PRODUCTION OF MADE BY: Akshay Srivastava

Shubham Paruthi

ACRYLIC ACID Kriti Sinha

Jai Gupta
OUTLINE OF THE
PRESENTATION
The table of content is as follows:
Introduction and market.
Current production scenario.
Methods of production.
Atom Economy
Economics of the process.
Material Balance of process
ACRYLIC ACID:
INTRODUCTION AND MARKET
•Acrylic acid (CH2=CHCOOH) is the simplest unsaturated carboxylic acid and exists as
a colourless liquid with pungent smell at standard temperature and pressure.
•Acrylic acid finds applications in varied industries due to its varying degree of
durability, tackiness and hardness. Crude acrylic acid is*:

 Used as a monomer in Superabsorbent polymers (SAPs) that have applications in baby diapers,
sanitary napkins, soaker pads for food packaging, etc.

 Used to produce acrylates that have applications in masonry and industrial coatings, adhesives,
paper and leather coatings, floor polishes, wood paints, tablet coatings etc.

 Used to make acrylic glass which is an alternative to glass in greenhouses

 Used as monomer in production of detergents

*Sarah Clark. Acrylic Acid Market- Global Opportunity Analysis and Industry Forecast, 2013-2020. Allied market research, 2014.
 ACRYLIC ACID:
INTRODUCTION AND MARKET
The market study for acrylic acid is as shown below*:

*Data obtained from https://economictimes.indiatimes.com/markets/stocks/news/global-demand-for-acrylic-acid-market-scenario-2011-2019-icra/articleshow/71953312.cms

 ACRYLIC ACID:
INTRODUCTION AND MARKET
•The demand supply gap is increasing very rapidly and has reached 260 kilo tonnes
per annum (KTPA)*.

*Data obtained from https://economictimes.indiatimes.com/markets/stocks/news/global-demand-for-acrylic-acid-market-scenario-2011-2019-icra/articleshow/71953312.cms

ACRYLIC ACID: CURRENT
PRODUCTION SCENARIO
• Industrially Acrylic acid is manufactured by the following processes:

1. Sequential Dehydration and Oxidation of Glycerol.

2. Acid Catalysed rearrangement of β-propiolacetone from ethylene.

3. Catalytic partial oxidation of propylene.

4. Catalytic oxy-dehydrogenation of propane.

5. Vapor phase dehydration of Lactic Acid.

 ACRYLIC ACID FROM
GLYCEROL*
The reaction process involves two steps
1. Dehydration of Glycerol to Acrolein:

2. Oxidation of Acrolein to Acrylic acid and water:

*J. Deleplanque, J.-L. Dubois, J.-F. Devaux, and W. Ueda. Production of acrolein and acrylic acid through dehydration and oxydehydration of glycerol with mixed oxide
catalysts. Catalysis Today, 157:351–358, 2010.
ACRYLIC ACID FROM
GLYCEROL*
• The reaction is carried out using two different types of packed bed catalyst in a
single fixed bed reactor because of higher yield (75%) as compared to single packed
bed catalyst where the yield is just 25%.
• For the dehydration step, Cs2.5H0.5PW12O40 supported on Nb2O5 (CsPW-Nb) is used
as a catalyst and for oxidation step, vanadiummolybdenum mixed oxides supported
on silicon carbide (VMo-SiC) is used (regenerated by coke burning at 500oC).
• Acetol and water which are the byproduct of the dehydration step do not have any
negative effects on the subsequent oxidation step.
• The reaction is carried out at an optimum temperature of 300oC and ambient
pressure because although increasing the temperature increases the conversion but
trade off is decrease in selectivity.

*Rong Liu, Tiefeng Wang; “Production of Acrylic Acid by Sequential Dehydration & Oxidation of Glycerol”, May, 2014
ACRYLIC ACID FROM
GLYCEROL

*Rong Liu, Tiefeng Wang; “Production of Acrylic Acid by Sequential Dehydration & Oxidation of Glycerol”, May, 2014
ACRYLIC ACID FROM
ETHYLENE*
•Acrylic Acid can be manufactured from ethylene in a three step process namely
oxidation of ethylene, carbonylation of ethylene oxide, and acid catalyzed
rearrangement of β-propiolactone.
•In the first step, ethylene is oxidized to ethylene oxide with highly pure oxygen so as
to minimize the reaction volume. Reaction conditions are as follows**:

*Patricia Campos, Minsik Jun; “Production of Acrylic Acid from Ethylene”, April, 2014
**Allen S. et al. Process for Β-Lactone Prod. United States Patent 2012/0123137. 2012.
ACRYLIC ACID FROM
ETHYLENE
•In the second step, ethylene oxide is carbonylated to produce β-propiolactone in the presence
of [Co(CO)4] as the catalyst and thiamine pyrophosphate (TPP) as the promoter*.
•The reaction is carried out in liquid phase under isobaric conditions (pressure of CO is kept
constant) and at a temperature of 240oC**.
•In the last step, β-propiolactone undergoes rearrangement to form acrylic acid in the presence
of phosphoric acid as catalyst and mono methyl ether hydroquinone (MEHQ) as inhibitor to
prevent the product from polymerizing.
•Small amount of water is added to catalyst to increase its viscosity & maintain phase as liquid.
Reaction is carried in vacuum at high temperature to achieve per pass conversion of 0.97&the
overall conversion of 0.995.
*Church T. L., Getzler Y. D. Y. L., Coates G. W. The Mechanism of Epoxide Carbonylation by [Lewis Acid]+[Co(CO)4]- Catalysts. J. Am. Chem. Soc. 2006, 128, 10125-
10133.
**Kakimoto Y., Sawada M., Kajimoto Y., Kiguchi I. Method for Recovery of Ethylene Oxide. United States Patent 4,875,909. 1989.
***Schnizer A. W., Wheeler N. E. Treating Propiolactone with Heated Phosphoric Acid to Produce Acrylic Acid. United States Patent 3,176,042. 1965 .
 ACRYLIC ACID FROM
ETHYLENE*

*Fashami S. Z. CO2 removal with 7M monoethanolamine (MEA) – Aspen Plus model for base case. Department of Chemical Engineering, University of Texas at Austin. 2007.
 ACRYLIC ACID FROM
PROPYLENE
•Production of acrylic acid takes place by two stage selective oxidation of propylene into
acrylic acid* where Acrolein is a fast acting intermediate**.

•Major side reactions are formation of acetic acid through activated propylene or Acrolein
and oxidation of hydrocarbons to give carbon dioxide. Side reactions can be minimized by
maintaining the temperature at desired level by removing the reaction heat**.

*Jeffrey S. Plotkin, “The Propylene Gap: How can it be filled?”, September, 2015
**Zhanling Ma, Xiangang Ma, Hongchao Liu, Wenliang Zhu, Xinwen Guo, Zhongmin Liu. One-step aldol condensation reaction of dimethoxymethane and methyl
acetate over supported Cs/ZSM-35 zeolite catalysts. Chinese Journal of Catalysis 2018, 39 (6) , 1129-1137. DOI: 10.1016/S1872-2067(18)63069-4.
 ACRYLIC ACID FROM
PROPYLENE*

*Zhanling Ma, Xiangang Ma, Hongchao Liu, Wenliang Zhu, Xinwen Guo, Zhongmin Liu. One-step aldol condensation reaction of dimethoxymethane and methyl acetate over supported
Cs/ZSM-35 zeolite catalysts. Chinese Journal of Catalysis 2018, 39 (6) , 1129-1137. DOI: 10.1016/S1872-2067(18)63069-4.
ACRYLIC ACID FROM
PROPANE OXIDATION*
•Acrylic acid can be manufactured from propane in an attractive way. This is mainly
because propane is very less expensive than propylene.
•In this method, propane is catalytically oxy-dehydrogenated to form a mixture of
propylene and propane.
•Then the mixture of propylene and propane are used to produce crude acrylic acid by
using the two stage propylene oxidation process as discussed previously.

*M.B. Ansari, S.-E. Park Energy Environ. Sci., 5 (2012), pp. 9419-9437
ACRYLIC ACID FROM LACTIC
ACID*
•Acrylic acid can be produced by the vapour phase dehydration of lactic acid.
•This method of production of acrylic acid is highly desirable as it is produced from a
bio-derivative, which is a renewable source of energy.
•The reaction conditions are as mentioned below**:

*Vidhya C. Ghantani; “Catalytic dehydration of lactic acid to acrylic acid using calcium hydroxyapatite catalysts”, Feb, 2013
**A.J.R. Castro, J.M. Soares, J.M. Filho, A.C. Oliveira, A. Campos, É.R.C. Bio-Synthesis-of-Acrylic-Acid, 108 (2013), Biosearch-pp. 740-748
ATOM ECONOMY OF THE
PROCESSES
ECONOMICS OF THE
PROCESSES*
From the above processes, production from lactic acid is eliminated.
For the remainder processes, the economic potential is as follows:

*https://www.indiamart.com/proddetail/acrylic-acid-9946698055.html\
*https://www.indiamart.com/proddetail/Glycerol-9961298078.html\
*https://www.indiamart.com/proddetail/Acetic-Acid-9546161.html\
*https://www.indiamart.com/proddetail/Acetol-95468828.html\
*https://www.indiamart.com/proddetail/propylene-gas-cylinder-21825666548.html
*https://www.indiamart.com/proddetail/CO-gas-cylinder-21825666548.html
 ECONOMICS OF THE
PROCESSES
By the previous basic calculations, it can be concluded that only the two following
processes retain their feasibility.
• Acrylic Acid from Ethylene
•Acrylic Acid from Propylene/Propane.

*Data obtained from Global Acrylic Acid Production to Reach 5.94 Mln Tonnes in 2017, According to Indemand Report by Merchant Research & Consulting. PRWeb. 2014. <
http://www.prweb.com/releases/2014/02/prweb11597545.htm>
MATERIAL BALANCES
The material Balance has been performed on the production of acrylic acid by Acid
Catalysed rearrangement of β-propiolacetone from ethylene.