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1.

0 INTRODUCTION

Acrylic acids chemical nature makes it a highly desirable component in a polymer


system. Besides polymer applications, the molecule also follows the characteristics of both a
carboxylic acid and acrylate ester, making it suitable for chemical intermediates as well. The
largest application for acrylic acid is in the industrial coatings area. And, because it is
miscible with water, alcohols, and ethers, the wetting ability can be enhanced based on the
specific employment. An area of growth for acrylic acid is with acrylic acid homo-polymers
and acrylic acid/starch grafts. These combinations provide a high rate of absorption, perfect
for use in hygiene products. Other minor uses include viscosity modifiers for rubber lattices
and adhesives, detergents, fiber sizing, and soil conditioner.

Acrylic acid is formed by the following reaction:

C3H6 + 1.5 O2 C3H4O2 + H2O

Complicating matters are two competing side reactions:

C3H6 + 2.5 O2 C2H4O2 + CO2 + H2O

C3H6 + 4.5 O2 3 CO2 + 3 H2O

The first competing reaction forms acetic acid, which is a marketable commodity. The second
competing reaction simply forms completely useless products.

The specifications to meet for the production of acrylic acid were:


Feedstock: Propylene
Product spec: 99.9 wt% minimum
Has to consider competing side reactions inside the reactor
Product capacity: 50,000 MTPA

2.0 CHEMICAL PROCESS SELECTION

Selection 1: Manufacture of Acrylic Acid by Single-step Catalytic Propylene Oxidation.


(Selected for PSD in the case study)

The first process involves direct catalytic oxidation of propylene to acrylic acid in a single
stage operation which comprises passing a starting reactant gas mixture containing propylene,
compressed air (compressor) and steam (mixer) through in a single reactor (Plug flow
reactor). The reactor effluent is sent to a separation unit (separator) in which all light gases
are separated as vapor in top stream. Bottom stream that contains mixture of liquid mainly
water, acetic acid and acrylic acid are distilled to produce purified acrylic acid (distillation
column).

Selection 2: Manufacture of Acrylic Acid by Two-step Catalytic Propylene Oxidation.

Another process involves producing acrylic acid from propylene through acrolein as an
intermediate by catalytic vapor phase oxidation, which comprises passing a starting reactant
gas mixture containing propylene, compressed air (compressor) and steam (mixer) through a
first-stage reactor packed with a molybdenum-containing multi-component catalyst (plug

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flow reactor), passing the resulting acrolein containing gas through a second-stage reactor
packed with a multi-component catalyst containing vanadium and molybdenum (plug flow
reactor). The resulting acrylic acid-containing gas is separated (separator), and absorbed in
water (absorber). A part of the exhaust gas is incorporated in the starting reactant gas mixture
(recycle).

3.0 DESIGN METHOD

Software Used: UniSim Software (Modular Based Method)


Unit Operation Function
Compressor (K-100) To compress air from atmospheric pressure
and increase the temperature.
Mixer (MIX-100) To mix propylene, compressed air and
steam.
Heater (E-100) To heat incoming mixture to required
temperature for reaction to be occurred.
Plug flow reactor (PFR-100) Oxidation of propylene to final desired
product acrylic acid, acetic acid as by-
product.
Separator (V-100) To separate gases and liquid components in
reactor effluent.
Distillation column (T-100) To produce purified distillation column after
gases and liquid components are separated.

4.0 SIMULATION OF PSD

Please refer to APPENDIX A.

5.0 RESULTS

Please refer to APPENDIX A.

6.0 ANALYSIS

Improvement to the PSD:


Lower temperature of incoming feed of reactant gases from 255.6 to 250
(min temperature required for the function of catalyst) increase mass flow of acrylic
acid since it is an exothermic reaction. (Refer APPENDIX B for results after
improvement)
Reduce size of reactor. Reactor length provided a more drastic reduction in reactor
size compare to diameter. The additional length and diameter does not influence much
on the product but is able to save the capital investment cost. (Refer APPENDIX B for
results after improvement)
Reduce pressure of compressed air reduces usage of compressor electricity, but has
little impact on the product produces. (Refer APPENDIX B for results after
improvement)
Consider only acrylic acid:

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When perform economic analysis, a number of economic criteria should be used. It is the
equivalent annual operating cost (EAOC). A negative EAOC means there is a profit. It is
desirable to minimize the EAOC; i.e., a large negative EAOC is very desirable.

Material Cost = Total Feed Cost + Total Energy Cost


= $ (49,470,400 + 205,871,005)
= $ 255,341,405
Unit Operation Cost = Total Purchase Cost + Installation Cost
= $ (930,236 + 5,245,219)
= $ 6,175,455
EAOC = - $ (product value - feed cost - other operating costs - capital cost annuity)
= - $ (131,998,720 49,470,400 205,871,005 1,230,472)
= $ 124,573,157
Payback period = $(49,470,400 + 205,871,005+ 1,230,472)/ $ 131,998,720
= 1.94 years
However, since this only considers the main unit operations of the process, true profit cannot
be calculated at this time. Also, there are assumed errors in such a cost study as the labor cost,
maintenance cost, other pumps or valves that are not considered.

Note: Economic or environmental analysis are shown in APPENDIX C.

7.0 DISCUSSION

This process produces 53,460 metric tons per year of 99.9 mole % of acrylic acid
(AA) product. The number of operating hours should be taken as 8000/yr, about 330 days
which allows the plant for periodic shut down and maintenance. The reactor in the process
shown uses a proprietary catalyst that eliminates the production of the intermediate, acrolein.
Therefore, this process requires only a single reactor.

After reaction, it is essential to cool the products (reactor effluent) quickly to avoid
further homogeneous oxidation reactions. The homogeneous combustion reactions will not
take place so long as the reactor effluent is cooled to below 100 oC immediately after the
reactor. Additional recovery of AA and acetic acid (a by-product) from the gas leaving the
phase separator is achieved in the distillation column.

The kinetics used for the 3 reactions involved are valid in the temperature range, 250
330oC (Refer to Appendix C). Above 330oC the catalyst starts to coke, and below 250 oC the
rate of reaction drops off rapidly. It is recommended that the steam-to-propylene ratio at the
reactor inlet never be set less than 4:1 on a mole basis. This steam is used to inhibit the
formation of coke on the catalyst below temperatures of 330oC.

8.0 CONCLUSION

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As a conclusion, oxidation of propylene produces acrylic acid as main product with
99.99% purity after purification in distillation column. Two other competing reactions which
produced acetic acid as useful by-product and carbon dioxide as non-added value by product
are also considered in the designing of the process. Acrylic acid is produced at a rate of
6682.5kg/h, which is equal to 53,460 metric tons per annum.

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9.0 APPENDIX
9.1 APPENDIX A: PSD AND RESULTS

A.1: Simulation of PSD:


(a) Simulation with producing acrylic acid:

(b) Simulation with further purification of acetic acid (predicted using shortcut distillation):

A.2: Raw material (Compressed air, propylene and steam):

Compressed air:

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Propylene:

Steam:

A.3: Product (Acrylic acid)

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A.4: By-product (Vent gas and acetic acid)

Vent gas:

Acetic acid for further purification:

Acetic acid (predicted using short cut


distillation):

9.2 APPENDIX B: IMPROVEMENT ANALYSIS FOR PSD

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Analysis results for lowering the temperature of incoming feed:

Temperature 255.6 250


Duty of heater (kJ/h) 4,658,710 547,882
Heater electricity ($) 621,120 73,050
Acrylic acid (kg/h) 6682.5 6724.2
Profit of acrylic acid per 131,998,720 132,823,040
annum ($)

Analysis results for reducing size of reactor:

Analysis results for reducing pressure of compressed air:

Pressure 5 atm 4.5atm 4 atm


Duty of 2662.03 2437.66 2196.35
compressor (kW)
Compressor 1,277,760 1,170,076 1,054,248
electricity ($)
Temperature of 255.6 244.7 233.0
reactants inlet
stream (
Acrylic acid (kg/h) 6682.5 6672.8 6656.9
Profit of acrylic 131,998,720 131,810,560 131,496,960
acid per annum ($)

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9.3 APPENDIX C: ECONOMIC OR ENVIRONMENTAL ANALYSIS

Raw material: Propylene $0.49 / lb


Product: Acetic acid $0.68 / lb
Acrylic acid $1.12 / lb
Utility: Low pressure steam (600kPa saturated) $6.62/1000kg
Electricity $0.06/kW h

Cooling water (516kPa and 30 C )


return pressure >308kPa
$0.16/GJ return temperature is no higher than 45 C

Refrigerated water (516kPa and 10 C )


return pressure >308kPa $1.60/GJ
return temperature is no higher than 20 C

Refrigeration $60/GJ
Equipment: <http://www.matche.com/equipcost/Reactor.html>
Compressor (Air, Centrifugal, 125psi)
Heater
Separator (57.6cm diameter)
Plug flow reactor - $20 to $50 per square foot of surface area
(D=3.6m, L=10m; A=133.45m2<437.8ft>)
Distillation column (4ft diameter, 19ft high)
Equipment cost factors:
Pressure (absolute) < 10atm, 0.0
10-20atm, 0.6
20-40atm, 3.0
40-50atm, 5.0
50-100atm, 10
Carbon steel 0.0
Stainless steel 4.0
Total installed cost = Purchased cost (4 + material factor + pressure factor)

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Cost Current Process ($)
Propylene Feed
49,470,400
Reboiler Electricity
90,912,000
Condenser Electricity
90,144,000
Air Compressor Electricity
1,277 ,760
Heater Electricity
621,120
Reactor Electricity
22,396,800
Steam from Boiler
519,325
Total
255,341,405

Equipment Purchase Cost ($) Installed cost ($)


Reactor (PFR-100)
21,890 306,460
Air Compressor (K-100)
690,400 2,761,600
Heater (E-100)
41,629 582,806
Mixer (MIX-100)
1,500 21,000
Separator (V-100)
15,900 143,100
Distillation Column (T-100)
158,917 1,430,253
Total
930,236 5,245,219
Total Capital Cost
6,175,455

Revenue Current Case ($)


Acrylic Acid
131,998,720
Acetic acid
14,042,816

Economic analysis:

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EAOC = - (product value - feed cost - other operating costs - capital cost annuity)

i(i+1)n
Capital cost annuity = FCI (i+ 1)n1
where FCI is the installed cost of all equipment; i is the interest rate, i = 0.15; and n is the
plant life for accounting purposes, n = 10.

Payback period = Initial investment / Annual cash flow.

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9.4 APPENDIX D: REACTION KINETICS

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10.0 REFERENCES

Acrylic Acid Prices and Pricing Information. (2011, August). Retrieved 3 rd April 2016 from
http://www.icis.com/resources/news/2007/11/01/9074869/acrylic-acid-prices-and
-pricing-information/

Acrylic Acid Production and Manufacturing Process. (2007, November 01). Retrieved 2 nd
April 2016 from http://www.icis.com/resources/news/2007/11/01/9074872/acrylic-
acid-production-and-manufacturing-process/

Acrylic Acid Uses and Market Data. (2007, November 01). Retrieved 3 rd April 2016 from
http://www.icis.com/resources/news/2007/11/01/9074870/acrylic-acid-uses-and-
market-data/

Anonymous. (2014). Design of Acrylic Acid Production. Retrieved 3 rd April 2016 from
http://www.chemeng.kmutt.ac.th/cheps/Project-4_Acrylic-Acid.pdf

Campbell, W. E., McDaniel, E. L., Reece, W. H., Williams, J. E., Young, H.S. (1970).
Oxidation of Propylene to Acrylic Acid over a Catalyst Containing Oxides of Arsenic,
Niobium, and Molybdenum. Retrieved 1st April 2016 from
http://pubs.acs.org/doi/abs/10.1021/i360035a012?journalCode=iepra6.1

Han, S. (2013). Method for preparing acrylic acid from propane and propylene. Retrieved 2 nd
April 2016 from http://www.google.com/patents/WO2013058888A1?cl=en

Lakowski, C., Hayenga, M., Castillo, M. (1998). Acrylic Acid Production via the Catalytic
Partial Oxidation of Propylene. Retrieved 3 rd April 2016 from
http://www.owlnet.rice.edu/~ceng403/gr1498/AcrylicAcid.htm

Process for producing acrylic acid from propylene. (1979). Retrieved 2 nd April from
http://www.google.com/patents/US4147885

Reactor Cost Estimate. (n.d.). Retrieved 3 rd April 2016 from


http://www.matche.com/equipcost/Reactor.html

Sood, S. (1995). One Step Oxidation of Propylene to Acrylic Acid. Retrieved 3 rd April 2016
from http://www.collectionscanada.gc.ca/obj/s4/f2/dsk3/ftp05/mq22044.pdf

Zhao, C., Wachs, I. E. Selectivity oxidation of propylene to acrolein over supported


V2O5/Nb2O5 catalysts. Retrieved 1st April 2016 from
http://lehigh.edu/operando/Publications/2006%20Propylene%20to%20acrolein%20V-
Nb2O5.pdf

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