Process Description
CHAPTER 2
Process Description
23
Process Description
2.0 INTRODUCTION
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.
2.1 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 200C, in the presence
of a soluble catalyst based on magnesium formate or carbonate, or in the vapor phase
between 250 and 350C, by passage over alumina. The molar yield is 90 per cent.
B.
Addition of hydrogen cyanide to acetylene has been conducted industrially in the liquid
phase, in the presence of a catalyst consisting of cuprous chloride and ammonium chloride in
solution in hydrochloric acid.
This highly exothermic reaction:
HC CH +HCN
H0298 -175 kJ / mol
CH2=CH-CN
24
Process Description
A large excess of acetylene is used (6 to 15 mol/mol HCN) at a pressure slightly above
0.1106 Pa absolute and a temperature of 80 to 90C. 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 byproducts are acetaldehyde, vinyl acetylene, di-vinyl acetylene, vinyl chloride, cyano butene,
lacto-nitrile, methyl vinyl ketone, etc.
The same reaction can be conducted in the vapor phase around 500 to 600C, 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 20C, at
pH between 7 and.7.5, with molar yield of 97 to 98 per cent. 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
700C 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
25
Process Description
It takes place at atmospheric pressure, between 450 and 550C, 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.
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 CO 2, 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 byproduct 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
26
Process Description
on silica base at 240-460C 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:
550-650C
CH3CH2CN
CH2 = CHCN + H2
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 +I2
CH2=CHCN + 2 HI
2HI + 1/2O2
The net reaction is:
H2O + I2
400-800C
CH3CH2CN + 1/2O2
CH2 = CHCN + H2O
About 2 wt % of iodine together with 0.1-2.0 moles of oxygen per mole of propionitrile is
required.
J. From Propionaldehyde.
27
Process Description
The reaction of ammonia with propionaldehyde proceeds according to the following
equation:
CH3CH2CHO + NH3
CH2 = CHCN + H2O + 2 H2
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:
10-20C
CH3CHO + HCN
600~700C
CH3CH (OH) CN
CH2=CHCN + H2O
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: 750-1000C. No catalyst is required for the reaction of ethylene,
propane, and butane with HCN.
Alternatively, propane or butane can react with oxygen and ammonia at temperatures of at
least 500C 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.
28
Process Description
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 + 1/2O2
CH2 = CHCN + H2O
The catalyst is palladium based. Bench-scale tests have given high conversions per pass, and
a flow diagram for the process has been proposed.
2.2 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
H0298 -515kJ/mol
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 + 1/2O2
CH2 = CH CN + H2O
29
Process Description
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=CHCH3 + 3NH3 + 3O2
3CH3CN + 6H2O
CH2=CHCH3 + 3NH3 + 3O2
3HCN + 6H2O
CH2=CHCH3 + 9O2
3CO + 3H2O
2CH2=CHCH3 + 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.
30
Process Description
Cooperation between Distillers and PCUK, followed by Border Chemicals, was originally
based on the development of a two-step process. In the first 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
31
Process Description
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 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 NH 3/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.. 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 500C and pressure remains below
6.310s Pa absolute. The acrylonitrile/acetonitrile molar ratio rises rapidly above 4000C, and
reaches a peak around 450C
32
Process Description
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 + H2O
CH2 = CH-CN +CO2+CO+H2
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.
33
