Production of Propionic Acid From Syngas: Team Echo: Sabah Basrawi Alex Guerrero Mrunal Patel Kevin Thompson
Production of Propionic Acid From Syngas: Team Echo: Sabah Basrawi Alex Guerrero Mrunal Patel Kevin Thompson
Production of Propionic Acid From Syngas: Team Echo: Sabah Basrawi Alex Guerrero Mrunal Patel Kevin Thompson
Team Echo:
Sabah Basrawi
Alex Guerrero
Mrunal Patel
Kevin Thompson
1. EXECUTIVE SUMMARY
I. Abstract
2. DISCUSSION
I. Process Overview
i. Production of Propionaldehyde
ii. Oxidation of Propionaldehyde
4. APPENDICES
I. Design Basis
i. Commercial Production
ii. Environmental Review
iii. Specifications to Meet Industry Standards
iv. Clear Statement of Feedstock
II. Block Flow Diagram
III. Process Flow Diagram
IV. Material and Energy Balances
V. Calculations
VI. Annotated Equipment list
VII. Economic Evaluation factored from equipment cost
VIII. Utilities
IX. Conceptual control Scheme
X. General Arrangement (Plant Layout)
XI. Distribution and End- Use Issues review
XII. Constraints Review
i. Feedstock Definition
ii. Conversion Technology Description
iii. Separation Technology Description
iv. Production Description
v. Location Sensitivity Analysis
vi. ESH Law Compliance
vii. Turndown Ratio
XIII. Applicable Standards
XIV. Project Communications
XV. Competing Processes
XVI. Information Sources and References
1. EXECUTIVE SUMMARY
I. Abstract
propionic acid is an important organic acid that does not receive much publicity. Propionic acid –
which occurs naturally in apples, strawberries, grains, cheese, and human sweat – is mainly used
as a mold inhibitor for various animal feed and baked goods as well as a preservative in cheeses.
plasticizers, textile and rubber auxiliaries, dye intermediates, as well as flavorings and cosmetics.
The plant designed for this project has a projected production rate of 16,000 tons of propionic
acid per year. The initial feedstock will comprise of sygnas (a mixture of CO and H2) and
ethylene, which will react in a process known as carbonylation in the presence of a rhodium
based catalyst to produce propionaldehyde and ethane. The ethane will be removed from the
system and sold back to Lyondellbasell (from where the ethylene is acquired) and the
propionaldehyde will then be oxidized to produce propionic acid. The market demand for
propionic acid is expected to grow at around 2.3% per year regardless of the state of the
economy since food production and preservation is highly dependent upon it.
The location of this plant, as well as the plant being designed by team foxtrot, will be
Lyondellbasell is because of the difficulty in transporting ethylene is much greater than that of
coal. The inconvenience experienced by team foxtrot by being a few hours away from their coal
source is minimal in comparison with the distress that would have been found by team echo with
ethylene transport.
Based upon the economics of the process it the recommendation of the process engineers
that the process not be completed. With a capital cost of 57.8 million dollars, yearly expenses of
around $28 million and yearly profit of around $ 29 million, it would take 18.5 years for the
project to break even. Thus the IRR and NPV values show that the process would be a non-
profitable venture.
2. DISCUSSION
I. Process Overview
The production of propionic acid was chosen due to the amount of industrial applications.
While the food industry will be a main target of Team Echo, other avenues will also be explored
i. Production of Propionaldehyde
Ethylene will be obtained at 450 psi pressure and 70 ° F temperature. Syngas will be obtained at
the prescribed temperature and pressure of 290 psia and 212 ° F. Ethylene will be heated to 212
° F which is the reaction temperature. Both ethylene and syngas will be fed into the reactor at the
Propionaldehyde is a precursor to propionic acid, and is the aldehyde for of propionic acid. The
conversion of the reactants to the aldehyde is not one hundred percent and thus there will be
unreacted reactants in the product stream. The amount of by-products produced was higher than
originally anticipated with a 50% selectivity towards the ethane by-product. Because of this the
33,000 ton per year goal will not be met due to a need for more hydrogen in the system. 16,000
tons/year will be produced thus halving the profit of this process. In order to purify the
Propionaldehyde from the ethane. The product will be distilled in order to remove some of the
Propionaldehyde. Once this has been done the product will be sent into an absorbing column in
which butane will be used to absorb the ethane from the major intermediate product. The ethane
and butane will be sent into a stripping column in order to be separated from one another. The
unreacted reactants, which also come from the absorber, will be also be separated from butane in
another stripping column. The reason for the recovery of butane is that it needs to be reused. The
purified propanal streams will be sent on to the second reaction process which will oxidize the
A heat exchange reactor will be used to carry out the aldehyde synthesis reaction and will
be purchased from Chart Energy & Chemicals, Inc. It will be made of stainless steel, which is
more expensive that carbon steel, but the corrosive properties of propionaldehyde are unable to
be supported by carbon steel. The reaction will be catalyzed using a rhodium catalyst which will
be immobilized in the reactor. Because of this, separation of the catalyst is not a problem and
because rhodium has a very long catalyst life, it will not have to be bought often.
The propionaldehyde product from the first reaction is heated to the proper reaction
conditions temp 122° F and pressure 14.7 psia. Oxygen is used to oxidize the aldehyde into its
carboxylic acid form. Oxygen is brought in as air and through a membrane separation; a gaseous
mixture of 85% oxygen at ambient conditions is acquired and heated to the proper temperature
using a feed-effluent heat exchanger. Propionic acid is produced in this reaction, with unreacted
reactants and catalyst also flows from the reactor. To catalyze the oxidation reaction, a cobalt
halide is dissolved in water and the cobalt ion acts as the catalyst. The water component of this
mixture is miscible with the propionic acid final product which is an issue that is dealt with
during the purification part of the process. The cobalt halide is precipitated by concentrating the
solution and separating in series until the final product has been appropriately purified. The mass
purity of the final product is slightly lower than the industrial standard at a purity of 99.3%.
The reason for choosing to produce Propionic acid was because of its wide range of uses, with a focus
on the food preservative aspects of the product. It was the assumption of the group that there would
always be a market for propionic acid as there is always a demand for food regardless of the state of the
economy, and in times of economic boom there will be a greater market for the other uses of Propionic
acid.
A project goal of 33,000 ton/year was selected after learning that the largest producer of Propionic
acid, BASF, produces 88,000 ton/year. As BASF is a majority of the market at approximately 40% team
echo felt it would be reasonable to target approximately 10% of the market as a new company with room
for expansion. Had the goal of 33,000 tons/year been met then the process would have been a profitable
one which could have been a viable option. As the need for more hydrogen was realized late in the
progression of the project it was not possible for team foxtrot to increase the hydrogen content of their
syngas. Due to the economics now that the process is running at half production team echo must
recommend that the process not be completed as it is. The break even point for the process occurs at 18.5
years and that coupled with a negative net present value indicates that the process not move forward
APPENDICES
I. Design Basis
I. Commercial Production
Propionic acid – which occurs naturally in apples, strawberries, grains, cheese, and
human sweat – is mainly used as a mold inhibitor for various animal feed and baked goods as
such as pharmaceuticals, plastics, plasticizers, textile and rubber auxiliaries, dye intermediates,
Safety concerns for the chemicals synthesized and utilized in this process are discussed
below:
It is possible to use propionic acid as a bactericide and fungicide because it has been EPA
certified to have low toxicity to fish, invertebrates, birds and mammals. Propionic acid is used
primarily indoors and use outdoors in small amounts, when used outdoors, propionic acid was
metabolized by organisms into harmless components and has thus been deemed not harmful to
the environment. Propionic acid is non-mutagenic and has overall been observed to not be
harmful. Contact with concentrated solutions of propionic acid however, may cause damage to
eye and bodily membranes as the solution is corrosive. Protective clothing should be used when
Propionaldehyde is the intermediate product produced in the two step reaction and while
it is only available in small amounts in the final product it is still necessary to know as much
about this as possible. Propionaldehyde, according to the EPA, is not a carcinogen, nor does it
have any reproductive effects on humans. Chronic effects: adverse effects on the body with
symptoms that develop slowly due to prolonged exposure to something harmful and do not
subside once the exposure is no more, are not associated with exposure to propionaldehyde.
Acute affects on the other hand, adverse effects that subside once exposure is terminated, results
have proved to be inconclusive in humans though animals have shown moderate to acute toxicity
to the substance.
Ethane is the side product of the first reaction and does travel through the process in
small quantities, therefore knowing the safety issues regarding this chemical is imperative.
According to OSHA, ethane is an asphyxiant which means that it will displace oxygen and lead
to suffocation in sufficient quantities. Also it is explosive as such should be kept from hot
Rhodium is a very rare platinum group element. It is combustible in dust when in the
powder form. Rhodium is quite toxic if inhaled, though this will not be a problem as the
Rhodium based catalyst will be used on graphite supports and immobilized in a packed bed. It is
also a skin irritant, fortunately as it is immobilized in a packed bed, there will be very little
handling of the catalyst. When disposing of the catalyst, very strict regulations disposal must be
followed: Currently Rhodium not classified as harmful to the environment, however this is due
more to a lack of information then it is a standard based on test results and observation. Over
time environmental regulations may come into being which will affect the method of disposal for
(II) iodide generally has a low toxicity; however, there are acute and chronic effects when
exposed to larger amounts of cobalt iodide. Acute effects include: shortness of breath, systemic
effects, skin irritation, eye irritation, and cornea damage. Chronic effects include: respiratory
sensitivity, nodular fibrosis, thyroid disease, pimples, boils, black and blue spots, hives, and
blisters. The probability of these effects occurring is minimal as contact with the chemical is
extremely limited and controlled. To control the exposure of the cobalt to the operator, a
containment box will be utilized so to avoid any health effects. Operation of Cobalt Iodide will
Of the two feeds, syngas is the one that can cause the most problems if there were to be a
leak in the piping. The components of the syngas being fed into the plant as mentioned
previously are hydrogen and carbon monoxide gas. These components are of course hazardous to
humans, the monoxide can be inhaled and cause carbon monoxide poisoning, while the hydrogen
gas can easily ignite and cause a major explosion. To assure a safe environment for the
employees the piping carrying the syngas will be reinforced and inspected regularly. Also the
initial reaction involving the syngas takes place in a bunker so to contain any explosion if it were
to occur.
Ethylene like ethane is an asphyxiant and can potentially suffocate anyone who breathes
in the gas. To prevent this from happening all workers will be required to have masks on while
on the process floor. Ethylene, also like ethane, is a threat to combust and cause a major
explosion so the pipes will be placed away from anything which can increase the temperature of
All pipes carrying large amounts of combustible compounds must be inspected regularly
The industry standard for propionic acid is currently to have 99.5 wt% purity. In order to
achieve this goal the product will be separated many times throughout the process before the
reaching having the solution concentrated and separated in series in order to remove the cobalt
and purify the product. This basis was not met as the propionic acid leaving the process has a
purity of 99.3%.
The feedstock to be used in this process is synthesis gas made by Team Foxtrot and
Ethylene obtained from Lyondellbasell. The synthesis gas or syngas will be created from coal
obtained from Illinois coal basin number 6 in southern Illinois. Because coal is being used as a
source for syngas, the coal will have to be heavily treated in order to have it meet the
specifications of the process. Desulfurization and CO2 sequestration are only two of the
processes that take place in the purification of syngas in order to obtain a 1:1 mole ratio of CO to
H2 which is the ratio necessary for the synthesis of propionaldehyde. The syngas will be received
at the conditions of 300 psi and 250 °F. The amount of impurities in the syngas is not a problem
as the Rhodium catalyst is extremely durable and able to tolerate many poisons, although team
The other feedstock for the synthesis of propionaldehyde is ethylene. It will be obtained
by pipeline an industrial standard purity of 95 wt%. It will be obtained at 420 psig and 70 °F
Oxygen will be fed into the second reaction which is the oxidation of propionaldehyde to
propionic acid. Oxygen will be obtained from the air around and thus is assumed to be at ambient
conditions. As mentioned before, as air is being fed in, it will enter a membrane separator which
will create a gaseous mixture of 85% oxygen and 15% nitrogen gas, which will then be used for
the oxidation. The nitrogen component is not known to react with any species in solution and as
Also the cobalt (II) iodide will need to be dissolved into water which does not contain
either potassium or carbonate ions, as potassium carbonate is the only know poison for the cobalt
catalyst.
V. Recovery Systems
Cobalt catalyst exiting the 2nd reactor is then precipitated out and filtered and
recycled
Ordinary steel is unsuitable for the handling of propionic acid. Aluminum is only resistant at
room temperature and to anhydrous, concentrated propionic acid; at higher temperature corrosiveness
toward aluminum varies with the concentration of acid. Thus the corrosion maximum for 50 oC lies at
75% acid, whereas there are two maxima at the boiling point, a weaker one at 1% and a strong one at
99.8% acid. Copper and copper alloys are stable toward propionic acid up to its boiling point, but only if
the solutions are free from air or oxidizing substances. Of the stainless steels, the ferritic chromium steels
(13 – 17% Cr) are unsuitable because propionic acid tends to cause pitting. Generally, austenitic CrNi
steels and CrNiMo steels are used for handling propionic acid. However, impurities in propionic acid can
make the use of titanium or Hastelloy (e.g., Hastelloy C-22) equipment necessary, even below the boiling
point. Above the boiling point, up to about 230 oC Hastelloy C-22 has shown excellent resistance even
under oxidizing and reducing conditions. Above 230 oC only silver has proved to be a suitable material.
Containers made of aluminum with a purity of 99.5% or alloyed steels are suitable for storing
pure propionic acid. Aluminum is unstable toward aqueous propionic acid. Polyethylene containers can
be used for temporary storage of propionic acid and as small packing drums. Plastics are not
recommended for long-term storage. Glass-reinforced plastics are unsuitable even for short-term storage.
HASTELLOY® C-22® alloy - Used to store the corrosive propionic acid, even at high enough
temperatures.
In figure II.1, a generic version of the process is shown in order to glean a generic sense
of what is happening in the process before going looking at the more detailed flowsheet and
In the above figure is an overall view of the process in which syngas will be transformed
into Propionic acid. Ethylene and syngas will be reacted at 212 ºF and 290 psi using a rhodium
catalyst there is a 50% selectivity towards ethane thus hindering the production of Propionic
acid. The ethane will be separated from the unreacted reactants and while the Propionaldehyde
will be sent onward to the second reactor and will be reacted with oxygen using a cobalt catalyst
in order to form Propionic acid. For a more detailed view of the process with stream summary
V. Calculations
𝑄 = 𝑚 × 𝑐𝑝 𝛥𝑇
𝐵𝑡𝑢
3821928 𝐵𝑡𝑢⁄ℎ𝑟 = 𝑚 × 1.1 × (1828 − 212℉)
𝑙𝑏 × ℉
𝑙𝑏
𝑚 = 3662
ℎ𝑟
The above figure VI.1 depicts each component in the process tagged with a component
ID in order to lessen the confusion with pieces of equipment that are utilized more than more.
The information from the above chart comes from an Aspen Plus simulation which was
sent to Aspen Icarus Process economic analyzer to determine sizing and costing of individual
pieces of equipment.
At full production, if 33000 ton/year were produced, the net present value and IRR were
quite favorable at $212 million and 38% respectively. The process, unfortunately, produces
16000 tons/year of Propionic acid and thus the economics are much less favorable at this
production rate. The actual NPV and IRR are -$20 million and 4% which is an extreme change
The capital cost of the process has been estimated to be $57.8 million with a yearly recurring
operating cost of $28.6 million. With the project grossing $28.8 million per year, with Propionic
acid prices at $1800 /ton the estimated break-even point was 18.5 years. Having a process with
such a long break-even point is inadvisable as the numbers from the economic evaluation are
projections into the future of what may happen and not what will. Because of this, 18 years is a
long time to wait to have the process pay for itself as the fluctuations in the industry and the
market could put the operation out of business before a profit has been made.
Because the economics that have been done are merely projections of what might happen
in the future it becomes necessary to determine the how sensitive the profitability is to the with
economics variables. The economic variables that were analyzed for profitability sensitivity are
capital cost, price of syngas and price of Propionic acid as shown in the following graphs.
The sensitivity of the capital cost shows the process the profitability of the process is very
much affected by the capital cost of the process. The wider range of IRR over the range of the
capital cost shows that the profitability is sensitive to the capital cost. Efforts were made to keep
1.00E+07
Syngas Cost ($/ton)
8.00E+06
6.00E+06
4.00E+06 Series1
2.00E+06
0.00E+00
-2% 0% 2% 4% 6% 8% 10% 12%
IRR
The amount that will be paid to team foxtrot for syngas is also quite sensitive to
profitability. If team echo were to pay more money to foxtrot it would not be long before echo
would reach a negative profit value. The profitability for team echo is so low at 16,000 ton/year
of Propionic acid that it is very difficult to find an economic variable that does not greatly affect
their profitability.
2.00E+03
Acid Price ($/ton)
1.50E+03
1.00E+03 Series1
5.00E+02
0.00E+00
-5% 0% 5% 10% 15% 20% 25%
IRR
Product price will always be an object of major sensitivity. Price of product is the income
of the plant thus it is highly unlikely that there exists a plant that us not sensitive to the price of
its products. While the graph shows that team echo should sell their Propionic acid at a higher
cost that would not be economically feasible as it would exceeds the current bounds of the
Heat Exchanger H2 20
Heat Exchanger H1 0.27
Shown in the above figure is a screen shot taken from google earth of the plot of land in
Morris, Il 60450 that will be used by teams echo and foxtrot to build their plants. The distances
shown in the figure were measured using google earth as well. Care was taken to ensure that
ample transports into and out of both facilities was available. Care was also taken to ensure that
the plants were a reasonable distance from any communities in the area.
Propionic acid was selected to be produced due to its wide range of uses. Uses of Propionic acid
include: Mold inhibitor for various animal feed, food preservatives, pharmaceuticals, plastics, plasticizers,
Propionic acid in the food preservative industry is the aim of this project. Not only do fast foods
use Propionic acid in their food preservatives but grocery stores also utilize Propionic acid to increase the
shelf life of food. With this the demand for food will never waver as people will always need to eat
Use of Propionic acid in plastics was also seriously considered as the main focal point for selling
of the final product. While plastics are common in daily life and always in use, it was decided that the
food market would be more stable and to primarily target, and to secondarily target the other uses of
Propionic acid.
i. Feedstock Definition
Synthesis gas or syngas is a gaseous mixture primarily comprised of carbon monoxide and
hydrogen. The syngas that will be utilized by Team Echo will be created from coal obtained from Illinois
Coal Basin number 6. Because the syngas is coming from coal, desulfurization will need to take place as
sulfur can poison the catalysts. CO2 sequestion will also take place in order to have a greater purity of
syngas. Coal is an abundant resource and is currently the second greatest provider of energy, coming in
second only to petroleum. This coupled with projections that coal will indeed be around for at least the
next two hundred years leaves hope that obtaining the necessary coal for synthesis gas will not be a
problem.
Ethylene is the other portion of feedstock utilized in the synthesis of propionaldehyde. Ethylene is
currently being produced and sold at large quantities at Lyondellbasell in Morris, IL. For this reason, as is
discussed in Location Sensitivity Analysis, both Team Echo and Foxtrot have decided to be located in
Morris. Due to the adjacent plant location to the ethylene supplier, transportation issues for this particular
feed has been eliminated. As for the production of ethylene, it is an abundant hydrocarbon that is easily
Both of our reactors will be compressed heat exchanger reactors, obtained from Chart
Energy and Chemicals Inc. This specific type of reactor allows for the reaction of gas phase as
well as liquid phase feeds and the immediate removal of heat from the system. The first reactor
will be made of stainless steel while the second will be made of hastelloy. Both reactions that
take place in this process to synthesize propionic acid (synthesis of propionaldehyde followed by
the oxidation of the aldehyde) are highly exothermic and will require a medium to absorb all that
heat in efforts to reduce the cost of energy for the plant as a whole. This specific type of reactor
allows for the immediate absorption of exothermic heat which can then be used to increase the
temperature for streams later in the process. The synthesis of the aldehyde intermediate takes
place under the influence of a rhodium based catalyst which will be on a solid support, to
account for this, Chart Energy and Chemicals creates a specific type of the compressed heat
exchanger reactor with room to place packing materials inside the open channels of the reactor.
The standard compressed heat exchanger, without room for packing materials, will be
used for the oxidation of propionaldehyde as the catalyst for this reaction is a dissolved cobalt
salt.
There are multiple methods of separation in this process such as distillation columns,
After the first reactor there is a flash column that will be used to separate some of the
Propionaldehyde from ethane and unreacted reactants and they will be flashed to 90 psi and 145
°F. The Propionaldehyde is sent onward to the second reactor in which it will be oxidized into
Propionic acid.
The by-product ethane will be removed from the system by using an absorption and two
stripping columns. The vaporous product from the flash in the preceding paragraph will be sent
into an absorbing column and the ethane will be absorbed into butane which will be fed into the
10 stage column at stage 5. The ethane-butane stream will exit the bottom of the absorption
column and sent into a stripping column. The unreacted reactants will exit at the top of the
absorbing column and sent into a stripping column in order to recover any butane that may have
The ethane-butane mixture from the preceding paragraph will be sent into a 15 stage
stripping column at stage 7 in order to purify the ethane to be sold, as well as to recover the
butane in order to reuse it. The rest of the butane will be recovered from the unreacted reactants
by utilizing another 10 stage stripping column. The feed to this stripping column will be fed in at
stage 5. 2 moles of butane will still be lost with the ethane stream and thus a make up stream of
Oxygen is separated from air by membrane separation. It was assumed that there would
be an 85% recovery of oxygen in the permeate stream based upon lab experiments performed in
the Unit operations laboratory class. Air will be taken in and used for the oxygen source. The
Cobalt is precipitated out of the solution by concentrating and separated. The solution
The end product of this process will be a 99.3 wt% propionic acid, which is slightly lower
than the industrial purity level of 99.5 wt%. Propionic acid is a colorless liquid which gives off a
pungent odor; chemically it is a three carbon chain carboxylic acid which has a similar density to
water at ambient conditions also this compound is miscible in water much like other short chain
organic acids.
IN
Ethylene
Syngas
Water
Cobalt Iodide (at startup or replacement of deactivated catalyst)
Rhodium (at startup or replacement of deactivated catalyst)
Air
OUT
Propionic acid
Ethane
Cobalt Iodide (deactivated catalyst)
Rhodium (deactivated catalyst)
Nitrogen Gas
According to the EPA both propionic acid and propionaldehyde have been classified as
Ethane and ethylene are both asphyxiants and as such must be contained, especially
Both catalysts are toxic and must be disposed of properly. This does not mean flushing
them down a drain as both are harmful to the environment. Both the rhodium catalyst and the
The turndown ratio for this process is set at 50%, the reason it is set at this value is to avoid any
weeping in the distillation column trays and also to avoid the pipes of the heat exchangers from cruding
up. With half the flow rate, it should be enough to have enough flow to keep all of the components of this
process in working order without any substantial and expensive buildups or backwash.
The Aspen simulations used were able to thermally rate all of the heat exchangers, but
provided little to no help in designing them. To help design heat exchangers for our applications
to withstand our operating temperatures and to meet our mechanical and thermal criteria we
Heat AEL Fixed tube No Yes Yes1 Yes1 Yes Yes Yes2 No
Exchanger sheet
Involving BEM
Cobalt
Catalyst
For all but one of the heat exchangers will there not be any hazardous liquids or gases. As
a result, these heat exchanges follow a certain type of arrangement. According to TEMA, these
externally sealed floating tube sheet heat exchanges follow one of two arrangements – these
being an AEW or BEW arrangement. For the one heat exchanger that involves a hazardous
liquid – containing our cobalt catalyst – the more basic heat exchanger that TEMA offers capable
of containing hazardous liquids was chosen. This fixed tube sheet heat exchanger comes in one
of two arrangements – either an AEL or BEM design. From these three-letter coding system a
picture can be built up of the final shell and tube assembly, consisting of a front-end stationary
head, a shell type, and a rear-end head. For most of our heat exchangers, their design will look
Coding Stationary
Majority of AEW
Heat
Exchangers
BEW
Heat AEL
Exchanger
Containing
Cobalt
Catalyst BEM
o google sketchUp
ISA symbology
Distillation column- temp, composition, temp change, over head receiver, not dry pump,
must have some level in the bottom of the columns, platform wert twenty or thirty feet,
Hx- must be able to pull tubes, need space for this, orient hot dog style,
control room, locker room, storage tanks, all equipment must be located, must have access
Engineering challenges Use block flow in presentation In Econ, total cost total profit, not all
components Spec on period of investment Cost of money that every group will use Interest cost
of money Every group will be using the same assumptions Removing gas, there is am adsorption
and stripping process Hotel used engineering world for costs or sizing? Must remember to
number slides Paired groups do economics together Look into what to do with waste, thermal
2. Next week, March 14-18, 2011: need to meet with Shannon possibly Tuesday but she’ll
email us
i. Finalizing PFD
4. The new reactor conditions for 1st and 2nd reactors need to be defined
a. price
Presentation questions:
sizing of the distillation column are usually ~85 ft for a 35 theoretical stages
We have more info on nickel carbonyl and it shows up in ASPEN as a gas phase only which
Method of recovering our catalyst (cobalt halide)? We’re getting high reflux ratio
CSTR deals with liquids but our design is not a CSTR, can use for place holder, think about
using PFR…
If it’s only one stream we’ll have to keep buying new, if we know price and what we need,
We need details on one of the operations in terms of sizing, looking at one area and making
sure we have everything we need, look at it more closely and make sure everything is
checked
Energy sinks, look at where energy is coming from and into deltaH across a reactor
We will have to see the design and sizing of reactor which ASPEN does not recognize
Email CoX manufacturers to get conversion rates and other important information
Heat of compression
Note the $/yr or day or month that are being calculated in the pricing and economics
Use scientific notation, commas, an overall number to describe an estimate without many and
There are equipment/steps needed in the process such as: decanter, recycle, to recover
place process overview with total #s in and out, this can be displayed in a diagram
improvise the block flow diagram to show what's in the streams and display numbers
o How much heat is generated should tell us how much cooling water we need
How long for 1st and 2nd…may not need large volume. How long we need to be in, residence
Have you contacted Adam Kenya about the Sulfur concentration of syngas from foxtrot?
o She talked to him but Adam will talk to foxtrot so that they find a solution for it.
Add a row for temps and pressures for each stream number
Enthalpy can be found from aspen in the stream summary, use those, they’re fine. If we
don’t want to use, address that we don’t and state how we’ll find it.
Nickel Carbonyl: OSHA has permissible exposure: 0.001ppm for gen industry, threshold
Cobalt Iodide: OSHA 0.1 cob/m3 (rate 3-reacts explosively with water)
Update competing process slide (we are doing 1st rxn but we’re not doing 2nd)
Interest on loans we’re getting to build…we have negative cash flow initially?
Plant Standards EPA, ASME (for pipe standards), OSHA, and FDA: find out product
MB in hand calc
Catalyst life? Nickel bought every yr but cobalt, include the cost as an initial cost as well
as annual
Selectivity of catalyst?
Aspen flowsheet
Hand calculations
Economics
pricing on catalysts
Nickel Carbonyl
Utility costs
Plant Economics
o economic evaluation
Location: Morris, Il
o make sure its close to a railroad so its easy for foxtrot to transport coal.
On the table:
o Send an email to Foxtrot, Shannon and Adam stating the composition and the feed
rate required
o its easier to transfer coal compared to transferring ethylene, so this decision should be
o gulf coast
o Utility conditions?
o compare conditions with foxtrot and determine if there is anything we both can use
What we know:
o temp: 250-300 C
Notes from first meeting with Shannon (Jan 23, 2011) meeting:
On powerpoint
Look at schedule
Lowers temp to 45 C
State of catalyst?
Polyethylene
according to their density and molecular structure. For example, ultra-high molecular
manufacture moving machine parts, bearings, gears, artificial joints and some
margarine tubs and water pipes. Medium-density polyethylene (MDPE) is used for
packaging film, sacks and gas pipes and fittings. Low-density polyethylene (LDPE) is
soft and flexible and is used in the manufacture of squeeze bottles, sacks and sheets.
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thermoplastics.html#ixzz1BcBHf3eN
Teflon
o Teflon is the brand name given by DuPont Corp. for a polymer called
inert, it is used in making containers and pipes that come in contact with reactive
chemicals. It is also used as a lubricant to reduce wear from friction between sliding
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Propionic acid:
o Naturally occurring
o Analgesic
Formic acid:
o Cheapest to make?
Acetic acid:
Industrially, propionic acid is currently produced almost exclusively by three different processes:
2) Oxidation of Propanal
ethylene in a strongly acidic medium, it is a variant of the Reppe synthesis. However, compared
with the latter, it never achieved much industrial significance and was carried out with little
success.
Other possible sources of propionic acid, which are not used industrially for economic
reasons, are its formation as a byproduct in the high - and low - pressure carbonylation of
methanol to give acetic acid (2% formation of propionic acid), the direct reaction of ethylene,
Two-step reactions have been described, in which propionic acid is obtained directly
from synthesis gas (20 – 60 bar, 150 – 160 oC, Rh catalysts). With the current availability of
ethylene and naphtha these processes are, however, not yet competitive. It is sometimes
desirable, to use propionic acid produced by natural methods, particularly for the use of
propionic acid in flavors and fragrances. Appropriate microbiological and enzymatic processes
have been developed, which are usually based on the anaerobic fermentation of starch or sugars.
However, the expensive production of this “natural” propionic acid limits its use to special areas
of application.
In the Reppe synthesis ethylene is reacted with carbon monoxide and water in the
presence of Ni(CO)4 (Nickel Carbonyl) according to the following process: the reaction takes
place at high pressure and is characterized by low raw material costs, high conversion, high
yield, and a simple workup. Ethylene and carbon monoxide are compressed and continuously
pumped into the high-pressure reactor together with the feed solution. The crude propionic acid
formed at 100 – 300 bar and 250 – 320 oC is drawn off at the head of the reactor and cooled in a
heat exchanger with production of steam. Part of the cooled reaction product is recycled to the
reactor for temperature regulation, the majority of it is allowed to expand and is separated into an
off-gas and a crude acid stream. Nickel is recovered from the off-gas and led back into the
reactor. The off-gas is incinerated with recovery of heat. The crude acid stream is subsequently
dehydrated and worked up by distillation in several following columns. The nickel salts that are
formed are recycled into the process. The pure propionic acid is finally obtained by distillation.
The product residue is channeled out of the process. Variants of the Reppe and Koch syntheses
are possible, where the effect of inorganic salts on the reaction conditions and yield are important
factors. Boric acid is reported to accelerate the reaction and hinder the precipitation of catalyst
salts.
economically attractive although two steps (production of propanal and subsequent oxidation)
are required: (1) Propanal is formed in large quantities as an intermediate in the production of
npropanol by hydroformylation of ethylene, and (2) the oxidation takes place in plants in which
other aliphatic carboxylic acids (n-butyric and isobutyric acids, n-valeric and isovaleric acids)
are also produced. A high utilization of available capacity is therefore guaranteed in both steps.
Propanal Production
favored because, unlike the case of the higher aldehydes, n/isomixtures cannot be formed. Two
syntheses compete: the classical cobalt- catalyzed high-pressure carbonylation at 200 – 280 bar,
and 130 – 150 oC, and the rhodium- or iridium- catalyzed low-pressure carbonylation at about 20
bar, and about 100 oC. In the high-pressure synthesis the yield is generally impaired by partial
hydrogenation of propanal to give propanol. The isolation of the aldehyde takes place, after
removal of cobalt, by distillation of an azeotrope with ca. 98% aldehyde content. In the low-
pressure synthesis (Union Carbide), the aldehyde can be distilled directly from the reaction
Oxidation
acid with high selectivity. In the United States propionic acid is produced by the oxidation of
predominantly naphtha. In this process, which is principally used for acetic acid production,
formic acid, propionic acid, and an isomeric mixture of butyric acids are formed as byproducts.
Whether this process is considered economic for propionic acid production is principally a
question of the market evaluation of the different products. The process has favorable raw
material costs, but requires a relatively complex workup of the product mixture. The composition
of the acid mixture formed in the oxidation can be affected by the reaction conditions (pressure,
temperature), the type of reactor (tubular reactor, column reactor), the raw material (naphtha,
liquefied petroleum gas), and by the catalyst. If naphtha is used, the proportion of propionic acid
in the mixture is about 10 – 15%. In other cases like with 2- methylpentane as a raw material, the
proportion of propionic acid can increase to 31%. The total yield of acids does, however, vary
BP Chemicals Process
Naphtha is preheated to 170 oC and oxidized with air at 40 – 45 bar in several reactors in
series. Again, the heat of reaction is used for steam generation. The cooled discharge from the
reactors is separated from the reaction off-gas in a separator. Entrained liquid is recovered from
the off-gas and recycled to the reactor; the off-gas is then incinerated. The liquid reactor
discharge is separated into an organic phase, which contains unreacted hydrocarbons, and an
aqueous phase which contains the product mixture. The unreacted hydrocarbons are recycled to
the reactor. The low- and high-boilers are separated from the aqueous phase which then gives the
crude acid. From this the C1- to C4-acids are obtained by extractive dehydration followed by
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