The Manufacture of Hydrocyanic

Acid by the Andrussow Process

By J. M. Pirie, Ph.D., A.M.1.Chem.E.

The manufacture of hydrocyanic acid by the catalytic combination of

methane, ammonia and air has increased remarkably in recent years.
Some of the features of this process, particularly the variety of platinum
metal catalysts employed in it, are surveyed i n this article.

Cyanogen compounds have in the past been to form special-purpose synthetic rubbers
employed chiefly in the extractive metallurgy (G.R.“’). These nitrile rubbers are used for
of silver and gold, in electroplating and for mechanical rubber pads, textile and paper
the surface hardening of metals. Manufacture sizings, and for petrol and oil resistant goods.
was chiefly through the Landis and Castner They are marketed in the United States under
processes, neither of which however yielded brand names Hycar, Paracril, Butaprene and
hydrocyanic acid directly. Chemigum. Hycar will shortly be manufac-
The development since the thirties of tured in this country by British Geon Ltd.
extremely useful polymeric acrylic compounds Acrylonitrile polymers are also capable of
has created a demand for very considerable being spun into textile fibres, and its employ-
quantities of hydrocyanic acid, and several ment in such materials as Vinyon, Dynel,
methods of direct synthesis have been inten- Acrilan, Orlon and Creslan is now the
sively studied. A synthesis from carbon largest single use.
monoxide, methane and ammonia through Smaller proportions of hydrocyanic acid
an intermediate formate-formamide stage has are required for the manufacture of acrylates
been employed by the Koppers Company. and methacrylates, which can be polymerised
A large plant for the production of hydro- to form plastics, such as Perspex, with very
cyanic acid direct from carbon monoxide and high optical transmission, and in the grepara-
ammonia was built in Germany during the tion of adiponitrile, a necessary intermediate
war, but was never put into operation. in the manufacture of Nylon. Small quanti-
The method which has, in a variety of tities are also used in the production of
modifications, proved generally successful, is acrylic acid, which forms polymers exhibiting
based on that first described by Andrussow strong hydrophilic properties.
in 1930 (I) which employs methane, ammonia
and air. The Principles of the Process
The endothermic conversion of methane
The Uses of Hydrocyanic Acid and ammonia into hydrocyanic acid and
The greater part of the hydrocyanic acid hydrogen according to the reaction
manufactured in this way is consumed in CH, j NH, >HCN 1 3H8-60K Cal.
the manufacture of acrylonitrile, either by is theoretically possible, but the practical
condensation with ethylene oxide to form difficulties of supplying heat to maintain
ethylene cyanhydrin, or directly by liquid- the required reaction temperature of 1000to
phase catalytic combination with acetylene. 1200°C make it unattractive. The strongly
Acrylonitrile is polymerised with butadiene exothermic reaction obtained by the catalytic

Platinum Metals Rev., 1958, 2, (l), 7-1 1 7

combination of methane, ammonia and air arrangements, the operating characteristics of
the process are closely similar to those of the
CH,t-NH,+ 140,-tHCNi 3H20-I-115KCal.
old established ammonia oxidation process.
is better suited to large-scale manufacture, Low-cost anhydrous ammonia can easily
since after it is initiated, at a temperature of be obtained in any major centre of chemical
about IOOO~C, it becomes self-sustaining. industry. At present natural gas forms the
Although other hydrocarbons could be principal source of cheap methane, and is
substituted for methane, this does not appear used by the Montecatini Company in
to have been done in any of the successful Lombardy and by manufacturers in the United
processes. States. Where natural gas is not available,
To obtain an optimum yield a very short town's gas or coke-oven gas must be methan-
contact time, of the order of 0.0003 second, ised over a nickel catalyst. Petroleum refinery
is desirable and consequently a high operating gases may also be employed.
temperature is necessary to reach equilibrium.
In practice, some carbon monoxide and Platinum Gauze Catalysts
nitrogen are formed by direct combustion and Although the use of base metal oxides, or
some ammonia is decomposed at the high iron, bismuth and cobalt have been described
operating temperature, so that the product in patents, all the reported processes employ
gases contain hydrogen cyanide, nitrogen, platinum-group metal catalysts. A pad of
carbon monoxide, carbon dioxide, hydrogen gauzes woven from platinum or platinum
and water vapour, as well as unconverted alloy wire, similar to the catalyst pads used
ammonia that must be recovered. Apart from for ammonia oxidation, enables a short
the greater complexity of the recovery contact time to be obtained and offers little

A general view of the hydrogen cyanide unit in the Fortier Plant of the American
Cyanamid Company at A'ew Orleans

Platinum Metals Rev., 1958, 2, (1) 8

Rhodium-platinum alloy wire
gauze before use (left) and
after about 1,000 hours expo-
sure to catalytic reaction

resistance to the high velocity gas flow. It a pilot unit operated by the Freeport Sulphur
can also be preheated with little difficulty to Company.
initiate the reaction. Catalysts of this sort Catalyst operating temperatures are higher
were in fact proposed by Andrussow. Their than in ammonia oxidation, ranging from
use has however been accompanied by some 900 to 1200 'C, so thattheuseofrhodium alloys
difficulty. which have much greater mechanical strength
Chretien and Thomas ( 2 ) and Maffezzoni and lower recrystallisation rates than pure
(3) found that after a short period of use, platinum at these temperatures is evidently
embrittlement of the wires and deposition desirable. No differences in conversion
of carbon occur. The trouble is particularly efficiency between pure platinum, rhodium-
pronounced at the periphery, and it was platinum or iridium-platinum have been
proposed in United States Patent 1,957,749 reported. Although Andrussow (5) has
(assigned to B. F. Goodrich & Co.) to clamp recommended the use of gauze with thicker
the gauze pad between ceramic or refractory wire and larger meshes than normal, only
rings and to flush the catalyst edges with conventional ammonia-oxidation gauze has
carbon-free gas. generally been used.
It is probable that the difficulties are Either 5 per cent and 10per cent rhodium-
mostly associated with impurities in the feed, platinum, 0.06 mm or 0.076 mm x 1024 mesh
or with imperfect control of feed composition, are typical specifications. The growth of
since in the Rohm and Haas plant at Darm- dendritic crystals on the surface of the catalyst
stadt, described by Kautter and Leitenberger wires, which is always observed during the
(4, a gauze life of 4,000 hours was being oxidation of ammonia, is evidently character-
obtained, and a life of 8,009 hours-approxi- istic of this process also. Heavy metals, as
mately a year-was expected with more well as arsenic and sulphur compounds, are
experience. In this plant, 10per cent rhodium acute poisons to the platinum and platinum
platinum alloy gauzes are employed, several alloy catalysts.
being placed together in a pad and supported
so as to minimise mechanical stress. No Supported Platinum Catalysts
volatilisation of the platinum occurs, and The high operating temperatures and gas
the operational conditions are controlled so velocities essential to this process impose
as to avoid deposition or over-heating. relatively severe stresses on gauze catalysts,
A catalyst loss rate of 0.6 gm per ton of and a great deal of attention to supporting
hydrogen cyanide produced was reported in the pads has been necessary. Ceramic rod

Platinum Metals Rev., 1958, 2, (1) 9

 I%w diagram of the Montecatini process j o r the catalytic synthesis
of hydrogen cyanide from methane, ammonia and air

supports were used at Darmstadt. Metal intended for use at 1000 to 12oo"C. In
supports made of heat-resisting materials British Patent 737,995, in the name of
which are not catalyst poisons are described Lonza Elektrizitatswerke, the use of tubular
by B. I;. Goodrich in British Patent 739,277. reactors with the active material dispersed
There has consequently been considerable on the tube walls is proposed. United
interest in the development of supported States Patent 2,666,689 assigned to Monsanto
catalysts capable of withstanding the high Chemical Company claims the use of a novel
operating temperatures, and a number of catalyst, a bed of electrodeposited rhodium
proposals have been made, some of which crystals B inch thick supported on non-
have been satisfactorily put into operation. reactive material. The reaction is to be
In this, the process is notably different from conducted at IZOO'Cwith a contact time of
that of ammonia oxidation. only o.oo02 second.
Maffezzoni made experiments with
platinum dispersed on a considerable variety Processes and Plants
of carriers, and the Montecatini plants now Although they all adhere to the same
employ supported catalysts of this sort in fundamental catalytic method, the various
their operations with natural gas. Supported modifications of the Andrussow process
catalysts containing mixtures of platinum differ in their sources of methane, in the
metals-for example, rhodium and platinum proportions of reacting gases, in the nature of
-have been employed. the platinum metal catalyst, and in the
In the United States Patent 2,726,931 means of collecting and purifying the product,
assigned to du Pont, a supported catalyst and recovering or recycling the excess
comprising 20 per cent rhodium and 80 per ammonia. The technical and commercial
cent platinum on an alumina-zirconia por- developments of the various modifications
celain base is described. The platinum up to the beginning of 1954 have been
metals are applied to the base by successive reviewed by Sherwood (6).
depositions and firings. The catalyst is Although natural gas is the preferred

Platinum Metals Rev., 1958, 2, (1) 10

source of methane, there are of course few before the hydrocyanic acid is condensed.
areas where it is readily available and in the It is usual to add small quantities of sulphuric
German plant of Rohm and Haas, methane is or phosphoric acids to act as polymerisation
obtained from Ruhr grid gas (town's gas) inhibitors.
by reacting the carbon monoxide and carbon In the novel recovery process developed
dioxide with hydrogen over nickel catalysts. by the Freeport Sulphur Company (United
Other synthetic sources of methane are also States Patent 2,590,146) both hydrogen
employed. cyanide and ammonia are simultaneously
B. F. Goodrich & Company, in various absorbed. The absorption medium is based
patents, claim the advantages of a high on a polyhydroxy boric acid complex-an
methane to ammonia ratio and are able to aqueous solution of pentaerythritol and boric
employ unpurified natural gas in a gauze acid-in which the hydrogen cyanide dis-
catalyst process at an operating temperature solves, but with which the ammonia combines.
of 1100 to 1260rC. The advantages of em- The hydrogen cyanide can be recovered by
ploying a high air to gas ratio in the feed vacuum distillation at moderate temperature;
are claimed in United States Patent 2,706,675, the cyanide-free solution is subsequently
assigned to Freeport Sulphur Company. stripped at a higher temperature at which
Rapid cooling of the reacted gases is the ammonium salt is dissociated.
necessary to minimise decomposition, and The manufacture of hydrogen cyanide
it is usual to have a waste heat boiler immedi- obviously involves great toxic and explosive
ately following the converter. There are hazards and a significant part OF the cost of
numerous variations in the methods of all modern plants results from the elaborate
recovery, but most of them comprise the safety precautions necessary to protect
two basic steps of ammonia recovery by operating personnel. Great care must also be
washing with acidified ammonia sulphate devoted to the effcctive treatment of plant
solution, followed by absorption of the effluents because of the toxicity of cyanide
hydrogen cyanide in water, sometimes under to aquatic life.
pressure, from which it is subsequently Among European chemical manufacturers
recovered by distillation and condensation. interested in this process arc Imperial
The hydrogen cyanide can be recovered Chemical Industries, Montecatini (3), Rohm
from the still overhead at a concentration of and Haas (4), Ugilot and Lonza. In the
98.5 per cent or better, and it must be con- United States similar processes have been
tinuously stabilised since hydrogen cyanide developed by B. F. Goodrich & Company,
has a pronounced tendency to polymerise Rohm and Haas (7), Freeport Sulphur Com-
and explode, particularly under alkaline pany (S), Monsanto Chemical Company, du
conditions. For this reason, it is essential in Pont, American Cyanamid Company, Carbide
all recovery processes that uncombined and Carbon Chemical Company and The
ammonia is removed from the product stream Girdler Company.

References
I L. Andrussow .. .. .. D.R.P., 549,005
Angem. C h m . , 1935,48, 593-595
2 A. Chrctien and A. Thomas . . .. Bull. Soc. Chim. France, 1948, 15, 354-357
3 U. Maffezzoni . . .. .. .. Chimica e Industria, 1952, 34, 46~-465
Chim. et Ind., I953,69, 842-847
4 C. T. Kautter and W. Lcitenberger . . Chem. Ing. Techn., 1953, 25, 697-701
5 L. Andrussow . . .. .. .. Chem. Ing. Techn., 1955, 27, 469-472
6 P. W. Sherwood .. .. .. Petroleum Processing, 1954, 9, 384-389
7 J. A. Lee .. .. .. .. Chern. Eng., 1949, 56, (Feb.), 134-136
8 N. Updegraff . . .. .. .. Petroleum Refiner, 1953, 32, (Sepr.), 196-201

Platinum Metals Rev., 1958, 2, (1) 11