The Dry Reforming of Methane To Syngas and Subsequent Products PDF

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Honors Theses AY 16/17 Undergraduate Honors Theses
Spring 5-12-2017
The Dry Reforming of Methane to Syngas and

Subsequent Products
Sean Kasprisin 4347974
University of Wyoming, skaspris@uwyo.edu
Timothy Poppert
University of Wyoming, tpoppert@uwyo.edu
Nykyta Vovk
University of Wyoming, nvovk@uwyo.edu
Alexander Fox
University of Wyoming, aox10@uwyo.edu
Hussain Alsukairi
University of Wyoming, halsukai@uwyo.edu
Follow this and additional works at: http://repository.uwyo.edu/honors_theses_16-17

Part of the Catalysis and Reaction Engineering Commons
Recommended Citation
Kasprisin, Sean 4347974; Poppert, Timothy; Vovk, Nykyta; Fox, Alexander; and Alsukairi, Hussain, "The Dry Reforming of Methane
to Syngas and Subsequent Products" (2017). Honors Theses AY 16/17. 84.
http://repository.uwyo.edu/honors_theses_16-17/84
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The Dry Reforming of Methane
By The Reformation
CHE 4080 Process Design 2
05/05/2017
Hussain Alsukairi
Alexander Fox
Sean Kasprisin
Timothy Poppert
Nykyta Olegovich Vovk
1
Table of Contents
Executive Summary . . . . . . . . . 6
Scope of Work . . . . . . . . . 7
Introduction . . . . . . . . . . 11
Base Case . . . . . . . . . . 21
Overall Design . . . . . . . . 21
Basic science . . . . . . . . . 22
Assumptions . . . . . . . . . 24
Design of Each Section . . . . . . . 25
Flowsheets . . . . . . . . . . 35
Stream Tables . . . . . . . . . 37
Design Alternatives . . . . . . . . . 57
Permitting and Environmental Concerns . . . . . . 57
Safety and Risk Management . . . . . . . 61
Economic Analysis . . . . . . . . . 85
Global Impacts . . . . . . . . . 95
Conclusion . . . . . . . . . . 96
Future Work . . . . . . . . . . 97
Acknowledgements . . . . . . . . . 99
Appendices . . . . . . . . . . 100
Works Cited . . . . . . . . . . 103
Contribution Breakdown . . . . . . . . 106
2
Table of Figures
Figure 1. Acetic Acid Prices: 10 Year Span . . . . . 15
Figure 2. World Consumption of Acetic Acid-2016 . . . . 16
Figure 3. Global Propionic Acid Market 2014-2020 . . . . 18
Figure 4. World Consumption of Propionic Acid-2016 . . . . 29
Figure 5. Syngas to Acetic Acid Reaction Mechanism . . . . 23
Figure 6. Dry Methane Reformation Flowsheet . . . . . 35
Figure 7. Acetic Acid from Synthesis Gas Flowsheet . . . . 36
Figure 8. IRR With a 50% change in parameter . . . . 93
Figure 9. IRR With a 25% change in parameter . . . . 94
3
Table of Tables
Table 1. FEEDCOMP Results . . . . . . . 25
Table 2. HX Results . . . . . . . . . 26
Table 3. DRMREACT Results . . . . . . . 26
Table 4. COMP1 Results . . . . . . . . 27
Table 5. COOL1 Results . . . . . . . . 27
Table 7. COOL2 Results . . . . . . . . 28
Table 9. EQREACTOR Results . . . . . . . 29
Table 10. VAPFLASH Results . . . . . . . 29
Table 11. LIQFLASH Results . . . . . . . . 30
Table 12. FLASH2 Results . . . . . . . . 30
Table 13. FLASH3 Results . . . . . . . . 31
Table 14. HEATER Results . . . . . . . . 31
Table 15. DIST1 Condenser Results . . . . . . 32
Table 16. DIST1 Reboiler Results . . . . . . . 32
Table 17. HEATER2 Results . . . . . . . . 33
Table 18. DIST2 Condenser Results . . . . . . 33
Table 19. DIST2 Reboiler Results . . . . . . . 33
Table 20. MIXBURN Results. . . . . . . . 34
Table 21. TURBINE Results . . . . . . . . 34
Stream Tables . . . . . . . . .
Table 22. FEEDMIX . . . . . . . . 37
Table 23. FEEDCOMP . . . . . . . 38
4
Table 24. HX . . . . . . . . . 39
Table 25. DRMREACT . . . . . . . 40
Table 26. COMP1 . . . . . . . . 41
Table 27. COOL1 . . . . . . . . 42
Table 28. COMP2 . . . . . . . . 43
Table 29. COOL2 . . . . . . . . 44
Table 30. COMP3 . . . . . . . . 45
Table 31. EQREACT . . . . . . . . 46
Table 32. VAPFLASH . . . . . . . . 47
Table 33. LIQFLASH . . . . . . . . 48
Table 34. FLASH2 . . . . . . . . 49
Table 35. FLASH3 . . . . . . . . 50
Table 36. HEATER . . . . . . . . 51
Table 37. DIST1 . . . . . . . . 52
Table 38. HEATER2 . . . . . . . . 53
Table 39. DIST2 . . . . . . . . 54
Table 40. MIXBURN . . . . . . . . 55
Table 41. TURBINE . . . . . . . . 56
Table 42. TOTAL FCI and Additional Figures . . . . . 88
Table 43. Equipment List . . . . . . . . 89
Table 44. Cash Flows and Resulting NPV, NPV12, and IRR . . . 92
5
Executive Summary
The main goal of this project is to explore the possibilities of creating a plant to convert
methane and carbon dioxide into synthesis gas (syngas) and then directly to the decided
subsequent product of acetic acid utilizing a dry methane reforming process (DRM). Assuming a
1,000kmol/hr basis of each feed gas a product stream of 45.3 lbmol/hr of 99.95% mole purity
acetic acid and 74.7lbmol/hr of propionic acid are produced. This is done with a 35% conversion
of feed gas into syngas, and 90% of equilibrium values for acetic acid from synthesis gas. An
increase in the conversion rates for both reactions was considered in the alternatives and
tornado plot. No recycle streams were included in the simulation due to the complexity of the
gas-gas separation of multiple gaseous compounds. In place of recycle streams, the waste
stream was used as a burn stream to provide heat. A significant amount of assumptions were
made in order to handle the ambiguity that was provided in the limited literature that was
available for the catalysts and other aspects of the process. With the assumptions that were
made, as well as the available information the overall net present value with a 12 percent
discount factor was negative 675 million dollars along with an internal rate of return of negative
11%. This is due to both the high capital cost of the reactors and compressors as well as the
annual costs of maintenance, utilities, taxes and insurance. The annual utility costs were able
to be decreased with heat integration of the burning the waste stream and gas and liquid
turbine integration to decrease the need for external utilities. Overall, the process to utilize
DRM and direct conversion to acetic acid is physically possible with the assumptions that were
made. However, the process is not economically viable under the current conditions. The
conversion of syngas directly to acetic acid is the main issue affecting viability of the process.
6
There are several items that were the focus for this project. Those items included the pressure,
conversion rates, product prices, and utility costs. The best process was then determined.
Combining the base case with varying the key items that were looked at provided a guide on
what necessary steps in the research and development phase to allow the process to become
an achievable alternative to Steam Reforming. With multiple factors adjusted to optimal an
unverified values, a positive IRR of up to 15% could be achieved. At this point however, it is
advised to not commit more time or resources to this process until more accurate testing
results are available.
Scope of Work
The project was taken through an initial base case attempting to determine if it was
economically feasible and technically possible. The results showed it to have significant losses
economically, but it was technically possible. From that base case along with the guidance
provided by the board of advisors on the initial presentation, the project started to focus on
minimizing costs and maximizing profit by integrating heat and a spin-wheel/turbine to
decrease utility costs, altering the design to decrease capital cost, and utilizing by-products
(propionic acid as the main focus) to increase profit. The changes were made to develop an
improved base case which was then used to determine what select variables needed to be
changed in order to make the process profitable. From there the final conclusions of the project
report what the necessary values for the selected variables (pressure, temperature, and
percent conversion) were in order to give a list of necessary goals to the research and
development phase to attempt to achieve. This would determine if the process would be able
to become a real world alternative to SRM or other used industrial methods of creating syngas,
7
acetic acid, and propionic acid.
To ensure that the technical and economic analyses were not unobtainable values, a list
of constraints was developed for the process. The first set of constraints was focused on the
safety of the experiment. The process operates at high pressure and high temperatures. These
large values had to be considered for the safety of the workers, local community, as well as the
ability of the process itself to ensure that there was equipment and reactions taking place
inside the process would be able to occur at these values and that equipment is able to be
manufactured to handle these high values. With the high pressure, the streams also had to be
depressurized which could introduce possible vibration issues. The use of a turbine to integrate
the depressurization into an energy source is explained in-depth to mitigate this issue. The
process creates H2 and then uses it to create the final products, but with H2 in the process
careful consideration of how the system would be kept clean of oxygen to avoid any reaction
between the two had to be considered. The process is used to create acid, which can corrode
the equipment and pipes, and thus a regular monitoring method had to be developed to ensure
there was no corrosion from the acids or hydrogen embrittlement (discussed later and
mitigated through the use of Novolac coating).
The second portion of constraints focused on the economic side of the project. Acetic
and propionic acid are the two main products of the overall process and thus the process
viability heavily relies on the price of the two. Water is a by-product of the process with syngas
as an intermediate, which allows some fluctuation in what the end product of the process could
be if product prices drop drastically. From the initial base case it was determine that the cost of
utilities was a major component leading the economic infeasibility of the process. This was
8
mitigated through integrating heat and energy in the process to decrease the total utility costs.
The other method to decrease utility cost was to determine the most cost-effective method of
compressing the reagents due to the energy for the compressing being a large portion of the
utility costs. A constraint on the products for high purity would result in higher sales prices and
the possibility of capturing a niche part of the market. This would increase the overall profit of
the process.
Scientific constraints were the next focus of the process. The main focus of the scientific
constraints were the two reactors, especially the conversion rates of each reactor. The lack of
literature on these type of processes along with the conversion rates being focused on batch
reactors in an experimental lab, not an industrial build up lab, resulted in the base case utilizing
the minimal conversion rates for the base case. This along with the overall economic fallibility
of the process led to the new focus of the project to be determining the necessary
requirements needed to be met for a catalyst for each reactor in the research and development
phase. The literature also created an element balance issue with the second reactor, which was
resolved by utilizing an equilibrium reactor, which resolved the issue.
Another major constraint that had to be considered for the project was any restraints
for the production of the product. This would include the feed rate, and production rate based
upon the annual amount of each product produced, as well as a comparison to the feed rates of
other plants that use similar feed compounds. With 1000 kmol/hr used for this project, these
constraints were met.
There were also practical constraints that had to be considered. One of the constraints
was dealing with a cascade refrigeration system in a distillation tower after the conversion to
9
acetic acid reactor. This issue was removed when the property set (NRTL-HOC) was changed
and flash tanks were integrated into the process to replace some of the distillation towers.
Another practical constraint was the materials used to line the equipment to avoid any
corrosion. Novolac coatings were picked in place of glass which was more expensive.
Along with the production rate constraints, additional constraints were needed for the
product and feed streams. For the feed, sulfur is expected to be in the feed stream, and will
need to be purged from the streams before they are sent to the reactor to prevent catalyst
poisoning. This was done by adding a scrubber to the first step of the process. The purity of the
product must meet the industrial standards not only for a niche market, but to be able to be
sold on an industrial level.
There are environmental constraints that must always be considered when developing a
process. EPA regulates materials that can be considered waste or emitted into the air. For this
process CO2, sulfur, methyl acetate, ethyl acetate, n-propyl acetate, water, hydrogen gas,
propionic acid, CO, acetic acid all as waste products are being emitted to the environment. The
permitting and environmental section goes into detail for any necessary permits as well as the
results of a BACT for the process. Due to the complexity of the process and the additional costs
of recycling CO2 into the process, no recycle stream was included, but could be integrated to
minimize some of the environmental constraints.
There are general feasibility constraints that have to be considered for the process. They
include whether or not the process is technically possible, economically feasible, and current
catalysts available and affiliated values with the catalysts. The process is technically sound with
the set conditions in this report. The only caveat for its technical feasibility is the actual catalyst
10
values, since most values were used from batch reactors on a research lab level. The process is
not economically feasible.
The last amount of constraints that need to be considered are the legal constraints that
must be considered. The items that were considered for legal constraints are any current
patents on DRM or direct conversion to acetic acid. From the patent search, the process is new
enough that no current patents are limiting the project.
Introduction
Chemical processing plants need to utilize a wide variety of chemicals in order to create
the products that are used in many daily activities and products. Among these chemicals there
are a few that are applicable to a wider range of processes than others. Hydrogen (H2) and
carbon monoxide (CO) are two such compounds that have a wide variety of applications. The
mixture of CO and H2 is called synthesis gas or syngas for short. There have been a large range
of ways to create syngas from using coal to using natural gas. In recent years, natural gas
consisting of mostly methane has been the common method to create syngas.(4)
The main process that is used to create syngas is called the steam reforming of methane
(SRM). This is where methane and water are reacted to create carbon monoxide and hydrogen
as seen in Equation 1
CH4 + H2O → CO + 3H2 (1)(4)
The main issue that occurs with this process is the unequal ratio of CO to H2. Most
subsequent compounds require equal ratios of CO and H2. This means that an additional
reaction must occur in order to provide the necessary ratios of CO to H2 to be useful in other
processes. This is done by utilizing a water-gas shift reaction where carbon monoxide reacts
11
with water in order to create carbon dioxide and hydrogen as seen in Equation 2 below.
CO + H2O → CO2 + H2 (2)(4)
This method of steam reforming is the basis for gas-to-liquid technology. This type of
technology was first utilized by Germany during World War II when it became significantly
difficult to obtain and refine oil. To deal with the imbalance of CO to H2 ratios, a secondary
reactor is needed for the water-gas shift reaction.(11) Steam reforming also utilizes an immense
amount of steam in order to operate. The water-gas shift reaction also creates carbon dioxide
as a by-product, which is a greenhouse gas. The carbon dioxide needs to be removed or
sequestrated, which costs money as well adversely affecting the environment.(15)
Based upon literature findings steam reforming plants can be either large or small scale.
The difference is best understood by comparing the amount of natural gas feed rates between
the two. A large scale Plant uses 167.8 million cubic feet per day of natural gas, while a small
scale plant use 0.024 million cubic feet per day of natural gas.(16) The total investment for the
large and small scale SMR are 368.5 million dollars and 0.39 million dollars respectively. Both
the feed rates and the plant investments were determined utilizing a 2005 basis.(13)
Steam reforming of methane is not the only approach possible to create syngas.
Additional methods include auto-thermal reforming, oxidative combustion, and dry reforming
of methane, which will be the main alternative that is considered.(4)
The dry reforming of methane has several main differences from the SRM method,
which provide certain benefits for the method to be explored further. The first difference is the
reaction itself. Dry reforming of methane utilizes methane (CH4) and carbon dioxide (CO2) as
reactants to create the syngas. This is visible in Equation 3 below.
12
CH4 + CO2 → 2CO + 2H2 (3)(4)
As Equation 3 shows, the syngas created using this method has equal ratios of CO to H2
immediately. This allows for the water-gas shift reaction and reactor to be excluded from the
process. Another critical difference is the use of CO2 in the reaction. Unlike the water-gas shift
reaction, CO2 is used as a reactant instead of as a by-product. The importance of this point
cannot be stressed enough. The dry reforming of methane would be one of very few if not the
only process that would utilize industrial amount of a harmful greenhouse gas as reactant. Due
to the complex setup of the process along with the possible conversion rates, carbon dioxide
would be consumed, but there would still be waste carbon dioxide that would have to be
emitted with the burning of other waste products, or additional equipment would need to be
emplaced to separate CO2 to allow for it to be recycled. The possibility of a CO2 recycle stream
will be discussed in greater detail in the future work section. Either way the amount of CO 2 for
the DRM process would be less than that for a SRM process which would help improve the
environment, instead of polluting it with as much CO2 as the SRM process. A more in-depth
explanation of any emissions out of the process are provided in the environmental section of
the report.
Another item to consider is that most power plants use CH4 as well as producing CO2.
These CO2 is usually by-products that have to be removed and then discarded in accordance
with state and federal regulations. With a DRM nearby, these power plants would be able to
send the CO2 and any CH4 directly to the DRM plant instead. The Green River Basin in Wyoming
is home to a number of these types of power plants, and would thus be an ideal location for a
DRM Plant. The only item that would need to be addressed would be the need to scrub the
13
feed gases of unwanted compounds such as sulfur. Since the DRM would be located in an area
that has a lot of power plants that also use CH4, finding an inexpensive methane provider would
not be difficult. Due to the conversion rate of 35-50% of feed to syngas for the DRM reaction,
there would be left over methane in the process. This left over methane would then be
integrated into the process as a source of heat to decreasing utility costs.
The reason there are so many ways to synthesize syngas is due to its wide variety of
applications. Methanol, ammonia, acetic acid, and motor fuels are just a few of the chemicals
and compounds that can be made with syngas. DRM, provides a unique advantage when acetic
acid is the chosen as a subsequent product due to the ratio of CO to H2 produced from DRM
and the ration needed to directly convert syngas into Acetic Acid. Equation 4 shows the basic
reaction for the direct conversion of syngas into Acetic Acid.
2CO + 2H2 → CH3COOH (4)(14)
As Equations 3 and 4 show, the ratio produced in DRM and the one used in direct acetic
acid conversion are equal. This allows the complete bypassing of the water-gas shift reaction,
which does not occur when trying to produce some of the other possible products. Directly
converting into acetic acid from syngas is another unique process in itself. Acetic acid is
normally created by utilizing a methanol intermediate. Equations 5 and 6 below illustrate the
basic reactions to convert syngas to acetic acid through the methanol intermediate.
CO + 2H2 → CH3OH (5)(17)
CO + CH3COH → CH3COOH (6)(25)
When Equations 5 and 6 and combined, the net reaction is the same as the basic
reaction for directly converting syngas into acetic acid. This would translate to mean that
14
utilizing the methanol intermediate would also enable the water-gas shift reaction to be
bypassed. Due to the fact that utilizing a methanol intermediate is the common industrial
process for producing acetic acid, and under the directions of the project advisor, Dr. Joseph
Holles, the methanol intermediate method will not be investigated further. Acetic Acid was not
only chosen due to the reactant ratios, but also due to the many applications and business
opportunities that acetic acid provides. Figure 1 below shows a ten year span for the pricing of
acetic acid per ton for multiple countries.(3)
Figure 1: Price of Acetic Acid for Varying Locations in USD/ton versus Time in Years.
As seen in Figure 1, the price of acetic acid does not fluctuate a large amount. (1) This
allows for the process to enter a fairly stable market. The demand for acetic acid has been
steadily increasing from 12 million tons in 2012, and is projected to continue to do so. (1) Acetic
Acid is not only steady in price and increasing in demand, but it also provides a global market.(2)
The Southeast Asia area including China and Japan consume the largest amount of acetic acid in
15
the world. They are closely followed by Europe and then North America.(18) The steady pricing,
global market, and increasing demand for acetic acid enables it to be a promising and reliable
area for business. Figure 2 below shows the demand for acetic acid by region.(26)
Figure 2: World Consumption of Acetic Acid in 2016.
The steady pricing and increasing demand for acetic could be results from various
reasons, one of which could be due to the fact that acetic acid has a wide variety of applications
itself. Acetic acid is utilized to create a range of other chemicals used in processes such as vinyl
acetate monomer (VAM), polyethylene terephthalate (PETE), anhydrides, and acetate esters.
VAM is commonly used in textiles, adhesive resins, and surface coatings. It can also be used as a
water-based coating. PETE is an extremely common and useful thermoplastic polymer resin. It
is used in multiple fields such as clothing, food container, thermoforming (the forming of
specific shapes of plastic sheets at certain temperatures) and other engineering resins when
16
combined with glass fiber. The anhydrides created from acetic acid are another industrially
used chemical. They can be used as precursors for copolymerization reactions and preparing
esters. Acetate esters are very common in certain food and drinks. This does not include the
use of acetic acid in the food industry as vinegar as well as its capabilities in fermentation.
Acetic acid has a plethora of applications that result in the desire of developing the DRM
and direct conversion to Acetic acid from syngas process. However, there are several issues that
must be considered along with all of the benefits. The main reason that the DRM process is not
being utilized instead of steam reforming is due to the economic differences between the two.
A major component of the cost of DRM is the capabilities of the catalyst utilized in converting
syngas directly to acetic acid.
Acetic Acid is not the only useful product that is gained from this process. Water and
propionic acid are both produced at rates of 334.6 lbmol/hr and 74.7 lbmol/hr respectively in
the process. Propionic acid is the only other by-product considered for sale. In 2006, the global
capacity of propionic acid was 349,000 tonnes/year. With most chemical compounds, the purity
of the product affects the sales price. For propionic acid in 2007, the price of 99.5% pure
propionic acid was 58-63 cents/lb. Based upon economic reports, and trends the demand for
propionic acid will rapidly increase and total $1.55 billion dollars in 2020. This increase is
shown in the figure below.(24)
17
Figure 3: Predicted Global Propionic Acid Market for 2014-2020.
Propionic acid has a variety of uses, but its main use is as a preservative for animal feed
and grains for human consumption. Propionic acid is effective at reducing the mold and
bacteria. It is also an intermediate for herbicides, cellulose acetate, sodium, calcium, and
trimethylolpropane propionates. It also has uses as a flavoring agent and pharmaceuticals.
Propionic acid is used worldwide, however the United States and Western Europe are the
highest consumers of propionic acid. A plot of propionic acid consumption by region is shown
below.
18
Figure 4: World Consumption of Propionic Acid in 2016.
The literature information on the catalyst for the direct conversion of syngas to acetic
acid has several factors that result in the need for more research and development. The catalyst
information was determined based upon a research laboratory experiment done with a batch
system.(14) This translates to meaning that a large residence time and small scale results were
provided. This had to be scaled up as well as converted into a continuous system with a much
smaller residence time. The other main issue with the catalyst is that the longevity as well as
the percent conversion do not have the necessary information to be accurately be utilized and
scaled for a continuous DRM process.
The catalyst issues are the most directly applicable factors with the DRM process, but
not the only item to be considered. The one thing that must always be considered when
designing a process is the safety issues that are involved. The DRM process has multiple safety
issues to consider.
The first safety concern is that there is a high temperature reactor (900 0C) with solely
19
gas inputs and outputs. Dealing with gas in general has certain issues when it is possible to leak.
Inhaling CH4 or CO can result in serious issues such as asphyxiation. H2 is also extremely
flammable with an overall NFPA 704’s rating of 4.(12) If not handled correctly could result in
explosions and death. These issues can be avoided with proper preparation (insulating
necessary equipment) as well putting warning systems in place for any malfunctions.
Temperature is not the only factor that affects the safety of the process. For the conversion of
syngas into acetic acid, the syngas needs to be pressurized to close to 500 bar. High pressures
and gases can be a mixture for disaster if not handled properly. High pressures allow for
asphyxiation even easier when gases can readily expand. High pressure can also increase the
risks of fire as well as explosions. This can be resolved by developing safe methods to release
the pressure incrementally.
Both the temperature and pressure if not properly handled can result in disaster,
however they are not the only safety concerns. Hydrogen gas is unique due to its ability to
cause Hydrogen embrittlement. Hydrogen embrittlement is a process of weakening steel and
other metals with hydrogen resulting in brittle equipment that can easily break. This is done by
hydrogen atoms diffusing into the metals and then recombining into hydrogen molecules. This
will cause a pressure to build up in the metal surfaces. This will continue to weaken the
capabilities of the metal until it cracks. When there is a concentration gradient present,
hydrogen embrittlement can occur at even lower temperatures.(28) This would have similar end
results as improperly managed temperature or pressure, but allows it to become more of a risk
factor to consider when designing the plant. There are steps to take to minimize the effects of
hydrogen embrittlement such as coating the inside of metal equipment with certain materials
20
that are impermeable to hydrogen atoms. This equipment would also affect the costs of the
plant. The above items are just some of the major components that are a part of the risk
assessment for the project. These items along with a more comprehensive list of risks and the
efforts to minimize risk are included in the hazard and operability reports (HAZOP) included in
the safety section of the report.
Base case description
Overall design
The overall design for this process involves the dry reformation of methane using carbon
dioxide to form a one to one ratio of synthesis gas which is, in turn, used to synthesize acetic
acid. A basis of 1000 kmol/hr of each of the feed gasses was assumed and equates to a feed of
20.7 MMCUFT/day of methane.
The dry reformation process was modeled in Aspen+ using the WILS-RK property set.
This property set was picked due to the involvement of non-polar components and a reaction
which takes place at relatively low pressure. In this process, the methane feed stream was
purified using an absorber in which impurities were removed from the feed by
monoethanolamine. Following this purification, the purified methane and carbon dioxide feed
streams were mixed, compressed, heated, reacted, and finally cooled and compressed to
prepare for conversion to acetic acid.
For the synthesis gas to acetic acid, the NRTL-HOC property set was used to model the
process in Aspen+. After the second reactor there was a concern for acid corrosion, even
though acetic acid is not a strong acid. To help prevent this issue, the equipment was lined with
Novolac resin.
21
Basic chemistry, physics, separations that make design work
The first half of the overall process was the dry reforming of methane. This reaction
converts a 1:1 feed of carbon dioxide and methane to two moles of synthesis gas in a 1:1 ratio
of H2 and CO. This reaction is carried out at a pressure of two atmospheres and a temperature
of 900 °C. The catalyst chosen for this reaction from literature is a nickel catalyst promoted with
rhodium and supported on boron nitride. This catalyst was chosen because it was less
susceptible to coking reactions which deactivate the catalyst.(20) As a whole, this process is
rather straightforward because there is neither a need to separate unreacted feed from the
product stream nor a need to separate the products. The reaction mechanism and coking
reactions are presented below.
𝐶𝐻4+𝐶𝑂2→2𝐻2+2𝐶𝑂 (7)
𝐶𝐻4→(𝑠)+2𝐻2 (8)
2𝐶𝑂→(𝑠)+𝐶𝑂2 (9)
Separation of products from unreacted feed was unnecessary because methane and
carbon dioxide are easier to remove following the conversion to acetic acid. Compression to
475 atm and cooling to 220 °C is necessary to prepare the effluent stream for conversion to
acetic acid.
The second half of the overall process converts 1:1 ratio synthesis gas to acetic acid via a
catalyzed reaction. This reaction is carried out at 482 bar and 220 degrees Celsius. The catalyst
precursor chosen from literature was Ru(acac)3 – CoI2. This precursor was chosen because it
provided a favorable distribution yield maximizing acetic acid while minimizing formation of
byproducts. The catalyst itself was cobalt and ruthenium dispersed on the quaternary salt
22
Bu4PBr. A potential problem with this catalytic reaction is that formation of cobalt-iodide
species in large concentrations can inhibit the subsequent formation of acetic acid. (1) Yield
distribution resulting from using the above mentioned catalyst precursor was as follows: 110
mmol CH3COOH, 1 mmol C2H5COOH, 2 mmol CH3COOMe, 9 mmol CH3COOEt, 2 mol CH3COOPr,
20 mmol H2O, 53 mmol CH4, and 432 mmol CO2. Amount of synthesis gas used to obtain this
distribution was not reported. Figure 5 below presents the reaction mechanism for this
catalyzed reaction. (1)
(10)
(11)
(12)
(13)
(14)
Figure 5: Reaction Mechanism for Catalyzed Acetic Acid Reaction
Figure 5. The reaction mechanism for the catalyzed reaction of 1:1 ratio synthesis gas to acetic acid. (1)
Because of the poor information provided by the paper used to choose a catalyst, an
equilibrium reactor was used to model the process. An assumption was used that the catalyst
would attain 90% of equilibrium conversion. This assumption is what the economics were based
off. Due to the variety and high gas content of the products, four flash tanks were used to
remove the hydrogen, methane, carbon monoxide and carbon dioxide from the reactor product
23
stream. These four flash tanks were needed to achieve the desired amount of separation, and
to bypass the need for a refrigerated distillation tower. Instead of having a distillation tower
running at -127 Fahrenheit, four flash tanks were used at various pressures to separate the
methane, carbon monoxide, carbon dioxide and hydrogen.
The next step in the separation process was to extract water from the product stream to
leave propionic acid and acetic acid in the bottoms steam of the first distillation tower. Using
the fact that propionic acid and acetic acid both have relatively high boiling points, water was
distilled with the aim to recover as much acetic acid in the bottoms as possible. At one
atmosphere, acetic acid has a boiling point of 118.1 degrees Celsius and propionic acid has a
boiling point of 141.2 degrees Celsius. For this separation step, acetic acid was used as the
heavy key. The bottoms from this first distillation tower consisted of acetic acid and propionic
acid.
Lastly, the second tower in the separation process distills the acetic acid. The final
product stream is the distillate from this distillation tower. 99% mole recovery of acetic acid in
the distillate was achieved with the use of this tower. The distillate product stream was 99.7%
mole purity acetic acid. Such a high purity will allow the product to be marketed to a wide
range of industries. The bottoms stream consisted of 99.39% mole purity propionic acid.
Assumptions and approximations
Based on the literature, the DRM reaction was assumed to proceed with 35% conversion
of the feed, which is an underestimate of the performance of the catalyst. This conversion was
chosen to ensure that, were this process to become a reality, it would not result in a lower
revenue than predicted. This reaction takes place in a multi-tubular reactor with a total volume
24
of five thousand cubic feet containing a fixed bed catalyst, allowing for a residence time of 3.9
seconds. All compressor in this process were assumed to have a 72% efficiency. A maximum
compressor temperature of 450 °C was assumed after consulting Perry’s Chemical Engineers’
Handbook for operating limits of carbon steel machinery.(21)
Experimentally, the catalytic conversion of synthesis gas into acetic acid was carried out in a
batch reactor with a residence time of eighteen hours. To make this into a continuous process,
a residence time of one hour was assumed. Instead of a batch reactor, a multi-tubular reactor
was used to provide a continuous flow for the process. Based off the literature yield
distribution; a ten percent conversion was assumed to acetic acid from synthesis gas. Literature
was not exactly clear on how the yield distribution was calculated and how much synthesis gas
was used during each experiment. Because of this, an equilibrium reactor was used to model
the reaction. Ninety percent of equilibrium conversion was assumed to be achieved with a
catalyzed reaction to carry out the economic analysis.
Describe each section of design
The two feed streams (CO2FEED and CH4FEED) were combined into a single feed stream
(COMPFEED) in a simple mixer (FEEDMIX). This feed stream was then pressurized to two
atmospheres in a compressor (FEEDCOMP) to prepare for the reaction.
Table 1. FEEDCOMP Results

Brake horsepower 1891.9 hp
Net work required 1410.79 kW
Outlet pressure 29.3919 Psia
Outlet temperature 191.319 °F
Efficiency .72
Vapor fraction 1
In order to achieve the desired reaction temperature, a countercurrent heat exchanger
25
(HX) was implemented to raise the temperature of the compressor effluent stream (HXFEED)
using the reactor effluent stream (RXOUT). This also serves to avoid high temperatures in the
product stream during the subsequent compressions.
Table 2. HX Results
Temp (°F) Pressure (Psia) Vapor fraction
Hot side inlet (RXOUT) 1652 29.3919 1
Hot side outlet (1) 320.557 29.3919 1
Cold side inlet (HXFEED) 191.319 29.3919 1
Cold side outlet (DMRFEED) 1607 29.3919 1
A stoichiometric based reactor (DMRREACT) was used to simulate the reformation
reaction in Aspen+. This reactor was operated at a temperature of 900 °C and a pressure of 2
atmospheres. In order to maintain this temperature for such an endothermic reaction, waste
streams from the final separation stages following the conversion to acetic acid are used to
provide heat for the reaction. Due to the coking reactions, which deactivate the catalyst, a set of
two identical reactors in parallel was designed. This allows us to burn carbon off the catalyst in
the reactor using a portion of the same burn stream previously mentioned without having to halt
the entire process in order to improve the lifespan of the catalyst. There is no need to worry
about not being able to provide enough heat for the reactor and catalyst recovery as the burn
stream can ideally be used as a source of 335 MMBtu/hr.
Table 3. DMRREACT Results

Outlet temp 1652 °F
Heat duty 89.2418 MMBtu/hr
Vapor fraction 1
Following the heat exchanger, a series of three centrifugal compressors and two coolers
was implemented to prepare the synthesis gas stream for conversion to acetic acid in the second
26
half of the process. These serve to compress the stream to 482 bar and cool it to 224 °C, the
operating conditions for the second reactor. The cooling units utilized cooling water at 90 °F.
The compressors are electric powered with a portion of the power being drawn from a turbine,
which is decompressing a stream in the second portion of the process. There will also be power
drawn from a liquid turbine, which is decompressing the liquid stream from the reactor.
The first compressor (COMP1) compressed the hot side outlet (1) stream of HX to 12
bar.
Table 4. COMP1 Results

Efficiency .72
Vapor fraction 1
The first cooler (COOL1) serves to cool the compressor outlet stream (2) to 122 °F from
827 °F for the second compression. This was done to prevent mechanical issues with the
compressors, which arise at temperatures above 450 °C.
Table 5. COOL1 Results

Outlet temp 122 °F
Heat duty -37.9718 MMBtu/hr
Vapor fraction 1
The second compressor (COMP2) compresses the cooler outlet stream (3) to 120 bar.

Efficiency .72
Vapor fraction 1
27
The second cooler (COOL2) serves to cool the compressor outlet stream (4) to 50 °C
from 394 °C for the third compression. This was done to prevent mechanical issues with the
compressors, which arise at temperatures above 450 °C.
Table 7. COOL2 Results

Outlet temp 122 °F
Heat duty -31.6587 MMBtu/hr
Vapor fraction 1
The third compressor (COMP3) compresses the cooler outlet stream (5) to 482 bar. This
ensures the second reaction will proceed at correct temperature and pressure.

Efficiency .72
Vapor fraction 1
An equilibrium reactor (EQREACTOR) was used to simulate the synthesis gas to acetic
acid reaction in Aspen+. The acetic acid reactor was operated at 220 degrees Celsius and 482
bar. The pressurized stream (FEED) from the dry reforming methane process was used as feed
to this reactor. An important note on this reaction simulation is that in literature, the
experimental results were not presented clearly leading to ambiguity in interpretation. Due to
this ambiguity, the equilibrium reactor was used in simulation. It was assumed that the
literature catalyst would allow the reaction to attain 90% of the product yield at equilibrium.
The yield distribution reported in literature was assumed to have resulted from converting all
synthesis gas into products. These two assumptions are something to be closely looked at
28
before proceeding because they will have a major impact on how well the process can operate
continuously.
Table 9. EQREACTOR Results

Outlet temp 428 F
Heat duty -6.75366E+07 Btu/hr
Vapor fraction 0.802411
A flash tank (VAPFLASH) was used to separate the hydrogen, carbon monoxide,
methane, and carbon dioxide from the other products in the vapor stream (VAPPROD) exiting
the reactor (EQREACT). To achieve this separation the flash tank was run at 158 degrees
Fahrenheit and 367.399 Psia. The vapor stream exiting this flash tank was the first of four burn
streams (BURN) to be mixed into one burn stream (MAINBURN) to be used in the heating
process of the dry reforming reactor. The liquid stream (VFLPROD) exiting this flash tank was
fed into another flash tank (FLASH2) to achieve further separation of products. This high-
pressure flash tank was one of four flash tanks used to replace needing a refrigerated
distillation tower.
Table 10. VAPFLASH Results

Outlet temperature 158 F
A flash tank (LIQFLASH) was used to separate the hydrogen, carbon monoxide, methane,
and carbon dioxide from the other products in the liquid stream (LIQPROD) exiting the reactor
(EQREACT). To achieve this separation the flash tank was run at 176 degrees Fahrenheit and
146.959 Psia. The vapor stream exiting this flash tank was the second of four burn streams
(BURN2) to be mixed into one burn stream (MAINBURN) to be used in the heating process of
29
the dry reforming reactor. The liquid stream (LFLPROD) exiting this flash tank was fed into
another flash tank (FLASH2) to achieve further separation of products. This high-pressure flash
tank was one of four flash tanks used to replace needing a refrigerated distillation tower.
Table 11. LIQFLASH Results

A third flash tank (FLASH2) was used to separate the hydrogen, carbon monoxide,
methane, and carbon dioxide from the other products further in the liquid streams (VFLPROD)
and (LFLPROD) exiting the previous flash tanks (VAPFLASH) and (LIQFLASH). To achieve this
separation the flash tank was run at 140 degrees Fahrenheit and 14.6959 Psia. The vapor
stream exiting this flash tank was the third of four burn streams (BURN3) to be mixed into one
burn stream (MAINBURN) to be used in the heating process of the dry reforming reactor. The
liquid stream (PROD2) exiting this flash tank was fed into another flash tank (FLASH3) to achieve
further separation of products. This flash tank was one of four flash tanks used to replace
needing a refrigerated distillation tower.
Table 12. FLASH2 Results

Heat duty 673864 Btu/hr
A fourth flash tank (FLASH3) was used to separate the hydrogen, carbon monoxide,
30
methane, and carbon dioxide from the other products further in the liquid stream (PROD2)
exiting the previous flash tank (FLASH2). To achieve this separation the flash tank was run at
194 degrees Fahrenheit and 14.6959 Psia. The vapor stream exiting this flash tank was the
fourth of four burn streams (BURN4) to be mixed into one burn stream (MAINBURN) to be used
in the heating process of the dry reforming reactor. The liquid stream (PROD3) exiting this flash
tank was fed into the first heat exchanger (HEATER) which prepared the stream for the first
distillation tower (DIST1). This flash tank was one of four flash tanks used to replace needing a
refrigerated distillation tower.
Table 13. FLASH3 Results

Heat duty 1.73432E+06 Btu/hr
The first heat exchanger (HEATER) was used to heat the liquid stream (PROD3) from the
fourth flash tank (FLASH3) from 194 to 212 degrees Fahrenheit and partially vaporize it. The
partially vaporized stream (DISTFEED) exiting the first heat exchanger was used as the feed
stream for the first distillation tower (DIST1). A partially vaporized feed stream allowed
reduction of the reboiler duty for the first distillation tower. The partially vaporized feed also
helped reduce the reflux ratio which further reduced utility costs.
Table 14. HEATER Results

The first distillation tower (DIST1) was used to separate water from propionic and acetic
31
acid in the feed stream (DISTFEED). Two design specifications were used to achieve high
recovery of water in the distillate stream (WATER) and high recovery of acetic acid in the
bottoms stream (BTMPROD). First, 99.97% mass recovery of water in the distillate stream was
set by varying the distillate rate of the first distillation tower. Secondly, 99% mole recovery of
acetic acid was set by varying the reflux ratio. Such a high recovery of water in the distillate
stream allowed for a higher purity product to be attained by the second distillation tower
(DIST2). The bottoms stream (BTMPROD) contained a mix of propionic acid and acetic acid. The
reboiler and condenser in this tower were both sized as standard heat exchangers.
Table 15. DIST1 Condenser Results

Temperature 209.746 F
Distillate rate 360.959 Lbmol/hr
Reflux rate 4970.22 Lbmol/hr
Reflux ratio 13.7695
Table 16. DIST1 Reboiler Results

Bottoms rate 120.637 Lbmol/hr
Boilup rate 7682.08 Lbmol/hr
Boilup ratio 63.6792
The second heat exchanger (HEATER2) was used to heat the liquid stream (BTMPROD)
from the first distillation tower (DIST1) from 267.345 to 269.6 degrees Fahrenheit and partially
vaporize it. The partially vaporized stream (DISFEED2) exiting the second heat exchanger was
used as the feed stream for the second distillation tower (DIST2). A partially vaporized feed
stream allowed reduction of the reboiler duty for the second distillation tower. The partially
vaporized feed also helped reduce the reflux ratio, which further reduced utility costs.
32
Table 17. HEATER2 Results
Outlet temperature 269.6 F
The second distillation tower (DIST2) was used to separate acetic acid from propionic
acid in the feed stream (DISFEED2). Two design specifications were used to achieve high purity
of acetic acid in the distillate stream (ACEPROD) and high purity of propionic acid in the
bottoms stream (PROPPROD). First, 99% mole recovery of acetic acid in the distillate stream
was set by varying the distillate rate of the second distillation tower. Secondly, 99.7% mole
purity of acetic acid was set by varying the reflux ratio. Such a high recovery of acetic acid in the
distillate stream allowed for a higher purity propionic acid to be attained in the bottoms stream
(PROPPROD).
Table 18. DIST2 Condenser Results

Distillate rate 45.4789 Lbmol/hr
Reflux rate 524.532 Lbmol/hr
Reflux ratio 11.5335
Table 19. DIST2 Reboiler Results

Bottoms rate 75.1583 Lbmol/hr
Boilup rate 384.449 Lbmol/hr
Boilup ratio 5.11518
The mixer (MIXBURN) was used to combine the four burn gas streams (BURN), (BURN2),
33
(BURN3) and (BURN4) into one stream (MAINBURN) to be used for heating the first dry
reforming of methane reactor. The outlet stream (MAINBRUN) had a flow of 3795.16 lbmol/hr
composed mainly of hydrogen gas, carbon monoxide gas, water vapor, methane gas, and
carbon dioxide.
Table 20. MIXBURN Results

Outlet temperature 142.16 F
Vapor fraction 1
The turbine (TURBINE) was use to recover some of the energy used to compress the
feed stream (FEED) entering the reactor (EQREACT). The gas stream (VAPPROD) entering the
turbine had a pressure of 6990.82 psia. The mixed stream (VFLFEED) leaving the turbine had a
pressure of 382.095 psia. The turbine generated 2626.89 kW of power.
Table 21. TURBINE Results

34
Flowsheets
Figure 6: Dry Methane Reformation Flowsheet
35
Figure 7: Acetic Acid From Synthesis Gas Flowsheet
36
Dry Methane Reforming Flowsheet Streams
Table 22. FEEDMIX

Heat and Material Balance Table
Stream ID Units CH4FEED CO2FEED COMPFEED
From FEEDMIX
To FEEDMIX FEEDMIX FEEDCOMP
Stream Class CONVEN CONVEN CONVEN
Maximum Relative Error
Cost Flow $/sec
MIXED Substream
Phase Vapor Vapor Vapor
Temperature F 70 70 69.95729569
Pressure Psia 14.69594878 14.69594878 14.69594878
Molar Vapor Fraction 1 1 1
Molar Liquid Fraction 0 0 0
Molar Solid Fraction 0 0 0
Mass Vapor Fraction 1 1 1
Mass Liquid Fraction 0 0 0
Mass Solid Fraction 0 0 0
Molar Enthalpy Btu/lbmol -32104.42822 -169256.4828 -100680.4555
Mass Enthalpy Btu/lb -2001.178614 -3845.881663 -3353.077888
Molar Entropy Btu/lbmol-R -19.37140317 0.553372624 -8.032810597
Mass Entropy Btu/lb-R -1.207485693 0.01257385 -0.267526
Molar Density lbmol/cuft 0.002590474 0.002598866 0.002594507
Mass Density lb/cuft 0.041558359 0.114375561 0.077903404
Enthalpy Flow Btu/hr -70778148.72 -373146670.9 -443924819.6
Average MW 16.04276 44.0098 30.02628
Mole Flows lbmol/hr 2204.622622 2204.622622 4409.245244
CO2 lbmol/hr 0 2204.622622 2204.622622
CH4 lbmol/hr 2204.622622 0 2204.622622
CO lbmol/hr 0 0 0
H2 lbmol/hr 0 0 0
Mole Fractions
Mass Flows kg/hr 16042.76 44009.8 60052.56
Mass Fractions
Volume Flow cuft/hr 851049.7597 848301.8575 1699453.749
37
Table 23. FEEDCOMP
Stream ID Units COMPFEED HXFEED
From FEEDMIX FEEDCOMP
To FEEDCOMP HX
Stream Class CONVEN CONVEN
Cost Flow $/sec
MIXED Substream
Phase Vapor Vapor
Temperature F 69.95729569 191.3188951
Pressure Psia 14.69594878 29.39189755
Molar Vapor Fraction 1 1
Molar Liquid Fraction 0 0
Molar Solid Fraction 0 0
Mass Vapor Fraction 1 1
Mass Liquid Fraction 0 0
Mass Solid Fraction 0 0
Molar Enthalpy Btu/lbmol -100680.4555 -99588.70132
Mass Enthalpy Btu/lb -3353.077888 -3316.717932
Molar Entropy Btu/lbmol-R -8.032810597 -7.55106743
Mass Entropy Btu/lb-R -0.267526 -0.251481949
Molar Density lbmol/cuft 0.002594507 0.004222154
Mass Density lb/cuft 0.077903404 0.126775575
Enthalpy Flow Btu/hr -443924819.6 -439111007.6
Average MW 30.02628 30.02628
Mole Flows lbmol/hr 4409.245244 4409.245244
CO2 lbmol/hr 2204.622622 2204.622622
CH4 lbmol/hr 2204.622622 2204.622622
CO lbmol/hr 0 0
H2 lbmol/hr 0 0
Mole Fractions
Mass Flows kg/hr 60052.56 60052.56
Mass Fractions
Volume Flow cuft/hr 1699453.749 1044311.825
38
Table 24. HX
Stream ID Units HXFEED DMRFEED RXOUT 1
From FEEDCOMP HX DMRREACT HX
To HX DMRREACT HX COMP1
Stream Class CONVEN CONVEN CONVEN CONVEN
Maximum Relative
Error
Cost Flow $/sec
MIXED Substream
Phase Vapor Vapor Vapor Vapor
Temperature F 191.3188951 1607 1652 320.5573692
Pressure Psia 29.39189755 29.39189755 29.39189755 29.39189755
Molar Vapor Fraction 1 1 1 1
Molar Liquid Fraction 0 0 0 0
Molar Solid Fraction 0 0 0 0
Mass Vapor Fraction 1 1 1 1
Mass Liquid Fraction 0 0 0 0
Mass Solid Fraction 0 0 0 0
Molar Enthalpy Btu/lbmol -99588.7013 -81004.6283 -45011.0622 -58777.0422
Mass Enthalpy Btu/lb -3316.71793 -2697.79101 -2023.72502 -2642.65194
Molar Entropy Btu/lbmol-R -7.55106743 6.871681617 15.49800204 5.475817485
Mass Entropy Btu/lb-R -0.25148194 0.228855576 0.696799695 0.246196119
Molar Density lbmol/cuft 0.004222154 0.001324827 0.001296487 0.003510946
Mass Density lb/cuft 0.126775575 0.039779635 0.028836069 0.078089371
Enthalpy Flow Btu/hr -439111007 -357169272 -267927496 -349869232
Average MW 30.02628 30.02628 22.24168889 22.24168889
Mole Flows lbmol/hr 4409.245244 4409.245244 5952.481079 5952.481079
CO2 lbmol/hr 2204.622622 2204.622622 1433.004704 1433.004704
CH4 lbmol/hr 2204.622622 2204.622622 1433.004704 1433.004704
CO lbmol/hr 0 0 1543.235835 1543.235835
H2 lbmol/hr 0 0 1543.235835 1543.235835
Mole Fractions
Mass Flows kg/hr 60052.56 60052.56 60052.56 60052.56
Mass Fractions
Volume Flow cuft/hr 1044311.825 3328166.129 4591237.169 1695406.572
39
Table 25. DMRREACT
Stream ID Units DMRFEED RXOUT
From HX DMRREACT
To DMRREACT HX
Cost Flow $/sec
MIXED Substream
Phase Vapor Vapor
Temperature F 1607 1652
Pressure Psia 29.39189755 29.39189755
Molar Entropy Btu/lbmol-R 6.871681617 15.49800204
Mass Entropy Btu/lb-R 0.228855576 0.696799695
Average MW 30.02628 22.24168889
CO2 lbmol/hr 2204.622622 1433.004704
CH4 lbmol/hr 2204.622622 1433.004704
CO lbmol/hr 0 1543.235835
H2 lbmol/hr 0 1543.235835
Mole Fractions
Mass Flows kg/hr 60052.56 60052.56
Mass Fractions
40
Table 26. COMP1
Stream ID Units 1 2
From HX COMP1
To COMP1 COOL1
Cost Flow $/sec
MIXED Substream
Phase Vapor Vapor
Temperature F 320.5573692 769.4950617
Pressure Psia 29.39189755 145.0377377
Molar Entropy Btu/lbmol-R 5.475817485 6.46603648
Mass Entropy Btu/lb-R 0.246196119 0.290716974
Average MW 22.24168889 22.24168889
CO2 lbmol/hr 1433.004704 1433.004704
CH4 lbmol/hr 1433.004704 1433.004704
CO lbmol/hr 1543.235835 1543.235835
H2 lbmol/hr 1543.235835 1543.235835
Mole Fractions
Mass Flows kg/hr 60052.56 60052.56
Mass Fractions
41
Table 27. COOL1
Stream ID Units 2 3
From COMP1 COOL1
To COOL1 COMP2
Cost Flow $/sec
MIXED Substream
Phase Vapor Vapor
Temperature F 769.4950617 122
Pressure Psia 145.0377377 145.0377377
Molar Entropy Btu/lbmol-R 6.46603648 -0.152937965
Mass Entropy Btu/lb-R 0.290716974 -0.006876185
Average MW 22.24168889 22.24168889
CO2 lbmol/hr 1433.004704 1433.004704
CH4 lbmol/hr 1433.004704 1433.004704
CO lbmol/hr 1543.235835 1543.235835
H2 lbmol/hr 1543.235835 1543.235835
Mole Fractions
Mass Flows kg/hr 60052.56 60052.56
Mass Fractions
42
Table 28. COMP2
Stream ID Units 3 4
From COOL1 COMP2
To COMP2 COOL2
Cost Flow $/sec
MIXED Substream
Phase Vapor Vapor
Temperature F 122 740.4459557
Pressure Psia 145.0377377 1740.452853
Molar Entropy Btu/lbmol-R -0.152937965 1.214986174
Mass Entropy Btu/lb-R -0.006876185 0.054626525
Average MW 22.24168889 22.24168889
CO2 lbmol/hr 1433.004704 1433.004704
CH4 lbmol/hr 1433.004704 1433.004704
CO lbmol/hr 1543.235835 1543.235835
H2 lbmol/hr 1543.235835 1543.235835
Mole Fractions
Mass Flows kg/hr 60052.56 60052.56
Mass Fractions
43
Table 29. COOL2
Stream ID Units 4 5
From COMP2 COOL2
To COOL2 COMP3
Cost Flow $/sec
MIXED Substream
Phase Vapor Vapor
Temperature F 740.4459557 122
Pressure Psia 1740.452853 1740.452853
Molar Entropy Btu/lbmol-R 1.214986174 -5.600412661
Mass Entropy Btu/lb-R 0.054626525 -0.251797995
Average MW 22.24168889 22.24168889
CO2 lbmol/hr 1433.004704 1433.004704
CH4 lbmol/hr 1433.004704 1433.004704
CO lbmol/hr 1543.235835 1543.235835
H2 lbmol/hr 1543.235835 1543.235835
Mole Fractions
Mass Flows kg/hr 60052.56 60052.56
Mass Fractions
44
Table 30. COMP3
Stream ID Units 5 SYNGAS
From COOL2 COMP3
To COMP3
Cost Flow $/sec
MIXED Substream
Phase Vapor Vapor
Pressure Psia 1740.452853 6990.818959
Average MW 22.24168889 22.24168889
CO2 lbmol/hr 1433.004704 1433.004704
CH4 lbmol/hr 1433.004704 1433.004704
CO lbmol/hr 1543.235835 1543.235835
H2 lbmol/hr 1543.235835 1543.235835
Mole Fractions
Mass Flows kg/hr 60052.56 60052.56
Mass Fractions
45
Acetic Acid from synthesis gas flow sheet streams.
Table 31. EQREACT (Equilibrium reactor)

From EQREACT EQREACT
To EQREACT LIQFLASH VAPFLASH
Cost Flow $/hr
MIXED Substream
Phase Vapor Liquid Vapor
Temperature F 428 428 428
Pressure Psia 6980.575668 6990.82 6990.82
Mass Vapor Fraction 1 0 0.738425156
Mass Liquid Fraction 0 1 0.261574844
Molar Entropy Btu/lbmol-R -0.34778813 -29.39460601 -13.42442456
Mass Entropy Btu/lb-R -0.015636765 -0.855689365 -0.445691475
Average MW 22.24169263 34.35195905 30.12044275
H2 lbmol/hr 1543.24 0.067026512 9.342737686
CO lbmol/hr 1543.24 24.25027059 550.9569781
ACETIC ACID lbmol/hr 0 40.72385721 10.226021
PROPIONIC ACID lbmol/hr 0 68.30644495 22.04803513
WATER lbmol/hr 0 327.5127682 119.8707811
CH4 lbmol/hr 1433.01 120.2408674 1431.183068
CO2 lbmol/hr 1433.01 232.2646683 1200.745332
METHYL ACETATE lbmol/hr 0 0.00438778 0.011443683
ETHYL ACETATE lbmol/hr 0 31.52895359 86.88498166
N-PROPYL ACETATE lbmol/hr 0 0.140126838 0.450351126
Mole Fractions
Mass Flows lb/hr 132393.6754 29028.75788 103364.9176
Mass Fractions
46
Table 32. VAPFLASH (First flash tank)
From EQREACT VAPFLASH VAPFLASH
To VAPFLASH MIXBURN FLASH2
Cost Flow $/hr
MIXED Substream
Phase Vapor Vapor Liquid
Pressure Psia 6990.82 367.3987194 367.3987194
Mass Vapor Fraction 0.738425156 1 0
Mass Liquid Fraction 0.261574844 0 1
Average MW 30.12044275 29.39094421 40.90030486
H2 lbmol/hr 9.342737686 9.340819085 0.001918601
CO lbmol/hr 550.9569781 547.9753411 2.981636915
ACETIC ACID lbmol/hr 10.226021 0.601852718 9.624168281
PROPIONIC ACID lbmol/hr 22.04803513 0.940149239 21.10788589
WATER lbmol/hr 119.8707811 29.26975733 90.60102375
CH4 lbmol/hr 1431.183068 1405.439943 25.74312431
CO2 lbmol/hr 1200.745332 1170.793064 29.95226806
METHYL ACETATE lbmol/hr 0.011443683 0.007575853 0.003867829
ETHYL ACETATE lbmol/hr 86.88498166 49.65957544 37.22540622
N-PROPYL ACETATE lbmol/hr 0.450351126 0.178742356 0.27160877
Mole Fractions
Mass Flows lb/hr 103364.9176 94468.57333 8896.344274
Mass Fractions
47
Table 33. LIQFLASH (Second flash tank)
From EQREACT LIQFLASH LIQFLASH
To LIQFLASH MIXBURN FLASH2
Cost Flow $/hr
MIXED Substream
Phase Liquid Vapor Liquid
Pressure Psia 6990.82 146.9594878 146.9594878
Average MW 34.35195905 34.41540215 34.30992253
H2 lbmol/hr 0.067026512 0.066898432 0.000128079
CO lbmol/hr 24.25027059 23.13620105 1.114069542
WATER lbmol/hr 327.5127682 12.8574079 314.6553603
CH4 lbmol/hr 120.2408674 103.7969459 16.44392148
CO2 lbmol/hr 232.2646683 187.6784431 44.5862252
Mole Fractions
Mass Flows lb/hr 29028.75788 11590.12358 17438.6343
Mass Fractions
48
Table 34. FLASH2 (Third flash tank)
From LIQFLASH VAPFLASH FLASH2 FLASH2
To FLASH2 FLASH2 MIXBURN FLASH3
Stream Class CONVEN CONVEN CONVEN CONVEN
Cost Flow $/hr
MIXED Substream
Phase Liquid Liquid Vapor Liquid
Temperature F 176 158 140 140
Pressure Psia 146.9594878 367.3987194 14.69594878 14.69595
Molar Vapor Fraction 0 0 1 0
Molar Liquid Fraction 1 1 0 1
Molar Solid Fraction 0 0 0 0
Mass Vapor Fraction 0 0 1 0
Mass Liquid Fraction 1 1 0 1
Mass Solid Fraction 0 0 0 0
Molar Enthalpy Btu/lbmol -145105.9209 -143399.7676 -127023.8932 -148925
Mass Enthalpy Btu/lb -4229.269849 -3506.080653 -3153.744723 -4252.16
Molar Entropy Btu/lbmol-R -45.17285218 -48.73978917 -17.54241546 -52.2655
Mass Entropy Btu/lb-R -1.316611897 -1.191673004 -0.43554247 -1.4923
Molar Density lbmol/cuft 1.585433944 1.211151768 0.002316108 1.635696
Mass Density lb/cuft 54.39611577 49.53647655 0.093286277 57.28771
Enthalpy Flow Btu/hr -73752690.27 -31191300.54 -22138033.26 -8.2E+07
Average MW 34.30992253 40.90030486 40.27716393 35.02345
Mole Flows lbmol/hr 508.2679593 217.5129086 174.2824338 551.4984
H2 lbmol/hr 0.000128079 0.001918601 0.002045696 9.85E-07
CO lbmol/hr 1.114069542 2.981636915 4.035357719 0.060349
ACETIC ACID lbmol/hr 40.12958511 9.624168281 1.283763736 48.46999
PROPIONIC ACID lbmol/hr 67.45856379 21.10788589 1.970658996 86.59579
WATER lbmol/hr 314.6553603 90.60102375 29.90903317 375.3474
CH4 lbmol/hr 16.44392148 25.74312431 40.02683486 2.160211
CO2 lbmol/hr 44.5862252 29.95226806 69.17061725 5.367876
METHYL ACETATE lbmol/hr 0.003172804 0.003867829 0.003522451 0.003518
ETHYL ACETATE lbmol/hr 23.75811281 37.22540622 27.76482984 33.21869
N-PROPYL ACETATE lbmol/hr 0.118820107 0.27160877 0.115770075 0.274659
Mole Fractions
Mass Flows lb/hr 17438.6343 8896.344274 7019.602156 19315.38
Mass Fractions
Volume Flow cuft/hr 320.5860208 179.5917856 75247.9613 337.1644
49
Table 35. FLASH3 (Fourth flash tank)
From FLASH2 FLASH3 FLASH3
To FLASH3 MIXBURN HEATER
Cost Flow $/hr
MIXED Substream
Phase Liquid Vapor Liquid
Pressure Psia 14.69594878 14.69594878 14.69594878
Average MW 35.02344744 40.67234957 34.20353033
H2 lbmol/hr 9.85E-07 9.84E-07 9.98E-10
CO lbmol/hr 0.060348738 0.058936465 0.001412273
WATER lbmol/hr 375.3473509 40.6044898 334.7428611
CH4 lbmol/hr 2.160210936 2.006245536 0.153965401
CO2 lbmol/hr 5.367876007 4.773713296 0.594162711
Mole Fractions
Mass Flows lb/hr 19315.37642 2843.076073 16472.30035
Mass Fractions
50
Table 36. HEATER (First heater)
From FLASH3 HEATER
To HEATER DIST1
Cost Flow $/hr
MIXED Substream
Phase Liquid Mixed
Temperature F 194 212
Pressure Psia 14.69594878 14.69594878
Molar Vapor Fraction 0 0.467172784
Molar Liquid Fraction 1 0.532827216
Mass Vapor Fraction 0 0.423186971
Mass Liquid Fraction 1 0.576813029
Average MW 34.20353033 34.20353033
H2 lbmol/hr 9.98E-10 9.98E-10
CO lbmol/hr 0.001412273 0.001412273
ACETIC ACID lbmol/hr 46.26307487 46.26307487
PROPIONIC ACID lbmol/hr 82.98939306 82.98939306
WATER lbmol/hr 334.7428611 334.7428611
CH4 lbmol/hr 0.153965401 0.153965401
CO2 lbmol/hr 0.594162711 0.594162711
METHYL ACETATE lbmol/hr 0.001739372 0.001739372
ETHYL ACETATE lbmol/hr 16.67727661 16.67727661
N-PROPYL ACETATE lbmol/hr 0.172610311 0.172610311
Mole Fractions
Mass Flows lb/hr 16472.30035 16472.30035
Mass Fractions
51
Table 37. DIST1 (First distillation tower)
From HEATER DIST1 DIST1
To DIST1 HEATER2
Cost Flow $/hr
MIXED Substream
Phase Mixed Liquid Vapor
Temperature F 212 267.3444755 209.7464038
Pressure Psia 14.69594878 14.7 14.7
Molar Vapor Fraction 0.467172784 0 1
Molar Liquid Fraction 0.532827216 1 0
Average MW 34.20353033 68.70738475 22.67188474
H2 lbmol/hr 9.98E-10 2.24E-136 9.98E-10
CO lbmol/hr 0.001412273 6.31E-88 0.001412273
WATER lbmol/hr 334.7428611 0.100476734 334.6423844
CH4 lbmol/hr 0.153965401 1.97E-70 0.153965401
CO2 lbmol/hr 0.594162711 7.61E-62 0.594162711
METHYL ACETATE lbmol/hr 0.001739372 1.25E-42 0.001739372
ETHYL ACETATE lbmol/hr 16.67727661 9.29E-42 16.67727661
N-PROPYL ACETATE lbmol/hr 0.172610311 3.51E-40 0.172610311
Mole Fractions
Mass Flows lb/hr 16472.30035 8288.675894 8183.624455
Mass Fractions
52
Table 38. HEATER2 (Second heater)
From DIST1 HEATER2
To HEATER2 DIST2
Cost Flow $/hr
MIXED Substream
Phase Liquid Mixed
Temperature F 267.3444755 269.6
Pressure Psia 14.7 14.69594878
Mass Vapor Fraction 0 0.413084696
Mass Liquid Fraction 1 0.586915304
Average MW 68.70738475 68.70738475
H2 lbmol/hr 2.24E-136 2.24E-136
CO lbmol/hr 6.31E-88 6.31E-88
WATER lbmol/hr 0.100476734 0.100476734
CH4 lbmol/hr 1.97E-70 1.97E-70
CO2 lbmol/hr 7.61E-62 7.61E-62
METHYL ACETATE lbmol/hr 1.25E-42 1.25E-42
ETHYL ACETATE lbmol/hr 9.29E-42 9.29E-42
N-PROPYL ACETATE lbmol/hr 3.51E-40 3.51E-40
Mole Fractions
Mass Flows lb/hr 8288.675894 8288.675894
Mass Fractions
53
Table 39. DIST2 (Second distillation tower)
From HEATER2 DIST2 DIST2
To DIST2
Cost Flow $/hr
MIXED Substream
Phase Mixed Vapor Liquid
Temperature F 269.6 244.3517817 285.7350899
Pressure Psia 14.69594878 14.69594878 14.69594878
Molar Vapor Fraction 0.419023769 1 0
Molar Liquid Fraction 0.580976231 0 1
Average MW 68.70738475 59.97077773 73.99396232
H2 lbmol/hr 2.24E-136 0.00E+00 0.00E+00
CO lbmol/hr 6.31E-88 0.00E+00 0
WATER lbmol/hr 0.100476734 0.100476734 2.14E-15
CH4 lbmol/hr 1.97E-70 0.00E+00 0
CO2 lbmol/hr 7.61E-62 0.00E+00 0
METHYL ACETATE lbmol/hr 1.25E-42 0.00E+00 0
ETHYL ACETATE lbmol/hr 9.29E-42 0.00E+00 0
N-PROPYL ACETATE lbmol/hr 3.51E-40 0.00E+00 0
Mole Fractions
Mass Flows lb/hr 8288.675894 2727.403414 5561.272481
Mass Fractions
54
Table 40. MIXBURN (Burn streams mixer)
From VAPFLASH LIQFLASH FLASH2 FLASH3 MIXBURN
To MIXBURN MIXBURN MIXBURN MIXBURN
Stream Class CONVEN CONVEN CONVEN CONVEN CONVEN
Cost Flow $/hr
MIXED Substream
Phase Vapor Vapor Vapor Vapor Vapor
Temperature F 158 176 140 194 142.155
Pressure Psia 367.39872 146.95949 14.695949 14.69595 14.69595
Molar Vapor Fraction 1 1 1 1 1
Molar Liquid Fraction 0 0 0 0 0
Molar Solid Fraction 0 0 0 0 0
Mass Vapor Fraction 1 1 1 1 1
Mass Liquid Fraction 0 0 0 0 0
Mass Solid Fraction 0 0 0 0 0
Molar Enthalpy Btu/lbmol -87196.17 -115836.6 -127023.89 -133388 -92417.4
Mass Enthalpy Btu/lb -2966.77 -3365.836 -3153.7447 -3279.56 -3025.66
Molar Entropy Btu/lbmol-R -9.145893 -7.835643 -17.542415 -29.6909 -3.88653
Mass Entropy Btu/lb-R -0.311181 -0.227678 -0.4355425 -0.73 -0.12724
Molar Density lbmol/cuft 0.05774 0.0221408 0.0023161 0.002181 0.002282
Mass Density lb/cuft 1.6970336 0.7619831 0.0932863 0.088703 0.069713
Enthalpy Flow Btu/hr -2.8E+08 -39010452 -22138033 -9324051 -3.5E+08
Average MW 29.390944 34.415402 40.277164 40.67235 30.54451
Mole Flows lbmol/hr 3214.2068 336.77141 174.28243 69.90194 3795.163
H2 lbmol/hr 9.34E+00 6.69E-02 2.05E-03 9.84E-07 9.409764
CO lbmol/hr 5.48E+02 2.31E+01 4.0353577 0.058936 575.2058
ACETIC ACID lbmol/hr 0.6018527 0.5942721 1.2837637 2.206915 4.686803
PROPIONIC ACID lbmol/hr 0.9401492 0.8478812 1.970659 3.606398 7.365087
WATER lbmol/hr 29.269757 12.857408 2.99E+01 40.60449 112.6407
CH4 lbmol/hr 1.41E+03 1.04E+02 40.026835 2.006246 1551.27
CO2 lbmol/hr 1.17E+03 1.88E+02 69.170617 4.773713 1432.416
METHYL ACETATE lbmol/hr 7.58E-03 1.21E-03 0.0035225 0.001779 0.014092
ETHYL ACETATE lbmol/hr 4.97E+01 7.77E+00 27.76483 16.54141 101.7367
N-PROPYL ACETATE lbmol/hr 1.79E-01 2.13E-02 0.1157701 0.102048 0.417868
Mole Fractions
Mass Flows lb/hr 94468.573 11590.124 7019.6022 2843.076 115921.4
Mass Fractions
Volume Flow cuft/hr 55666.883 15210.474 75247.961 32051.47 1662829
55
Table 41. TURBINE (Turbine for gas stream from reactor)
From
EQREACT TURBINE
To TURBINE VAPFLASH
Cost Flow $/hr
MIXED Substream
Phase Vapor Mixed
Pressure psia 6990.82 382.0946682
Mass Vapor Fraction 0.738425156 0.919610926
Mass Liquid Fraction 0.261574844 0.080389074
Average MW 30.12044275 30.12044275
H2 lbmol/hr 9.342737686 9.342737686
CO lbmol/hr 550.9569781 550.9569781
WATER lbmol/hr 119.8707811 119.8707811
CH4 lbmol/hr 1431.183068 1431.183068
CO2 lbmol/hr 1200.745332 1200.745332
METHYL ACETATE lbmol/hr 0.011443683 0.011443683
ETHYL ACETATE lbmol/hr 86.88498166 86.88498166
N-PROPYL ACETATE lbmol/hr 0.450351126 0.450351126
Mole Fractions
Mass Flows lb/hr 103364.9176 103364.9176
Mass Fractions
56
Design Alternatives
The alternative methods for this design discussed in the initial study on this process, i.e.
the CHE 4070 final paper, were considered and many resulted in a change in the final design.
Further alternatives on this design are discussed in the future work section as they are primarily
developments which need to take place to improve the chemical and physical properties of the
process, not the design itself.
Permitting and Environmental Concerns
The process design has one major environmental issue associated with it. The issue that
is observed deals with air emissions. Due to the setup of the process, all waste products are
gaseous. The major component of the process that results in the high emission rate of 508,000
tons/year of waste. The major components of the waste will be CO2 and H2O due to a complete
combustion assumption. Even with the complete combustion assumption, there are several
component that will be emitted are considered priority pollutants. Without the complete
combustion reaction there are three priority pollutants that must be considered. The first
possible priority pollutant is SOx. The total amount of sulfur that would be emitted with a
1000kmol/hr basis of natural gas feed was determined to be 0.96tons/year utilizing the
assumption of methane as the molar mass of natural gas and a density of 0.48kg/m3. This is
well under the 100tons/year to become a major source of SOx emissions. Even though it is
under the emissions, since it is a poison for the catalyst it will be removed with a solid
adsorption to prevent SOx emissions. The other priority pollutants would be CO, NOx, and
Particulates. These were all determined below using the emission factors from the EPA.
The CO emission rate is found by utilizing the CO emission factor rater for uncontrolled post-
57
nsps value of 84 lbs/106 scf. Utilizing a density of 0.48kg/m3 of natural gas, and the
508000tons/year burn stream; the emission rate of CO was determine to be 1424tons/year.
This is well above the 10ton/year limit of a major source of CO emissions. This was stated at a B
Rating for the emission factor. The main control method for CO emissions is CO to air ratio
present in the heating of the DRM reactor. The smaller the ratio of CO to air, the better the
emission values. The trade-off with this is that the addition of air will affect the efficiency of the
heating process.(7)
The last priority pollutant that was involved with complete combustion is NOx. No
nitrogen is entered into the burn stream from the process, but thermal NO x from the nitrogen
in the air stream that is combined with the burn stream in the heating process. The un-
controlled post NSPS emission factor for NOx is 190lb/ 106 scf. This is a grade A rating for the
emission factor. This would result in a total emission of 3221tons/years of NOx. There are two
main focuses of NOx control. The first is low NOx burner. This reduces the emission factor to
140lb/106 scf, a grade A rating for emissions. With this reduced emission factor the overall
emission of NOx was reduced to 2373tons/year. This is still well above the 100tons/year for a
major source of NOx emissions. Low NOx burners are relatively inexpensive, and will be the
most utilized NOx control. The other major NOx control is the Flue gas recirculation (FGR) which
lowers the emission factor to 100lbs/106scf. This is a grade D emission factor rating. The total
emissions of NOx would be reduced to 1695 tons/year. Even though this value is 10 times
higher than the 100tons/year limit for NOx emissions, it is also decreasing the overall emissions
by close to a factor of 2. The pricing for a FGR is difficult to determine, with a limited amount of
literature data. The FGR is the main alternative compared to the low NOx burners. There is also
58
selective catalytic reduction (SCR) for NOx reduction. SCR factors are not readily available, and
the complexity of the SCR would increase cost by a factor that would make it an illogical
replacement for the FGR or low NOx burners.
Natural gas, even though it is a gaseous mixture, particulate emissions are still a
possibility. The particulate emissions factor is 7.6 lb/106scf of natural gas. This correlates to a
value of 128tons/year which is above the limitations, making it a major source. The other
compounds in the waste stream that are considered Volatile Organic Compounds (VOC’s)
include: Methyl acetate, ethyl acetate, n-propyl acetate, acetic acid, propionic acid, and
methane. The assumption that the burn stream is pure methane allows for all of the VOC’s and
other compounds to be converted into CO2, H2O and the priority emissions based upon
information from the EPA emissions of natural gas. Purifying and separating the by-products
from the burn stream was considered, however the already large capital cost, and the
additional equipment that would be needed resulted in the decision to not work on separating
the by-products. It is an item that will be mentioned in the future work section.
With the above calculations it was determined that multiple permits for this process.
The permits would include permits for NOx, CO, and particulates. These would all have to be for
major sources of pollutants. With the high values, purchasing of other pollutant limits will be
necessary, or reconsideration of the material rates would have to be implemented.
Due to the complexity of the process and the specific equipment requirements, the only
method that could be used to reduce emissions is pollution control equipment. Since all waste
is in gaseous form the only two types of pollution controls are dry or wet absorption to then
have a liquid or solid waste. The only other method to control the CO2 would be to separate the
59
CO2 and recycle it back into the process or to develop a higher percent conversion for the
reactions. The recycle stream would be as effective as the separation of the CO 2. Due to the
complexity of separating the gaseous compounds this method was not investigated further. The
conversion rate was considered in the design alternative and provided in the tornado plot of
the process.
The economic impact could not be determined. The only economic impact that could be
considered is the cost of the permits required. The major impact would be to the environment.
With complete combustion the amount of CO2 emissions is the remainder of the 508,000
tons/year minus the conversion of the pollutants converted to CO2. This could not be directly
compared to the emissions for Steam reforming, since the literature sources on steam
reforming utilize CO2 sequestration.(19) If the total need of natural gas for a steam reforming
plant stated in the introduction was emitted, then a large scale SRM would emit 1,254,114
tons/year and a small scale SRM would emit 179tons/year. Compared to an acetic acid
producing plant which has an expected CO2 emissions of 9944tons/year.(23) This amount is
significantly smaller than what the proposed design would emit, however the production rate
of acetic acid for the reported CO2 emissions is not known. Since there was not very accurate
information on SRM plants or acetic acid plants the comparison between DRM and SRM CO2
emissions were not able to be accurately conducted. The emissions for the proposed process
are extremely high, and has a very negative impact on the local environment. The buying of
limits would have to be implemented to have these emissions. The amount of air fed into the
burn stream would have to be large enough to mitigate the concentration of the emissions to
lower the harm to the local community. This causes the efficiency of the burn stream to be
60
decreased since it would be flooded with water. The other environmental effects would be the
acid rain from SOx, and then NOx issues. There are no considered energy impacts for the
emissions.
Based upon the possible control methods, as well as the emissions there was not a BACT
conducted due to the lack of information on the costs of the pollution control technology. This
is due to the lack of set regulations on greenhouse gases, and the low amount of SO x emissions.
Safety and Risk Management
With the process and the quantity of unit operations that are needed, there are several
factors that need to be considered when looking at Safety issues, and how to manage and the
risk associated with this process
The first and most important factor that needs to be considered is the pressure at which
the second reaction needs to occur. With close to 500bar pressure needed, if there is anything
that cause the compressors or reactor to malfunction it could have catastrophic results. The
blast that could occur could potentially destroy the entire plant, kill everyone inside, and
adversely affect the local community. There are several steps that could be taken to mitigate
this issue. The first is attempting to have the reaction occur at lower pressures. Even if this was
possible, a high pressure would still need to be dealt with. Separating the high pressure systems
from the rest of the process with blast walls would help to mitigate a domino effect of damage
if the high pressure systems malfunction. Additional steps to monitor the high pressure
systems, train employees on the proper responses to issues with the systems, and methods to
communicate with the local community would help address the potential safety risks of the
high pressure system.
61
The second factor that is a major consideration is the temperature at which the first
reaction must occur. With high temperatures there are risks of explosions with malfunctions
which would be addressed in a similar manner to the high pressure systems. Another safety risk
is extensive burns due to the temperature of the equipment. This would be mitigated through
employee training as well as insulating all necessary equipment.
The process contains Carbon monoxide, which is known to cause brain damage and
death if it is not properly ventilated. If CO leaked out of the system it could kill employees very
easily since it is both colorless and odorless. The way to minimize the potential risk of CO
poisoning would be to train employees to know the signs and symptoms of CO poisoning. Also
CO detectors would be installed in key locations throughout the plant. The plant would also be
designed to provide large amount of ventilation quickly as a backup/ response plan to CO leaks.
Hydrogen gas is also being run through the process. Hydrogen gas is extremely
dangerous if it is leaked into the plant since it can be ignited and cause explosions. To mitigate
this, employees will be trained on the proper response for a H2 leak. Monitors will be placed to
determine if any H2 is being leaked, and there will be periodic sweeps of each part of the
process to ensure there is no degradation of the equipment or any gas leaks. This set up will be
done for any of the other gaseous products that are in the process.
Since both propionic and acetic acid are produced, considerations for handling acids
have to be conducted. Acid spills can be a major safety risk in and outside the plant. Acid spills
can then allow vapors to be released along with other detrimental effects to humans and the
environment. The other thing is that depending on the acid concentration, acid burns can be
62
very harmful to humans. To mitigate the risk of acid spills would be to conduct employee
training on proper handling and storing of acids. Also hazardous waste training should be
conducted, as well as how to clean up acid spills. If acid is spilled and could affect the local
environment by being absorbed into the soil, a response and local community outreach plan
would need to be established in case of an acid spill.
Additional risk assessments on each unit operation are provided below in the HAZOPs
for the process.
63
Equipment Deviations What event Consequences Additional Process Notes and
reference and from could cause of this implication of indications questions
operating operating this deviation on this
conditions conditions deviation? item of consequence
equipment
under
consideration
Acetic acid
reactor Reactor How much
Feed 1. Feed is Damage to
EQREACT obstructed collapse under reactor and flow deviation
Less vacuum explosion can reactor
2. Upstream handle?
process is Possible Possible
compromised reactant damage to Consider
compromise reactor and possible shut
downstream off valves
units between
reactor and
3. Upstream downstream
process Reactor units.
ruptures Explosion
More producing Consider flow
more feed than restricting
expected valve upstream
from reactor.
No Same as less
Composition 4. Impurity in Consider

reactant5. Possible side Damage to sampling feed
As well as reactor/explosi stream.
Wrong reactions or
reactant run away on
How can other
reaction Damage to materials make
Other than it into DRM?
Side reactions reactor
64
Pressure
Less 6. Reactor Catastrophic Explosion Consider
leak failure periodic
checks/mainte
nance
7. Reactor stops
Compromised producing Units
feed pressure product downstream Consider
potentially pressure
damaged sensors on the
8. feed stream.
More
Compromised Consider
feed pressure Possible Explosion
reactor rupture pressure
9. Runaway sensors on the
reactions feed stream.
10. Obstructed Keep track of

outlet all reaction
happening in
vessel.
No Same as less Regular
maintenance
on outlet
piping.
65
Temperature
Less 11. Reactor stops Thermal stress What are
Temperature producing on reactor. thermal limits
of feed is specified of reactor?
colder. product.
What are
12. Lower See events 6-7. Thermal stress pressure limits
reactor on reactor. of reactor?
pressure
What are
More 13. Reactor thermal limits
overheats, Reactants/prod
Temperature ucts released. of reactor?
of feed is possible vessel
rupture. Explosion. What are
hotter.
Thermal stress pressure limits
14. Higher See events 8- of reactor?
10. on reactor.
reactor
pressure
66
equipment
under
consideration
First flash Feed

drum Possible What are the
Less 1. Reactor Vessel
VAPFLASH output pressure drop. collapse. pressure
changed. ratings of the
vessel?
2. Feed is Possible
obstructed Vessel Could a flow
vacuum. collapse. control be used
More to ensure that
material is not
3. Reactor Over leaving the
output Vessel rupture.
pressurization. vessel faster
changed. than it enters?
Could a flow
Same as less. restriction
No
valve be used
to ensure that
flow to the
vessel does not
exceed
specifications?
Pressure
What are the
Less 4. Leak in lower vessel
Possible vessel
vessel. Products leak. pressure
rupture.
specifications?
5. Reactor Possible Vessel Can the vessel
output vacuum. collapse. be isolated in
compromised. case of
rupture?
67
More 6. Output Vessel over What are the
streams pressurization. upper pressure
obstructed. Possible vessel limits of the
rupture. vessel?
7. Reactor
output Possible Can a flow cut
compromised. compromize of off valve be
separation Downstream
units may used if reactor
process. output stream
No malfunction.
Same as less. does not meet
specifications?
Temperature
What is the
Less
8. Temperature Vessel will not lower
of input stream achieve Thermal stress temperature
is lower. desired on flash drum. rating on the
separation. vessel?
9. Lower Thermal stress
vessel See events 4-5. on flash drum. What is the
pressure. lower pressure
rating of the
vessel?
10. Thermal stress What is the
More Vessel may
Temperature on drum. upper
of input stream become
temperature
is higher. compromised. Possible specification
See events 6-7. rupture and on the vessel?
11. Higher explosion.
vessel What is the
pressure. higher pressure
rating on the
vessel?
68
equipment
under
consideration
Second flash Feed

Less 1. Input stream Vessel
LIQFLASH changed. pressure drop. collapse. pressure
ratings of the
2. Feed is vessel?
obstructed Possible Vessel Could a flow
More to ensure that
3. Input stream material is not
changed. Over leaving the
Vessel rupture.
than it enters?
Same as less.
Could a flow
restriction
No
valve be used
to ensure that
flow to the
vessel does not
exceed
specifications?
Pressure
What are the
vessel. Possible vessel
Products leak. pressure
rupture.
specifications?
5. Input stream Possible Vessel Can the vessel
compromised. vacuum. collapse. be isolated in
case of
rupture?
69
rupture. vessel?
7. Input stream
compromised. Possible Can a flow cut
compromize of off valve be
units may used if input
process. stream does
No Same as less. malfunction.
not meet
specifications?
Temperature
8. Temperature What is the
Less
of input stream Vessel will not lower
is lower. achieve Thermal stress temperature
desired on flash drum. rating on the
9. Lower separation. vessel?
vessel Thermal stress
pressure. See events 4-5. on flash drum. What is the
lower pressure
rating of the
vessel?
10.
Temperature Thermal stress What is the
More Vessel may
of input stream on drum. upper
is higher. become
temperature
compromised. Possible specification
11. Higher rupture and
See events 6-7. on the vessel?
vessel explosion.
pressure. What is the
higher pressure
rating on the
vessel?
70
equipment
under
consideration
Third flash Feed

FLASH2 changed. pressure drop. collapse. pressure
ratings of the
2. Feed is vessel?
More to ensure that
Vessel rupture.
than it enters?
Same as less.
Could a flow
restriction
No
valve be used
to ensure that
flow to the
vessel does not
exceed
specifications?
Pressure
What are the
rupture.
specifications?
case of
rupture?
71
rupture. vessel?
7. Input stream
not meet
specifications?
Temperature
Less
lower pressure
rating of the
vessel?
10.
More Vessel may
is higher. become
temperature
vessel explosion.
higher pressure
rating on the
vessel?
72
equipment
under
consideration
Fourth flash Feed

FLASH3 changed. pressure drop. collapse. pressure
ratings of the
2. Feed is vessel?
More to ensure that
Vessel rupture.
than it enters?
Same as less.
Could a flow
restriction
No
valve be used
to ensure that
flow to the
vessel does not
exceed
specifications?
Pressure
What are the
rupture.
specifications?
case of
rupture?
73
rupture. vessel?
7. Input stream
not meet
specifications?
Temperature
Less
lower pressure
rating of the
vessel?
10.
More Vessel may
is higher. become
temperature
vessel explosion.
higher pressure
rating on the
vessel?
74
equipment
under
consideration
First Feed
distillation Possible What are the
tower Less 1. Input stream Vessel
flowrate pressure drop. collapse. pressure
DIST1 changed. ratings of the
vessel?
2. Input stream Possible
is obstructed. Vessel Could a flow
More to ensure that
material is not
3. Input stream Over leaving the
flowrate Vessel rupture.
Could a flow
No
valve be used
to ensure that
flow to the
vessel does not
exceed
specifications?
What are the

Pressure 4. Leak in lower vessel
Possible vessel
Less rupture.
ratings? Can
5. Input stream Possible Vessel the vessel be
compromised. vacuum. collapse. isolated in case
of rupture?
75
More 6. Output Vessel over Possible vessel What are the
streams pressurization. rupture. upper pressure
obstructed. ratings of the
vessel?
7. Input stream
compromised. Possible Downstream Can a flow cut
compromize of units may off valve be
separation malfunction. used if input
No Same as less.
not meet
specifications?
Temperature
8. Temperature Thermal stress What is the
Less
of input stream Vessel will not on distillation lower
is lower. achieve tower. temperature
desired rating on the
9. Lower separation. Thermal stress vessel?
vessel on distillation
pressure. See events 4-5. tower. What is the
lower pressure
rating of the
vessel?
10. Thermal stress
Temperature distillation What is the
More Vessel may
of input stream tower. upper
is higher. become
temperature
compromised. Possible
specification
vessel explosion.
higher pressure
rating on the
vessel?
76
equipment
under
consideration
Second Feed
distillation Possible What are the
tower Less 1. Input stream Vessel
DIST2 changed. ratings of the
vessel?
2. Input stream Possible
More to ensure that
material is not
3. Input stream Over leaving the
Could a flow
No
valve be used
to ensure that
flow to the
vessel does not
exceed
specifications?
What are the

Possible vessel
Less rupture.
ratings? Can
5. Input stream Possible Vessel the vessel be
of rupture?
77
More 6. Output Vessel over Possible vessel What are the
vessel?
7. Input stream
compromised. Possible Downstream Can a flow cut
compromize of units may off valve be
separation malfunction. used if input
No Same as less.
not meet
specifications?
Temperature
8. Temperature Thermal stress What is the
Less
of input stream Vessel will not on distillation lower
is lower. achieve tower. temperature
desired rating on the
9. Lower separation. Thermal stress vessel?
vessel on distillation
pressure. See events 4-5. tower. What is the
lower pressure
rating of the
vessel?
10. Thermal stress
Temperature distillation What is the
More Vessel may
of input stream tower. upper
is higher. become
temperature
compromised. Possible
specification
vessel explosion.
higher pressure
rating on the
vessel?
78
equipment
under
consideration
First heater Feed

HEATER Less 1. Cold stream Possible Vessel What are the
vessel?
2. Cold stream Possible
More to ensure that
material is not
3. Cold stream Over leaving the
Could a flow
No
valve be used
to ensure that
flow to the
vessel does not
exceed
specifications?
What are the

Possible vessel
Less rupture.
ratings? Can
5. Hot stream Possible Vessel the vessel be
of rupture?
79
More 6. Hot streams Vessel over Possible vessel What are the
obstructed. pressurization. rupture. upper pressure
ratings of the
7. Hot stream vessel?
compromised.
Downstream Can a flow cut
units may off valve be
malfunction. used if input
Same as less.
stream does
No not meet
specifications?
Temperature 8. Temperature
of hot stream Vessel will not Thermal stress What is the
Less achieve
is lower. on heat lower
desired heat exchanger. temperature
9. Lower exchange. rating on the
vessel Thermal stress vessel?
pressure. See events 4-5. on heat
exchanger. What is the
lower pressure
rating of the
10.
vessel?
Temperature Vessel may Thermal stress
of hot stream become on hear What is the
More
is higher. compromised. exchanger. upper
temperature
11. Higher See events 6-7. Possible
specification
vessel rupture and
on the vessel?
pressure. explosion.
What is the
higher pressure
rating on the
vessel?
80
equipment
under
consideration
First heater Feed

HEATER2 Less 1. Cold stream Possible Vessel What are the
vessel?
2. Cold stream Possible
More to ensure that
material is not
3. Cold stream Over leaving the
Could a flow
No
valve be used
to ensure that
flow to the
vessel does not
exceed
specifications?
What are the

Possible vessel
Less rupture.
ratings? Can
5. Hot stream Possible Vessel the vessel be
of rupture?
81
More 6. Hot streams Vessel over Possible vessel What are the
obstructed. pressurization. rupture. upper pressure
ratings of the
7. Hot stream vessel?
compromised.
Downstream Can a flow cut
units may off valve be
Same as less.
stream does
No not meet
specifications?
Temperature 8. Temperature
of hot stream Vessel will not Thermal stress What is the
Less achieve
is lower. on heat lower
desired heat exchanger. temperature
9. Lower exchange. rating on the
vessel Thermal stress vessel?
pressure. See events 4-5. on heat
exchanger. What is the
lower pressure
rating of the
10.
vessel?
Temperature Vessel may Thermal stress
of hot stream become on hear What is the
More
is higher. compromised. exchanger. upper
temperature
11. Higher See events 6-7. Possible
specification
vessel rupture and
on the vessel?
pressure. explosion.
What is the
higher pressure
rating on the
vessel?
82
equipment
under
consideration
Burn stream Feed

mixer Possible What are the
Less 1. Feed Vessel
MIXBURN streams pressure drop. collapse. pressure
flowrate ratings of the
changed. vessel?
Possible Vessel Could a flow
2. Feed vacuum.
streams are collapse. control be used
More obstructed. to ensure that
material is not
3. Feed Over Vessel rupture. leaving the
streams pressurization. vessel faster
flowrate than it enters?
changed.
Could a flow
restriction
No
valve be used
Same as less. to ensure that
flow to the
vessel does not
exceed
specifications?
What are the

Pressure lower vessel
Possible vessel
Burn streams pressure
4. Leak in rupture.
Less leak. ratings? Can
vessel.
Vessel the vessel be
5. Feed Possible collapse. isolated in case
streams vacuum. of rupture?
compromised.
83
More 6. Feed Vessel over Possible vessel What are the
vessel?
7. Feed
streams Downstream Can a flow cut
compromised. units may off valve be
stream does
No not meet
Same as less.
specifications?
Temperature
Thermal stress What is the
Less
8. Temperature on mixer. lower
of feed streams temperature
is lower. rating on the
vessel?
9. Lower See events 4-5. Thermal stress
vessel on mixer. What is the
pressure. lower pressure
rating of the
vessel?
10. Vessel may What is the
More become Thermal stress
Temperature on mixer. upper
of feed streams compromised.
temperature
is higher. Possible specification
See events 6-7.
rupture and on the vessel?
11. Higher explosion.
vessel What is the
pressure. higher pressure
rating on the
vessel?
84
Economic Analysis
Full data and Calculations for the FCI, NPV, and IRR can be found in the Economic
Information folder of the database in the Excel file named economics on the sheets labeled
Summary FCI, and NPV Calc.
The DRM process is not yet economically viable. This is largely due to the high annual
costs of the process. Due to the high value of our byproduct, propionic acid, and the sheer
volume produced per year, the variable costs come out to -23.2 million a year. However, there
are still significant annual costs, for example it costs 11.3 million a year to run the compressors
for the process for example. This is even after we implemented turbines that can recapture
2890 kW per hour of energy from decompression at the end of the process. This is based on the
most recent industrial price of electricity in Wyoming, which is 6.78 cents per kilowatt-hour(27).
The fixed costs are approximately 38.8 million per year, and are mainly comprised of 17.8
million needed for maintenance and the 14 million needed for taxes and insurance. These
estimates come from guidelines in the CHE 4070 lecture notes that state maintenance would be
about 4.2% of the ISBL costs.(22) This breakdown can be seen in the economics Excel file under
the summary FCI and Other Economics Info sheets. One of the only low annual costs is the feed
cost. The total feed cost is approximately 387 thousand dollars per year. This is based upon a
natural gas price of $3.56 per million cubic feet(29). The carbon dioxide cost is assumed zero due
to need of power plants to reduce their CO2 emissions. The annual expenses are the sum of the
fixed and variable costs, which is 15.7 million dollars. The annual revenue would only be
roughly forty percent of that at 6.31 million dollars a year with an assumed price of 25 cents/lb
of acetic acid(3) and 72 cents/lb of propionic acid. Propionic acid price was 63 cent/lb (5) in 2007
85
and it was indexed to 2016 values using the 2007 Chemical Engineering Plant Cost Index (CEPCI)
(8) and 2016 CEPCI(9). This means the process is economically unviable. While the annual costs
are most certainly the main reason for poor economic performance, large capital cost
contribute to the problem.
A large piece of the capital costs would be the two reactors; at 3.6 million dollars for the
DRM reactor and 19 million dollars for the acetic acid reactor. Due to the high pressures
involved in the second half of the process the second reactor would cost significantly more than
the first. Another factor that would make the second reactor so expensive is that a glass lining
would be required to prevent acetic acid from corroding the reactor to the point of catastrophic
failure and depressurization. The glass lining will also help prevent hydrogen embrittlement. A
few unit Operations after the reactor are also at a high enough temperature for embrittlement
to be an issue, but with monitoring and additional research into using “bake-out” methods the
hazard presented should be mitigated. In order to pressurize the feed to the acetic acid reactor
almost 30 million dollars would need to be spent on compressors, by far the largest portion of
the capital investment. In actuality, this price would likely to be even larger, as the figures used
from Peters and Timmerhaus only account for compressors that operate up to 70 bar, and the
process would operate around 485 bar(22). In order to account for this discrepancy, it was
assumed that the price of compressors scaled linearly with pressure increases, but the case may
be that prices are related exponentially to pressure. This should be further researched. So a
compressor running at 140bar would cost twice what a compressor running at 70 bar does,
holding all other conditions constant. The distillation towers for the process would cost around
800 thousand dollars. This was found by using figures 15-11 for the tower shell and 15-14 for
86
the internals from Peters and Timmerhaus(22). In order to protect distillation towers and
internals from corrosion, it was decided to use packed towers with acid resistant packing.
According to table 10-8 in P&T Novolac epoxies are resistant to both strong and weak acids and can
operate between 200-260C without significant deterioration. This process only goes up to 220C (428F)
for most unit operations. The acetic acid reactor is the only notable exception, and should still be
glass lined. Each tower would have a Novolac epoxy resin coating, and ceramic Intalox saddle
packing. To account for that coating the price of the distillation shell was multiplied by a factor
of 1.75(10). All of the heat exchangers necessary for the process would cost around 321
thousand dollars according to figures 14-18 and 14-32 from Peters and Timmerhaus. Two
turbines were added to the process in order to recapture energy from depressurization. One is
an axial gas turbine costing approximately one million dollars. The other is a liquid radial
expander turbine costing 195 thousand dollars. They recapture 12.5% of the electrical energy
put into the process, which saves 1.6 million dollars every year. A delivery factor of 1.1 and an
installation factor of 5.04 were assumed for all equipment costs based on Peters and
Timmerhaus guidelines(22). All costs were also indexed from the 2002 values in Peters and
Timmerhaus to 2016 values using Equation 15. Both the 2016 CEPCI (9) and the 2002 CEPCI (6)
were found online.
CEPCI 2016
Cost in 2016 = CEPCI 2002 ∗ Cost in 2002 (15)
The catalyst was assumed to have a two-year life, and was priced at 1% of the fixed capital
investment. The resulting amount allotted for both catalysts was 4.7 million dollars. This
assumption was made after consulting with the project supervisor, Dr. Joseph Holles. This all
adds up to a fixed capital investment of around 471 million dollars in today’s dollars. Table 42
87
below shows the Total FCI and pertinent figures. Table 43 is the equipment list used to calculate
the ISBL value. These massive capital costs, high annual costs, and low revenue estimates
Table 42. Total FCI and Additional Figures
Delivery factor 1.1

Installation factor 5.04 P&T table 6-9
ISBL FOB $76,389,472.72 TOTAL EQUIPMENT FCI
OSBL FOB $7,638,947.27 10% of ISBL
Installed ISBL (IISBL) $423,503,236.76 ISBL*Installation*Delivery
Installed OSBL (IOSBL) $42,350,323.68 OSBL*Installation*Delivery
Installed FCI (IFCI) $465,853,560.44 IISBL+IOSBL
Total Installed FCI (TIFCI) $470,559,151.95 IFCI/.99
Working Capital $117,639,787.99 25% of TIFCI
Start-up $47,055,915.20 10% of TIFCI
Total catalyst cost $4,705,591.52 1% of TIFCI
Assume a two year catalyst life with .5% of the FCI allotted for each catalyst
each year
88
Table 43. Equipment List
Equipment ID Description Feature(s) Used for Cost Estimation Source for Estimation FOB Cost
Compressors
COMP1 First compressor kWh Used P&T figure 12-28 $ 3,600,000.00
COMP2 Second compressor kWh Used P&T figure 12-28 $ 15,390,000.00
COMP3 Third compressor kWh Used P&T figure 12-28 $ 10,335,000.00
COMP4 Feed Compressor kWh Used P&T figure 12-28 $ 590,000.00
Distillation Towers
DIST1 Tower 1 Packed Height, TD, Packing size and shape, ACL P&T figures 15-11 15-14 $ 656,500.00
DIST2 Tower 2 Packed Height, TD, Packing size and shape, ACL P&T figures 15-11 15-14 $ 146,350.00
Flash Tanks
LIQFLASH Liquid seperator OP,ACL,TD P&T figure 12-54 $ 163,625.00
VAPFLASH gas seperator OP,ACL,TD P&T figure 12-54 $ 114,537.50
FLASH2 Liquid seperator OP,ACL,TD P&T figure 12-54 $ 20,212.50
Flash 3 Liquid seperator OP,ACL,TD P&T figure 12-54 $ 8,750.00
Heat Exchangers
HX Reactor Feed-Effluent ACL, SA, Heat Duty P&T figure 14-18 $ 42,000.00
COOL1 Intercompressor cooler ACL, SA, Heat Duty P&T figure 14-18 $ 35,000.00
COOL2 Intercompressor cooler ACL, SA, Heat Duty P&T figure 14-18 $ 40,000.00
COND1 DIST1 condenser ACL, SA, Heat Duty P&T figure 14-18 $ 52,500.00
REB1 DIST1 reboiler ACL, SA, Heat Duty P&T figure 14-18 $ 50,000.00
COND2 DIST2 condenser ACL, SA, Heat Duty P&T figure 14-18 $ 34,125.00
REB2 DIST2 reboiler ACL, SA, Heat Duty P&T figure 14-18 $ 23,000.00
HEATER Heater for PROD3 ACL, SA, Heat Duty P&T figure 14-18 $ 33,250.00
HEATER 2 Heaterfor BTMPROD ACL, SA, Heat Duty P&T figure 14-18 $ 11,375.00
Reactors
DMRREACT Multitubular Reactor OP, L, TD, SA P&T figure 14-19,21,22,23 $ 3,603,750.00
EQREACT Multitubular Reactor OP, L, TD, SA P&T figure 14-19,21,22,23 $ 19,031,040.00
Turbines
GASTURBINE Axil Gas Turbine kWh Recovered P&T figure 12-34,35 $ 1,050,000.00
LIQTURBINE Radial Expander Turbine kWh Recovered P&T figure 12-34,35 $ 195,000.00
Total Equipment Cost $ 55,226,015.00
Indexed Total Equipment Cost $ 76,389,472.72
Legend
ACL=Anti-Corrosion Lining kWh=Kilowatt hour L=Length OP=Operating Pressure SA=Surface Ares TD=Tank or Tower Diameter
The poor economic performance is reflected in the net present value (NPV12) and
Internal rate of return (IRR) values. Both were calculated with a 12% discount factor. The NPV12
value over 20 years would be -675.35 million dollars. The IRR was also highly negative, at -11%.
A MACRS5 depreciation system, 35% tax rate, 3 year construction period starting in year -2
ending in year 0, and a 2 year build up period with 75% in year one and 90% in year two were
assumed and utilized based upon process design guideline from Peters and Timmerhaus(22).
89
Table 44 at the end of this section shows annual cash flows, NPV, and IRR.
These poor economic results for NPV12 and IRR were the result of several problems in
the process. The first of which would be the aforementioned fact that the revenue is only 40%
of the production costs. Secondly, the estimated process capital costs were massive. The real
capital costs would likely be even higher since it is likely the compressors would cost more than
what was estimated.
There are several methods that could be investigated to assist with increasing revenue
and lowering costs. However, more research is needed to determine if it is feasible. Research
should be put into a process to separate out ethyl acetate from the waste stream. It is possible
that by passing the stream through a liquid phase with strong acid or base could pull it out of
the vapor mixture, more research should be done. The last and most important area for
investigation is the improvement of reaction yields, which would increase the process revenue
significantly. This is paramount for the process to become economically viable. Increasing the
conversion to propionic acid should be researched, since it is so valuable and the process makes
so much already. The increased conversion rate would also affect the utility prices when recycle
streams are considered.
Increasing revenue is only half of the equation when trying to improve economic
viability. Research in several areas was conducted to decrease capital costs. These areas include
cheaper anti-corrosion options, pressurization of the initial feed to reduce the first reactor’s
size, steam compressors, utilization of a fluidized bed reactor to reduce reactor size, and
recycling the catalyst if possible. Pressurizing the initial feed was slightly helpful but didn’t have
a large impact since the first reactor is relatively cheap. Pure steam compressors were not
90
considered since turbines on the back end of the process are transferring energy to the front
end. Also steam compressors could interfere with integrating energy from the burn stream.
Research into a catalyst that can operate at lower pressures in the acetic acid reactor is
paramount to make this process feasible. 482 bar is an extraordinarily high, and extraordinarily
expensive pressure to run at. Reducing the pressure will reduce the cost of the compressors,
which are the largest capital cost. There were also concepts investigated to lower the variable
costs. These areas were heat integration to lessen the overall heat demand, utilizing steam
compressors to lower electricity costs, and the recapture of energy when the second reactors
product stream is depressurized. Heat integration is accomplished by splitting the burn stream
up and directing it to where heat is needed. Steam compressors were not considered for the
reasons stated above. Two turbines were added to recapture energy from depressurization.
91
Table 44. Cash Flows and Resulting NPV, NPV12, and IRR
92
Sensitivity Analysis
In order to determine what parameters would affect the economics of the process and to what
degree a sensitivity analysis was performed. The IRR was analyzed by separately changing each
considered parameter by 25% and analyzing the effect on the IRR, and then analyzing a 50%
change. The parameters analyzed were the conversion of the DRM reactor, the price of acetic
acid, the price of propionic acid, and the cost of electricity. The results are displayed in Figures
8 & 9. Changing the pressure in the first reactor was examined and determined to be
inconsequential since that would only change the size, and therefore the cost, of the first
reactor which is a very small portion of our capital costs.
Figure 8: IRR with a 50% Change in Parameter
As seen in figure 8, the conversion has the largest effect on the IRR with -2 percent IRR if the
conversion were increased by 50 percent and with -28 percent IRR if the conversion were
decreased by 50 percent. The effect of the propionic acid price has a larger effect than the price
of acetic acid because it is worth more and the process makes roughly twice the amount of
93
propionic as acetic. The figure shows that increasing the price of propionic acid by 50 percent
would make the IRR -3 percent while decreasing it by 50 percent would make the IRR -25
percent. The price of electricity has the opposite effect on the IRR. So, if electricity usage is
decreased by 50 percent, the IRR would be -8 percent while it would be -14 percent if the
electricity usage was increased by 50 percent. That result is realistic because we spend money
on electricity while the other parameters all related to production. Lastly is the acetic acid price,
which has least effect on the IRR; increasing and decreasing it by only 2 percent if the price
were increased or decreased by 50 percent.
Figure 9: IRR with a 25% change in parameter.
Figure nine shows the resulting IRR from changing the parameters by 25%. The hierarchy of
which parameter affects the process the most is the same as for the 50% change case.
Increasing and decreasing the conversion would make IRR -6 percent or -18 percent. Changing
the propionic acid price by 25% would make the IRR -6 percent for a positive change and -17
percent for a negative change. Increasing and decreasing of usage of electricity by 25 percent
94
would make the IRR -10 percent and -13 percent. Changing in the price of acetic by 25% would
change the IRR by 1 percent up or down.
Global Impact
There are a few areas that this project will be able to effect on a global scale. A main
area is becoming a major competitor in the Acetic acid and Propionic acid markets. With the set
values for the feed and product rates the process could become an alternative source for both
products. This would have a global impact on acetic acid and propionic acid distributors, as well
as an impact on the local community by providing a plethora of new jobs, as well as feeding into
the local economy. The economic impact is not the only area that will be affected by this
process. The environment will have major effects both locally and on a global scale. Compared
to a SRM, the carbon emissions would hopefully be lower due to the use of carbon dioxide as a
feed gas. An actual comparison of CO2 emissions could not be conducted due to limited
literature information on CO2 emissions for an SRM. Due to the complexity of the separation
needed for unreacted CO2, the environment will also be impacted by the emissions of the plant.
These emissions will include Carbon dioxide as well as minimal amounts of sulfur based upon a
complete combustion of all waste products. This will have negative effects on the environment
by releasing greenhouse gases, but the amount of greenhouse gases will be lowered compared
to those from a SRM. On a global scale, this could affect the overall greenhouse emission,
especially if a higher conversion rate and CO2 separation and recycle streams can be integrated
into the process. On a local scale, this could affect the air quality of the local environment. Due
to complete combustion, the overall environmental impact would be alleviated, however
proper dispersion of the emissions must be implemented to prevent any harmful effects on the
95
local environment. The main ethical issues would be a part of the environmental considerations
to impact the carbon footprint of the local area, as well as the carbon emissions worldwide.
Conclusion
In conclusion, even though the process is not economically feasible with the current
condition, the process is physically possible. The main factor that makes the process unfeasible
is the low conversion rates and the cost due to the necessary pressure. With a conversion rate
of 35% in the DRM reactor from the feed causes the product ratio to be very one-sided. The
traditional method for producing acetic acid utilizes methanol as an intermediate, which is also
used on an industrial scale. The issue with a methanol intermediate is the additional reactor,
catalyst, and additional unit operations that are needed to alter the stream properties to the
necessary values. Considering these factors and following the advice by the project supervisor
(Dr. Joseph Holles) the traditional method was not explored. The focus of this project was to
determine the necessary steps that must be met in the research and development phase to
make the process possible. Ignoring the methanol intermediate method allowed for more time
and effort to be focused on exploring the different design alternatives inside each part of the
process and determining the additional research and development necessary to result in an
economically viable process. The methods that were explored the changing of the pressure, the
conversion rate, and the prices of products, by-products, and the utility costs. There were
several important results that were found when researching changes in the aforementioned
variables. The most important factors that contribute to increasing the IRR is Conversion and
the price at which propionic acid can be sold. Even with a 50% increase, no one variable can
affect the process to the point of making it profitable. However if the operating pressure of the
96
acetic acid reactor can be decreased by 50%, the conversion to syngas is increased to 50%, and
propionic acid could be sold for 150% the current price, then the process can become profitable
with an IRR of 13%. The other option is if there is an increase to 80% conversion to syngas and
both propionic and acetic acid can be sold at 150% the current price; the resulting IRR would be
15%. The other major factor that would help to make the process profitable would be to be
able to run the second reactor at a lower pressure. At half of the current pressure the capital
and utility cost would decrease resulting in an IRR of
-2%. If the reaction could occur at ¼ of the current pressure, then the resulting IRR would be
11%. More in depth calculations for these conditions can be seen in the sensitivity analysis
folder. The file name should describe what the sensitivity analysis is for. Even with all of these
items considered, the project still has a lot of room for improvements. At this point in time it
would advised to not move forward with the project since only very optimal, and unverified
cases show a possible profit.
Future Work and Recommendations
For future work, many aspects must be considered to improve the process. First, CO 2
recycle streams will be considered to take advantage of CO2 that was removed by the four flash
tanks and CO2 produced from the burn stream. The main issue with CO2 recycle streams is that
CO2 is in a burn stream with 9 other gaseous compounds and a gas-gas separation would
greatly increase the complexity of the process, along with the overall cost. The second aspect is
heat integration; heat is lost during the current process. In the future, heat could be taken from
streams 2, 4, and BURNMIX and used in the distillation reboilers. This was integrated to an
extent during this step of the process, but more in-depth analyses could be conducted. The
97
third aspect to be considered is utilities; the utilities would cost approximately 12 million dollars
per year utilizing the current basis. The main issue with the utilities is the electricity, which
costs 11 million dollars per year. That is around three quarters of the utilities cost. Most of the
electricity is being used to run the compressors. This was mitigated by utilizing turbines setup
to collect energy for the compressors after the acetic acid reactor.
In the future, the refining of byproducts should be explored to determine if this is
economically viable. Of these byproducts, ethyl acetate is the one which should be primarily
considered. Ethyl acetate would be the easiest to separate and could be purified and sold or
converted into acetic acid and sold in that form. Once these steps are met the future work
should then be shifted to research and development. It would have to start with batch testing
of catalyst types to try to achieve the stated conversion rates at the operating pressures and
temperatures listed in the conclusion section. Then the research and development phase would
have to be altered to a continuous reaction from a batch reaction to determine the viability of
the catalyst. Once a continuous reaction with the set catalyst meets the stated requirements on
a research based level, scaling up experiments would have to be conducted to determine the
viability on an industrial scale. All of these steps and more are needed to determine what is
necessary for a continuous DRM and direct acetic acid process to become a plausible
alternative to the other methods of creating syngas and acetic acid.
98
Acknowledgements
There are two major people that the group would like to acknowledge. The first person
is the group advisor, Dr. Joseph Holles, who helped steer the group as well as help develop the
process to focus on the necessary research and development requirements to make the
process profitable.
The second person that the group would like to acknowledge is Dr. Richard Horner for
providing insight into carbon processes through his work in the carbon initiative and his advice
during the fall final presentation and spring progress report.
99
Appendices
Business Info.zip
1. Business Information
a. Alternatives – Professor suggestions, problem statement
b. Benefits -
c. Marketability -
d. Contemporary issues -
Copy of Base case

econ 35per conv and 2 atm.xlsx
2. Economic Information
a. Capital Cost
i. Heater Costs – Sheet: hx
ii. Compressor Costs – Sheet: compressors
iii. Flash Drum Costs – Sheet: Flash Drums
iv. Distillation Tower Costs – Sheet: towers
v. Pump Costs – Sheet: pumps
vi. Reactor Costs – Sheet: reactor
vii. System Pressure for Corrections – Sheets: reactor, hx, Flash Drums,
compressors, pumps, towers
viii. Installation Factor – Sheet: Summary FCI
ix. Working Capital – Sheet: Summary FCI
b. Variable Costs
i. Feed Cost – Sheet: Other Economics Info
ii. By Product price – Sheet: Other Economics Info
iii. Product Price – Sheet: Other Economics Info
iv. Syngas Catalyst Cost – Sheet: Summary FCI
v. Acetic Acid Catalyst Cost – Sheet: Summary FCI
c. Utilities
i. CW Price – Sheet: Summary FCI
ii. Steam Price – Sheet: Summary FCI
iii. Natural Gas Price – Sheet: Summary FCI
d. Fixed Costs
i. Labor – Sheet: Production Cost Sheet
ii. Maintenance – Sheet: Production Cost Sheet
iii. Laboratory – Sheet: Production Cost Sheet
iv. Taxes and Insurance – Sheet: Production Cost Sheet
v. Plant Overhead – Sheet: Production Cost Sheet
e. Start Up – Sheet: Summary FCI
f. Tax Rate – Sheet: NPV Calc
g. MACRS5 Factor – Sheet: NPV Calc
h. NPV – Sheet: NPV Calc
i. IRR – Sheet: NPV Calc
100
Sensitivity Analysis.zip
j. Sensitivity analysis
Equipment
3. Equipment Design Design.zip
a. Feed composition
b. Mixer
c. Heat exchanger
d. Syngas Reactor
e. Compressors X3
f. Cooler x 2
g. Acetic Acid Reactor
h. Tower 1
i. Tower 2
j. Tower 3
k. Heater
l. Valve
m. Condenser
n. Reboiler
4. Physical Properties
a. Component List – See Aspen+ Simulations
b. Auxiliary fluid list – See Aspen+ Simulations
c. Property Method – See Aspen+ Simulations
d. Vapor Pressure Data – See Aspen+ Simulations
e. Vapor Liquid Equilibrium Data – See Aspen+ Simulations
5. Preliminary Designs, Progress Reports, Meeting Minutes & Presentations
Progress
Reports.zip
a. Progress Reports
Final Oral
b. Final Oral PresentationPresentation Spring 2017 (1).pptx
6. Process Information
DMR Process.zip
a. DRM Information
i. Product Purity
ii. Catalyst
1. Conversion rate
2. longevity
Syngas to Acetic
Acid Process.zip
b. Conversion to Acetic Acid Information
i. Feed Rate
ii. Product Purity
101
iii. Catalyst
1. Conversion rate
2. longevity
7. Background – See Problem Statement
8. General Chemistry – See additional Sources
a. Feed to Syngas via Dry Reforming
b. Syngas to Acetic Acid
c. Syngas to Methanol
d. Methanol to Acetic Acid
9. Safety
MSDS.zip
a. Material SDS
Enivornmental.zip
10. Environmental
a. Pollutants
b. Emission rates
c. BACT considerations
Aspen+
Simulations.zip
11. Aspen+ Simulations
Additional
Sources.zip
12. Additional Sources
102
Works Cited
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Wyoming, Laramie, WY.
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safety-data-sheet-sds-p4604.pdf?la=en. Retrieved December 8, 2016.
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Systems, Synthesis Gas Cleanup, and Oxygen Separation Equipment; Task 1: Cost
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(15) Leaky, A. D., Ainsworth, E. A., Bernacchi, C. J., Rogers, A., Long, S. P., & Ort, D. R. (2009).
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Design and Decision for Combined Steam Reforming Process with Dry Methane
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http://www.optience.com/sitefiles/rex/examples/Methanol-Synthesis.pdf
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(25) Synthesis of Acetic Acid from Methanol and Carbon Monoxide. (1935, August). Industrial
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105
Contribution Break down:
Hussain Alsukairi: Pg. 64-85, assisted with Econ.
Alexander Fox: Pg. 1-5, 21-57, with anything focusing on DRM, 103-106
Sean Kasprisin: Pg. 5-20, 57-61
Tim Poppert: Pg. 85-102
Nykyta Vovk: Pg. 21-57 with anything focusing on Acetic Acid, 61-64
106

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an achievable alternative to Steam Reforming. With multiple factors adjusted to optimal an

results are available.

minimizing costs and maximizing profit by integrating heat and a spin-wheel/turbine to

mitigated through the use of Novolac coating).

resolved by utilizing an equilibrium reactor, which resolved the issue.

constraints were met.

sold on an industrial level.

minimize some of the environmental constraints.

not economically feasible.

enough that no current patents are limiting the project.

CH4 + H2O → CO + 3H2 (1)(4)

CO + H2O → CO2 + H2 (2)(4)

as a by-product, which is a greenhouse gas. The carbon dioxide needs to be removed or

sequestrated, which costs money as well adversely affecting the environment.(15)

of methane, which will be the main alternative that is considered.(4)

reactants to create the syngas. This is visible in Equation 3 below.

integrated into the process as a source of heat to decreasing utility costs.

reaction for the direct conversion of syngas into Acetic Acid.

2CO + 2H2 → CH3COOH (4)(14)

CO + 2H2 → CH3OH (5)(17)

CO + CH3COH → CH3COOH (6)(25)

acetic acid per ton for multiple countries.(3)

Figure 2: World Consumption of Acetic Acid in 2016.

syngas directly to acetic acid.

shown in the figure below.(24)

trimethylolpropane propionates. It also has uses as a flavoring agent and pharmaceuticals.

scaled for a continuous DRM process.

the pressure incrementally.

cause Hydrogen embrittlement. Hydrogen embrittlement is a process of weakening steel and

the safety section of the report.

Base case description

20.7 MMCUFT/day of methane.

prepare for conversion to acetic acid.

reactions are presented below.

catalyzed reaction. (1)

Figure 5: Reaction Mechanism for Catalyzed Acetic Acid Reaction

methane, carbon monoxide, carbon dioxide and hydrogen.

Assumptions and approximations

Handbook for operating limits of carbon steel machinery.(21)

catalyzed reaction to carry out the economic analysis.

Describe each section of design

atmospheres in a compressor (FEEDCOMP) to prepare for the reaction.

Table 1. FEEDCOMP Results

In order to achieve the desired reaction temperature, a countercurrent heat exchanger

product stream during the subsequent compressions.

A stoichiometric based reactor (DMRREACT) was used to simulate the reformation

stream can ideally be used as a source of 335 MMBtu/hr.

Table 3. DMRREACT Results

Table 4. COMP1 Results

compressors, which arise at temperatures above 450 °C.

Table 5. COOL1 Results

Table 6. COMP2 Results

compressors, which arise at temperatures above 450 °C.

Table 7. COOL2 Results

Table 8. COMP3 Results

Table 9. EQREACTOR Results

Table 10. VAPFLASH Results

Table 11. LIQFLASH Results