KR790001480B1 - Process for preparation of carbonyl sulfide - Google Patents

Abstract

CO and S were reacted in the presence of >=1 calcium, strontium, Barium sulfides, sulfates and halides to give carbonyl sulfide which was used as pesticides, pharmaceuticals, and chemicals. Calcium, strontium, barium sulfides were prepd. by heating calcium oxide, barium oxide, strontium carbonate, calcium hydroxide in the presence of sulfur, hydrogen sulfide or carbonyl sulfide.

Description

Method of producing carbonyl sulfide

The accompanying drawings are schematic diagrams illustrating an example of an apparatus used in practicing the method of the present invention.

The present invention relates to an improved process for producing carbonyl sulfides useful as raw materials for pesticides, medicines and various chemicals.

More specifically, in the production of carbonyl sulfide by reacting carbon monoxide and sulfur, carbon monoxide and sulfur are reacted at a low temperature in the presence of a novel catalyst so that carbon disulfide is not a by-product and carbon by-products are produced. It is related with the method of suppressing and producing the target carbonyl sulfide in high purity and selectively efficiently.

Conventionally, as a method of producing carbonyl sulfide by reacting carbon monoxide and sulfur, a method of reacting carbon monoxide and sulfur at a relatively high temperature of 350 ° C to 510 ° C (German Patent No. 1222024) and the presence of aluminum silicate having a three-dimensional structure Under a method of reacting carbon monoxide and sulfur at a relatively low temperature of 500 ° F. to 90 ° F. (260 ° C. to 483 ° C.) (Specification No. 2983580) Groups V, VI, and VIII of the Periodic Table Or carbon monoxide in the presence of a metal sulfide selected from Group VIII (refer to US Pat. Nos. 3,416,893 and 95.95,102) and carbon monoxide in the presence of Group I alkali metal sulfides such as sodium or potassium. Methods for reacting with sulfur and sulfur (Specification No. 47-27632 and US Pat. No. 3,764,661) and the like are already known.

However, according to the researches of the present inventors, in the temperature range of 350 ° C.-510 ° C., the reaction rate between carbon monoxide and sulfur is very slow, and in order to obtain carbonyl sulfide with high yield in this temperature range, It was found that the reaction contact time had to be significantly lengthened.

However, by increasing the contact time, by-products of carbon sulfide and carbon dioxide cannot be avoided, and by using a higher reaction temperature in order to increase the reaction rate, the reverse reaction to the raw material system becomes large, and the carbonyl sulfide produced is reduced. In addition, the contents of carbon monoxide and sulfur in the reaction product gas are increased, and the corrosion of metals at the high temperature of carbonyl sulfide becomes strong, resulting in poor corrosion of structural materials of the reaction apparatus. Even in the method of reacting carbon monoxide with sulfur in the presence of aluminum silicate, the selectivity of aluminum silicate used as a catalyst is poor, and by-products of carbon disulfide and carbon dioxide cannot be avoided.

In addition, in the method of reacting carbon monoxide and sulfur in the presence of a metal sulfide selected from Group V, Group VI, Group VI or Group VI of the periodic table, any metal sulfide used as a catalyst has poor selectivity and carbon disulfide. And by-products of carbon dioxide cannot be avoided and catalytic activity is not sufficient.

Therefore, in order to produce carbonyl sulfide by inhibiting as much as byproducts of carbon disulfide and carbon dioxide, in spite of insufficient catalytic activity, the reaction efficiency is sacrificed again, that is, the reaction rate is lowered so that carbon monoxide and sulfur do not react. You must.

However, as the reaction rate is lowered, unreacted carbon monoxide contained in a large amount in the reaction product gas has to be separated and recovered from carbonyl sulfide, which is not a method to be satisfied industrially.

On the other hand, in the method of reacting carbon monoxide with sulfur in the presence of Group I alkali metal sulfides such as sodium or potassium, the catalytic activity of the alkali metal sulfides used is very strong and is excellent as a catalyst for promoting the reaction rate between carbon monoxide and sulfur. However, as a result, the selectivity is low and it is difficult to avoid byproducts of carbon disulfide and carbon dioxide.

또는 카르보닐기 〉C=0의 공급원으로서 유용한 원료로서, 특히 티올카르바민산 화합물 및 요소화합물의 제조원료로서 최근 주목을 받고 있으나, 이 황화카르보닐은 이황화탄소와 같은 화학반응을 나타낸다.The carbonyl sulfide targeted in the method of the present invention is a thiolcarbonyl group.

Or as a raw material useful as a source of the carbonyl group > C = 0, especially as a raw material for the preparation of thiolcarbamic acid compounds and urea compounds, this carbonyl sulfide exhibits a chemical reaction such as carbon disulfide.

For example, carbonyl sulfide reacts with a second amine in the presence of alkali hydroxides to produce thiolcarbamate. In this regard, carbon disulfide also reacts to produce thiolcarbamate. (Scheme-II)

Carbonyl sulfide also reacts with the first amine to form urea. In this regard, carbon disulfide produces the same reaction to form thiourea. (Scheme-VI)

On the other hand, carbon dioxide is not so much a problem compared to carbon disulfide. For example, carbon dioxide reacts with metal hydroxides to form carbonates, and excessive reaction conditions of high temperature and high pressure are required to form urea.

In addition, the separation of carbonyl sulfide and carbon dioxide is relatively easy as compared with the separation of carbonyl sulfide and carbon disulfide. Therefore, when carbonyl sulfide containing carbon disulfide, especially as a by-product, is produced as a raw material, a urea compound, a thiol carbamic acid compound, or the like is produced, causing a similar reaction represented by the above (I) to (IV). It has a bad effect on the purity of the product. However, as mentioned above, carbon by-products could not be selectively produced by suppressing the by-product of carbon disulfide completely by any conventional method.

The inventors of the present invention have conducted various studies on a method of suppressing by-products of carbon disulfide and producing high-purity carbonyl sulfide by reaction of carbon monoxide and sulfur, and as a result, sulfide of Group II alkaline earth metal of the periodic table. , Sulfates and halides have been found to exhibit excellent catalytic effects in the reaction for producing carbonyl sulfide from carbon monoxide and sulfur and have completed the present invention based on this knowledge.

That is, according to the method of the present invention, by reacting carbon monoxide and sulfur in the presence of at least one alkaline earth metal compound selected from sulfides, sulfates and halides of calcium, strontium or barium, and by-product carbon dioxide By-products of carbon dioxide can also be suppressed and carbonyl sulfide of high purity can be selectively produced at high yield with extremely low reaction temperature.

As sulfides, sulfates and halides of calcium, strontium or barium used in the method of the present invention, calcium sulfide, strontium sulfide, barium sulfide, calcium sulfate, strontium sulfate, barium sulfate, calcium chloride, strontium chloride, barium chloride, calcium bromide Strontium bromide, barium bromide, calcium iodide, strontium iodide, barium iodide, strontium fluoride, or barium fluoride, and as sulfides of calcium, strontium or barium, calcium oxide, strontium oxide, barium oxide, calcium carbonate, strontium carbonate , Barium carbonate, calcium hydroxide, strontium hydroxide or barium hydroxide in sulfur, hydrogen sulfide, carbon disulfide or carbonyl sulfide at 100 ° C to 1500 ° C for 30 minutes to 10 hours, preferably at 200 ° C to 700 ° C for 3 to 5 hours The sulfides converted from each other are also used. However, among the above, bromide and iodide are not easy to decompose.

The method of the present invention can be carried out by bringing a mixed gas of carbon monoxide and sulfur into contact with a surface of a catalyst of a predetermined alkaline earth metal compound heated at 250 to 450 ° C., preferably at 300 to 400 ° C., to cause a reaction. have.

The molar ratio of carbon monoxide and sulfur in the method of the present invention is preferably 1: 1, but may be used in an amount of 3 to 5 times molar excess of sulfur. The amount of the catalyst used is 0.2 to 50 (g hr / CO.Nl), preferably 1 to 20 (g.hr/CO.Nl), in W / F depending on the carbon monoxide to be introduced.

In the method of the present invention, a relatively low reaction temperature of 250 to 450 ° C. is used, and the reaction pressure is not limited to a pressure in which sulfur supplied as a raw material maintains a gaseous state. There is a number. Moreover, the reaction time in this invention is 0.5 second-1 minute, and usually 1 to 30 second is enough.

As a means for contacting a mixed gas of carbon monoxide and sulfur with a catalyst of a predetermined alkali earth metal, a method of allowing a reactant mixed gas to pass through a reaction tube in which a predetermined alkaline earth metal compound is formed on an inner wall, or a predetermined alkaline earth metal A method of introducing a reactant mixed gas into a reaction column filled with a compound is advantageous. The carbonyl sulfide thus obtained has an extremely high purity of about 96 mol% or more, carbon disulfide is not by-product, and carbon dioxide by-product is also very small.

Next, the advantages and features of the present invention will be described. First of all, it is possible to efficiently and efficiently produce high-purity carbonyl sulfide by suppressing the by-product of carbon dioxide without producing byproducts of carbon disulfide.

Secondly, since the reaction time between carbon monoxide and sulfur can be significantly shortened, the reaction apparatus can be miniaturized.

Thirdly, the reaction temperature can be lowered, the reaction is carried out under quiet conditions, and the catalyst used in the method of the present invention completely suppresses side reactions without promoting decomposition reaction of the produced carbonyl sulfide, and high purity carbon sulfide You can get the carbonyl.

Fourth, since carbonyl sulfide can be handled at a low temperature, corrosion of the reaction structural material due to carbonyl sulfide can be prevented, and the life of the reaction apparatus can be significantly extended.

Fifth, since carbon disulfide is not by-produced and carbon monoxide remaining as an unreacted substance is very small, no separation and purification process is required, and the manufacturing process is simplified and manufacturing management is easy.

Next, an example of embodiment of this invention is demonstrated according to attached drawing.

A predetermined alkaline earth metal compound is filled into the quartz glass reaction tube 1, the inert gas such as nitrogen gas is allowed to pass through, and the air in the reaction tube 1 is sufficiently substituted. Heated to ° C. Next, carbon monoxide is fed into the raw material mixer 3 from the supply port 2 in the range of 0.1 Nl / min to 15 ml / min, and at the same time, the metering pump 4 is operated to supply liquid sulfur to the carbon monoxide. The molar ratio between and is guided to the sulfur boiler 7 through the heating tube 6 in the range of 0.1 to 25 gr / min, and heated to vaporize sulfur. The sulfur in the gaseous state is led to the raw material mixer 3 through the heating tube 8 to form a mixed gas of carbon monoxide and sulfur.

This mixed gas is then guided into the reaction tube 1 heated via the heating tube 9 to react to produce carbonyl sulfide. The produced carbonyl sulfide is taken out from the outlet 10 at the top of the reaction tube. Next, an Example and a comparative example demonstrate this invention further in detail.

Example 1

Using the apparatus shown in the figure, a predetermined alkaline earth metal compound is filled into a quartz glass reaction tube, air is replaced with an inert gas such as nitrogen gas, and the alkaline earth metal compound packed layer is heated to adjust the temperature. And set the flow rate of carbon monoxide and at the same time operate the sulfur metering pump to supply sulfur to the sulfur boiler, heat the sulfur boiler to adjust the molar ratio of carbon monoxide and sulfur, and The reaction was carried out by contacting the earth metal compound. After cooling the generated gas, a predetermined amount was collected in a gas sampler, and gas adjustment was analyzed by gas chromatography.

In this manner, the results of the tests on the various metal compounds are shown in Table-1.

Table-1

T in Table-1 represents the temperature of the metal compound packed layer, and S / CO represents the molar ratio of carbon monoxide and sulfur. (The same also applies to Table-2 below)

Example 2

A small amount of water is added to 30 g of calcium hydroxide, strontium hydroxide or barium hydroxide, kneaded well, molded and dried into a columnar shape having a diameter of 4 mm and a height of 5 mm, and then filled into a quartz glass tube having a diameter of 4 mm and sulfur at the bottom of the glass tube. Nitrogen gas was induced like nitrogen gas, and the yellowish white columnar casted by heating and heating the glass tube at 400 ° C. to 500 ° C. for 3 hours was used as a metal compound filler, and carbon monoxide and sulfur were reacted as in Example 1 The composition was analyzed. The results are shown in Table-2.

Example 3

30 g of calcium carbonate, strontium carbonate or barium carbonate is used, and a metal compound adjusted by heating and calcining in sulfur vapor as in Example 2 is used as a filler, and carbon monoxide and sulfur are reacted as in Example 1. The gas composition was analyzed. The results are shown in Table-2.

TABLE 2

Claims (1)

Calcium sulfide, strontium sulfide, barium sulfide, calcium sulfate, strontium sulfate, barium sulfate, calcium chloride, strontium chloride, barium chloride, calcium bromide, at least one alkaline earth metal compound selected from sulfides, sulfates and halides of calcium, strontium or barium In the presence of strontium bromide, barium bromide, calcium iodide, strontium iodide, barium iodide, calcium fluoride, strontium fluoride or barium fluoride, carbon monoxide and sulfur are reacted, and sulfides of calcium, strontium or barium, calcium oxide, A process for producing carbonyl sulfide, characterized in that strontium, barium oxide, calcium carbonate, strontium carbonate, barium carbonate, calcium hydroxide, strontium hydroxide or barium hydroxide is heated in sulfur, hydrogen sulfide, carbon disulfide, or carbonyl sulfide.

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