Chapter 2 MANUFACTURING PROCESSES

Chapter 2
MANUFACTURING
PROCESSES
The economics of the various processes for the manufacture of acrylonitrile
are strongly dependent on the price of the feed stock used. In the
laboratory, acrylonitrile can be prepared from several different
reactants. For example, it can be made from Acetonitrile and
formaldehyde, from ethylene cyanohydrins or acrylamide, using
phosphorous pent oxide, or from lactonitrile, and so forth. For a
summary of the laboratory methods for the production of acrylonitrile,
refer to the literature
The commercial processes described below are organized around their
starting materials.

Early processes:-
. A. Passage through ethylene cyanohydrin
The following reactions are involved:
CH2-CH2 + HCN CH2OH-CH2-CN
O
CH2OH-CH2-CN CH2=CH-CN+H2O
The preparation of cyanohydrin was described in connection with the
synthesis of acrylates. As for dehydration, this can be conducted in the
liquid phase, around 200°C, in the presence of a soluble catalyst based on
magnesium formate or carbonate, or in the vapor phase between 250 and
350°C, by passage over alumina. The molar yield is 90 per cent.
B. Addition of hydrogen cyanide to acetylene
This highly exothermic reaction:
HC ≡ CH +HCN CH2=CH-CN
ΔH0298 ≈ -175 kJ / mol
has been conducted industrially in the liquid phase, in the presence of a
catalyst consisting of cuprous chloride and ammonium chloride in solution

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Chapter 2 MANUFACTURING PROCESSES

in hydrochloric acid. A large excess of acetylene is used (6 to 15 mol/mol

HCN) at a pressure slightly above 0.1×106 Pa absolute and a temperature of
80 to 90°C. The molar yield is up to 90 per cent in relation to hydrogen
cyanide, and 75 to 80 per cent in relation to acetylene. The main by-products
are acetaldehyde, vinyl acetylene, divinyl acetylene, vinyl chloride, cyano
butene, lacto-nitrile, methyl vinyl ketone, etc.
The same reaction can be conducted in the vapor phase around 500 to
600°C, on charcoal impregnated with caustic soda and cyanides.

C. Passage through lactonitrile

The raw material is acetaldehyde, converted in two steps to acrylonitrile:
(a) In the first step, lactonitrile is formed by the addition of hydrogen
cyanide to acetaldehyde:
CH3-CHO + HCN CH3CHOH-CN
This reaction, which is highly exothermic and very fast, takes place between
10 and 20°C, at pH between 7 and.7.5, with molar yield of 97 to 98 per cent
.(b) In the second step, the lactonitrile is dehydrated to acrylonitrile:
CH3CHOH-CN CH2+CH-CN + H2O
To prevent redecomposition into acetaldehyde and hydrogen cyanide, the
reaction -takes place with a large excess of phosphoric acid (three times by
volume) by spraying at 600 to 700°C in a reactor in which the lactonitrile is
placed in contact with a hot, oxygen-free inert gas, during an interval
shorter than 3 s. The total molar yields are about 90 per cent in relation to
acetaldehyde and 92 per cent in relation to hydrogen cyanide.

D. Nitric oxide with propylene

This involves the following conversion:
4CH2=CH-CH3+6NO 4CH2=CH-CN + 6H2O + N2

It takes place at atmospheric pressure, between 450 and 550°C, in the

presence of a silver oxide based catalyst deposited on silica or of earth alkali
metal oxides, thallium and lead, and with excess propylene. An inert
(nitrogen, steam, etc.) is used as diluent, in order to absorb the heat generated
during the conversion, whose molar yield is 70, per cent in relation to
propylene.

E. The BP (Distillers)-Ugine process.

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Chapter 2 MANUFACTURING PROCESSES

The BP (Distillers)-Ugine process is a two-step process for manufacturing

acrylonitrile from propylene. It involves the oxidation of propylene to
acrolein, using a Se-CuO catalyst, followed by the reaction of acrolein with
ammonia and air in the presence of a MoOs catalyst. High acrylonitrile
yields are obtained, with the main by-products being CO2, HCN, and
Acetonitrile. The production of acrylonitrile from acrolein was the
precursor to the ammoxidation of propylene, and spurred the research
for catalysts that could combine the above-described reactions to produce
acrylonitrile directly from propylene. As a result, in England and France,
the firms Distillers, Ugine, and Kuhlmann have developed a process for
direct ammoxidation of propylene using an antimony-tin oxide catalyst
with ferric oxide added.

F. Societa Nazionale Metanodotti (SNAM) Process

In the Societa Nazionale Metanodotti (SNAM) Process, the
ammoxidation of propylene is carried out in a fixed-bed reactor in the
presence of an Mo-V or Bi catalyst. The main by-product is acetonitrile.
Approximately 1.35 kg of propylene (100% basis) are required per kg
acrylonitrile produced. A commercial unit was in operation in Europe, in
1968.

G. Montedison Process
In the Montedison Process, the ammoxidation of propylene is carried
out in a fluid-bed reactor in the presence of a catalyst consisting of
tellurium, cerium, and molybdenum oxides on silica base at 240-460°C
and about 200 kPa (29 psi). The contact time is between 2 and 6 seconds
and the feed composition is in the range of 6.7-8 vol % propylene, 7.4-9
vol % ammonia, and 86 vol % air. Propylene requirement (100% basis) is
1.2 kg/kg acrylonitrile. The main by-products are HCN and acetonitrile.

H. Osterreichische Stickstoff Werke Process

The Osterreichische Stickstoff Werke Process makes use of a Bi/Mo
catalyst in a fixed-bed reactor. One commercial installation has been
reported.

I. From Propionitrile.
The dehydrogenation of propionitrile to acrylonitrile takes place according to
the following equation:
550-650°C
CH3CH2CN CH2 = CHCN + H2

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Chapter 2 MANUFACTURING PROCESSES

Atmospheric
pressure
The reaction is carried out in the vapor phase over a catalyst consisting of an
oxide of chromium or vanadium. Alternatively, an oxidative dehydrogenation
can take place in the presence of iodine to give the following reactions:
CH3CH2CN +I 2 CH2=CHCN + 2 HI
1
2HI + /202 H20 + I2

The net reaction is:

400-800°C
1
CH3CH2CN + /202 CH2 = CHCN + H20

About 2 wt % of iodine together with 0.1-2.0 moles of oxygen per

mole of propionitrile is required.

J. From Propionaldehyde.
The reaction of ammonia with propionaldehyde proceeds according
to the following equation:
CH3CH2CHO + NH3 CH2 = CHCN + H20 + 2 H 2
The catalyst is Cr2O3 on activated alumina. The reaction is carried out
in the vapor phase with an excess of ammonia.

K. From Acetaldehyde.
Knapsack-Greisheim A.G. developed a process according to the
reaction:
10-20°C 600~700°C
CH3CHO + HCN CH3CH (OH) CN CH2=CHCN + H20
Phosphoric acid
This is a two-stage synthesis. Caustic soda is used as a catalyst for
the lactonitrile production; phosphoric acid serves only to take up the
water formed from the dehydration of lactonitrile.

L. New Routes: From Ethylene, Propane, and Butane.

Ethylene, propane, and butane can react with HCN to give
acrylonitrile. The reaction temperatures are high: 750-1000°C. No
catalyst is required for the reaction of ethylene, propane, and butane
with HCN.

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Chapter 2 MANUFACTURING PROCESSES

Alternatively, propane or butane can react with oxygen and

ammonia at temperatures of at least 500°C to give acrylonitrile.
Catalysts made up of the oxides of tin and tungsten avoids the
formation of a large number of by-products. A propane feedstock is
of particular interest to manufacturers since it is a relatively low cost
material. Monsanto has published data which indicate that propane
could be competitive with propylene. Power Gas Ltd and IC1 have
announced the development of an ammoxidation process based on
propane, and claim to have obtained yields comparable to those
obtained using propylene as feed stock.
Patents have described several catalysts that can convert propane,
ammonia, and oxygen into acrylonitrile. Yields have been generally
low. Although propane is cheaper than propylene at this time, it would
have to be much cheaper to make the propane route economically
attractive, unless high acrylonitrile yields are obtained. It is not
expected that the Sohio process will be replaced before 1985.
Recently, the oxycyanation of olefins has been proposed.
Acrylonitrile is obtained from ethylene, hydrogen cyanide, and
oxygen according to the following reaction:
C2H4 + HCN + 1/202 CH2 = CHCN + H 2 0

The catalyst is palladium based. Bench-scale tests have given high

conversions per pass, and a flow diagram for the process has been
proposed.

Acrylonitrile manufacture by ammoxidation of propylene

Although a large number of its basic patents already lie in the public
domain, the process commercialized by Sohio, concerning the ammoxidation
of propylene, has acquired a virtual monopoly in view of the technological
know-how accumulated in the past decade.
Transformation principle
The formation of acrylonitrile by ammoxidation occurs according to the
following highly exothermic reaction.
CH2=CH-CH3+NH3+3/2O2 CH2=CH-CN+3H2O
0
ΔH 298 ≈ -515kJ/mol

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Chapter 2 MANUFACTURING PROCESSES

It now appears clear that this overall result-can-be explained by the

production of. Acrolein as the main intermediate. In these conditions, the
reaction scheme is as follows:
CH2 = CH – CH3 + O2 CH2 = CH – CHO + H2O
CH2 = CH – CHO + NH3 CH2 = CH – CH = NH + H2O
CH2 = CH – CH = NH + 1/202 CH2 = CH – CN + H2O
This transformation is also characterized by the importance assumed by
degradation side reactions of propylene and of its oxygen and nitrogen
derivatives, which lead simultaneously to the formation of hydrogen
cyanide, acetonitrile, nitrogen, carbon monoxide and carbon dioxide:
2CH2=CH–CH3 + 3NH3 + 3O2 3CH3CN + 6H2O
CH2=CH–CH3 + 3NH3 + 3O2 3HCN + 6H2O
CH2=CH–CH3 + 9O2 3CO + 3H2O
2CH2=CH–CH3 + 9O2 6CO2 + 6H2O

Since these reactions are themselves highly exothermic, it is found in

practice that the total exothermicity of acrylonitrile manufacture is higher
than indicated by theory, and is as high as 650 to 670 kJ/mol.
A. Catalysts
To offset the lower yield resulting from the development of side reactions,
many catalyst formulations have been suggested, and their performance has
steadily improved with time. They are all using mixed oxides based on
antimony, arsenic, bismuth, cobalt, tin, iron, molybdenum, nickel,
phosphorus, rare earths, tellurium, uranium, vanadium, etc., with or without
a support.
The most significant development was achieved by Sohio, who initially
employed bismuth phosphomolybdate. This system was replaced in 1967 by
a mixture based on oxides of antimony and uranium (catalyst 21). In 1972,
Sohio then returned to an iron and bismuth phosphomolybdate (catalyst 41)
doped by additions of cobalt, nickel and potassium, and achieving
acrylonitrile productivity gains of 10 to 35 per cent. A fourth generation of
catalysts (type 49) finally emerged in 1978, achieving a slight improvement
in yield, but offering better mechanical properties.
Cooperation between Distillers and PCUK, followed by Border Chemicals,
was originally based en the development of a two-step process. In the first

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Chapter 2 MANUFACTURING PROCESSES

step, propylene was converted to acrolein on a catalyst based on selenium

and copper oxides, and, in the second step, ammonia reacted in the presence
of a system including MoO3 and .various other compounds. A single-step
technology was subsequently developed, involving the use of molybdenum
oxide promoted by caustic soda, or cobalt molybdate and tellurium oxide,
followed by the use of systems of antimony and tin oxides. The best results
are now obtained with formulations based on cobalt, iron and molybdenum.
While SNAM developed mixtures based on the use of bismuth and
vanadium compounds, Montedison, whose exclusive operating license was
acquired in 1975 by UOP, preferred a supported catalyst based on oxides of
cerium, molybdenum and tellurium on silica. OSW employs a mixture of
metallic bismuth and molybdenum deposited on a support.
The latest developments in catalysts for manufacturing acrylonitrile are
those of the Japanese firm Nitto Chemical, which commercialized a system
in 1974 based on doped antimony and iron, called NS 73 3A or catalyst 13,
offering higher productivity in comparison with Sohio catalyst 41, as well as
lower production of acetonitrile and hydrogen cyanide by-products.
These formulations, which operate in the vapor phase, are preferably used in
a fluidized bed, to facilitate the removal of the heat generated by the
reaction, the homogenization of the thermal level within the reaction
medium, better temperature control and hence superior catalyst performance
(Sohio, Montedison/UOP, Nitto, etc.). However, this arrangement implies
improved mechanical properties. Fixed beds have also been used
(PCUK/Distillers/Border, SNAM, Chemie-Linz, etc.), the main problem
being the need to withstand a thermal gradient, and possibly the existence of
hot points causing the accelerated destruction of the Catalyst due to the
migration of active phases and to attrition. Apparent residence times range
from 2 to 15 s, and catalyst life is generally between one and three years,
and possibly more with the latest formulations.

B. Operating conditions
As a rule, the ammoxidation of propylene takes place in the presence of a
slight excess of ammonia and oxygen in comparison with stoichiometry.
The purity of the reactants employed is generally high (over 90 per cent
weight for propylene, and 99.5 per cent weight for ammonia). With certain
catalyst systems, especially the first-generation systems, the addition of steam
raises selectivity and limits the conversion of ammonia to nitrogen.
However, the current trend, due to the improvement in catalyst performance

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Chapter 2 MANUFACTURING PROCESSES

and the advances in metallurgy, is to eliminate this water hold-up to achieve

better optimization of the energy balance of the operation.
Experience shows that the acrylonitrile yield increases with the
NH3/propylene ratio. In practice, however, stoichiometry is approached as
closely as possible (ratio of 1), and, in certain cases, operations are even
conducted at sub-stoichiometric values (≈ 0.8). This is because the reaction
is normally incomplete, and the ammonia remaining in the reactor exit
gases, independent of the initial excess, gives rise to side reactions. These
can be avoided by rapidly neutralizing it by sulfuric acid. Thus increasing the
NH3/propylene ratio results in needless losses of raw materials, with
repercussions at the economic level. From this standpoint, research projects
under way are directed both for the development of better-performing catalysts
and the development of ammonia recovery techniques, which allow for its
recycling while maintaining high acrylonitrile selectivity.
The reaction temperature usually ranges between 400 and 500°C and
pressure remains below 6.3×10s Pa absolute. The acrylonitrile/acetonitrile
molar ratio rises rapidly above 4000C, and reaches a peak around 470 to
480°C
C. Performance
Once-through conversion of propylene is virtually complete, that of
ammonia is higher in a fluidized bed (over 95 per cent) than in a fixed bed
( = 85 per cent). Selectivity, and consequently the acrylonitrile
transformation yield, is very sensitive to the type of catalyst and to the
operating conditions, especially the residence time, which must remain above
1 s. The yield may be as high as 72 to 75 molar per cent with the latest catalyst
systems operating in a fluidized bed, and nearly 78 molar per cent with those
operating in a fixed bed.
. The high proportion of by-products, whose utilization after separation and
purification can influence the economics of the operation considerably. Thus
the acetonitrile, which could be used as a butadiene extraction solvent, is
usually burned. Another possibility is to convert it to acrylonitrile by the
following reaction :
CH3CN + CH4 + O2 + H20 CH2 = CH-CN +CO2+CO+H2

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Chapter 2 MANUFACTURING PROCESSES

This reaction takes place in the presence of a supported potassium bromide-

based catalyst. Hydrogen cyanide serves for the synthesis of methacrylic acid,
methionine, etc. In many cases, however, it is also incinerated, minimizing
the risks of pollution and accidents.

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