Hydrogen cyanide synthesis process

Details Hydrogen cyanide synthesis process Hydrogen cyanide synthesis process

2001-07-13

2004-06-01

Silverman, Stanley S. (Department: 1754)

Chemistry of inorganic compounds

Nitrogen or compound thereof

Carbon containing

Reexamination Certificate

active

06743407

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a process for the synthesis of hydrogen cyanide using a starting-gas stream containing methane or a methane-containing natural-gas stream, ammonia and oxygen.
2. Discussion of the Background
The synthesis of hydrogen cyanide (prussic acid; hydrocyanic acid) by the Andrussow method is described in Ullmann's Encyclopedia of Industrial Chemistry, Volume 8, VCH Verlagsgesellschaft, Weinheim, 1987, pp. 161-162. The starting-gas mixture, which comprises methane or a methane-containing natural-gas stream, ammonia and oxygen is passed into a reactor over catalyst gauze and reacted at temperatures of about 1000° C. The necessary oxygen is usually introduced in the form of air. The catalyst gauzes comprise platinum or platinum alloys. The composition of the starting-gas mixture corresponds approximately to the stoichiometry of the overall equation of the exothermic reaction
CH
4
+NH
3
+3/2 O
2
→HCN+3 H
2
O dHr=−473.9 kJ.
The discharged reaction gas contains the product HCN, unreacted NH
3
and CH
4
, the main by-products CO, H
2
, H
2
O and CO
2
, and a large proportion of N
2
.
The reaction gas is cooled rapidly to about 150 to 200° C. in a waste-heat boiler and then passed through a scrubbing column, in which the unreacted NH
3
is removed with dilute sulfuric acid and some of the water vapor is condensed. Also known is the absorption of NH
3
with sodium hydrogen phosphate solution followed by recycling of the ammonia. HCN is absorbed in cold water in a subsequent absorption column and then purified to better than 99.5 wt % in a downstream rectification unit. The HCN-containing water present in the column bottoms is cooled and recycled to the HCN absorption column.
A broad spectrum of possible embodiments of the Andrussow method is described in German Patent 549055. In one example, a catalyst comprising a plurality of fine-mesh gauzes of Pt with 10% rhodium disposed in series is used at temperatures of about 980 to 1050° C. The HCN yield is 66.1 % relative to the feed NH
3
.
A method for maximizing the HCN yield by optimal adjustment of the air
atural gas and air/ammonia ratios is described in U.S. Pat. No. 4,128,622.
In addition to the standard operating procedure with air as the oxygen supply, the use of oxygen-enriched air is described in various documents such as: German Patent 1283209, which corresponds to Netherlands Patent 6604519, Belgian Patent 679440 and U.S. Pat. No. 3,379,500; German Examined Application 1288575, which corresponds to Netherlands Patent 6604697 and Belgian Patent 679529; International Patent WO 97/09273; and U.S. Pat. No. 5,882,618. Table 1 lists some patents with the operating conditions cited therein.
TABLE 1
List of various patent claims regarding oxygen enrichment
German Patent
German
1283209, 1968,
Examined
Società Edison
Application
Netherlands
1288575, 1968,
Patent 6604519,
Società
Belgian Patent
Edison
International
679440
Netherlands
Patent WO
U.S. Pat. No.
Patent 6604697,
97/09273, 1997,
U.S. Pat. No.
3379500
Belgian Patent
ICI
5882618, 1999,
corresponds to
(italics)
679529
special reactor
Air Liquide
Starting-gas
—
200 to 400° C.
200 to 400° C.
preheating
300 to 380° C.
further
Gauze
1100 to 1200° C.
1100 to 1200° C.
temperature data
1100 ± 50° C.
temperature
for individual
starting-gas
streams
(O
2
+ N
2
)/CH
4
6.5 to 1.55
6.0 to 1.6
Ratios reported
molar ration
4.55 to 2.80
4.5 to 2.6
as relative to the
(O
2
+ N
2
)/NH
3
6.8 to 2.0
6.0 to 2.0
mode of
4.8 to 3.65
4.5 to 3.0
operation with
CH
4
/NH
3
1.4 to 1.05
1.3 to 1.0
1.0 to 1.5
air
1.3 to 1.1
1.25 to 1.05
O
2
/(O
2
+ N
2
)
0.245 to 0.4
0.245 to 0.35
0.3 to 1.0
0.27 to 0.317
0.25 to 0.30
U.S. Pat. No. 5,882,618 describes the synthesis of hydrocyanic acid by the Andrussow method using oxygen-enriched air. To circumvent the problems that occur under these conditions, such as proximity to the explosion limits of the mixture of NH
3
, CH
4
and oxygen-enriched air, as well as the elevated temperature of the catalyst gauze, which can lead to yield losses and shortened catalyst life, the following measures are proposed:
In a first process step, the system is started up with air as the oxygen source. During this first process step, the catalyst mesh reaches a well-defined temperature.
In a second process step, oxygen is then added and at the same time the contents of ammonia and methane are adjusted such that the mixture is situated above the upper explosion limit and the catalyst temperature corresponds to within 50 K of the reference temperature determined in step 1. The temperature of the catalyst gauze is about 1100° C. to 1200° C. By means of this procedure, safe use of the system is achieved during operation with oxygen-enriched air.
International Patent WO 97/09273 overcomes the disadvantages of high N
2
dilution of the reaction gases by the use of preheated, mixtures of methane, ammonia and oxygen-enriched air or pure oxygen capable of detonation.
The enrichment with oxygen of the starting gas for HCN synthesis according to Andrussow, described heretofore, has the following disadvantages:
proximity to the upper explosion limit of the starting gas mixture (danger of explosions, deflagrations and local temperature spikes, resulting in damage to the catalyst gauze);
low yield relative to NH
3
;
higher catalyst temperature and faster deactivation;
maximum O
2
enrichment in the standard Andrussow reaction is up to 40% O
2
in air;
high investment and maintenance costs for the use of special reactors (International Patent WO 97/09273).
The advantages of enriching the starting-gas stream with oxygen are essentially the following:
increased productivity (kg HCN per hour) in existing plants through reduction of the inert gas concentration; and
lower energy consumption for HCN absorption and rectification.
By adjusting conditions and concentration ratios in the starting gas to correspond to the solution described in the claims, the advantages of enrichment with oxygen can be achieved without having to tolerate the described disadvantages.
SUMMARY OF THE INVENTION
Thus, it is an object of the present invention to provide a process for synthesis of hydrogen cyanide wherein the starting gas is enriched with oxygen up to a degree of enrichment of O
2
/(O
2
+N
2
)=1.0 whereby the inert-gas stream is decreased and the HCN concentration in the reaction gas is increased, and so the productivity of existing plants is increased while at the same time the energy consumed per metric ton of produced HCN is reduced.
It is another object of the present invention to provide a process for synthesis of hydrogen cyanide wherein the HCN yields relative to the feed NH
3
are improved.
It is another object of the present invention to provide a process for synthesis of hydrogen cyanide wherein a high catalyst efficiency is achieved. The high catalyst activity refers to HCN production amount per kg of catalyst gauze.
It is yet another object of the present invention to provide a process for synthesis of hydrogen cyanide wherein the reactor is safely operated with a non-ignitable starling-gas mixture.
It is an additional object of the present invention to provide a process for synthesis of hydrogen cyanide which can be performed in existing reactors for the manufacture of hydrocyanic acid. The process can be performed in existing systems for hydrocyanic acid synthesis. Costly modifications are not necessary (Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A8, pp. 159 ff. (1987)). Since the reaction takes place outside the detonation limits of the mixture of ammonia, methane and oxygen or air, complex reactors such as described in International Patent WO 97/09273,
FIG. 1
, are not necessary. The need to maintain a wide margin of safety for the spontaneous ignition temperature of the mixture (minimum 50° C.), as described in WO 97/09273 (p. 1, line 35 to p. 2, line 2), is also obviated. Thus an improved space-time yield is also achieved in existin

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