[Date] Production of adipic acid from oxidation of

cyclohexene

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 Production of Adipic Acid from direct Oxidation of Cyclohexenes
with 30% Hydrogen Peroxide
Introduction:
Adipic acid is a straight chain dicarboxylic acid with chemical formula C 6H10O4. At standard
temperature and pressure condition, it is similar to white crystalline compound. It is an important
chemicals and used in many applications. It’s primary application is in the production of nylon-6,
6. It is used in auto parts, apparel, upholstery and many other products. In 1906, the French
chemist [Link] and [Link] claimed that cyclohexanol can be oxidized to produce fatty
acids. In the early 1930s, the [Link] of DuPont invented the nylon-6,6 polyamide. Nylon
66 polyamide has major applications in synthetic fiber industry which is leading to the
development of adipic acid. In 1940, a commercial method has been developed by DuPont that
produce adipic acid using crude oil from benzene. The historical development was reviewed in
1977.

In this project, we produced adipic acid from direct oxidation of cyclohexene by using 30% of
hydrogen peroxide as a catalyst. We used hydrogen peroxide as a catalyst as it’s does not
produce any harmful emissions and is environmental friendly.

Chemical and Physical Properties:

Adipic acid is colorless, odorless crystal with an acidic taste. It is highly soluble in methanol and
ethanol, soluble in water and acetone and slightly soluble in cyclohexane and benzene. It is
stable in air under most conditions but some decarboxylation takes place by heating more than
230-250◦C results cyclopentanone. Adipic acid forms salts, esters, amides and nitriles by reacting
with one or two carboxylic acid groups. When temperature increases to 180℃, nitric acid attacks
adipic acid to form water, carbon dioxide and nitrogen oxide.

Uses of Adipic Acid:

 The most common used of adipic acid is in the synthesis of nylon 66. Approximately
90% of adipic acid is used in the production of nylon 66 polyamide. Nylon is used in
many applications such as fiber, plastic, filament and food packaging material.
  Its used has been found in medicinal and pharmaceutical industries. Adipic acid also
included in tablets to aid in the controlled release of acid and base drug formulation.
When there is no stomach acid-like compound, the residue is released into the body as
soon as it hits the stomach. The use of adipic acid helps regulate the release of the
compound for a short period of time, which helps to avoid taking the preservative in a
short period of time.
 Adipic acid is used in the food industry as a flavoring and gel. Adipic acid is sometimes used
in antacid tablets.

Reactor Design:

There are different types of reactors used in the process industry. The primary purpose of reactor
is to produced a desired products from the reactants materials at operating conditions. We are
determining the reactor volume in this section.

Types of Reactor:

 Batch Flow Reactor

Batch Flow Reactor:

Since the process is all about the production of adipic acid through green pathway using
hydrogen peroxide as an oxidizing agent. The only by-product is water and the conversion
resulting from the optimum condition is 95%. We are using the batch reactor for the conversion
of cyclohexene into adipic acid. Following is the reaction occurs during the process:

C6H10 + 4H2O2 → C6H10O4 + 4H2O2

Na2WO4 and [CH3(n-C8H17)3N]HSO4 are used as surfactant that helps in the emulsion of two
phase liquids.
Required Data:
Production of adipic acid = 200,000 tons/year = 20711.98 kg/hr

 Isothermal process
 1st order reaction
 Temperature = 368 K (95◦C)
 Pressure = 1 atm
 Rotational speed of stirrer = 1000 rpm
 Conversion = 95%

Assumptions:

The following are the assumptions that are used during the design of reactor.

 Well mixed
 All reactants enter at same time
 No side reactions
 Negligible filling time

Calculations:

Design equation of Batch Reactor:

dXx

t=∫ rV ¿
0
¿

Where:

V= volume of tank

XA = Conversion

-rA = Rate of reaction

Integrated Form of batch reactor equation is:

t= ( 1k ) ln ⁡¿)
By using this equation, we can find out rate constant.

8= ( 1k ) ln ⁡¿) = 0.0374 hr -1

Production of adipic acid = 200,000 tons/day = 20711.98 kg/hr = 141.73 kmol/hr

Cao = 0.033 mol/L, Xa = 0.95

After putting all the values in this equation:

−rA=KCao (1−XA )=0.0374∗0.033 ( 1−0.95 ) = 6.17*10-5 mol/[Link]

Ca = 1.65*10-3mol/L

Volume of batch reactor =

Second Design of Reactor:

During this design, we take the assumptions from the reference of Sato, Aoki and Noyori
document.

Required Data:
Production of adipic acid = 200,000 tons/year = 20711.98 kg/hr

 Isothermal process
 1st order reaction
 Temperature = 368 K (95◦C)
 Pressure = 1 atm
 Rotational speed of stirrer = 1000 rpm
 Conversion = 95%
 At given condition value of Cao = 0.033 mol/L
 100 g of cyclohexene = 161 g of adipic acid

Production of adipic acid = 200,000 tons/day = 20711.98 kg/hr = 141.73 kmol/hr

Moles of Cyclohexene fed = Nao = 149.19 kmol/hr = 12254.9 kg/hr

Moles of unreacted cyclohexene = 7.46 kmol/hr = 612.8 kg/hr

From experimental data , we found the rate constant value = 1.36*10-3sec-1= 4.896 hr-1

After putting all the values in this equation:

XA 0.95
V= ∗FA= ∗149.19=17544 L
−rA 4.896∗( 0.033 ( 1−0.95 ) )

References:

 Max S. Peters, Klaus D. Timmerhaus, Ronald E. West, ‘Plant Design and Economics for
Chemical Engineers,’ Fifth Edition, University of Colorado.
 Zhang, S. G., Jiang, H., Gong, H., & Sun, Z. L. (2003). Green catalytic oxidation of
cyclohexanone to adipic acid. Petroleum science and technology, 21(1-2), 275-282.
 Clark, J. H., & Macquarrie, D. J. (Eds.). (2008). Handbook of green chemistry and
technology. John Wiley & Sons.
 Peñate, I. Q., Lesage, G., Cognet, P., & Poux, M. (2012). Clean synthesis of adipic acid from
cyclohexene in microemulsions with stearyl dimethyl benzyl ammonium chloride as
surfactant: From the laboratory to bench scale. Chemical engineering journal, 200, 357-364.
 Jiang, H., Gong, H., Yang, Z., Zhang, X., & Sun, Z. (2002). Clean synthesis of adipic acid by
direct oxidation of cyclohexene in the absence of phase transfer agents. Reaction Kinetics
and Catalysis Letters, 75(2), 315-321.

 Clark, J. H., & Macquarrie, D. J. (Eds.). (2008). Handbook of green chemistry and
technology. John Wiley & Sons.
 Peñate, I. Q., Lesage, G., Cognet, P., & Poux, M. (2012). Clean synthesis of adipic acid from
cyclohexene in microemulsions with stearyl dimethyl benzyl ammonium chloride as
surfactant: From the laboratory to bench scale. Chemical engineering journal, 200, 357-364.
 Jiang, H., Gong, H., Yang, Z., Zhang, X., & Sun, Z. (2002). Clean synthesis of adipic acid by
direct oxidation of cyclohexene in the absence of phase transfer agents. Reaction Kinetics
and Catalysis Letters, 75(2), 315-321.

 Fogler, H. S. (2020). Elements of chemical reaction engineering. Prentice Hall.