TẬP ĐOÀN DẦU KHÍ VIỆT NAM

TRƯỜNG ĐẠI HỌC DẦU KHÍ VIỆT NAM

PRODUCTION OF
ACRYLONITRILE

Presenter: Nguyen Cao Ky (Group 1)

Supervisor: Do Chiem Tai, PhD
 MEMBER

01 Phan Thị Mỹ Ái 06 Nguyễn Ngọc Hải

02 Nguyễn Lê Quang Anh 07 Nguyễn Thị Thanh Hà

03 Tô Văn Bão 08 Đồng Khánh Gia

04 Nguyễn Thị Bình 09 Nguyễn Cao Kỳ

05 Trần Phú Điền 10 Đỗ Duy Khánh

05/13/2022 Petrochemical Technology 2

 CONTENT

INTRODUCTION AND APPLICATIONS

01
02 PRODUCTION OF
ACRYLONITRILE

PROCESS FLOW
DIAGRAM 03
CONCLUSION
04

3
01
INTRODUCTION
&
APPLICATIONS

4
 1. INTRODUCTION

Acrylonitrile

Main name Orther name

2- prop-2-
vinylxyanua Xyanoetylen propynenitrile
propenenitrile enenitrile

5
 1. INTRODUCTION

77.3ºC

C₃H₃N

6
 1. INTRODUCTION

Chemical formula C₃H₃N

Molecular weight 53,06 g·molˉ¹

Status Colorless liquid

Density 0,81 g / cm³

melting point -84 °C

boiling point 77.3 °C

vapor pressure 83 mmHg

auto-ignition temperature 471 °C

Table 1: Some physical properties of acrylonitrile

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 1. APPLICATIONS

 Acrylonitrile is mainly used as a monomer for products such as

polyacrylonitrile:

 Production of ABS and SAN plastic:

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 1. APPLICATIONS

Adiponitrile
acrylamide

polyacry
SAN lonitrile
styren-
acrylonitrile Applications
of
acrylonitrile

ABS

Acryli
c yarn

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02
PRODUCTION OF
ACRYLONITRILE

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 2. PRODUCTION OF ACRYLONITRILE

2.1 Propylene Material

Table 2: Some physical properties of propylene

Molecular weight (đvC) 42,08

Melting point (°C) -185,2

boiling point (°C) -47,6

vapor pressure at 25°C 8690

Under normal conditions, propylene is an odorless, colorless, and non-toxic gas.

But it is flammable.

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 2. PRODUCTION OF ACRYLONITRILE
2.1 Propylene Material

Steam cracking

Catalytic Cracking

Propylene is produced from Fischer Tropsch Process

Dehydrogenation of propane

From Methanol

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 2. PRODUCTION OF ACRYLONITRILE
2.2 Ammonia Material

Table 3: Some physical properties of ammonia

Molecular weight (đvC) 17.031 g/mol

Melting point (°C) -77.7

boiling point (°C) -33.5

Density 0.771 g/L

NH3 is synthesized by the Haber–Bosch process according to the

following reaction:
3H2 + N2 → 2 NH3

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 2. PRODUCTION OF ACRYLONITRILE

2.3 The production of Acrylonitrile by Ammoxidation of Propylene

 Acrylonitrile is formed by the ammonium method, according to the

reaction:
CH2=CH-CH3 + NH₃ + 3/2 O2 → CH2=CHCN + 3 H2O

ΔΗ˚298=-515kJ/mol
 This reaction occurs through the formation of an intermediate compound
called acrolein:
CH­2=CH-CH­­3 + O2 CH2=CH-CHO + H­2O

CH2=CH-CHO + NH3 CH2=CH-CH=NH + H2O

CH­­2=CH-CH=NH + 1/2O2 CH2=CH-CN + H2O

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 2. PRODUCTION OF ACRYLONITRILE

2.3 The production of Acrylonitrile by Ammoxidation of Propylene

 Side reactions that break down propylene and its oxygen and nitrogen-
containing derivatives lead to the simultaneous formation of hydrogen
cyanide, acrylonitrile, nitrogen, carbon monoxide and carbon dioxide.

2CH2=CH-CH3 + 3NH3 + 3O2 → 3CH3CN + 6H2O

CH2=CH-CH3 + 3NH3 + 3O2 → 3HCN + 6H2O

CH2=CH-CH3 + 3O2 → 3CO + 3H2O

2CH2=CH-CH3 + 9O2 → 6CO2+ 6H2O

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 2. PRODUCTION OF ACRYLONITRILE

2.3 The production of Acrylonitrile by Ammoxidation of Propylene

Reaction conditions
Temperature 370-500 ºC

Optimal conditions 420-480 ºC

Pressure 0.3 MPa

Residence time T > 6s

 In principle, oxidation of propylene occurs with an excess of ammonia and

oxygen relative to the scale factor .

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 2. PRODUCTION OF ACRYLONITRILE
2.3 The production of Acrylonitrile by Ammoxidation of Propylene
Carrying out reactions
 The one-time conversion of ammonia is over 95% (in fluidized bed
catalysis) and 85% (in immobilized catalyst technology).

 Various by-products are also formed in large proportions. To avoid the

economic impact of the process, acetonitrile is usually converted to
acrylonitrile by the following KBr-based catalyst reaction:

CH3CN + CH4 + O2 + H2O → CH2=CH-CN + CO2 + CO + H2

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 2. PRODUCTIN OF ACRYLONITRILE
2.3 The production of Acrylonitrile by Ammoxidation of Propylene

 Catalyst for the process

Commonly used catalysts are oxides of antimony, arsenic, bismuth, cobalt,
tin, iron, molybdenum, nickel, phosphorus, rare earth elements, tellurium,
uranium, vanadium, etc., carried or not.
 Sohio's catalyst system

1960 1967 1972 1978

Catalyst 49:
Bi2O3 Catalyst 21: Catalyst 41: Molybdate Co,
/MoO3 (1/2) UO3+Sb2O4 Oxit Fe-Bi-P- Ni, Fe, Bi
with added Mo
P2O5

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03 PROCESS FLOW
DIAGRAM

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 3. SOHIO PROCESS
3.1 Propylene ammoxidation process with fluidized catalyst beds
1 Amoxidation tower.
2 Direct cooling tower.
3 Nitrile absorption tower.
4 AN evaporator tower.
5 Isoelectric distillation tower
separates AN from water.
6 Acetonitrile separation tower.
7 HCN . Separation Tower.
8 Carbonyl impurity separation
tower.
9 Acrylonitrile purification
tower.
10 AN Recovery Tower.

Figure 1: SOHIO Process Diagram - Fluidized Bed Catalytic

Reactor

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 3. SOHIO PROCESS
3.1 Propylene ammoxidation process with fluidized catalyst beds

Figure 2: Reactor

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 3. SOHIO PROCESS

 The propylene fraction is heated to 200°C and liquid NH3, after passing through
the heat exchanger, will be evaporated then together with compressed air enter
the central tank (1).
 The product gas mixture (acrylonitrile, HCN, CO, CO2, residual NH3, acetonitrile...)
coming out of the reactor (1) is cooled indirectly to produce medium pressure
vapor (80-85°C) which is then added to the absorption tower (2). H2SO4 solution is
also added from the middle of the tower (2) to clean excess NH3 and follow the
gas product line.
 Acrylonitrile is passed through the isotropic distillation tower to separate
Acrylonitrile from the water, and the ammonium sulfate solution is Regeneration
and crystallization will be collected, water is put into the device to wash to remove
excess acid.

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 3. SOHIO PROCESS

 The gaseous mixture at the top is cooled by a heat exchanger and then transferred
to a nitrile absorption tower (3). The outlet gas at the top of the tower contains a
small amount of nitrile and hydrocarbons that are burned to produce water vapor
or release to the atmosphere.
 At (5) occurs the process of separation of products from water. At the bottom of
the tower, acetonitrile in the aqueous phase is transferred to the isotropic
distillation column (6) to obtain acetonitrile with a concentration of 97% by mass.
 The remaining water is returned to the tower (2) as an absorbent after it has been
cooled to 50°C.
 The product mixture from the top of the tower (5) is transferred to the HCN
separation tower (7). The bottom product mixture contains Acrylonitrile with The
light products of acrylonitrile purification tower are transferred to the carbonyl
impurity separation tower (8)

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 3. SOHIO PROCESS
 Products containing Acrylonitrile are transferred to acrylonitrile purification tower
(9), performed under vacuum to obtain pure Acrylonitrile, light products after
cooling the peak circulation will return to the tower (8). For devices (7), (8), (9)
people also use inhibitors to limit the polymerization that reduces the yield of the
main reaction.
 In the device (9), the bottom product will be transferred to acrylonitrile recovery
(10), the top product that still contains Acrylonitrile after circulating cooling will be
returned to the device (4). The resulting bottom product is a polymer.

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 3. SOHIO PROCESS
3.2 Propylene ammoxidation process with fixed catalyst beds

Figure 2: Propylene Ammoxidation Process With Fixed Catalyst

Beds.

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 3. SOHIO PROCESS

 Liquid propylene and NH3 fractions will be evaporated, then combined with the
compressed air will enter the reactor (1) in the appropriate proportion.
 The product gas mixture comes out of the reactor (1) and passes through the heat
exchanger (indirect cooling) to generate medium pressure steam, then the
gaseous product is cleaned of excess NH3 in the absorber (2). In the absorption
tower (2), we use a solution of H2SO4 combined with a solution of (NH4)2SO4 in
H2SO4
 The remaining amount of bottom product of the absorption tower combines with
the top product of the light separation tower (13) and is passed through the
organic compound recovery device in the water phase (4). Here occurs the
separation of solution (NH4)2SO4 from AN.

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 3. SOHIO PROCESS

 And the top product of tower (4) is AN, this amount of AN will be passed through
isostatic distillation tower to separate water.
 The exit gas mixture at the top of the tower (2) is cooled and then transferred to
the nitrile absorption tower (3) to recover hydrocyanide, acetonitrile, acrylonitrile
and heavy components from the bottom of the tower, then transferred to an
isostatic distillation column (5)
 At the bottom of the tower (5), acetonitrile mixed with AN in the water phase is
boiled back to the bottom of the tower, the remaining amount is combined with
water and the bottom product of the acetonitrile purification tower (12) and then
returned to the absorption tower (2) to collect the remaining amount of AN.

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 3. SOHIO PROCESS

 The organic phase is obtained from the separator, which is passed through a
device that converts acrolein to Cyanohydrin (6) by the hydrocyanide itself present
in the product mixture.
 The product mixture, after leaving the device (6), is passed through the residual
alkaline neutralization device (7), where the excess alkali will be neutralized by the
appropriate amount of H2SO4 acid.
 The product exiting the apparatus (7) combines with the top product of the
Cyanohydrin separator (8) and the bottom product of the acrylonitrile purification
tower (14) and is then fed to the Cyanohydrin separator (9)
 The top product is acrylonitrile, acetonitrile, hydrocyanide back to the Cyanohydrin
separation tower (9).

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 3. SOHIO PROCESS
 The peak product of the separator (9) is acrylonitrile, acetonitrile, hydrocyanide
combined with SO2 and then passed through the hydrocyanide distillation column
(10).
 The bottom product of the tower (10) is acrylonitrile, acetonitrile will be partially
refluxed, the rest continues to be passed through the acetonitrile distillation
column (11).
 The bottom product is also boiled and refluxed in an amount to make the
distillation process more thorough, the rest is passed through the acetonitrile
purification tower (12).
 The top product of the acetonitrin purification tower is pure acetonitrile, the
bottom product is the amount of acrylonitrile mixed with acetonitrile, this amount
will be returned to the AN (4) evaporation tower to collect the remaining
acrylonitrile.

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 3. SOHIO PROCESS
 The peak product of the acetonitrile distillation column (11) is acrylonitrile and
some light products are combined with the peak product of the acrylonitrile
purification column (14) and then passed through the light product distillation
column (13).
 The product at the bottom of the tower (13) mainly acrylonitrile will be led
through the acrylonitrile purification tower (14) and pure acrylonitrile product was
removed from the middle section of the tower.
 The top product of the tower is led to the light product separation tower (13), the
bottom product of the tower will be returned to the cyanhydrin separation tower
to separate the acrylonitrile.

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 3. SOHIO PROCESS
Table 4: Advantages and disadvantages of two acrylonitrile production technologies
FLUIDIZED CATALYST BEDS FIXED CATALYST BEDS

Advantages Better control the temperature thus Simple equipment, so the price
increasing the working efficiency of the is cheap
catalyst.

High efficiency due to being able to Prolong the mechanical stability

perform at high ammonia/propylene of the catalyst
ratio

Small amount of catalyst

Easy regeneration and recovery process

Disadvantages Design of reactor is more difficult to Lower performance

increase cost
The mechanical strength of the catalyst Large thermal gradient, rapid
is reduced catalyst destruction due to
migration of active phases and
catalyst wear

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04 CONCLUSION

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 4. CONCLUSION

 We find that the fluidized bed catalyzed propylene ammoxidation

technology has superior advantages, although it is expensive, it has high
efficiency, easy regeneration and recovery of the catalyst.

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 REFERENCES
1. Petrochemical Process HandBook_2005
2. https://123docz.net/document/3781756-tong-hop-acrylonitril-va-san-xu
at-pan-2.htm
3. http://luanvan.co/luan-van/de-tai-tong-hop-acylonitrile-ch2-ch-c-n-
56469/

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05/13/2022 Petrochemical Technology 35