Master Thesis Proposal

Optimization of Adipic acid batch process to get

maximum yield

Zeeshan Arif (2016-MS-CH-38)

Masters Student at Department of Chemical Engineering

Thesis Supervisor

Dr. Ing Naveed Ramzan

Chairman / Professor at Department of Chemical Engineering
University of Engineering & Technology Lahore, Pakistan.

Industrial Partner

BINRASHEED (Pvt.) Ltd.

Colors & Chemicals Manufacturing Company, Lahore, Pakistan.

DEPARTMENTOF Chemical ENGINEERING

(University of Engineering & Technology Lahore, Pakistan)
Contents
Introduction:.................................................................................................................................................. 3
Problem Statement: ....................................................................................................................................... 3
Objective: ...................................................................................................................................................... 3
Literature Survey: ......................................................................................................................................... 4
Material & Methodology: ............................................................................................................................. 6
Equipment Required: .................................................................................................................................... 7
Process Diagram: ......................................................................................................................................... 7
Research Time Table: ................................................................................................................................... 7
Supervisor Comments ................................................................................................................................. 10
Introduction:
Adipic acid is one of the most important industrial chemical required all over the world.The
worldwide industrial production of adipic acid is 2.2 million metric tons per year. It is considered
to be the building block for number of different products that are manufactured in chemical,
pharmaceutical and food industries. It is the main precursor to Nylon-6,6 and also used for the
production of polyester, polyresin, polyvinyl chloride.2 Adipic acid is also used in cosmetics,
fertilizers, paper and wax industry. At present adipic acid is produced industrially by catalytic
oxidation of a mixture of cyclohexanol and cyclohexanone using nitric acid. The major drawback
for this process is the emission of harmful nitrous oxide N2O that is commonly thought to cause
global warming and ozone depletion as well as acid rain and smog.4 Adipic acid producers have
to face challenge to decompose this N2O safely without causing any impact on the pollution.
Efforts have been made to develop process for synthesis of adipic acid that can
overcome conventional process. For this purpose synthesis of adipic acid has been carried out in
the presence of hydrogen per oxide to make the process environment friendly [1]. Nylon 6,6
polyamide is one of the most common building blocks of textile and plastics. In 2010, the
global adipic acid capacity was about 2.6 million tons per year, and will reach 3.3 million
tons per year in 2016 [2]. Adipic acid is one of the most important industrial acids with 2.
5 million tons consumption per annum.

Problem Statement:
Due to increasing consumption of adipic acid in Pakistan the import of adipic acid is
increasing exponentially which create bad effect on the economy of Pakistan. In Pakistan
according to import data, 1.6 million kg adipic acid imported in Pakistan last year. To
overcome the consumption need of adipic acid it should be synthesize In Pakistan to
minimize the import from other countries. The objective of this research is to synthesize
the adipic acid with optimized and cost effective condition. This research will not only
minimize the import of adipic acid but also create a positive impact on the economy of
Pakistan.

Objective:
The objective for the project is to find the optimized condition for the reaction (i.e
Temperature and time) and optimized the amount of catalyst and oxidizing agent. To get
most easy and optimized reaction which give us reasonable yield. Different catalyst,
oxidizing agent and chemicals will be use to get the maximum yield by using minimum
resourses.
Literature Survey:
Currently, most adipic acid is produced industrially in two steps. The first step is the
aerobic oxidation of cyclohexane to obtain cyclohexanone and cyclohexanol, which
employs cobalt salts as catalysts. In the second step, the cyclohexanone and the
cyclohexanol are oxidized by nitric acid to obtain adipic acid. However, in order to
maintain high selectivity of cyclohexanone and cyclohexanol in the first
step, it is necessary to keep the conversion of cyclohexane low (e.g. 38 mol%) [3].
Furthermore, this traditional process releases a great amount of nitrous oxide due to the
utilization of nitric acid, which represents 58% of the worldwide anthropogenic N2O
emission. Nitrous oxide causes serious environmental problems, such as air pollution,
greenhouse effect, and ozone depletion. Driven by environmental restrictions and large
cost of dealing with nitrous oxide, research has been inspired to explore a more
environmentally friendly strategy for adipic acid synthesis. One alternative is the
oxidation of cyclohexene with H2O2 to produce adipic acid. Although the current
commercial process for producing hydrogen peroxide is an energy and pollution intensive
process [4], H2O2 itself is considered as an eco-friendly chemical since its sole
degradation product is water [5]. The first process employing hydrogen peroxide for
producing adipic acid was reported by Sato et al. [6]. This process employed cyclohexene
as the starting material and allowed to obtain 90% yield of adipic acid at 90 C after 8 h.
This landmark paper has inspired several other research groups to develop new strategies
to achieve a more efficient adipic acid synthesis starting from cyclohexene and H2O2
[7]. These reports have been mainly focused on the development of novel catalysts and
the optimization of new reaction processes.Cheng et al. [8] modified an SBA-15
mesoporous catalyst with tungsten oxide and then used it to catalyze the cyclohexene
oxidation to produce adipic acid. In this process, the yield of adipic acid reached 30%
after 13 h at 85 C. Furthermore, aiming to improve the mixing efficiency between H2O2
(aqueous phase) and cyclohexene (organic phase), mesoporous oxides with built-in active
tungsten oxide were applied to produce adipic acid, inside which the immiscible two
phases contacted with each other and reacted under the effect of immobilized catalyst. In
this operational mode, the yield of adipic acid could reach 95% at 80 C after 24 h, but the
reusability of catalyst still needed to be improved [9]. Vafaeezadeh et al. [10] developed
silica-supported ionic liquid catalysts to create an amphiphilic reaction environment for
the oxidation of cyclohexene, and obtained 87% yield of adipic acid within 18 h at 75 C.
For most processes utilizing a heterogeneous catalyst [811], extremely long reaction
times were needed and thus rather low spacetime yields of adipic acid were achieved.
Homogeneous catalysts can also be used and can reduce the reaction time significantly.
Jin et al. [12] have used peroxy tungstate as catalyst and studied the influence of reaction
conditions on the adipic acid production. They obtained 95% yield of adipic acid at 80
95 C after 9 h reaction time. The main difficulty in this type of reaction is the poor
contact between the hydrophobic and the hydrophilic reagents . Different methods have
been proposed in order to improve this contact. The synthesis of adipic acid in a water
emulsion by hydrogen peroxide oxidation of cyclohexene without surfactant and under
strong stirring was proposed by Deng and co-workers . In their work a good yield of pure
adipic acid was obtained only by addition of an organic acid as ligand (co-catalyst) and
harsh reaction conditions (20 h at 94 C). The use of a phase transfer agent
(methyltrioctylammonium hydrogenosulphate) in water to produce adipic acid with a
good yield was proposed by Sato and co-workers but the reuse of the system required an
additional amount of phase transfer agent to be effective. The use of microemulsions as
aqueous media for organic reactions is a way to improve the contact between the different
reagents and to overcome the use of polluting organic solvents. Although microemulsions
are described as versatile reaction media for many organic reactions, there is still no
industrial process based on microemulsions, essentially because of the difficulty in
recovering the products and reusing the system .Blach and co-workers have described the
use of hydrogen peroxide micro emulsions as reaction media for the oxidation of
cyclohexene to adipic acid. The micro emulsion was obtained by using a low-cost
commercial mixture of benzalkonium chloride containing 60 wt.% of dodecyl- and 40
wt.% of tetradecylbenzyldimethylammonium chloride (BenzCl C12-14). The process
leads to pure adipic acid that can be recovered by simple Bchner filtration at room
temperature, but in order to recycle the system, a water evaporation step at 70 C under
reduced pressure (1 kPa) is needed.[13]Various alternative methods including
biosynthesis [14] and ozonolysis [15] have been elaborated for the clean synthesis of
adipic acid. But these method are difficult to adopt in the industrial production of the
adipic acid.
Material & Methodology:
Analytical grade of chemicals used during complete research are following.

Base Chemical (Cyclohexene, Cyclohexanone, Cyclohexanol)

Oxidizing Agent (Nitric Acid , Hydrogen Peroxide, Potassium Permanganate)
Catalyst (Vanadium/Copper, Sodium tungstate, H2WO4)
Other (Phenolphthalein , Sulfuric acid , Hydrochloric acid, Sodium Hydroxide)

Methods for Synthesis of Adipic Acid :

Method 1 :Synthesis of Adipic acid By using Nitric acid as a catalyst

Method 2 : Synthesis of Adipic acid by potassium permagnate :

Method 3: Synthesis of Adipic acid by hydrogen peroxide:

Equipment Required:
Erlenmeyer flask, Filter paper, Buchner funnel , Beaker, side arm test tube , Two-neck flask,
reflux condenser, suction flask, ice bath , heat able magnetic stirrer, magnetic stir bar,
desiccators, oil bath.

Process Diagram:

Reaction Stirring Cooling Filtration

Testing Drying

Characterization Techniques
Titration
Titration is used to measure the concentration of adipic acid in resultant reaction mixture.
Phenolphthalein and sodium hydroxide used for this purpose[14].

FTIR
The IR spectra of the product compare with the standard spectra of adipic acid to confirmation / identify
the product.

Research Time Table:

Literature review and Collection of necessary data 3 Weeks

Analysis of Available data 2 Weeks

Analysis of Availability of chemicals 1 Week

Experimentation for the synthesis of the Adipic Acid and Analytical Testing 6 Weeks

Results compilation and thesis submission 4 Weeks

Reference:
[1] Nale, S. D., et al.. "Manganese incorporated on glucose as an efficient catalyst for the
synthesis of adipic acid using molecular O 2 in aqueous medium." Applied Catalysis A:
General 546: (2017) 122-125.
[2] Merchant Research & Consulting Ltd., Adipic acid 2011 World Market Outlook and
Forecast, 2011.
[3] D.D. Davis, fifth ed., in: W. Gerhartz (Ed.), Ullmans Encyclopedia of Industrial
Chemistry, John Wiley and Sons, New York, 1985.
[4] Q. Wang, I. Vural Grsel, M. Shang, V. Hessel, Life cycle assessment for the direct
synthesis of adipic acid in micro reactors and benchmarking to the commercial process,
Chem. Eng. J. 234 (2013) 300311.
[5] J.M. Campos-Martin, G. Blanco-Brieva, J.L.G. Fierro, Hydrogen peroxide synthesis:
an outlook beyond the anthraquinone process, Angew. Chem. Int. Ed. Engl. 45 (2006)
69626984.
[6] K. Sato, M. Aoki, R. Noyori, A green route to adipic acid: direct oxidation of
cyclohexenes with 30 percent hydrogen peroxide, Science 281 (1998) 1646 1647.
[7] S.V. Vyver, Y. Romn-Leskov, Emerging catalytic processes for the production of
adipic acid, Catal. Sci. Technol. 3 (2013) 14651479.
[8] C.-Y. Cheng, K.-J. Lin, M.R. Prasad, S.-J. Fu, S.-Y. Chang, S.-G. Shyu, H.-S.Sheu,
C.- H. Chen, C.-H. Chuang, M.-T. Lin, Synthesis of a reusable oxotungsten containing
SBA-15 mesoporous catalyst for the organic solvent-free conversion of cyclohexene to
adipic acid, Catal. Commun. 8 (2007) 10601064.
[9] Z. Bohstrm, I. Rico-Lattes, K. Holmberg, Oxidation of cyclohexene into adipic acid
in aqueous dispersions of mesoporous oxides with built-in catalytical sites, Green Chem.
12 (2010) 18611869.
[10] M. Vafaeezadeh, M.M. Hashemi, M. Shakourian-Fard, Design of silica supported
task-specific ionic liquid catalyst system for oxidation of cyclohexene to adipic acid with
30% H2O2, Catal. Commun. 26 (2012) 5457.
[11] H. Wei, H. Li, Y. Liu, P. Jin, X. Wang, B. Li, Oxidation- resistant acidic resins
prepared by partial carbonization as cocatalysts in synthesis of adipic acid, ACS Appl.
Mater. Interfaces 4 (2012) 41064112.
[12] P. Jin, Z. Zhao, Z. Dai, D. Wei, M. Tang, X. Wang, Influence of reaction conditions
on product distribution in the green oxidation of cyclohexene to adipic acid with hydrog-
en peroxide, Catal. Today 175 (2011) 619624.
[13] Peate ,I Q., et al. . "Clean synthesis of adipicacid from cyclohexene in micro
emulsions with stearyl dimethyl benzyl ammonium chloride as surfactant : From the
laboratory to bench scale." Chemical Engineering Journal 200-202: (2012) 357-364.

[14] Capelli, S., et al. "Bio-adipic acid production by catalyzed hydrogenation of

muconic acid in mild operating conditions." Applied Catalysis B: Environmental 218:
(2017) ; 220-229.

[15] Rokhum, L. and G. Bez. "Excellent Synthesis of Adipic Acid." Synthetic

Communications 41(4): (2011) 548-552.

[16] MONOGRAPHS, D., Adipic Acid.

Supervisor Comments
_____________________________________________________________________________________
_____________________________________________________________________________________
_____________________________________________________________________________________
_____________________________________________________________________________________
__________________________________________________

Industrial Partner Project Supervisor Student

BINRASHEED Prof. Dr. Ing Naveed Ramzan Zeeshan Arif
Colors & Chemicals Pvt. Ltd Chemical Engineering Department 2016-MS-CH-38
Lahore, Pakistan. UET Lahore, Pakistan. UET Lahore, Pakistan.

Endst. No. Univ/ _______________ Dated: ____________

The above proposal duly recommended by the Departmental Board of Post-Graduate Studies in its
meeting held on ____________ is forwarded to the Director of Research for obtaining the approval of
the Vice-Chancellor.

Chairman
Department of Chemical Engineering
University of Engineering and Technology Lahore