. 3
Figure 2-1: Process flow diagram for chemical absorption[42] ...................................................................................... 10
Figure 2-2: Process flow diagram of CLC[48] .................................................................................................................. 12
Figure 2-3: Process flow diagram of cryogenic CC[53] ................................................................................................... 13
Figure 3-1: Process Flow Diagram for Design 1 .............................................................................................................. 15
Figure 4-1: Process Flow diagram for design 2 ............................................................................................................... 20
Figure 6-1: PSA Adsorption Isotherm [63] ...................................................................................................................... 29
Figure 6-2: PSA Adsorption Isotherm [63] ...................................................................................................................... 29
Figure 6-3: CO2 loading as a function of its partial pressure [65] .................................................................................. 31
Figure 11-1: Proposed designs ........................................................................................................................................ 54
List of Tables
Table 1-1: Product specifications ...................................................................................................................................... 2
Table 2-1: SWOT of the two proposed Desulphurisation Techniques .............................................................................. 8
Table 2-2: SWOT for Hydrogen production techniques .................................................................................................... 9
Table 2-3: SWOT analysis for Carbon Capture techniques ............................................................................................. 13
Table 2-4: Proposed Designs ........................................................................................................................................... 14
Table 3-1: Design 1 HEN ................................................................................................................................................. 19
Table 4-1: Design 2 HEN .................................................................................................................................................. 22
Table 5-1: Overall Mass Balance for Design 1 ................................................................................................................. 23
Table 5-2: Overall Energy Balance for Design 1, Part 1................................................................................................... 23
Table 5-3: Overall Energy Balance for Design 1, Part 2................................................................................................... 24
Table 5-4: Overall Mass Balance for Design 2 ................................................................................................................. 24
Table 5-5: Overall Energy Balance for Design 2 .............................................................................................................. 25
Table 6-1: Reactions in Design 1 ..................................................................................................................................... 26
Table 6-2: Rates of Reaction in Design 1 ......................................................................................................................... 27
Table 6-3: Pre-exponential factors and Equilibrium Constants in Design 1.................................................................... 27
Table 6-4: Adsorption Constants in Design 1 .................................................................................................................. 28
Table 6-5: PSA cycles ....................................................................................................................................................... 29
Table 6-6: Reactions in Design 2 ..................................................................................................................................... 32
4
GROUP 1
GROUP 1
Volume 1
Design Brief
The design brief stated that a high purity hydrogen production plant with integrated Carbon Dioxide Capture must
be designed. The plant was required to have a capacity of 5 tonnes/h of product hydrogen and was to be situated
near a chemical production site in the United Kingdom. All utilities were readily available including our natural gas
feed supply, which was available by pipeline at 33 bar(a). The final requirement was the pressurisation of the carbon
dioxide product to 150 bar(a) for transportation. Carbon dioxide and hydrogen had specific product composition
requirements, detailed below.
Table 1-1: Product specifications
Component
Carbon dioxide, CO2
Carbon monoxide, CO
Methane, CH4
Oxygen, O2
Nitrogen, N2
Hydrogen, H2
Moisture
Total Carbons
Hydrogen Product
< 5vpm
< 100vpm
>99.98%
< 8vpm
< 10vpm
GROUP 1
GROUP 1
GROUP 1
GROUP 1
Volume 1
Process Selection
The plant was divided into four main sections: desulphurisation, hydrogen production, carbon capture and hydrogen
purification. For each of these different sections different techniques were considered and compared to each other
in order to choose the best options for the design phase. The evaluation of each of these techniques consisted of an
environmental, safety, economical and maturity analysis which was complimented by a SWOT (strength weaknesses,
opportunities and threats) analysis and a scoring system (Appendix F).
2.1 Desulphurisation of the Feed
2.1.1 Initial Considerations
It was decided that a desulphurising unit was required in both designs due to the presence of sulphur in the natural
gas feed (5.1 ppm wt).[15], [16], and [17] suggest that hydrogen sulphide (H2S) is usually the most prevalent sulphur
compound present followed by mercaptans and organic sulphur compounds. As the sulphur compound in the feed
was never explicitly specified, it was assumed that only hydrogen sulphide (H2S) was present. In addition, it was
found from [18] that H2S concentrations in the order of 5 ppm poisons the (nickel) catalyst used in the SMR process.
While the provided natural gas feed is only slightly above the suggested poisoning concentration, it was decided that
a desulphurising unit would be used to remove the H2S completely or down until extremely trace amounts.
Desulphurisation would therefore be the first process in both designs as its goal is to ensure that there is no H2S in all
of the downstream processes. In addition, this section of the plant would also treat the fuel gas used in H 2
production.
2.1.2 Options for Desulphurisation of the Feed
Desulphurisation processes are usually split into two distinct categories which are wet or dry based processes. Only a
select few desulphurisation processes were considered for use in the plant.
2.2 Wet based processes
Description: The operating principle is that the H2S in the feed gas stream will be absorbed using basic solution of
most commonly monoethanolamine (MEA), Diethanolamine (DEA), or hot potassium carbonate. In addition, MEA
process derivatives like the Sulfiban process are modern variations of the basic MEA system where a few other
chemicals are added to minimise degradation of the amine sorbent. Almost all absorption based desulphurisation
processes are scalable with great flexibility toward the concentration of H2S in the feed.
Maturity: The basic MEA process was developed in the 1920s; the Sulfiban process has been commercially used
since 1954. As of 1978, around 100 units had been constructed, treating a combined gas volume of 4.7 x 10 7 m3 per
day[19]. In essence, MEA based processes are considered the standard way to treat sour gas in the chemical
industry.
Technical: The sour feed gas enters the bottom of an absorber while the lean amine solution (often 12-30 wt% MEA)
enters the top. The purified product gas leaves the top of the absorber and should be clean enough to continue to
the SMR reactor. The sulphur-rich amine solution is pumped to the stripping column where it is heated and reverse
chemical reaction occurs, stripping the acid gases into the vapour phase, where they are treated for sulphur
recovery. The sulphur-lean amine solution is returned to the absorber.
The reactions occurring in the absorber are as follows:
2 + ( )
Eq. 1
( ) + 2
Eq. 2
Reactions in the stripper are the exact reverse of these. A process flow diagram (figure G-2) can be found in
Appendix G.
Environmental: In general, amine based desulphurisation processes release very little to the surroundings due to
regeneration of the sorbent. However, MEA, DEA, Caustic Soda or other absorbents are usually highly soluble in
water and present a serious threat to aquatic environments. Safe disposal will incur additional taxes due to the
active nature of the absorbents.
Economic: Regenerative absorbent based processes for desulphurisation like MEA are considered economical for
treating high H2S concentrations (2% mole fraction+) in the feed. The ability to scale the process with H2S
6
GROUP 1
Eq. 3
= 22 25 1
The PFD (figure G-3) in Appendix G represents a typical flow sheet for the iron oxide desulphurisation process but
can be applied to almost all other dry based desulphurisation processes. In this two-column design, one column will
undergo gas sweetening via adsorption and the other will either be on standby, regenerating or dumped and
replaced with fresh adsorbent. In some cases, water is added to saturate the feed stream, which enhances the
adsorptive capabilities of the adsorbent (iron oxide). However, zinc oxide based processes must operate dry
otherwise the adsorbent material will be ruined.
Environmental: In terms of environmental impact, most dry based desulphurisation processes are material heavy
and require change-outs every year or quarter year depending on the estimated breakthrough time. However, the
spent adsorbents are usually inert in nature and require no special disposal considerations. For example, spent
Sulfatreat is essentially pyrite which is both safe, inert and reusable as supplement material in bricks, roads and sand
stabilisers[21]. Zinc oxide on the other hand is not as environmentally friendly and is indeed toxic to aquatic bodies
but present no problems otherwise[22].
Safety: Almost all dry based adsorbents are safe to handle and present no safety risk to the staff or the plant. Iron
oxide was an example of a fire hazard earlier but the modern variant of it completely solves the problem. Table F-2
shows the SWOT of the Desulphurisation Section; the resulting scoring matrix is in Appendix F, Table F-1.
7
GROUP 1
2.4
Volume 1
Conclusion
Table 2-1: SWOT of the two proposed Desulphurisation Techniques
Strengths
Amine absorption or
similar wet based
processes (Sulfiban
process)
Flexibility in
sulphur removal
Weaknesses
May incur large
operating and capital
expenses that far
outweigh low sulphur
removal applications
Opportunities
Possibility to save
on material costs
due to
regeneration
Low release to
environment
Threats
Additional costs
due to tail gas
treatment unit to
separate H2S and
CO2 waste gas
stream
Dry based
limited H2S
Good removal
Not able to cope
desulphurisation
concentration operating
Economical for
efficiency for low
with high H2S feed
processes (Sulfatreat,
range with significant
current plant
H2S applications
streams
Zinc oxide)
waste material footprint
Dry based desulphurisation via Sulfatreat (Iron oxide) is our primary choice for desulphurisation as it is able to
reliably remove the trace H2S concentration in the feed from 5.1 ppm (wt%) down to < 0.1 ppm (wt%) whilst still
being very economical when compared to the wet based amine absorption desulphurisation method. The scoring
matrix for the proposed desulphurisation techniques are presented in Appendix F, Table F-2.
2.5 Hydrogen Production
There are three main processes used for producing H2 from natural gas.
2.5.1 Steam Methane Reforming (SMR)
Description: Steam methane reforming is a traditional method used to convert natural gas to syngas, it requires an
external heat source due to the endothermic reactions that occur. This method for producing reformate can
therefore only achieve its potential when effective heat integration in the plant can be conducted. Subsequently, in
what is called the "water-gas shift reaction," the carbon monoxide are converted to carbon dioxide and increasing
the concentration of hydrogen at the same time. Finally, a process step called "pressure-swing adsorption (PSA) is
used, which will be covered in a later section. [23-26]
Maturity: SMR has been around for more than 80 years. It was first introduced in 1930 and has been the leading
method for producing hydrogen at large scale. Examples of SMR plant would be the one located in Texas from Linde
with a capacity of 10 tonnes/hr and Air product have major hydrogen pipelines in places such as Lousiana USA and
Rotterdam in the Nether. [2, 24, 27]
Technical: In steam-methane reforming, methane reacts with steam (700 C -1000 C) under high pressure in the
presence of a nickel catalyst to produce hydrogen, carbon monoxide, and a relatively small amount of carbon
dioxide. The main processes involved are[28]:
: + + 3
Eq. 4
: + +
Eq. 5
Safety: Safety hazard of dealing with flammable gases like methane and hydrogen under a high temperature is
considerable, however with the maturity of this production method, appropriate control techniques and procedures
exist.
Economic: The cost of conventional steam reforming catalysts is relatively low although they tend to be vulnerable
to the sulphur-based catalyst poisons. According to a survey conducted by Petroleum energy centre in 1999 [29]
SMR has the highest relative cost out of the three technologies, it was used as a based case and has been given 100
as the value.[30]
2.5.2 Partial Oxidation (Pox)
Description: In partial oxidation, hydrocarbons in natural gas react with a rich air-fuel ratio. The reaction products
contain primarily hydrogen and carbon monoxide (and nitrogen, if the reaction is carried out with air rather than
pure oxygen), and a relatively small amount of carbon dioxide and other compounds. Subsequently, in a water-gas
shift reaction, the carbon monoxide are converted to carbon dioxide and increasing the concentration of hydrogen
at the same time.[25, 26]
8
GROUP 1
Eq. 7
+ (1 ) + + (3 ) 0 < < 1
2
Safety: On the downside, a more extensive control system is needed for ATRs to ensure a safe and robust operation
of the fuel processing system.
Economic: According to a survey conducted by Petroleum energy centre in 1999 [29] ATR was given a value of
ranging from 85 - 95 compared to 100 given to SMR. This can be interpreted as 5 - 15% cheaper than the SMR
method. [30]
2.5.4
Conclusion
Table 2-2: SWOT for Hydrogen production techniques
Strengths
Weaknesses
SMR
CPOx
An exothermic process
ATR
Opportunities
Threats
Most conventional
method: reliable
Many recent
developments on newer
technologies
GROUP 1
10
GROUP 1
11
GROUP 1
Maturity: Chemical looping combustion (CLC) dates from the early 1980s when it was proposed as a system for
augmenting power station efficiency[49]. A number of CL concepts are being researched around the globe to test the
system design and to estimate capital and operating costs for commercial-scale systems. Currently, NETL supports
several CL projects in collaboration with industry, academia, and NETLs Office of Research and Development (ORD)
ranging from lab and bench scale testing to evaluation of pilot-scale prototypes. [50, 51] Nowadays, Chemical
looping for oxy-combustion has reached a TRL of 6 as it has been demonstrated at 1MWth pilot plant using hard coal
and ilmenite as oxygen carrier where the total time of operational experience exceeds 7000h[36]. Presently, more
than a thousand materials have been tested in the laboratory. Also, from testing, it was established that >99%
conversion of the fuel can be obtained and that 100% CO2 capture is possible using gaseous fuels[36]. Chemical
looping reforming however has been tested in a pilot plant.
Environmental/Safety: There should be no formation of thermal NOx since the regeneration of the carrier is
achieved at moderate temperatures. The exit streams are relatively clean. The exit stream of the fuel reactor is
mainly composed of water and CO2 while the exit stream from the air reactor is mainly composed of nitrogen and
oxygen. Most metal oxides are toxic to aquatic life. Dust is irritating to the eyes, skin and respiratory system. Eye
contact may cause corneal damage. In addition it may cause dermatitis.
Economic: A study estimated that by including CLC in a hydrogen production and power plant in order to capture
93.5% of the CO2 led to an additional cost of 81.5/t CO2. [47] The incremental total capital requirement (TCR) for
capture was estimated to be 413US$/kW and the incremental Cost of Electricity (COE) was estimated to be 13.1
US$/MWh[46].
12
GROUP 1
Volume 1
Conclusion
Table 2-3: SWOT analysis for Carbon Capture techniques
Strengths
Weaknesses
Opportunities
Threats
PSA
Safe adsorbent
Low maturity
High cost
MEA
Corrosive
SERP
Low temperatures
Harmful sorbent
CLC
No formation of thermal
NOx
Harmful sorbent
Membranes
Surface poisoning
Cryogenic
Energy efficient
Energy intensive
Durability
Durability
Not mature enough
13
GROUP 1
Design 1
Sulfatreat
SMR
MEA
PSA
Design 2
Sulfatreat
Membrane SMR
CLC
Water knock-out
14
GROUP 1
3
3.1
Volume 1
GROUP 1
3.2
Volume 1
Design 1
GROUP 1
GROUP 1
18
GROUP 1
Stream
9-9a
8-8a
16-16a
17a-17b
29e-29f
1a-1b
E-403 Utility
U4
U3
Volume 1
Stream description
Description
Cooling of the gas stream after high Used to heat utility stream U4 (liquid) then
temperature water gas shift reactor
cooled via E-202
Cooling of the gas stream after main SMR Used to heat utility stream U4 during its
reactor
phase change then cooled via E-201
Used to superheat U4 to 688 [K] then fully
Cooling of the post furnace flue gas stream
superheat U3 from liquid to 673 [K] and
and condensing the water present
finally cooled using E-401
Used to heat E-403 utility until it becomes a
Cooling and condensing the water present
saturated vapour at 406.5 [K] before being
following compression via P-401
cooled by E-402
Used to supply heat to the natural gas feed
Cooling of the compressed CO2 product
so that it can enter the desulphurization
stream before condensing at its critical
section at 303 [K] before being cooled by Etemperature
505
Natural gas feed that enters the
Heated completely using 29e-29f
desulphurization section at 303 [K]
Reboiler water that is pre-heated to
saturated steam before entering E-403 Heated completely using 17a-17b
(reboiler)
Heated completely using streams 9-9a, 8-8a
Make up steam that is required for SMR
and 16-16a before being sent to the furnace
reaction
for further heating
Make up steam that is required for the pre- Heated completely using stream 16-16a
reformer
before being sent to the pre-reformer
19
GROUP 1
4
4.1
Volume 1
20
GROUP 1
4.2
Volume 1
Design 2
GROUP 1
Stream description
Cooling of product gas exiting the SMR-membrane via
outer membrane (not in the membrane tube)
Cooling of product gas exiting the SMR-membrane via
inner membrane (membrane tube)
21-21a
15-15a
U3
U4
U10
14-14a
6a-6b
Description
Used to heat U4 (sensible) and U4 (sensible
and latent) before being cooled via E-206
Used to heat U10 (sensible), U4 (latent) and
U10 (sensible) before being cooled via E-205
Used to heat U10 (sensible), U3 (sensible)
before being cooled by E-208
Used to heat 14-14a (sensible), 6-6a
(sensible), U3 (sensible and latent), cooled
via E-204 (sensible) before final heating of
U4 (sensible)
Used to heat U4 (latent)
Used to completely heat 1a-1b (sensible)
before being cooled by E-301
Completely heated by 16a-16b
Completely heated by 21-21a, E-606 (latent)
and 15-15a
Completely heated by 15-15a, 11-11a, U9,
E-612 (latent), 8-8a, and E-609 (sensible)
Completely heated by 8-8a, 21-21a
Completely heated by 15-15a
Completely heated by 6a-6b
22
GROUP 1
Volume 1
5.1
Assumptions made
20% of the heat produced by the furnace is lost to the surroundings
Less than 5% of the heat produced by the CLC system is lost to surroundings
5.2
Design 1
5.2.1
kg/h
2.02 x104
[-]
5.37 x103
4.02 x104
1.55 x105
Total
2.21 x105
Streams Out
12
27
30
U2
U5
U8
U9
Total
kg/h
5.23 x103
127x105
5.15x104
1.00 x10-1
1.89 x104
1.75 x104
5.52 x103
2.26 x105
Difference (kg/h)
4.82 x103
Overall percentage difference
2.19%
The table above shows the inlet and outlet streams of the plant. The values were obtained following the calculation
method described in Section 3.1 and 3.2 in Appendix D. The basis of calculation followed the standard procedure for
mass balances, with an analysis on the mass flowrates in and out of the process. The error in the overall mass
balance was found to be 2.19%. This error was considered acceptable and likely due to just rounding errors.
5.2.2 Overall Energy Balance
The overall energy balance was separated into two sections; Part one being the Desulphurisation unit to the Furnace
outlet, and part two being the MEA process to the CO2 compression train. The reason for this being the two
different methods of energy balance calculations used. The conventional energy balance equation was used for
calculations in part one, while Unisim was implemented using the amine package for energy calculations in the MEA
process. Please refer to section 3.1 and 3.2 in Appendix D for further clarification on equations utilised.
Part 1: Desulphurisation to Furnace Outlet
The energy balance is illustrated by Table 5-2. It shows the energies of the streams, energy provided by heaters and
coolers, and finally the energy of the various reactions.
Table 5-2: Overall Energy Balance for Design 1, Part 1
Energy In
1
U1
U3
U4
U7
Total
Energy In
E-101
E-205
Total
MW
1.04 x10-1
3.30 x101
1.44 x10-7
4.90 x10-2
-6.88 x101
MW
-3.34 x101
-1.15 x101
-1.13 x101
-5.60 x101
MW
1.19 x102
4.43 x101
-2.67 x10-1
-3.74
23
GROUP 1
MW
6.28 x102
Total
6.28 x102
Energy in
E-403
E-502
P-401
P-502
P-503
P-504
MW
5.26 x103
0.00
9.78 x101
-3.29 x103
2.60 x101
1.56 x101
Total
2.10 x103
Absorption column
Stripping column
MW
1.41 x102
-1.70 x103
-8.07 x101
-3.64 x101
-1.68 x103
MW
-5.08 x102
-1.46 x102
-2.00 x102
-3.45 x103
-2.72 x101
-2.96 x101
-5.78 x101
-4.41 x103
-9.20 MW
-10.5 MW
Overall Balance
Overall difference
21.7 MW
Overall percentage error
0.8 %
As can be seen from the table above an error of 0.8% was obtained which was considered to be insignificant. This
result was calculated following the method in section 3.1 and 3.2 in Appendix D.
5.3
5.3.1
Design 2
Overall Mass Balance
Table 5-4: Overall Mass Balance for Design 2
Streams In
1
U1
U3
U4
U7
U9
kg/h
1.59 x104
0.00
5.37 x103
3.01 x104
4.00 x104
1.07 x105
Total
1.99 x105
Streams Out
U2
9
10
13
17
18
21
Total
kg/h
8.00 x10-2
5.24 x103
1.07 x105
1.05 x104
3.73 x104
5.78 x103
3.77 x104
1.97 x105
Difference
-1.92 x103
Overall percentage difference
-0.97%
The table above shows the inlet and outlet streams of the plant. The values in the table were obtained following the
calculation method described in section 3.1 and 3.2 in Appendix D. The basis of calculation followed the standard
procedure for mass balances, with an analysis on the mass flowrates in and out of the process. The error in the
overall mass balance was found to be -0.97%. This error was considered acceptable and was likely to be caused by
rounding errors.
24
GROUP 1
5.3.2
Volume 1
MW
-1.20 x10-1
0.00
1.04
8.47
-1.69 x10-1
3.01 x101
Total
3.93 x101
Energy in
E-101
E-201
E-202
E-203
P-101
P-202
P-304
P-301
Total
MW
1.60 x10-1
4.01
1.86
6.32
0.00
7.03
4.90 x10-1
1.31
2.12 x101
MW
-1.03 x101
-1.06 x102
-1.33 x101
-1.05
-1.31
-2.40 x10-2
-2.72 x10-1
-1.32 x102
Total
Heat Generated by Reactions
Reaction
CLC
Membrane SMR
Pre Reformer
MW
1.04x10-7
0.00
-6.55 x101
-5.38
4.9x10-1
-2.97
4.52
-6.88 x101
MW
-3.24 x101
-3.33 x101
-2.41 x10-1
Other Sources
1.29 MW
Overall Balance
Overall difference
1.23 MW
Overall percentage error
2.03 %
As can be seen from the table above an error of 0.25% was obtained which was considered to be insignificant. This
result was calculated following the method in section 3.1 and 3.2 in Appendix D.
Excel online was used for overall flowsheets in Design 1 and 2. This allowed all group members to keep up-to-date
with flowsheet and design changes.
25
GROUP 1
Volume 1
This section will focus on the thermodynamics behind the design of reactors and separators. This section is divided
into two parts: Design 1 and Design 2. These are divided further to discuss reactions and separations.
6.1
Design 1
6.1.1 Reactions
All reactions taking place is reactors in Design 1 are summarised in the table below:
Table 6-1: Reactions in Design 1
1
2
+ 6 13 + 6
+ 5 11 + 5
Hrx (298K)
(J/mol)
79600
59210
+ 4 9 + 4
38370
Pre-reformer
100% conversion
+ 3 7 + 3
19530
Pre-reformer
100% conversion
+ 2 5 + 2
-2440
Pre-reformer
100% conversion
+ 3 +
-206310
Pre-reformer
UniSim
+ +
-41200
+ + 3
206310
Pre-reformer,
SMR,
WGS
SMR
UniSim, Rate
equations*
Rate
equations*
No.
Reaction
165110
+ 2 + 4
1
-283150
10
+
2
1
-242000
11
+
2
12
-802910
+ 2 +
7
-1428800
13
+ 2 + 3
2
14
-2658850
+ 5 3 + 4
13
-2650470
15
+ 4 + 5
2
16
-3274310
+ 8 5 + 6
19
-3889320
17
+ 6 + 7
2
* The rate equations are based on literature data summarised in Table 6-2.
9
Pre-reformer
Pre-reformer
Location
SMR
Rate equations*
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Furnace
Total combustion
Main assumptions
For the reactions taking place in the SMR tubes and the WGS reactors, the mixture was assumed to behave like an
ideal gas. This can introduce errors in the mass and energy flows as the gas is very unlikely to behave like an ideal gas
as the pressures inside these reactors are very high (25bar). The Peng-Robinson fluid package was used for the prereformer, which should not introduce significant error as the pressure is elevated.
The viscosity of mixtures for the reactions taking place in the SMR and WGS was assumed to be equal to the mass
average of the viscosities of the individual components. This should not introduce high error, as the pressure drop is
very small in the SMR tubes due to the low velocities.
Heats of Reaction
Heats of Reactions in Design 1 and 2 were calculated at 298K by:
=
Eq. 10
26
GROUP 1
Eq. 11
Eq. 12
Rates of Reaction
The kinetic data obtained for SMR was based on various sources. All sources were in agreement as the SMR process
is a well known process. The kinetic data for the WGS is vastly dependent on the type of catalyst used. Therefore,
the kinetic data might not be the most accurate as finding sources (for comparison purposes) that used exactly the
same catalyst was challenging. The rates of the reactions 7-9 summarised in table 6-1 are described in the table
below:
Table 6-2: Rates of Reaction in Design 1
Rate
Location
(
.
SMR[57-59]
(
.
With = 1 +
=
=
+ +
HWGS[60]
(1
With = 1 + 10 ( +
LWGS[60]
The parameters used in the equations from Table 6-2 are summarised in Table 6-3.
Table 6-3: Pre-exponential factors and Equilibrium Constants in Design 1
Pre-exponential factor, k
Equilibrium constant, K
67100
4400
= 1.96 10 (
)
= (
4.036)
240100
= 4.23 10 (
)
243900
= 1.02 10 (
)
11000
= 10 .
3600 exp (
)
= 60 1000 exp (
29364
40.32
+
)
1.987 1.987
26830
= 1.0267 (
+ 30.114)
Location
SMR[57-59]
4577.8
= exp (
4.33)
HWGS[60]
4577.8
= exp (
4.33)
LWGS[60]
27
GROUP 1
Volume 1
38300
= 6.67 10 exp(
)
=0
82900
= 6.12 10 exp (
)
70700
= 8.23 10 exp (
)
88700
= 1.77 10 exp (
)
Units
bar-1
[-]
LWGS[60]
=0
bar-1
bar-1
[-]
Units
Pa-1
12542
18.45
= exp (
)
1.987 1.987
=0
Pa-1
3064
6.74
= exp (
)
1.987 1.987
6216
12.77
= exp (
+
)
1.987 1.987
Pa-1
Pa-1
Pa-1
6.1.2 Separations
Desulphurisation
Sulphur removal reaction using iron oxide adsorption [20]:
1
1
() + () () + ()
3
3
= 22 25 1
Eq. 13
This reaction performs better at room temperature, otherwise the iron oxide complex is dehydrated which reduces
the reaction rate and increases difficulty of regeneration. The regeneration reaction is shown below for reference:
1
1
1
() + () () + ()
3
2
3
= 198 25 1
Eq. 14
For short cut design, [16] provides a step-by-step short cut design for desulphurization, however the equations used
are entirely empirical. Therefore, the sulphur loading (mass of sulphur adsorbed per mass of adsorbent) equation
[61] was used to recalculate the breakthrough time based on dimensions calculated from[16].
,
Eq. 15
Where VH2S is the volumetric rate of feed stream [m3 s-1], tb is the breakthrough time [s], CA,in is the H2S concentration
[mol m-3], MWS is the molecular weight of elemental sulphur and Wfb the adsorbent loading in the reactor [g]. Using
experimental data from [61] for sulphur loading (23.29% on average), the check-through method yielded a ~8%
difference in results for breakthrough time which was taken as satisfactory.
PSA
=
Reference [62] explains the short-cut method employed in PSA design. In essence there are 4 mole balance
equations and a product recovery equation that govern the 4 step PSA cycle. The 4 step PSA cycle is then
extrapolated to an 11 step cycle with 3 pressure equalization stages to improve recovery. A critical assumption is
that the feed gas is a binary mixture of 80% H2 and 20% CO2. The previous process section (SMR-WGS) provides a
feed that is 78% H2 and 22% CO2 with negligible amounts of other gases, therefore it was decided that the
preliminary assumption was valid. Using the relevant isotherms from [63] shown below in Figures 6-1 and 6-2, along
with operating conditions of 25 bar(a) and 30C, inlet flowrates, the stated 4 mole balance equations, recovery
equation and suggested PSA cycle schedule (Table 6-5), the required dimensions of the PSA column were obtained.
28
GROUP 1
Volume 1
For PSA design, the constants will be explained before the main equations.
Constant i (ratio of hold-up component i in void space as fraction of total hold-up):
=
1
1
1+
Eq. 16
Where is the void fraction of the bed [-] and Ki represents the adsorption equilibrium constant or isotherm slope [-]
The method at which Ki is calculated in the case of KCO2 for example:
Eq. 17
29
GROUP 1
Although complicated,
( )
Eq. 18
simply represents the gradient of the chord between two points on the
isotherm graph and PH is the adsorption pressure [Pa]. This means that i = i for linear isotherms. For clean beds,
the value of the first point in the calculation of i is (0,0).
The moles required for the feed step:
Eq. 19
Where Qin is the inlet feed flowrate [mol s-1], tfeed is the feed step time [s], Pratio is the ratio between the adsorption
and desorption pressure of the adsorption column [-] and is a constant as defined by [62]
The moles required for the purge step:
Where tPU is the purge time of the cycle [s]. The ratio
Eq. 20
=
is equal to 1 for clean beds.
The moles of pure, light product withdrawn during the feed step:
1 + ( 1)
Eq. 21
Where Qout is the outlet flowrate [mol s-1], is the selectivity parameter [-] which is the ratio of CO2 to H2 and yCO2F
is the mole fraction of CO2 if the feed [-]
The pressurization with product step:
= [
1]
Eq. 22
Where tPR is the time of product recovery (re-pressurisation) [s] and 0 is the ratio of CO2 to H2 [-].
Recovery of the light component for this 4 step cycle using pressurization by product:
=
Eq. 23
Where Rb is the recovery of the H2product [-] and yH2F is the mole fraction of the H2 in the feed [-].
Constant
(used to determine column dimensions):
[] =
[ ][] []
[]
Eq. 24
Where ACS is the cross-sectional area of the bed [m2], L is the bed length [m], PL is the desorption pressure of the
column [Pa], CO20 which equals CO2 if the purge gas is presumed to be pure [-] and T the operating temperature of
the column [K].
30
GROUP 1
Volume 1
MEA
Monoethanolamine (MEA) is a primary amine with two hydrogen atoms attached to the nitrogen atom, and is used
to absorb CO2 from a flue gas stream. This absorption is classified as a chemical absorption, as opposed to a physical
absorption due to the equilibrium reactions taking place between the MEA and the CO2, the details of which are
given below [64]:
1. Ionization of water
2 +
Eq. 25
Eq. 26
+ +
Eq. 27
3. Dissociation of bicarbonate
4. Dissociation of MEAH+
( ) + + ()
Eq. 28
Eq. 29
6. to model the MEA absorption process, equilibrium data is used to estimate the required amount of MEA to
In order
be fed into the absorption column based on the partial pressure of CO2 in the flue gas. Figure 6-3 shows the
relationship between CO2 feed partial pressure and the loading CO2 using 30 wt% MEA solution.
Eq. 30
31
GROUP 1
6.2
Volume 1
Design 2
6.2.1 Reactions
All reactions taking place is reactors in Design 2 are summarised in the table below:
Table 6-6: Reactions in Design 2
no.
Reaction
Hrx (298K)
(J/mol)
Location
+ 6 13 + 6
79600
Pre-reformer
100% conversion
+ 5 11 + 5
59210
Pre-reformer
100% conversion
+ 4 9 + 4
38370
Pre-reformer
100% conversion
+ 3 7 + 3
19530
Pre-reformer
100% conversion
+ 2 5 + 2
-2440
Pre-reformer
100% conversion
+ 3 +
-206310
Pre-reformer
UniSim
+ +
-41200
Pre-reformer &
SMR
+ + 3
206310
SMR
Rate equations*
+ 2 + 4
165110
SMR
Rate equations*
10
0.5 +
-938200
Air reactor
Rate equations*[66]
11
+ + 2 +
-35800
Fuel reactor
Rate equations*[67]
12
+ +
-242000
Fuel reactor
Rate equations*[67]
13
+ +
-283000
Fuel reactor
Rate equations*[67]
* The rate equations are based on literature data summarised in tables 6-2 and 6-7
k (s-1)
K(/)
Air Reactor[66]
Where CA=0.349kmol/m3
= 0.00067
Fuel Reactor[67]
2366
= 1.3 10 exp (
)
26500
= 9.4 10 exp (
)
= 0.0063
26410
= 1.3 exp (
)
= 0.003
Where =30
32
GROUP 1
Volume 1
Main assumptions:
There are more than three reactions in the fuel reactor; however, the combustion reactions for higher alkanes were
not considered for simplification purposes. In addition to that, the fuel and air reaction for CL were assumed to be
isothermal for simplification purposes. This is because the heat carried by the nickel carriers introduced a lot of
complications in the modelling of the temperature changes. These assumptions could impact the design significantly
as the heats of reactions are relatively big.
For the reactions taking place in the SMR tubes and the CL reactors, the mixture was assumed to behave like an ideal
gas. This can introduce errors in the mass and energy flows as the gas is very unlikely to behave like an ideal gas as
the pressures inside these reactors are very high (25bar). The Peng-Robinson fluid package was used for the prereformer which should not introduce significant error as the pressure is elevated.
The viscosity of mixtures for the reactions taking place in the SMR was assumed to be equal to the mass average of
the viscosities of the individual components. This should not introduce high error, as the pressure drop is very small
in the SMR tubes due to the low velocities.
The kinetics for the reactions taking place in the CLC reactor can be found in table 6-7. While the kinetics for the
reactions taking place in the SMR are summarised in table 6-2.
The heat of reactions and specific heat capacities are calculated in a similar way as in design 1 (eq.12-14).
The kinetic data obtained for SMR was based on various sources. All sources were in agreement as the SMR process
is a well-known process. However, the kinetic data for the CL reactors can be less accurate as there are a limited
amount of papers that provided kinetic data for CL as it is a relatively new process. Therefore, there is a higher
degree of uncertainty for the results obtained for this process.
6.2.2 Separations
Membrane separation in SMR
In the SMR tubes the hydrogen flows through the membranes with the following molar flux (kmol/m2 h) [57-59, 68]
296 10
Eq. 31
.
.
=
( ,
,
)
Where pi is the partial pressure (bar) and is the membrane thickness (m).
Desulphurisation
The same desulphurisation process is used as in design 1 (see section 6.1.2).
33
GROUP 1
Volume 1
Activated carbon
TWA
Aluminium oxide[B][C]
TWA
Butane[70]
TWA
Carbon[C]
TWA
Carbon dioxide
TWA
TWA
Caesium carbonate[D]
TWA
TWA
TWA
TWA
Ethane[72]
TWA
Hexane
TWA
Hydrogen[73]
Hydrogen sulphide[74]
TWA
Exposure Limits
Concentration
10 mg/m3 (Total inhalable dust)
4 mg/m3 (Respirable dust)
10 mg/m3 (Total inhalable dust)
4 mg/m3 (Respirable dust)
600 ppm
750 ppm
3
3.5 mg/m (Total inhalable dust)
5,000 ppm
9150 mg/m3
15,000 ppm
27,400
3 3
30 ppm
35mg/m
mg/m
200 ppm
232 mg/m3
3
10 mg/m (Total inhalable dust)
4 mg/m3 (Respirable dust)
0.5 mg/m3
0.005 mg/m3
0.2 mg/m3 (Fume)
1 mg/m3 (Dust and mist)
1,000 ppm
20 ppm
72 mg/m
5 ppm
10 ppm
Duration
Flammability/Explosive Limits
Lower
Upper
8 hours
8 hours
8 hours
15 mins
8 hours
8 hours
15 mins
8 hours
15 mins
Toxicological Information
Results
Dose
Duration
Oral LD50
2,000 mg/kg
Inhalation LD50
8.5 mg/L
1 hour
-
1.40%
9.40%
Inhalation LC50
658 mg/L
4 hours
(50 g/m3)
Oral LD50
8,000 mg/kg
Extremely flammable
(12.5%)
(74%)
Inhalation LC50
1,300 ppm
4 hours
8 hours
Oral LD50
2,333 mg/kg
8 hours
8 hours
Oral LD50
80 mg/kg
8 hours
Oral LD50
470 mg/kg
Inhalation LC50
Oral LD50
Inhalation LC50
1.443 mg/L
25 g/kg
48,000 ppm
-
0.25 hours
4 hours
Inhalation LC50
356 ppm
4 hours
8 hours
2.40%
16%
8 hours
1.20%
8.30%
4%
77%
3.90%
45.50%
8 hours
15 mins
34
GROUP 1
TWA
Methane[75]
Volume 1
Inhalation LC50
Oral LD50
Inhalation LC50
Dermal LD50
Pentane[81]
TWA
600 ppm
8 hours
1.10%
7.80%
Oral LD50
Inhalation LC50
5,396,000 ppm
1,089 mg/kg
1,487 mg/m3
2,504 mg/kg
0.46 ppm
0.16 ppm
11,000 mg/kg
50 mg/kg
2,000 mg/kg
25.3 mg/L
Propane[82]
TWA
10.8%
Inhalation LC50
800,000 ppm
TWA
8 hours
15 mins
8 hours
8 hours
8 hours
1.7%
Silica[A]
1,000 ppm
1,250 ppm
0.05 mg/m3
10 mg/m3 (Total inhalable dust)
4 mg/m3 (Respirable dust)
3
5 mg/m (Fume)
10 mg/m3 (Total inhalable dust)
4 mg/m3 (Respirable dust)
10 mg/m3 (Fume)
Monoethanolamine
(MEA)[76]
TWA
Nickel[77]
TWA
1 mg/m3
8 hours
Inhalation LC50
TWA
0.5 mg/m3
8 hours
Oral LD50
Dermal LD50
Nitrogen[79]
Oxygen[80]
[83]
Sulphur
TWA
Water
Zinc oxide[84]
where:
Note:
TWA
TWA
Flammability/Explosive limits
LD50
LC50
[A]
[B]
[C]
[D]
35 g/m
400 g/m
0.25 hours
Oral LD50
2 hours
4 hours
10 mins
1 hour
-
5,000 mg/kg
Oral LD50
10,000 mg/kg
15 mins
35
GROUP 1
Volume 1
GROUP 1
Hazards Ranking
Table 7-2: Hazard ranking
Number
1.
Potential Risk
Changing of catalyst beds
2.
Leakage of nitrogen
during purging pipelines
and equipment
Incomplete combustion
in the furnace or the fuel
reactor of chemical
looping
Leakage of extremely hot
flue gas from furnace
3.
4.
5.
6.
7.
8.
Exposure to MEA
9.
Temperature fluctuation
in the CLC reactors
Outcome
Physical injury to personnel,
chronic diseases if exposed to
catalysts above the safe limit
Asphyxiation, loss of
consciousness, death
Production of unwanted
carbon monoxide, causing
injury or suffocation to
personnel if leaked
Serious burns
Mitigation
Make use of dump trucks and lifting
equipment such as cranes; PPE must be
worn
Venting systems; alarms and gas
detectors should be installed, evacuation
required in case of emergencies
Venting systems; alarms and gas
detectors should be installed, evacuation
required in case of emergencies
Proper monitor and control of abnormal
pressure and temperature; PPE must be
worn; immediate shutdown allowing the
furnace to cool before carrying out
inspection
Alarms and gas detectors should be
installed; inspections carried out regularly
in the fuel line; PPE such as masks
PPE; regular inspection and maintenance
of steam line
Gas leak inspections should be carried
out regularly; any ignition source is
inhibited around the area; emergency
response teams (ERT) present during
leaks/change out
Venting systems; PPE must be worn; staff
training; check for leakages regularly
Trip system installed to terminate flow
immediately; staff training to deal with
equipment overheating
37
GROUP 1
10.
11.
12.
38
GROUP 1
Volume 1
Environmental Impact
The material inventory list for Design 1 is presented in Table 8-1 below.
Table 8-1: Design 1 Material inventory list
Section /
[Equipment]
Material or
Waste
Held inventory
[tonne]
1 / [T-101
A/B]
Sulfatreat 410
CHP
(Iron oxide)
2 / [R-201]
2 / [R-202]
2 / [R-203]
2 / [R-204]
3 / [T-301306]
Release likelihood
Release quantity
[tonne yr-1]
Environmental impact
Non-hazardous
[85], [86]
1. No release hazards
in storage
2. Bed change once
per year
Nickel catalyst
(PRICAT 9920)
8 tonnes in service
with 8 tonnes in
reserve
Slightly-hazardous
Spent material may be
hazardous but can be
recycled [87]
1. No release hazards
in storage
2. Estimated change
out in 4 years
1. 8 tonnes at the
end of service life
(4 years)
Nickel catalyst
(PRICAT 9920)
35 tonnes in service
with no additional
inventory
Slightly-hazardous
Spent material may be
hazardous but can be
recycled [87]
1. No release hazards
in storage
2. Estimated change
out in 4 years
1. 35 tonnes at the
end of service life (4
years)
Slightly-hazardous
May be toxic to aquatic
life [88]
Slightly-hazardous
Product contains zinc
oxide which is classified as
toxic to aquatic bodies[89]
Non-hazardous
[90]
1. No release hazards
in storage
1. Estimated change
out in 4 years
1. No release hazards
in storage
2. Estimated change
out in 4 years
1. No release hazards
in storage
2. Estimated changeout of 1 column
per 1.5 years
1. 7.02 tonnes at
the end of
service life (4
years)
1. 7.39 tonnes at
the end of
service life (4
years)
Change-out not
specified, ~12.34
tonnes per 1.5 years
for single column
change-out
Iron-chrome
HWGS catalyst
(HiFUEL
W210)
LK-823
copper/zinc
(LWGS
catalyst)
Norit R2030
Activated
carbon
GROUP 1
4 / [T-403]
4 / [V-403]
MEA
NA
75 tonnes of MEA in
reserve (30 % of surge
drum volume for make
up to full drum volume
of 30 wt% solution)
In service: 183 tonnes
per hour of MEA
circulating in MEA
system
Non-hazardous
1. MEA disposal limits at
about 6 [mg m-3]
TWA8 OSHA [91]
2. Other gases not
hazardous to health
3. Greenhouse gas
emissions discussed
further on
1. Fixed quantity
released per hour
2. Within emission
boundaries (6 ppm
wt STEL; ours is
1.78 ppm vol or
3.87 ppm wt)
Hazardous [91]
1. Toxic to aquatic life
2. Safety hazard
3. Additional disposal
considerations
required
1. No real fixed
quantity release
2. No accidental
release should
occur if proper
procedures are
followed
Volume 1
~0.126 ktonne/hr or
~1008 ktonne/year
total flue gas release
~0.49 kg/hr or 3920
kg/yr MEA release
~2742 kg/hr or 21.9
ktonne/yr CO2
release
Estimated to be 0
tonnes per year with
the exception of end
of life change outs
40
GROUP 1
Section /
[Equipment]
Material or
Waste
1 / [T-101
A/B]
Sulfatreat 410
CHP
Nickel
catalyst
(PRICAT 9920)
2 / [R-201]
2 / [R-202]
2 / [R-203]
2 / [R-202]
2 / [C-201]
Nickel
catalyst
(PRICAT 9920)
Held
inventory
[tonne]
Same as
design 1
Same as
design 1
85.7 tonnes
in service
with no
additional
inventory
Nickel
~10 tonnes
oxidised in
service
Nickel Oxide
~10 tonnes
reduced in
service
Cyclone flue
gas.
Mole
fraction:
~100% N2
NA
Volume 1
Release likelihood
Release quantity
[tonne yr-1]
Environmental impact
Same as design 1
1. Same as design 1
Same as design 1
Same as design 1
Same as design 1
1. Same as design 1
Same as design 1
Same as design 1
Slightly-hazardous
Spent material may be hazardous
but can be recycled [87]
1. No release hazards
in storage
2. Estimated change
out in 4 years
85.7 tonnes at
the end of service
life (4 years)
~ 0.03 ktonnes
per hour
~ 245 ktonnes per
year
Non-hazardous[92]
Non-hazardous[93]
Slightly-hazardous
1. May cause an oxygen deprived
atmosphere surrounding the
release area
2. Can be solved with air mixing
before release to reach safe
conditions
1. Scheduled
regeneration once
attrition rates are
severe
2. No release hazards
in storage
1. Scheduled
regeneration once
attrition rates are
severe
2. No release hazards
in storage
41
GROUP 1
Volume 1
8.1 General
The six digit EWC code corresponds to the European Waste Catalogues classification of waste [94]. Six digit codes
that end with * are considered active/hazardous waste and additional steps should be carried out to dispose of it.
This plant would be classified under Section 5: Wastes from Petroleum Refining, Natural Gas Purification and
Pyrolytic Treatment of Coal but spent catalysts would be under Section 16: Wastes not otherwise specified in the list.
Although there is no difference between the 2002 EWC and the current EWC, [95] is the most up to date website. In
relation to regulations in the UK, [96] was used to re-check the EWC classifications and were found to be similar. In
terms of importance (priority), flue gas treatment and release should be discussed followed by solid and liquid waste
treatment options.
8.2 Flue gas treatment and disposal
Following table 8-1, only CO2 and vaporized MEA will be discussed in terms of disposal and treatment. Note that the
MEA has already been pre-treated prior to removal via water present in the cooled stream (26a) and the MEA
released is due to the remaining water present in the stack. MEA is considered hazardous to aquatic life with a
minimum toxicity limit of 33 [mg L-1] with a TWA8 OSHA limit of 6 [mg m-3] [91]. Calculations were completed to
determine the maximum concentration of MEA (~0.14 [g s-1]) downstream using a designed stack height of 80 [m]
(Appendix B: Environmental impact sample calculations). The results show that the maximum concentration lies 200
[m] downstream of the plant with a concentration of 0.09 [mg m-3]. Due to the lack of information regarding MEA
emission rates in flue gas, it is not possible to state whether or not this 0.09 [mg m -3] is above or below allowed
limits. Note that this does not take into account the fact that MEA is highly soluble in water and may condense much
closer to the stack. Should further reduction be required, the stack could be re-designed to periodically inject water
vapor at different heights to ensure that more MEA condenses before reaching the top. Additionally, MEA does not
persist in the environment and trace emissions should be viable so long as the plant is not situated near any large
aquatic bodies.
In Design 1, CO2 is released at a rate of 21.9 kt yr-1. Through the use of MEA carbon capture, the plant is already
using the BAT (Best Available Technique) based on the process selection employed. Although not a hazardous gas,
the European Union Emission Trading Scheme (EU ETS) was put in place to reduce CO2 emissions as a way to combat
climate change due to greenhouse gas effects. Following the reference document provided [97], H2 production has
an allocated 8.85 allowances per tonne of product produced (1 allowance = 1 tonne of CO2 free release). Taking into
account the estimated decrease in free allocation by 2019 [97], this value comes to ~3.27 allowances per tonne
product or ~131476 allowances per year of operation (Appendix B: Environmental impact sample calculations).
However, the plant will only use ~21900 allowances based on the flue gas release and the remainder of that
(~109576 allowances) will be sold on the carbon market. The price per allowance fluctuates greatly and depending
on which side of an argument one takes, it can range from a pessimistic ~5.5 per allowance [98] or an optimistic
~13.3 per allowance [99] in the year 2020. Taking an in-between value of 10, the allowances (if all auctioned) will
net the plant an additional ~1 million a year. Finally, it is worthwhile to note that the UK carbon floor standards
were not taken into account as the EU ETS represents a more stable foundation to base off CO2 release.
In Design 2, no greenhouse gases are released due to the assumptions made regarding nitrogen in the chemical
looping system (negligible NOx). Should this be the case, pure N2 gas will be released to the atmosphere at a rate of ~
245 [kt yr-1]. Although there are no known laws with regards to nitrogen release, this release rate may cause an
oxygen deprived atmosphere surrounding the plant stack which could endanger flight based wildlife. The simplest
option that would allow safer release of the chemical looping flue gas would be to simply feed air through the stack
so that the oxygen levels at the point of release are satisfactory. However, it is worthwhile to consider selling the
pure N2 from the stack but it is beyond the scope of this plant. Additionally, the full ~131476 carbon allowances will
still be allocated to the H2 plant which should net an additional profit of ~1.3 million a year.
Although mentioned in the earlier sections, it was assumed that there is no significant production of NOx for either
design. This was considered valid for Design 1 as the Furnace operates at temperatures (507C) lower than thermal
NOx formation (1600C) and proper composition control for the Furnace inlet gas would reduce the amount of fuel
NOx formed. In addition, chemical looping combustion in Design 2 is inherently a low NOX producer.
42
GROUP 1
Volume 1
43
GROUP 1
Volume 1
Eq. 32
Where Ce is the purchase cost of the equipment, a, b and n are dimensionless numbers, S is a size rating and the
CEPCI numbers refer to the CEPCI index in 2010 and 2018 respectively.
44
GROUP 1
Parameter
ISBL
OSBL
EC
CC
PCI
LF
FCI
WC
TCI
Table 9-1: Calculated steps involved in the estimate of the Total Capital Investment
Value
Definition
Design 1
Design 2
Inside Battery Limits Cost
43.7
28.4
Outside Battery Limits Cost
21.9
14.2
Engineering Costs
13.1
8.51
Contingency Charges
6.56
4.26
Partial Fixed Capital Investment
85.3
55.3
Location Factor
1.02
1.02
Fixed Capital Investment
87.0
56.4
Working Capital
8.70
5.64
Total Capital Investment
95.7
62.1
Unit
M
M
M
M
M
M
M
M
9.4 Estimating the Hydrogen and CO2 revenues, and Natural Gas Annualised Cost
The feed and product flowrates of natural gas, hydrogen and CO2 respectively have been calculated and are
presented in the Table C-2-2 and Table C-3-1 in Appendices C-2 and C-3. In order to calculate the revenues generated
from selling the hydrogen and CO2, a selling price of hydrogen and CO2 must be established. There are a few ways to
approach this problem. One is to consider who the main buyer of the hydrogen is, and agree a price with them. Since
all of the product hydrogen is being sold to chemical companies based in the UK, as stated in the remit, this is how
the price should be established in practice; however, since the chemical companies are not realised, a firm price
would be difficult. Therefore, the other method is to research typical hydrogen selling prices from SMR plants,
compressed liquid CO2 selling prices, and current natural gas prices, in order to get annualised revenues and costs for
product and feedstock. This was the method adopted for both of these designs.
45
GROUP 1
GROUP 1
Design 1
98.6
4.00
25.9
Volume 1
Design 2
98.6
2.90
18.7
Design 1
63.9
Design 2
44.8
Eq. 33
Table 9-6 displays the net profit of the mode price range for both designs.
Design 1
38.7
Design 2
56.8
GROUP 1
Millions of
400
Mode, 2600/te H2
Expected Value, 2360/te
H2
300
200
100
0
0
10
-100
12
14
16
18
20
Year
Figure 9-2: Discounted Cumulative Cash Flow for Design 2 (CLC with Membrane SMR)
500
P10, 3170/te H2
400
Mode, 2600/te H2
Expected Value, 2360/te
H2
Millions of
300
200
100
0
0
-100
10
12
14
16
18
20
Year
Table 9-7: Expected price of H2
Economic indicators
Design 1
Design 2
Fixed Capital (M)
87.0
56.4
Cost of Production (M/year)
63.9
44.8
NPV (M)
141
265
Payback Period (y)
5.5
3.5
DCFRoR
0.25
0.41
Profit to Investment Ratio
1.62
4.69
Details on how each of the parameters were calculated in Table 9-7 are given in Appendix C-6.
48
GROUP 1
Volume 1
GROUP 1
GROUP 1
GROUP 1
52
GROUP 1
53
GROUP 1
Volume 1
Design 2
GROUP 1
GROUP 1
56
GROUP 1
Volume 1
References:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
GROUP 1
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
GROUP 1
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
GROUP 1
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.
108.
109.
110.
111.
112.
113.
114.
60
GROUP 1
Volume 1
GROUP 1
Volume 1
Description
E-101
Gas-Gas exchange
E-601
E-602
Gas-Gas exchange
(Superheated water)
E-603
E-604
E-605
E-505
E-402
E-401
E-201
E-202
Heat transfer
coefficients
[kW m-2 K-1]
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 2
Cold: 2
Overall: 1
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 2
Cold: 2
Overall: 1
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
TLMTD
[K]
91.4
Estimated
duty
[MW]
0.23
Estimated heat
transfer area
[m2]
12.6
10.4
7.74
744
152
3.98
131
526
20.0
126
255
7.47
97
656
4.13
21.0
50
1.02
70.0
50
73.8
1476
50
105
7000
50
7.08
472
50
2.24
149
62
GROUP 1
Volume 1
63
GROUP 1
Volume 1
Description
Gas-Gas exchange
E-202
Gas-Gas exchange
E-607
Gas-Gas exchange
E-610
Gas-Gas exchange
E-605
E-207
E-611
E-608
Gas-Gas exchange
Heat transfer
coefficients
[kW m-2 K-1]
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 0.4
Overall: 0.2
TLMTD
[K]
4.45
Estimated
duty
[MW]
0.97
Estimated heat
transfer area
[m2]
1090
13.6
0.20
73.5
69.4
2.35
169
14.3
13.3
4650
55
2.307
140
302
0.946
10.4
38.8
7.17
615
21.4
3.77
880
64
GROUP 1
E-612
E-606
E-609
Volume 1
6.89
137.8
0.83
16.6
0.63
42
65
GROUP 1
Heat
exchanger
(Below pinch)
E-101
Description
Gas-Gas exchange
E-601
Liquid-liquid exchange
E-602
Gas-liquid exchange
E-603
Gas-liquid exchange
E-604
Gas-Gas exchange
E-301
E-204
E-208
E-205
Gas,Liquid-Cooling water
exchange with phase change
E-206
Heat transfer
coefficients
[kW m-2 K-1]
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 2
Cold: 2
Overall: 1
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 0.4
Cold: 0.4
Overall: 0.2
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 2
Cold: 2
Overall: 1
Hot: 0.4
Cold: 2
Overall: 0.3
Hot: 2
Cold: 2
Overall: 1
Hot: 2
Cold: 2
Overall: 1
TLMTD
[K]
Volume 1
95.4
Estimated
duty
[MW]
0.18
Estimated heat
transfer area
[m2]
9.43
0.78
5.64
7230
40.1
1.06
88.1
3.4
0.29
284
21.6
6.77
1567
50
0.75
50
50
11.1
222
50
0.96
64
50
112.8
2256
50
19.4
388
66
GROUP 1
Volume 1
(, , ) =
B-1
Where c is the concentration in [g m-3], Q is the component release rate [g s-1], u is the wind speed [m s-1], H is the
stack height [m]. y is the concentration variation, z is the vertical coordinate [m] and x is the horizontal distance [m].
Only the maximum ground level concentration needs to be calculated. Therefore, y = 0 for maximum concentration
and z = 0 for ground level conditions. Furthermore, at an elevated source (stack height) of 50 [m] or more:
= = 0.0707
B-2
The overall equation for elevated continuous point source release simplifies to:
(, , ) =
2(0.05
(
( .
( )
.
( .
B-3
Therefore, the maximum concentration at ground level as a function of distance away from the source at a release
rate of 0.49 [kg h-1] or 136111 [g s-1], designed stack height of 80 [m] and a conservative wind speed of 5 [m s-1]
[112]is:
Table B-1:
X [m]
10
50
100
200
300
400
500
1000
C [g m-3]
C [mg m-3]
0.04047
0.029018 0.009393
5
8000 0.3714 131476
B-4
67
GROUP 1
Volume 1
Figure C-1-3: Costing Plates in Columns (1 = Sieve plate, 2= valve caps, 3= bubble caps)
68
GROUP 1
Volume 1
650
= 66,500
440
C-1-1
C-1-2
The installation cost of the equipment was then calculated by multiplying the purchase cost by the relevant Wroth
factor. For tanks, the Wroth factor is 3.5.
= 66,500 3.5 = 233,000
C-1-3
As for the purchase cost of heat exchangers, pumps and compressors; the method employed was the same for all.
Either the volumetric flowrate (pump), power requirement (compressor) or heat exchange area (HX) were used in
the equation as the parameter S:
= +
C-1-4
Where a, b and n change depending on the application. If the sizing parameter S was above the upper limit described
in the six tenths rule was used to scale up the cost of the item. The six tenths rule can be found from a wide variety
of literature and is thus:
=
C-1-5
Where C1 and S1 are the cost and size of equipment item 1 respectively, and C2 and S2 are the cost and size of
equipment item 2 respectively. N is 0.6 to represent that the cost of items generally dont scale up linearly; hence
being dubbed the six tenths rule.
The sum of the installation cost of every piece of process equipment is the Inside Battery Limits Cost. For brevity, this
is not shown. Table C-1 shows the steps required to calculate the Total Capital Cost.
Table C-1: Total Capital Cost Estimate
Variable
ISBL
OSBL (50 % of the ISBL)
Engineering Costs (20% of ISBL + OSBL)
Contingency (10% of ISBL + OSBL)
Partial Fixed Capital Investment
Location Factor [UK]
Fixed Capital Investment (FCI)
Working Capital (10 % FCI)
Total Capital (FCI + WC)
The annualised fixed capital investment (AFCI) payable to the investor for providing the capital investment is given
by equation (X). A =n I = 5% interest rate was used, payable over the n = 20 year lifetime of the project. For Design 1:
=
(1 + )
(1 + ) 1
C-1-6
69
GROUP 1
Volume 1
C-1-7
For Design 2, under the same loan conditions, the AFCI was found to be 4.53 million.
=
= 2.08 0.0325 3600 8000
= 1.95
C-2-1
Summing up the annual operating cost of the major process equipment gives the annual equipment cost portion of
the variable costs; the other portion regards the quantity of natural gas feed taken into the process. Table C-2-1
gives the Total Annual Operating Cost of the plant:
Table C-2-1: Total Annual Operating Cost of the Plant
Annual Operating Cost (M/year)
Table C-2-2 gives the flowrates of natural gas for the two designs, and the estimated price of natural gas for the
project duration. The annual cost of the gas is simply calculated by multiplying the two together. It should be noted
that 100 % operating capacity was assumed whenever the plant is running.
Table C-2-2: Natural Gas Consumption of the Two Designs
Natural Gas Consumed (tonne/year)
Cost of Natural Gas (/tonne)
Annual Cost of Feed Gas (M/year)
Table C-2-3 Total Variable Costs (Annual Operating Cost + Cost of Feed Gas)
Annual Variable Costs (/year)
70
GROUP 1
Volume 1
Variable Costs
Operating Labour (0.02 *
FCI)
Supervision (0.2 * Operating
Labour)
Maintenance (0.05 * FCI)
Supply (0.15 * Maintenance)
Laboratory (0.15 * Operating
Labour)
Fixed Manufacturing
Taxes and Insurance (0.03 *
FCI)
Overheads (0.6*(Operating Labour + Supervision +
Maintenance))
General Expenses
Admin (0.15*(OL + M + S))
Distribution and Selling
R&D
Annualised Capital
Total Cost of Production
0.348
0.226
4.35
0.652
0.261
2.82
0.423
0.169
2.61
1.69
3.86
2.50
0.966
2.00
1.00
6.96
63.9
0.626
2.00
1.00
4.51
44.7
2360
C-3-1
71
GROUP 1
=
Table C-4-1: Annual Profits of the Two Proposed Plants
Variable
Net Profit (/year)
Design 1
Design 2
Year
0
1
2
3
4
5
6
7
8
Book Value
Depreciation []
86,995,611
78,296,050
70,466,445
63,419,800
57,077,820
51,370,038
46,233,034
41,609,731
37,448,758
0
8,699,561.07
7,829,604.96
7,046,644.46
6,341,980.02
5,707,782.02
5,137,003.81
4,623,303.43
4,160,973.09
33,703,882
3,744,875.78
10
11
12
13
14
15
30,333,494
27,300,144
24,570,130
22,113,117
19,901,805
17,911,625
3,370,388.20
3,033,349.38
2,730,014.44
2,457,013.00
2,211,311.70
1,990,180.53
16
16,120,462
1,791,162.48
17
14,508,416
1,612,046.23
18
13,057,574
1,450,841.61
19
11,751,817
1,305,757.45
20
10,576,635
1,175,181.70
Total
76,418,975
Year
Book Value
Depreciation []
0
1
2
3
4
5
6
7
8
56,426,085
40,062,520
28,444,390
20,195,517
14,338,817
10,180,560
7,228,198
5,132,020
3,643,734
0
16,363,564.70
11,618,130.94
8,248,872.97
5,856,699.81
4,158,256.86
2,952,362.37
2,096,177.28
1,488,285.87
9
10
11
12
13
14
15
2,587,051
1,836,806
1,304,133
925,934
657,413
466,763
331,402
1,056,682.97
750,244.91
532,673.88
378,198.46
268,520.91
190,649.84
135,361.39
16
235,295
96,106.59
17
167,060
68,235.68
18
118,612
48,447.33
19
20
84,215
59,793
34,397.60
24,422.30
Total
56,366,293
72
GROUP 1
Volume 1
C-5-1
= 1,2,3 20
Dk is the depreciation in year k; Fd = 2/N where N is the project lifetime, so in this case Fd = 2/20 = 0.1; FCI is the fixed
capital investment and the sum of Dj means the sum of the depreciations in previous years.
Gross
Profit
-8.70
-17.40
-26.10
-26.10
-9
23
38.04
38.04
38.04
38.04
38.04
Depreciation
Charge
0
0
0
0
0
8.70
7.83
7.05
6.34
5.71
5.14
Taxable
Income
0
0
0
0
0
0
30
31
32
32
33
Taxes
Paid
0
0
0
0
0
0
0
11
11
11
11
Cash
Flow
-9
-17
-26
-26
-9
23
38
27
27
27
27
9
10
11
12
13
14
15
16
17
18
19
20
38.04
38.04
38.04
38.04
38.04
38.04
38.04
38.04
38.04
38.04
38.04
38.04
4.62
4.16
3.74
3.37
3.03
2.73
2.46
2.21
1.99
1.79
1.61
1.45
33
34
34
35
35
35
36
36
36
36
36
37
12
12
12
12
12
12
12
12
13
13
13
13
27
26
26
26
26
26
26
26
25
25
25
25
Discount
Factor
1.00
0.96
0.93
0.89
0.86
0.79
0.74
0.68
0.63
0.58
0.54
0.50
0.46
0.43
0.40
0.37
0.34
0.32
0.29
0.27
0.25
0.23
0.21
Present Value
of CF
-9
-17
-24
-23
-7
18
28
19
17
16
14
Cum. CF
[]
-9
-25
-50
-73
-80
-62
-34
-16
2
17
32
13
12
11
10
10
9
8
7
7
6
6
5
45
57
68
79
88
97
105
113
120
126
132
137
73
GROUP 1
Volume 1
Gross
Profit
-5.64
-11.29
-16.93
-16.93
-6
34
56.29
56.29
56.29
56.29
56.29
Depreciation
Charge
0
0
0
0
0
16.36
11.62
8.25
5.86
4.16
2.95
Taxable
Income
0
0
0
0
0
0
45
48
50
52
53
Taxes
Paid
0
0
0
0
0
0
0
16
17
18
18
Cash
Flow
-6
-11
-17
-17
-6
34
56
41
39
39
38
9
10
11
12
13
14
15
16
17
18
19
20
56.29
56.29
56.29
56.29
56.29
56.29
56.29
56.29
56.29
56.29
56.29
56.29
2.10
1.49
1.06
0.75
0.53
0.38
0.27
0.19
0.14
0.10
0.07
0.05
54
55
55
56
56
56
56
56
56
56
56
56
19
19
19
19
19
20
20
20
20
20
20
20
38
37
37
37
37
37
37
37
37
37
37
37
Discount
Factor
1.00
0.96
0.93
0.89
0.86
0.79
0.74
0.68
0.63
0.58
0.54
0.50
0.46
0.43
0.40
0.37
0.34
0.32
0.29
0.27
0.25
0.23
0.21
Present Value
of CF
-6
-11
-16
-15
-5
27
41
28
25
23
21
Cumulativ
e CF
-6
-17
-32
-47
-52
-25
16
44
69
91
112
19
17
16
15
14
13
12
11
10
9
8
8
131
148
164
178
192
205
216
227
237
246
254
262
An explanation of the table shall be provided here. It is assumed for the first two years of the project, the equipment
is being bought and installed; this phase is where capital is being spent and no revenue is being made. Production
begins in year 2, at which point depreciation of the equipment begins. It is predicted the plant starts to make profit
in year 3; this first year is tax-free. Henceforth, taxation occurs at 35 % of (profit-depreciation). The cash flow is equal
to the gross profit for the year minus the taxes paid for the year. The discount factor is a complicated expression
which allows the cash flow in year x to be converted to the value of the money at the start of the project, in 2018.
The discount factor can be expressed as:
=
1
(1 + )
C-6-1
i is the interest rate and it takes into account the rate of return on the loan the investors gave to Costain; it has been
assigned a high value of 10% for this economic analysis as a test for the economic performance of the plant.
However, inflation must also be accounted for; the general trend obtained from the CEPCI chart was that inflation is
increasing every year at approximately 2% per annum; thus i is amended by 0.1 0.02 = 0.08. So the final settled
value for i was 0.08.
74
GROUP 1
Figure C-6-1: CEPCI chart used in the calculation of inflation rates. 2018 was estimated to be 650.
75
GROUP 1
Volume 1
Part Of Process
Name
0.063
774
1,548
E-101
60.320
1,524
4.8
7,314
T-101
SulfaTreat Beds
2.5 x 6
169,127
676,508
R-201
Pre-Reformer
1.9x6.65
19,600
78,400
R-202
2x12
1,677,000
6,708,000
1.4 x 3.08
23,524
94,096
1.4 x 4
31,040
124,161
5 x 10
280,583
3.5
982,042
Estimated
50,000
3.5
175,000
E-201
SMR Reactor
High Temp WGS
Reactor
Low Temp WGS
Reactor
Steam Drum
Water KnockOut Drum
Gas Cooler
350
6,251
4.8
30,005
E-202
BFW Heater
250
5,108
4.8
24,520
E-203
20
1,122
4.8
5,387
1000
11,736
4.8
56,332
E-205
12 m high
4,576,696
4.8
21,968,138
E-206
Backup Heater
50.000
1,945
4.8
9,336
P-201
Gas Expander
Unsized
negligible
N/A
P-202
Pump
100
18,479
129,350
R-203
R-204
V-201
V-202
SMR + WGS
Backup Feed
Compressor
Feed Heater
P-101
Desulphurisation
Description
E-204
76
GROUP 1
PSA
P-203
Pump
T-301
PSA Towers
Absorption
Column
Stripping
Column
Stack
Water-Gas
Separator
Surge Drum
T-401
T-402
T-403
V-401
V-402
V-403
E-401
Carbon Capture
E-402
E-403
E-404
E-405
P-401
P-402
P-403
P-404
V-501
CO2
Compression
V-502
E-501
E-502
Reflux Drum
First Furnace
Gas Cooler
Second Furnace
Gas Cooler
Reboiler
Rich/Lean
Exchanger
Flue Gas Cooler
Flue
Compressor
First Lean Pump
Second Lean
Pump
Reflux Pump
Water KnockOut Drum
CO2 Hold-Up
Tank
Stripper Gas
Cooler
Backup Water
Volume 1
1,254
8,779
2.5 x 6
904,283
3,617,132
4.8 x 20.8
665,500
2,662,000
0.5 x 7.2
18,010
72,040
1,000,000
2,000,000
Estimated
50,000
3.5
175,000
5 x 13
148,000
3.5
518,000
Estimated
50,000
3.5
175,000
Estimated
50,000
4.8
240,000
1464.000
14,752
4.8
70,808
Estimated
250,000
4.8
1,200,000
60.000
2,170
4.8
10,415
8000.000
40,867
4.8
196,161
5.678
16,465
32,929
68
13,086
91,601
68
26,172
183,201
57
22,290
156,029
Estimated
50,000
3.5
175,000
4 x 11
75,000
3.5
262,500
Estimated
150,000
4.8
720,000
2.000
282
4.8
1,353
77
GROUP 1
Volume 1
Heater
E-503
Cooler #1
3.164
290
4.8
1,394
E-504
Cooler #2
3.407
315
4.8
1,511
E-505
Cooler #3
7.050
714
4.8
3,428
P-501
Compressor #1
9,018
18,036
P-502
Compressor #2
2.082
2.093
9,047
18,094
P-503
Compressor #3
1.209
Liquid CO2
14.219
Pump
TOTAL Inside Battery Limits Costs
6,509
13,018
6,400
44,800
P-504
10,454,932
43,738,366
Part Of Process
Name
P-101
Desulphurisation
E-101
T-101
R-201
R-202
R-202a
R-203
V-201
Description
Backup Feed
Compressor
Feed Heater
SulfaTreat Beds
Pre-Reformer
Fuel Reactor
SMR in Fuel
Raeactor
Air Reactor
Water
Condenser
V, T, R: Dimensions [D x L] in m. E: Heat
Transfer Area in m^2. Compressor: Power
Rating in MW. Pump: Flowrate in l/s
0.063
774
1,548
60.320
2.5 x 6
1.9x6.65
2.9 x 9.8
1
2
1
1
2,177
101,430
19,600
31,500
4.8
4
4
4
10,448
405,720
78,400
126,000
2x9.8
6,380,000
25,520,000
3.1 x 10
37,100
148,400
Estimated
50,000
3.5
175,000
78
GROUP 1
E-301
Water
Condenser
Pre-Reformer
Heater
Pre-SMR Heater
Fuel Reactor
Pre-Heater
CLC Flue Gas
Cooler
Membrane
Cooler
Membrane Flue
Gas Cooler
Compressed Air
Cooler
Make Up Gas
Expander
Make Up Air
Compressor
Cyclone
Water
Condenser
CO2 Hold-Up
Tank
CO2 Condenser
P-301
CO2 Compressor
0.77
4,965
9,930
P-302
CO2 Pump
14
6,311
44,180
28
7,088,300
V-202
E-201
E-202
E-203
E-204
E-205
E-206
E-207
P-201
P-202
C-201
V-301
Product Separation
and Compression
Volume 1
V-302
Estimated
50,000
3.5
175,000
Estimated
50,000
4.8
240,000
Estimated
20,000
4.8
96,000
Estimated
100,000
4.8
480,000
720
9,636
4.8
46,255
2400
19,845
4.8
95,254
720
9,636
4.8
46,255
27
1,344
4.8
6,450
Estimated
10,000
20,000
2.077
9,005
18,010
Estimated
2,000
12,000
Estimated
100,000
3.5
350,000
4x9
66,204
3.5
231,713
400
6,773
4.8
32,508
28,369,072
79
GROUP 1
Volume 1
MW
1.04x10-7
5.70x10-2
5.70x10-2
MW
0
Overall
0 MW
Overall percentage error
0%
The table above contains the inlet and outlet energy streams, plus the energy generated by equipment in the
Desulphurisation section.
Table D-2: Furnace
Stream Energy Balance
MW
Energy out
MW
-2
3.7 x10
4a
4.49
1.49 x101
7a
4.40 x101
4.40 x101
8
4.99 x101
-5.47 x10-1
16
3.30 x101
1
5.839 x10
Total
1.314 x102
Equipment Energy Balance
Energy in
MW
Energy out
MW
Heat produced by
Heat lost to the
1.19 x102
-2.38 x101
furnace
surroundings
Heat generated by reactions
Pre-reformer
2.67 x10-1 MW
SMR
5.83 MW
Overall Balance
Overall
-2.21 x101 MW
Overall percentage error
-12.5%
The table above contains the inlet and outlet energy streams, plus the energy generated by reactions and equipment
in the Furnace section.
Energy in
4
7
7a
15
Total
80
GROUP 1
Volume 1
Energy in
8
Total
Energy in
HWGS
LWGS
MW
2.06 x10-1
2.06 x10-1
MW
-3.34 x101
-1.15 x101
-1.13 x101
4.38
2.18
Overall Balance
Overall
0 MW
Overall percentage error
0%
The table above contains the inlet and outlet energy streams, plus the energy generated by reactions and equipment
in the water gas shift section.
Table D-4: PSA
Stream Energy Balance
MW
Energy out
-1
1.57 x10
12
13
1.57 x10-1
Total
Overall Balance
Energy in
11
Total
MW
1.04 x10-1
5.30 x10-2
1.57 x10-1
Overall
0 MW
Overall percentage error
0%
The table above contains the inlet and outlet energy streams in the PSA section.
Table D-5: Summary of Energy Balance Errors in Design 1
Unit
Desulphurisation
0.00
Furnace
12.5
WGS
0.00
PSA
0.00
OVERALL
12.5
The table above contains the error in the energy balance for each section
GROUP 1
= ( )
D-1-2
Method 2
The energy balance for the rest of Design 1 and Design 2 (bar MEA) was calculated with:
D-1-3
Method 2
Percentage error
Preheat PR (Stream 4a
Stream 4)
2.78 MW
4.45 MW
37.5 %
1.91 x101 MW
2.91 x101 MW
34.3 %
2.58 x101 MW
3.30 x101 MW
21.8 %
Total
4.77 x101 MW
6.66 x101 MW
28.4 %
1.89 x101 MW
Difference
283 + 11.974 10
283 + 1.132 10
283 = 34.71
Converting to Watts
82
GROUP 1
Volume 1
298.01 + 10.55 10
298.01 + 3.596 10
298.01 = 33.66
Converting to Watts
= 2.00 10
1000
= 5.56 10
3600
The value obtained is for the vapour phase of the water, thus to obtain the total enthalpy the latent heat of water
were added. At 303K the value for the latent heat capacity of water is 39628.8 J/molK
= 5.56 10 + 39628.8 5950
1000
= 6.55 10
3600
3.1 Design 1
Overall Mass Balance
=
D-1-5
kg
= 2.25 10 220 10 = 4.82 10
2.25 10 220 10
100 =
100 = 2.19%
220 10
= ++
= (
D-1-6
+ + )
D-1-7
83
GROUP 1
Volume 1
3.2 Design 2
Overall Mass Balance
Equation D-1-5 was again used.
= = 1.97 10 1.99 10 = 1.92 10
kg
1.97 10 1.99 10
100 =
100 = 0.97%
1.99 10
+ + )
1.23
100 = 2.03 %
3.93 10 + 2.12 10
84
GROUP 1
Volume 1
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
MEA
Temperature (K)
Component | Stream No.
Pressure (bar)
Total
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
1
1.46x104
2.63 x103
1.16x103
2.52 x102
1.26 x102
7.48 x101
8.93 x101
2
9.54 x10
2.90 x102
0
0
-1
1 x10
0
0
0
283
33
2.02 x104
8
2
2.75 x10
0
0
0
1a
1.46x104
2.63 x103
1.16x103
2.52 x102
1.26 x102
7.48 x101
8.93 x101
2
9.54 x10
2.90 x102
0
0
-1
1 x10
0
0
0
283
33
2.02 x104
8a
2
2.75 x10
0
0
0
1b
1.46x104
2.63 x103
1.16x103
2.52 x102
1.26 x102
7.48 x101
8.93 x101
2
9.54 x10
2.90 x102
0
0
-1
1 x10
0
0
0
303
33
2.02 x104
9
2
2.75 x10
0
0
0
2
1.46x104
2.63 x103
1.16x103
2.52 x102
1.26 x102
7.48 x101
8.93 x101
2
9.54 x10
2.90 x102
0
0
-1
1 x10
0
0
0
303
33
2.02 x104
9b
2
2.75 x10
0
0
0
3
1.46x104
2.63 x103
1.16x103
2.52 x102
1.26 x102
7.48 x101
8.93 x101
2
9.54 x10
2.90 x102
0
0
-1
1 x10
0
0
0
303
32.93
2.02 x104
10
2
2.75 x10
0
0
0
5a
9.47x103
1.71 x103
7.50 x102
1.65 x102
8.24 x101
4.77 x101
5.7 x101
2
6.24 x10
1.85 x102
3
5.37 x10
0
0
6
1.19 x104
0
0
0
0
0
0
3
2.17 x10
1.85 x102
3
4.10 x10
1
1.97 x10
0
7
1.19 x104
0
0
0
0
0
0
3
2.17 x10
1.85 x102
3
4.10 x10
1
1.97 x10
0
7a
1.19 x104
0
0
0
0
0
0
3
2.17 x10
1.85 x102
3
4.10 x10
1
1.97 x10
0
0
0
0
303
32.93
1.31x104
10a
2
2.75 x10
0
0
0
0
0
0
673
32.93
1.85x104
13
2
2.75 x10
0
0
0
6.62 x10
0
0
688
30
1.85x104
14
2
2.75 x10
0
0
0
6.62 x10
0
0
688
30
5.86 x104
15
3
5.42 x10
9.25 x102
4.13 x102
8.72 x101
6.62 x10
0
0
1223
30
5.86 x104
16
0
0
0
0
0
0
0
303
32.93
1.31x104
11
2
2.75 x10
0
0
0
0
0
0
673
32.93
1.85x104
12
0
0
0
0
85
GROUP 1
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
MEA
Temperature (K)
Pressure (bar)
Total
0
0
0
8.76 x103
1.85 x102
4
2.85 x10
1.62 x104
0
0
0
0
8.76 x103
1.85 x102
4
2.85 x10
1.62 x104
0
0
0
0
2.44 x104
1.85 x102
4
2.21 x10
6.19 x103
0
4.76 x103
0
0
1295
29.88
5.86x104
4.76 x103
0
0
675
29.78
5.86x104
5.48 x103
0
0
757
29.3
5.86x104
5.48 x103
0
0
513
29.1
5.86x104
16a
0
0
0
0
0
0
0
5.39 x104
1.19 x105
4
2.02 x10
0
0
0
17
0
0
0
0
0
0
0
5.39 x104
1.19 x105
3
8.0 x10
0
0
0
17a
0
0
0
0
0
0
0
5.39 x104
1.19 x105
3
8.0 x10
0
0
0
17b
0
0
0
0
0
0
0
5.39 x104
1.19 x105
3
8.0 x10
0
0
0
5.84 x103
0
0
558.1
28.4
5.86x104
5.84 x103
0
0
303
25
5.86x104
5.84 x103
0
0
303
25
3.98x104
Volume 1
5.23x103
0
0
303
25
5.23x103
0
0
0
3.23 x104
1.85 x102
0
1.18 x103
0
0
0
0
3.23 x104
1.19 x105
0
1.18 x103
0
4.36 x101
1
2.71 x10
3.23 x101
3.26 x104
1.19 x105
0
1.18 x103
0
0
0
0
5.39 x104
1.19 x105
4
2.02 x10
0
0
6.1 x102
0
0
303
1
3.46 x104
6.1 x102
3.6 x104
0
303
1
1.89 x105
6.1 x102
3.6 x104
0
288.55
1
1.96 x105
0
3.27 x103
0
787.17
1
1.96 x105
20
0
0
0
0
0
0
0
5.16 x104
6.32
5
5.69 x10
0
0
0
21
0
0
0
0
0
0
0
5.12
0
5
1.96 x10
0
0
0
21a
0
0
0
0
0
0
0
5.12
0
5
1.96 x10
0
0
0
22
0
0
0
0
0
0
0
3.30 x104
0
5
5.82 x10
0
0
0
86
GROUP 1
Oxygen, O2
MEA
Temperature (K)
Pressure (bar)
Total
Component | Stream No.
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide, H2S
Hydrogen , H2
Oxygen, O2
MEA
Temperature (K)
Pressure (bar)
Total
3.27 x103
0
313
1
1.96 x105
23
0
0
0
0
0
0
0
4
2.23 x10
0
5.38 x105
0
0
0
0
1.88 x105
393
1
7.48 x105
3.27 x103
0
313
1
1.84 x105
24
0
0
0
0
0
0
0
4
1.07 x10
0
4.35 x104
0
0
0
0
1.83 x105
393
1
2.37 x105
3.27 x103
0
381
3.1
1.84 x105
24a
0
0
0
0
0
0
0
4
1.07 x10
0
4.35 x104
0
0
0
0
1.83 x105
364
1
2.37 x105
28a
0
0
0
0
0
0
0
29
0
0
0
0
0
0
0
29a
0
0
0
0
0
0
0
Volume 1
0
3
2.08 x10
371
1
6.23 x105
26
0
0
0
0
0
0
0
3
2.74x10
5
1.19 x10
1.88 x104
0
0
0
3
3.28 x10
3.13 x102
343
1.5
1.44 x105
0
3
1.85 x10
371
1
1.99 x105
26a
0
0
0
0
0
0
0
3
2.74x10
5
1.19 x10
1.88 x104
0
0
0
3
3.28 x10
3.13 x102
298
1
1.44 x105
0
3
1.85 x10
371
1
1.99 x105
27
0
0
0
0
0
0
0
3
2.74x10
5
1.19 x10
1.72 x103
0
0
0
3
3.28 x10
4.9 x10-1
298
1
1.27 x105
0
5
3.71 x10
376
1
9.85 x105
28
0
0
0
0
0
0
0
4
5.146 x10
6.29
3.7 x105
0
0
0
0
2.23 x102
371
1
4.22 x105
29f
0
0
0
0
0
0
0
29g
0
0
0
0
0
0
0
30
0
0
0
0
0
0
0
U1
0
0
0
0
0
0
0
87
GROUP 1
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide, H2S
Hydrogen , H2
Oxygen, O2
MEA
Temperature (K)
#Pressure (bar)
Total
Component | Stream No.
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide, H2S
Hydrogen , H2
Oxygen, O2
MEA
Temperature (K)
Pressure (bar)
Total
5.15 x104
6.29
3.7 x105
0
0
0
0
2
2.23 x10
298
1
5
4.22 x10
U2
0
0
0
0
0
0
0
0
0
0
0
-1
1 x10
0
0
0
303
33
1 x10-1
5.15 x104
6.29
0
0
0
0
0
0
298
1
4
5.15 x10
U3
0
0
0
0
0
0
0
0
0
3
5.37 x10
0
0
0
0
0
673
32.93
5.37 x103
5.15 x104
6.29
0
0
0
0
0
0
468
5
4
5.15 x10
U4
0
0
0
0
0
0
0
0
0
4
4.02 x10
0
0
0
0
0
688
30
4.02 x104
Volume 1
5.15 x104
6.29
0
0
0
0
0
0
293
70
4
5.15 x10
U8
0
0
0
0
0
0
0
0
0
4
1.22 x10
0
0
0
0
0
313.15
3.1
1.22 x104
5.15 x104
6.29
0
0
0
0
0
0
293
70
4
5.15 x10
U9
0
0
0
0
0
0
0
0
0
3
5.5 x10
0
0
0
0
0
313.15
3.1
5.52 x103
5.15 x104
6.29
0
0
0
0
0
0
293
71
4
5.15 x10
R1
0
0
0
0
0
0
0
5.18 x102
0
5
3.7 x10
0
0
0
0
2
2.23 x10
298
1
3.7 x105
0
0
0
0
0
0
0
0
303
33
0.00
R1a
0
0
0
0
0
0
0
5.18 x102
0
5
3.7 x10
0
0
0
0
2
2.23 x10
313
1
3.7 x105
88
GROUP 1
Volume 1
89
GROUP 1
Volume 1
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Temperature (K)
Pressure (bar)
Total
1
1.06 x104
1.90 x103
8.38 x102
2
1.86 x10
9.30 x101
5.10 x101
1
6.00 x10
6.95 x102
2
2.07 x10
0
1a
1.06 x104
1.90 x103
8.38 x102
2
1.86 x10
9.30 x101
5.10 x101
1
6.00 x10
6.95 x102
2
2.07 x10
0
1b
1.06 x104
1.90 x103
8.38 x102
2
1.86 x10
9.30 x101
5.10 x101
1
6.00 x10
6.95 x102
2
2.07 x10
0
2
1.06 x104
1.90 x103
8.38 x102
2
1.86 x10
9.30 x101
5.10 x101
1
6.00 x10
6.95 x102
2
2.07 x10
0
3
1.06 x104
1.90 x103
8.38 x102
2
1.84 x10
9.20 x101
5.30 x101
1
6.40 x10
6.96 x102
2
2.07 x10
0
1.80 x10
0
0
0
0
0
283
33
1.46 x104
8a
0
0
0
0
0
0
0
0
0
303
33
1.46 x104
9
0
0
0
0
0
0
0
0
0
303
32.9
1.46 x104
10
0
0
0
0
0
0
0
0
0
303.00
32.93
1.46x104
11
2.82 x102
0
0
0
0
0
0
0
0
303
32.93
1.18x104
11a
2.82 x102
0
0
0
0
0
0
0
0
673
32.83
1.18x104
12
2.82 x102
0
0
0
0
0
0
0
0
673
32.93
1.66x104
13
0
0
0
0
0
6 x101
0
0
0
688
25
1.66x104
14
2.23 x103
3.69 x102
2
1.63 x10
3.50 x101
0
0
0
0
0
283
33
1.46 x104
Component | Stream No. 8
Methane, CH4
0
Ethane, C2H6
0
Propane, C3H8
0
n-Butane, C4H10
0
6
10734
0
0
0
0
0
0
1.95 x103
2
1.67 x10
3.69 x103
1
6a
10734
0
0
0
0
0
0
1.95 x103
2
1.67 x10
3.69 x103
6b
10734
0
0
0
0
0
0
1.95 x103
2
1.67 x10
3.69 x103
1.80 x10
0
6 x101
0
0
0
672.6
25
1.66x104
14a
2.23 x103
3.69 x102
2
1.63 x10
3.50 x101
0
6 x101
0
0
0
773
25
1.66x104
15
0
0
0
0
1.80 x10
7
10734
0
0
0
0
0
0
1.95 x103
2
1.67 x10
3.38 x104
1.80 x10
0
6 x101
0
0
0
773
25
4.67x104
15a
0
0
0
0
90
GROUP 1
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Temperature (K)
Pressure (bar)
Total
0
0
0
0
0
1.07 x105
0
0
0
0
0
1.07 x105
0
0
0
0
0
0
2.1 x10
0
3
5.23 x10
0
0
0
771
2
1.12 x105
0
3
5.23 x10
0
0
0
298.01
1.9
1.12 x105
0
3
5.23 x10
0
0
0
298
1.9
5.23x103
0
0
0
0
0
298
1.9
1.07 x105
0
1
6.6 x10
0
0
0
771.4
24.995
4.15 x104
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
0
0
0
0
0
0
0
4
3.71 x10
2.07 x102
0
0
16a
0
0
0
0
0
0
0
4
3.71 x10
2.07 x102
0
0
16b
0
0
0
0
0
0
0
4
3.71 x10
2.07 x102
0
0
16c
0
0
0
0
0
0
0
4
3.71 x10
2.07 x102
0
0
2.1 x10
0
1
6.6 x10
0
0
0
298.01
24.97
4.15 x104
2.1 x10
0
1
6.6 x10
0
0
0
298.01
24.97
3.1 x104
Volume 1
0
0
0
0
0
1.05 x104
1.80 x101
1
1.00 x10
1
1.20 x10
3.05 x104
2
2.07 x10
0
2.1 x10
0
0
0
0
0
298
24.97
1.05x104
0
1
6.6 x10
0
0
0
296.53
25
3.39 x104
20
0
0
0
0
0
0
0
0
3.07 x104
0
0
1.80 x101
1
1.00 x10
1
1.20 x10
3.05 x104
2
2.07 x10
0
2.1 x10
0
1
6.6 x10
0
0
0
773.15
25
3.39 x104
21
0
0
0
0
0
0
0
0
3.07 x104
0
0
0
0
0
3.71 x104
2
2.07 x10
5.78 x103
0
0
0
3.71 x104
2
2.07 x10
5.78 x103
0
0
0
0
0
773
24.78
4.31 x104
0
0
0
0
0
298.01
24.68
4.31 x104
21a
0
0
0
0
0
0
0
0
3.07 x104
0
0
22
0
0
0
0
0
0
0
0
0
0
0
91
GROUP 1
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Temperature (K)
Pressure (bar)
Total
0
0
0
0
0
298
25
3.73 x104
Component | Stream No. U1
Methane, CH4
0
Ethane, C2H6
0
Propane, C3H8
0
n-Butane, C4H10
0
i-Butane, C4H10
0
n-Pentane, C5H12
0
n-Hexane, C6H14
0
Carbon Dioxide, CO2 0
Nitrogen, N2
0
Water, H2O
0
Carbon Monoxide, CO 0
Hydrogen Sulphide,
H2S
0
Hydrogen , H2
0
Oxygen, O2
0
Nickel Oxide
0
Nickel
0
Temperature (K)
303
Pressure (bar)
33
Total
0
Volume 1
0
0
0
0
0
398
70
3.73 x104
U2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
298
70
3.73 x104
U3
0
0
0
0
0
0
0
0
0
3
4.83 x10
0
0
0
0
0
0
298
70
3.73 x104
U4
0
0
0
0
0
0
0
0
0
4
3.01 x10
0
0
0
0
0
0
317.55
150
3.73 x104
U5
3
2.05 x10
2
3.69 x10
1.63 x101
3.5 x101
1.8 x101
1
1 x10
1.2 x101
1.34 x102
4.1 x101
0
0
0
0
0
0
0
298
25
5.78x103
U6
3
2.05 x10
2
3.69 x10
1.63 x101
3.5 x101
1.8 x101
1
1 x10
1.2 x101
1.34 x102
4.1 x101
0
0
0
0
0
0
3.06 x104
773
25
3.06 x104
U7
0
0
0
0
0
0
0
0
3.07 x104
0
0
0
0
0
3.9 x104
0
773
25
6.96 x104
U8
0
0
0
0
0
0
0
0
3.07 x104
0
0
0
0
0
0
0
773
25
3.07 x104
U9
0
0
0
0
0
0
0
0
3.07 x104
0
0
0
0
0
0
0
298
24.9
3.07 x104
U10
0
0
0
0
0
0
0
0
0
5
1.07 x10
0
7 x10-2
0
0
0
0
303
32.83
7.00 x10-2
0
0
0
0
0
673
32.93
4.83 x103
0
0
0
0
0
773
25
3.01 x104
0
0
0
0
0
303
32.93
2.84 x103
0
0
0
0
0
287.75
25
2.84 x103
0
0
9.31 x103
0
0
283
1
4.00 x104
0
0
9.31 x103
0
0
849.8
25
4.00 x104
0
0
9.31 x103
0
0
773
25
4.00 x104
0
0
0
0
0
773
2
1.07 x105
0
0
0
3.9 x104
0
773
25
3.90 x104
92
GROUP 1
Volume 1
1
-1
-1.32x10
-1.84x10-2
-3
-7.75 x10
-3
-1.70 x10
-8.43x10-4
-4
-4.96x10
-5.91x10-4
-3.30x10-4
-3
-1.26x10
0
0
-4.30x10-7
0
0
0
Vapor
-1.66x10-1
7a
1
1.53 x10
0
0
0
0
0
0
7.23x10-1
5.65x10-2
2.77 x101
1a
-1
-1.32x10
-1.84x10-2
-3
-7.75x10
-3
-1.70x10
-8.43x10-4
-4
-4.96x10
-5.91 x10-4
-3.30x10-4
-3
-1.26x10
0
0
-4.30x10-7
0
0
0
Vapor
-1.66x10-1
8
-1
3.90x10
0
0
0
0
0
0
3.21
6.07x10-2
1.95 x101
1b
-2
4.53x10
6.47x10-3
-3
2.75x10
-4
5.99x10
2.98x10-4
-4
1.75x10
2.09x10-4
1.13x10-4
-4
4.20x10
0
0
1.44x10-7
0
0
0
Vapor
5.74x10-2
8a
-1
1.01x10
0
0
0
0
0
0
1.02
2.12x10-2
6.17
2
-2
4.53x10
6.47x10-3
-3
2.75x10
-4
5.99x10
2.98x10-4
-4
1.75x10
2.09x10-4
1.13x10-4
-4
4.20x10
0
0
1.44x10-7
0
0
0
Vapor
5.74x10-2
9
-1
1.32x10
0
0
0
0
0
0
3.59
2.63x10-2
5.97
5
3.46
5.70x10-1
-1
2.48x10
-2
5.35 x10
2.70 x10-2
-2
1.54 x10
1.83 x10-2
7.25 x10-2
-2
2.11 x10
1.16
0
0
0
0
0
Vapor
5.65
11
-4
8.52x10
0
0
0
0
0
0
3.81x10-2
2.68x10-4
0
5a
3.46
5.70x10-1
-1
2.48x10
-2
5.35 x10
2.70 x10-2
-2
1.54 x10
1.83 x10-2
7.25 x10-2
-2
2.11 x10
1.16E+06
0
0
0
0
0
Vapor
5.65
12
0
0
0
0
0
0
0
0
0
0
6
4.60
0
0
0
0
0
0
2.63x10-1
-2
2.20x10
9.21x10-1
-3
2.37x10
0
0
0
0
Vapor
5.91
13
-4
8.52x10
0
0
0
0
0
0
3.81x10-2
2.68x10-4
0
7
4.60
0
0
0
0
0
0
2.63x10-1
-2
2.20x10
9.96
-3
2.37x10
1.05x10-1
0
0
Vapor
14.9
14
-4
8.52x10
0
0
0
0
0
0
3.81x10-2
1.72x10-1
0
93
GROUP 1
Carbon Monoxide, CO
Hydrogen Sulphide, H2S
Hydrogen , H2
Oxygen, O2
Phase
MEA
Total
Component | Stream No.
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide, H2S
Hydrogen , H2
Oxygen, O2
MEA
Phase
Total
6.08x10-3
0
2.69x10-1
0
Vapor
0
1
4.4 x10
15
-3.10x10-2
-3
-4.14x10
-1.76x10-3
-3.77x10-4
-1.87x10-4
-1.15x10-4
-4
-1.37x10
-2
-7.15x10
-3.25x10-1
0
-3.24x10-3
0
-2.29x10-2
-8.66x10-2
0
Vapor
-5.47x10-1
5.34
0
2.13 x101
0
Vapor
0
1
4.99 x10
16
0
0
0
0
0
0
0
8.53
1.81 x101
5.89
0
0
0
4.69x10-1
Vapor
3.3 x101
Volume 1
1.71x10-3
0
1.16x10-1
0
Vapor
0
-1
1.57x10
U6
1.60x10-2
-3
2.27x10
9.75x10-4
2.07x10-4
1.03x10-4
6.35x10-5
-5
7.56x10
-4
3.89x10
1.52x10-4
0
0
0
0
0
0
Vapor
2.02x10-2
0
0
1.04x10-1
0
Vapor
0
-1
1.04x10
U6a
1.60x10-2
-3
2.27x10
9.75x10-4
2.07x10-4
1.03x10-4
6.35x10-5
-5
7.56x10
-4
3.89x10
1.52x10-4
0
0
0
0
0
0
Vapor
2.02x10-2
1.71x10-3
0
1.21x10-2
0
Vapor
0
-2
5.31x10
U7
0
0
0
0
0
0
0
0
-5.15x10-1
0
0
0
0
-1.37x10-1
0
Vapor
-6.52x10-1
1.71x10-3
0
1.21x10-2
-2
4.60x10
Vapor
0
-1
2.71x10
94
GROUP 1
Volume 1
16
Vapor
2
6.26 x10
22
Liquid
3
-2.67 x10
28
Vapor
9.66 x102
R1
Liquid
3
-2.52 x10
16a
Mixed
2
1.22 x10
23
Liquid
3
2.46 x10
28a
Mixed
-2.48 x103
R1a
Liquid
3
-2.52 x10
17
Vapor
2
2.03 x10
24
Liquid
2
1.21 x10
29
Vapor
1.66 x103
R2
Liquid
2
-1.32 x10
17a
Vapor
2
3.01 x10
24a
Liquid
1
4.13 x10
29a
Vapor
-1.63 x103
R3
Liquid
3
-2.65 x10
19a
Liquid
3
-2.560 x10
25c
Liquid
3
-2.61 x10
29e
Vapor
-1.65 x103
20
Vapor
3
1.460 x10
26
2
2.1 x10
29f
Liquid
-1.71 x103
21
Liquid
3
-1.1 x10
26a
21a
Liquid
3
-1.1 x10
27
9.59
29g
Liquid
-1.71 x103
1.41 x10
30
Liquid
-1.7 x103
95
GROUP 1
Volume 1
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide,
CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide,
CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Phase
Total
1
-9.54x10-2
-1.33x10-2
-3
-5.58x10
-3
-1.26x10
-6.22x10-4
-3.35x10-4
-4
-3.99x10
1a
-9.54x10-2
-1.33x10-2
-3
-5.58x10
-3
-1.26x10
-6.22x10-4
-3.35x10-4
-4
-3.99x10
1b
3.28x10-2
4.68x10-3
-3
1.98x10
-4
4.42x10
2.20x10-4
1.18x10-4
-4
1.41x10
2
3.28x10-2
4.68x10-3
-3
1.98x10
-4
4.42x10
2.20x10-4
1.18x10-4
-4
1.41x10
-2.40x10-3
-2.40x10-3
8.20x10-4
8.20x10-4
8.20x10-4
-9.00x10
0
-3
-9.00x10
0
-3
0
-7
-3.11x10
0
0
0
0
Vapor
-1.20x10-1
Component | Stream No. 7
Methane, CH4
5.43
Ethane, C2H6
0
Propane, C3H8
0
n-Butane, C4H10
0
3.00x10
0
-4
0
-7
-3.11x10
0
0
0
0
Vapor
-1.20x10-1
8
0
0
0
0
3.00x10
0
-4
0
-7
1.04x10
0
0
0
0
Vapor
4.15x10-2
8a
0
0
0
0
-7
1.04x10
0
0
0
0
Vapor
4.15x10-2
9
0
0
0
0
3.00x10
0
-4
6.63x10-4
2.41x10
0
-4
6.52x10-2
1.90x10
0
-2
5
3.12
5.13x10-1
-1
2.23x10
-2
4.82x10
2.43x10-2
1.39x10-2
-2
1.65x10
6
4.14
0
0
0
0
0
0
6a
3.92
0
0
0
0
0
0
6b
5.43
0
0
0
0
0
0
6.52x10-2
2.37x10-1
2.26x10-1
2.98x10-1
-2
1.98x10
8.29x10-1
-2
1.90x10
7.93x10-1
-2
2.46x10
1.04
-2
-3
2.04x10
-3
2.66x10
-3
1.90x10
1.04
2.14x10
0
0
0
0
0
Vapor
4.15x10-2
10
0
0
0
0
0
0
0
0
0
Vapor
3.35x10-2
11
-1
1.42x10
0
0
0
0
0
0
0
0
Vapor
4.04
11a
1.73
0
0
0
0
0
0
0
0
Vapor
5.08
12
1.73
0
0
0
0
9.45x10-2
0
0
0
Vapor
5.32
13
0
0
0
0
0
9.07x10-2
0
0
0
Vapor
5.05
14
-3
-2.11x10
-4
-2.63x10
-1.11x10-4
-5
-2.44x10
0
1.16x10-1
0
0
0
Vapor
6.90
14a
1.18
-1
1.71x10
7.45x10-2
-2
1.59x10
96
GROUP 1
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide,
CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide,
CO
Hydrogen Sulphide,
H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Phase
Total
0
0
0
0
0
0
0
0
0
2.46x10-2
9.51
0
0
1
3 x10
0
0
1
-6.55 x10
0
0
0
0
0
1
-6.55 x10
2.66x10-3
0
1.01 x101
0
0
0
Vapor
4.01 x101
15a
0
0
0
0
0
0
0
0
2.08x10-4
0
0
0
Mixed
-6.55 x101
16
0
0
0
0
0
0
0
0
0
0
0
0
Vapor
0
16a
0
0
0
0
0
0
0
2.98x10-1
0
1.16x10-1
0
0
0
Vapor
1.54 x101
Component | Stream No. 15
Methane, CH4
0
Ethane, C2H6
0
Propane, C3H8
0
n-Butane, C4H10
0
i-Butane, C4H10
0
n-Pentane, C5H12 0
n-Hexane, C6H14 0
Carbon Dioxide,
5.68
CO2
-2
Nitrogen, N2
3.05x10
Water, H2O
1.62
Carbon Monoxide,
CO
0
Hydrogen Sulphide,
H2S
0
Hydrogen , H2
0
8.71x10-5
6.00x10
-2.97
-7
0
0
0
1.30
1.14x10
0
-2
Volume 1
0
0
0
0
0
0
-1.21x10-5
-7.03
-8.37
8.01x10-3
-3
4.63x10
5.49x10-3
4.62
7.11x10-5
7.11x10-5
-1.05x10-2
4.66
2.45x10-2
2.93
4.83x10-7
-5
5.43x10
4.83x10-7
0
0
-5.38
-8.82x10-5
0
3.05x10-2
0
3.12x10-2
-5.38
6.07x10-7
-8.92x10-5
3.14x10-2
0
0
0
0
0
Liquid
-6.55 x101
16b
0
0
0
0
0
0
0
0
1.27x10-1
0
0
0
Vapor
7.88
16c
0
0
0
0
0
0
0
0
2.62
0
0
0
Mixed
-5.38
17
0
0
0
0
0
0
0
0
2.62
0
0
0
Vapor
7.66x10-5
18
0
0
0
0
0
0
0
0
0
0
0
0
Liquid
-5.38
19
0
0
0
0
0
0
0
0
-3.85x10-4
0
0
0
Vapor
-1.36x10-2
20
0
0
0
0
0
0
0
0
1.27x10-1
0
0
0
Vapor
6.31
21
0
0
0
0
0
0
0
0
0
0
0
0
0
4.86x10-1
0
0
-2.97
0
0
0
0
4.52
0
0
4.52
0
4.26x10
0
-3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
97
GROUP 1
Oxygen, O2
Nickel Oxide
Nickel
Phase
Total
0
0
0
Vapor
7.33
Component | Stream No. 21a
Methane, CH4
0
Ethane, C2H6
0
Propane, C3H8
0
n-Butane, C4H10
0
i-Butane, C4H10
0
n-Pentane, C5H12 0
n-Hexane, C6H14 0
Carbon Dioxide,
CO2
0
Nitrogen, N2
0
Water, H2O
0
Carbon Monoxide,
CO
0
Hydrogen Sulphide,
H2S
0
Hydrogen , H2
0
Oxygen, O2
0
Nickel Oxide
0
Nickel
0
Phase
Vapor
Total
0
0
0
0
Vapor
-2.97
22
0
0
0
0
0
0
0
0
0
0
Vapor
0
U1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.04x10-7
0
0
8.47
0
0
0
2.94
0
Vapor
2.94
0
0
0
0
0
Vapor
0
1.04
0
0
0
0
Vapor
1.04
0
0
0
0
0
Vapor
1.04x10-7
0
0
0
0
0
Vapor
8.47
0
0
0
0
0
Vapor
8.06x10-3
1.58x10
-4
5.88x10
0
-5
Volume 1
0
0
0
Liquid
-2.97
U6
-1.27x10-2
-3
-1.79x10
-4
-7.53x10
-1.66x10-4
-8.23x10-5
-4.78x10-5
-5
-5.69x10
0
0
2.94
Vapor
2.94
U7
0
0
0
0
0
0
0
0
2.94
Vapor
7.46
U8
0
0
0
0
0
0
0
0
0
0
Vapor
4.52
U9
0
0
0
0
0
0
0
0
-1.33x10-1
0
0
5.3
0
0
4.52
0
0
0
0
0
0
Vapor
-1.61x10-2
0
0
-3.55x10-2
0
0
Vapor
-1.69x10-1
0
0
1.52
0
0
Vapor
6.86
0
0
1.29
0
0
Vapor
5.81
-3.19x10
-4
-1.20x10
0
-4
98
GROUP 1
Component | Stream No.
Methane, CH4
Ethane, C2H6
Propane, C3H8
n-Butane, C4H10
i-Butane, C4H10
n-Pentane, C5H12
n-Hexane, C6H14
Carbon Dioxide, CO2
Nitrogen, N2
Water, H2O
Carbon Monoxide, CO
Hydrogen Sulphide, H2S
Hydrogen , H2
Oxygen, O2
Nickel Oxide
Nickel
Phase
Total
Volume 1
U10
0
0
0
0
0
0
0
0
0
3.01 x101
0
0
0
0
0
0
Vapor
3.01 x101
99
GROUP 1
Volume 1
0
Relatively
harmless
No evidence of
corrosiveness
1
Slightly toxic
2
Moderately toxic
3
Highly toxic
4
Extremely toxic
Corrosion of little
concern
Corrosion may be a
concern
Concern:
requires
special
materials
Suggestive
evidence of
carcinogenicity but
not sufficient to
assess
Combustible liquid
flash point of 100F
to 200F
Likely to be
carcinogenic
to humans
Special
materials and
process
alterations
required
Carcinogenic to
humans
Carcinogenicity
Not likely to be
carcinogenic to
humans
Data is
inadequate to
assess human
carcinogenicity
Flammability
Not
combustible
Combustible if
heated
Reactivity
Temperature
(deg C)
Pressure
(absolute value
- bar)
Minimal
Below 200
Slight
200-500
Atmospheric
Safety
Environmental
Maturity
Capital Cost
Economical
Operating Cost
Moderate
500-800
Flammable
liquid flash
point below
100F
Serious
800-1000
Flammable gas
or extremely
flammable
liquid
Severe
Above 1000
1-50
50-100
100-150
150 or greater
No effect on
environment
Possible small
disturbance to
local ecosystem
Toxic release
Hazard to
public health
and ecosystem
TRL=8-9
Cheapest
Cheapest
TRL=6-7
Cheap
Cheap
TRL=5-4
Moderate
Moderate
TRL=3-2
Expensive
Expensive
Long term
effect or need
for emergency
evacuation
TRL=1
Most expensive
Most expensive
100
GROUP 1
Volume 1
Safety
Economical
Flammability
Reactivity
Temperature
Pressure
Environmental
Maturity
Capital Cost
Operating Cost
Dry based
0.57
3.57
Total
Carcinogenicity
AVERAGE
Corrosiveness
AVERAGE
Toxicity
Wet based
Economical
Flammability
Reactivity
Temperature
Pressure
Environmental
Maturity
Capital Cost
Operating Cost
1.28
2.5
4.78
CPOx
1.28
2.5
4.78
ATR
1.14
5.14
Total
Carcinogenicity
AVERAGE
Corrosiveness
AVERAGE
Toxicity
SMR
Economical
Maturity
CAPEX
OPEX
AV
1.57
6.57
PSA
3.5
5.5
CL
Cryogenic
0.14
6.14
AV
Total
Environmental
Pressure
Temperature
Reactivity
Flammability
Carcinogenicity
Corrosiveness
Toxicity
Amine Absorption
At SMR stage
SERP
1.43
7.43
Membranes
0.86
2.86
101
GROUP 1
Volume 1
Figure G-1: Block Flow Diagram of the Hydrogen Production Plant with identification of the streams containing
CO2[113]
GROUP 1
Volume 1
Duration (hours)
8.5
2
10.5
13.5
6.5
3.5
0.5
0.5
22
Duration (hours)
10
6.5
0.5
0.5
1
10.5
103
GROUP 1
Volume 1
Universal assumptions:
1. Inspection and testing has already been conducted.
2. Heating and cooling water is already at specification.
3. Pumps are already primed.
Design 1 assumptions:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Design 2 assumptions:
1.
2.
3.
4.
5.
6.
7.
= 112/60
= 1.867
This was rounded up to 2 hours.
104
GROUP 1
Volume 1
28
=
(1.867 60) 8
=
= 0.03125.
From here the pressure difference in the WGS pressurisation stage was calculated:
=
= 30 1
= 29
These 2 values were then used to calculate the time required to pressurise the WGS reactors.
29
=
6 0.0135
= 154.7
=
This was converted to 2.58 hours for inclusion in the overall start-up table.
Heating of membrane SMR:
First the difference in temperature of the membrane SMR after heating and ambient temperature was calculated:
=
= 500 30
= 470
This difference in temperature, along with the heating rate for the membrane SMR reactor, was used to calculate
the time required to heat the reactor:
=
470
50
= 9.4
Table H-3: Nomenclature list for Appendix H
= 1 ()
= 2 ()
= 1 ( )
= 2 ( )
= ( )
= ()
= ( .
Nomenclature
= (. . )
= ()
= ( )
= 1 ( )
= 2 ( )
= ( . )
)
105