Production of Acrylic Acid form
propylene
Group Members:
Ashwani Prasad
Advisor:
14BCH1007
Dr.R.C Katyal
Kumar Gaurav (HOD)
14BCH1022
Mohammed Ismail Shaikh
14BCH1025
University Institute Of Engineering
Department of Chemical Engineering
Acknowledgement
we would like to express our gratitude to Dr. R.C katyal, our
HOD, whose help and encouragement made this project
possible’ we would like to thanks Bindu madam, lab
instructor for her help during the completion of the project.
Ashwani prasad
Kumar gaurav
Mohammed Ismail Shaikh
B.E(CHE)
Chandigarh University(Gharuan)
Section 1 - Objective
Production of Acrylic Acid form propylene
The objective of this project is to design an acrylic acid plant that will
produce glacial acrylic acid, which is at 99.0% purity. Because acetic acid,
a byproduct, is also a marketable commodity, purification of acetic acid to
95% purity is also desirable. Acrylic acid is produced via the catalytic
partial oxidation of propylene. The desired products must be separated
from the rest of the reactor product stream. This stream consists of acrylic
acid, acetic acid, water, oxygen, nitrogen, and carbon dioxide. Goal is to
produce 20 TPD of 99.0% acrylic acid utilizing 8000 hours a year. The one
month of shut-down time is most likely for catalyst regeneration and
equipment
Section 2 - Introduction
Production of Acrylic Acid form propylene
2.1 Product
•Acrylic acid is the simplest unsaturated carboxylic acid and is a building block
for thousands of consumer products.
•It is a commodity chemical with a current market demand of nearly 10 billion
pounds per year, projected to surpass 13 billion pounds worth $14 billion by the
end of 2018.
•The majority of the market growth is projected to occur in China and India as
these countries produce increasing amounts of products using acrylic acid as
intermediates with application including detergents, coatings, adhesives,
sealants, as well as personal care items.
•Currently, the US accounts for 25% of global production.
•Generally, acrylic acid is produced using propylene.
•Propylene is a byproduct of hydrocarbon cracking and
naphtha refining, and the price very closely follows that of
oil.
•The purpose of this project was to determine best process
to produce Acrylic acid for the business.
Production of Acrylic Acid form propylene
2.2 Current Methods of Production
•The earliest synthesis of acrylic acid occurred in 1843 via the oxidation
of acrolein. Since 1927, the commodity chemical has been commercially
available through many different production means, including the
Ethylene cyanohydrins process, the Reppe Process, the β-Propiolactone
Process, and the Acrylonitrile hydrolysis.
Production of Acrylic Acid form propylene
2.3 Proposed Production Method
•This design project investigates a propylene based production platform.
i.e. the two stage oxidation of propylene.
•This process employs highly active and very selective heterogeneous
catalysts consisting of metal oxides such as vanadium and molybdenum to
oxidize propylene to acrolein in the first step. Yields of greater than 85%
are possible.
Step 1: CH₂ = CHCH₃ + O₂ → CH₂ = CHCHO + H₂0
(propylene) (acrolein)
Step 2: CH₂ = CHCHO + ½O₂ → CH₂ = CHCOOH
(acrolein) (acrylic acid)
•The second step involves the further oxidation of acrolein to acrylic acid
using cobaltmolybdenum oxides at reactions temperatures of 200 to
300°C with contact times of around 2 seconds.
•This current process gives acrylic acid yields of around 80-90% after
absorption by water.
Production of Acrylic Acid form propylene
2.4 Customer requirements
•Acrylic acid is a commodity chemical with a market demand of nearly 10
billion pounds per year.
•About 65% of production is used as a platform for ester synthesis while
the other 35% is purified to glacial acetic acid.
•Acrylic acid is generally produced in two grades including the crude or
technical grade which has a mass purity of about 94%.
•Maleic anhydride, propionic acid, and acetic acid constitute the main
impurities.
Production of Acrylic Acid form propylene
2.4 Commercial Applications
•The main use of acrylic acid is as feedstock for the production of
commodity chemicals, notably acrylate esters.
•The esters are responsible for many desirable features in polymers such
as acid and base resistance, optical properties, in addition to heat and
aging resistance.
•Acrylic acid polymerizes easily to give polyacrylic acid.
•This polymer is important for coatings, paints, adhesives, and other
textiles.
Section 3 – Process Description
Production of Acrylic Acid form propylene
3.1 Overview
Figure 1: two stage vapour phase oxidation of propylene to acrylic acid
Production of Acrylic Acid form propylene
3.2 Details
•The oxidation process flow sheet shows equipment and typical operating
conditions.
•The reactors are of the fixed-bed shell-and-tube type (about 3-5m long
and 2.5cm in diameter) with a molten salt coolant on the shell side.
•The tubes are packed with catalyst, a small amount of inert material at
the top serving as a preheater section for the feed gases.
•Vaporized propylene is mixed with steam and air and fed to the firststage
reactor.
Production of Acrylic Acid form propylene
3.3 First stage
•The preheated gases react exothermically over the first-stage catalyst
with the peak temperature in the range of 330-430o C, depending on
conditions and catalyst selectivity.
•At the end of the catalyst bed, the temperature of the mixture drops
toward that of the molten salt coolant
Production of Acrylic Acid form propylene
3.4 Second stage
•The acrolein rich gaseous mixture containing some acrylic acid is
then passed to the second stage reactor, which is similar to the first stage
reactor but packed with catalyst designed for selective conversion of
acrolein to acrylic acid.
•Here the temperature peaks in the range of 280- 360Û & DJDLQ
Gepending on condition.
•The temperature of the effluent from the second stage reactor again
approximates that of the salt coolant.
•The heat of reaction is recovered as steam in external waste heat boiler.
Production of Acrylic Acid form propylene
3.5 Absorber
•The acrylic acid is extracted from the absorber effluent with a solvent.
The acid extractor is a liquid-liquid extraction column.
•The acid containing water enters through the bottom feed stream.
•The top feed stream contains an organic solvent .
•The two liquid phases flow counter-currently through a liquid-liquid
extractor.
•The acids enter solution with the solvent and exit out the top stream
with a fraction of the water, and the water exits out the bottom stream
with a very small amount of solvent.
Production of Acrylic Acid form propylene
3.6 Solvent Extraction Column
•The top stream continues on to the solvent tower, which is a packed
distillation column.
•Because of acrylic acid's ability to dimerize easily at high temperatures,
all of the distillation processes are performed in part with vacuum
distillation.
•The solvent and remaining water leave in the distillate stream at 0.12
bar and 13oC.
•Refrigerated water is used to condense the distillate. Some is refluxed
back into the column, but the distillate is then heated up to 40oC and
used as a recycle and is re-fed into the acid extractor.
Production of Acrylic Acid form propylene
3.7 Acid tower
•Meanwhile, the acids leave the solvent tower in the bottoms and are fed
into the acid tower.
•The acid tower is a distillation column that again operates in vacuum
conditions.
•The acetic acid leaves the top at 0.07 bar, while the acrylic acid leaves in
the bottoms.
•Both the acrylic and acetic acids are warmed and compressed to normal
pressure levels.
•Both now meet the given requirements. Namely, that acrylic acid must
be 99% pure andthat acetic acid must be 95% pure
Production of Acrylic Acid form propylene
3.8 Recycling
•Only one detail remains. The bottom stream from the acid extractor is
nearly completely water save for a small amount of solvent.
•This stream is fed to another distillation column.
•Here, the solvent is separated out the top stream and then joins the
solvent recycle stream re-entering the acid extractor tower.
•The bottom stream is sent to wastewater treatment
Section 4 – Material Balance
Production of Acrylic Acid form propylene
4.1 Compounds and Molecular weights
Compound Molecular weight
propylene 42
Acrylic acid 72
Acetic acid 60
Acrolein 56
Oxygen 16
Carbon dioxide 44
Production of Acrylic Acid form propylene
4.2 Propylene required to produce 20 TPD of acrylic acid
(At steady state condition)
1 kmol of C₃H₆ → 1 kmol of acrylic acid
42 kg/hr of C₃H₆ → 72 kg/hr of acrylic acid
C₃H₆ required to produce 20 TPD of acrylic acid
=20 x (42/72) = 11.667 TPD of acrylic acid
(Assumption) At a yield of 78% ….[literature]
So, kmol of C₃H₆ supply or feed = 11.667/0.78
= 14.95 TPD (Ton Per Day)
4.3 Oxygen required
1 kmol of C₃H₆ required
= 3/2 x 14.95 kmol/hr
=22.425 kmol/hr
Production of Acrylic Acid form propylene
Reactor 1
4.4 Oxidation of propylene to acrolene
(from literature)
CH₂ = CHCH₃ + O₂ → CH₂ = CHCHO + H₂0
(propylene) (acrolein)
Catalyst composition: Ni. Fe. Zn. Bi. Or Zn + Co (Fe promotion)
Feed composition : C₃H₆ : Air :Steam :: 1 : 7.75 : 3.75
Contact time = 3.6 sec
Average temperature = 355°C
Overall conversion of C₃H₆ = 100%
Conversion to Acrolein = 70%
Conversion to Acrylic Acid = 11%
Conversion of (CO₂ + Acetic acid) = 19%
C₃H₆ fed = 14.95 kmol/hr
Steam fed = 14.95 x 3.75 = 56.062 kmol/hr
Air fed = 14.95 x 7.75 = 115.862 kmol/hr
O₂ entering = 0.21 x 115.862 = 24.311 kmol/hr
N₂ entering = 0.79 x 1150862 = 91.53 kmol/hr
Production of Acrylic Acid form propylene
O₂ left = 24.311 – 14.95
= 9.31 kmol/hr
Acrolein produced = 0.7 x 14.95
= 10.465 kmol/hr
Acrylic acid produced = 14.95 x 0.11
= 1.644 kmol/hr
Steam produced = 10.46 (1 kmol/hr of acrolein
= 1 kmol/hr of water)
Side product (CO₂ + Acetic acid) = 14.95 x 0.19
= 2.840 kmol/hrr
(in equal quantities)
Total steam leaving the reactor = 56.062 +10.462
= 66.625 kmol/hr
Production of Acrylic Acid form propylene
Reactor 2
4.5 Oxidation of Acrolein to Acrylic acid
(from literature)
CH₂ = CHCHO + ½O₂ → CH₂ = CHCOOH
(acrolein) (acrylic acid)
Catalyst composition: Mo12 V1.9 Al 1.0 Cu 2.2 ( support – Al sponge)
Contact time - 1 – 3 sec
Average temperation - 300°C
Acrolein conversion - 100%
Yield of Acrylic Acid - 97.5%
Feed:
O₂ = 93.1 kmol/hr
N₂ = 91.53 kmol/hr
Stream = 66.625 kmol/hr
Acrolein = 103.866 kmol/hr
Acylic acid =16.32 kmol/hr
Acetic acid = 14.096 kmol/hr
CO₂ =14.096 kmol/hr
Production of Acrylic Acid form propylene
Acrylic Acid formed in reactor 2 = 10.465 x 0.975
= 10.203 kmol/hr
by products formed = 0.262 kmol/hr
O₂ reacted = 10.465/2
= 5.23 kmol/hr
O₂ unreacted = 9.31 – 5.25
= 4.216 kmol/hr
N₂ in = N₂ out = 91.53 kmol/hr
Total Acrylic Acid formed in 2 reactors = 10.203 + 1.649
= 11.758 kmol/hr
Total Acetic acid produced = 1.4096 + 1.129
= 1.53 kmol/hr
Total CO₂ produced = 1.4096 + 0.1205
= 1.53 kmol/hr
Production of Acrylic Acid form propylene
4.6 Absorber:
Feed entring from the bottom of the absorber.
Acrylic Acid = 11.847 kmol/hr
Acetic acid = 1.55 kmol/hr
CO₂ = 1.55 kmol/hr
O₂ = 4.148 kmol/hr
N₂ = 91.53 kmol/hr
Steam = 66.527 kmol/hr
From literature:
Acetic acid and acrylic acid is absorbed using
water as solvent.
Gases CO₂, O₂, N₂ and small amount of steam
leave the absorber at the top.
Assumptions :
90% of the steam entering gets condensed.
Production of Acrylic Acid form propylene
Solvent:
water entering at the top = 488.6 kmol/hr
Off gases leaving at the top:
Acrylic Acid = 11.847 kmol/hr
Acetic acid = 1.55 kmol/hr
CO₂ = 1.56 kmol/hr
O₂ = 4.148 kmol/hr
N₂ = 91.53 kmol/hr
Product liquid leaving at the bottom of the bottom of the absorber to recovery
section: Acrylic Acid = 11.728 kmol/hr
Acetic acid = 1.534 kmol/hr
water = 108.73 kmol/hr
Mol fraction of Acrylic Acid in the product stream
= 0.0958 = 9.58%
Weight fraction of Acrylic Acid in the product stream
=0.2911 = 29.11%
Production of Acrylic Acid form propylene
4.7 Solvent Extraction column :
Feed from the bottom of the observer:
Acrylic Acid = 11.728 kmol/hr
Acetic acid = 1.534 kmol/hr
water = 108.73 kmol/hr
Solvent with high solubility for acrylic acid and acetic acid, and low solubility
with water is used to extract acrylic acid from absorber stream.
Assumption: Solvent (chloroform) required for 99.5% extraction of acrylic
acid is 500 kmol/hr.
Recycled stream from solvent recovery column and
waste tower.
Acrylic Acid = 0.053 kmol/hr
Acetic acid = 0.008 kmol/hr
water = 12.99 kmol/hr
Production of Acrylic Acid form propylene
Total Acrylic Acid in = 11.78 kmol/hr
Total Acetic acid in = 1.542 kmol/hr
Total water in = 121.72 kmol/hr
Extract phase contains (to solvent recovery plant):
Acrylic Acid = 11.66936 kmol/hr
Acetic acid = 1.53429 kmol/hr
water = 121.114 kmol/hr
solvent = 48.85 kmol/hr
Raffinate phase contains (to waste tower):
Acrylic Acid = 0.1104 kmol/hr
Acetic acid = 0.0156 kmol/hr
water = 119.23 kmol/hr
solvent = 11 kmol/hr
Production of Acrylic Acid form propylene
4.8 Solvent Recovery column:
Assumption: Complete recovery of solvent occurs.
bottom product contains only acetic acid and acrylic acid.
Feed: Extract phase from liquid – liquid extractor:
Acrylic Acid = 11.75 kmol/hr
Acetic acid = 1.542 kmol/hr
water = 2.1657 kmol/hr
solvent = 48.85 kmol/hr
Upstream contains (recycled to extraction column):
Acrylic Acid = 0.053 kmol/hr
Acetic acid = 0.008 kmol/hr
water = 2.1657 kmol/hr
solvent = 48.85kmol/hr
Column bottoms contains (to acid tower):
Acrylic Acid = 11.53 kmol/hr
Acetic acid = 1.508 kmol/hr
Production of Acrylic Acid form propylene
4.9 Waste tower:
Assumption: Bottom product contains water and all acrylic acid, acetic acid
entering the column.
Feed: Raffinate phase from the liquid – liquid extractor.
Acrylic Acid = 0.1104 kmol/hr
Acetic acid = 0.0156kmol/hr
water = 119.113 kmol/hr
solvent = 1.15 kmol/hr
Column bottom steam (to waste water treatment plant)
Acrylic Acid = 0.1104 kmol/hr
Acetic acid = 0.0156 kmol/hr
water = 108.28 kmol/hr
Column overhead stream (recycled to extraction column)
water = 1.15 kmol/hr
solvent = 10.82kmol/hr
Production of Acrylic Acid form propylene
4.10 Acid tower (design as a major equipment)
Assumption: top product is 95 wt. % acetic acid
Bottom product is 99.5 wt.% acrylic acid.
Feed:
Acrylic Acid = 11.53kmol/hr
Acetic acid = 1.508 kmol/hr
Top product:
Acrylic Acid = 1.488kmol/hr
Acetic acid = 0.014kmol/hr
Acerylic Acid produced =
Bottom Product:
Acrylic Acid = 11.516 kmol/hr
Acetic acid = 0.0197kmol/hr
Acerylic Acid produced =
