CN1184139C

CN1184139C - Method for preparing sulfur dichloride

Info

Publication number: CN1184139C
Application number: CNB031387276A
Authority: CN
Inventors: 朱永国; 王文举; 黄东华
Original assignee: NEW MATERIALS INST ZIBO CITY
Current assignee: NEW MATERIALS INST ZIBO CITY
Priority date: 2003-06-26
Filing date: 2003-06-26
Publication date: 2005-01-12
Anticipated expiration: 2023-06-26
Also published as: CN1473758A

Abstract

The present invention relates to a new method for preparing sulfur dichloride, which belongs to the technical field of chemosynthesis. The sulfur dichloride is prepared by means that gas-solid reaction is implemented between chlorine and sulfur, and then, the mixture is cooled. After firstly produced by the gas-solid reaction between the chlorine and the sulfur, disulfur dichloride is cooled, and the chlorine is continuously led in to react with the disulfur dichloride to prepare the sulfur dichloride. After the reaction ends, a stabilizing agent is added to obtain a finished product. The method for preparing sulfur dichloride of the present invention has the advantages of high product yield, high stability, high purity, low cost, easy operation, easy operation, industrialization implementation and no environmental pollution. The purity can achieve more than 98 %. The method is beneficial to popularization and application.

Description

Preparation method of sulfur dichloride

Technical Field

The invention relates to a novel method for preparing sulfur dichloride, belonging to the technical field of chemical synthesis.

Background

The existing sulfur dichloride preparation is carried out by taking chlorine and sulfur as raw materials, and the preparation process adopts a distillation method, namely, the sulfur and chlorine react under the action of a catalyst, then the reaction liquid is distilled to obtain the fraction of sulfur dichloride, and in order to enhance the stability of the product and prevent unstable sulfur dichloride from being decomposed into disulfide dichloride, a phosphorus trichloride stabilizer is added. The preparation method has high raw material consumption, high distillation process cost and low product yield, only 70 percent of the distillation residue liquid can not be utilized, and the stability of the product is poor, so that the content of the disulfide dichloride impurity is high, the purity of the product is low, more seriously, the product decomposition in the distillation process can generate harmful gas, the body health of an operator is harmed, the implementation is inconvenient, and the surrounding environment is also seriously polluted.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the novel method for preparing the sulfur dichloride has the advantages of low cost, high product yield, good stability, high purity, simple and convenient operation, easy implementation and no environmental pollution.

The preparation methodof the sulfur dichloride is prepared by reacting chlorine and sulfur, and has the technical key point that the sulfur dichloride is prepared by carrying out gas-solid reaction on the chlorine and the sulfur and then cooling.

The preparation method of the invention changes the prior method of heating and distilling the product after reaction into cooling treatment, thereby obtaining remarkable harvest. The method has the advantages of reducing the production cost, stabilizing the product performance, improving the product yield and purity, along with simple and convenient operation, easy implementation, environmental pollution avoidance and good economic and social benefits.

The preparation method comprises the following steps:

the chlorine and sulfur are first gas-solid reacted to produce dichlorinated disulfide, and then cooled and reacted with chlorine to produce dichlorinated sulfur. Wherein the reaction temperature of the chlorine and the sulfur for gas-solid reaction to generate the disulfide dichloride is 80-120 ℃.

The reactant ingredients in the reaction process are carried out according to a reaction formula, and generally, the ingredient molar ratio of chlorine to sulfur is 2.00-2.06: 1.

The reaction formula of the preparation method is as follows:

and after the reaction is finished, adding a stabilizer to ensure the stability of the product. The stabilizer is one or a combination of phosphite ester and hydrogen phosphite diester in any proportion. The phosphite ester comprises ethyl phosphite, butyl phosphite, triethyl phosphite, trimethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite and the like, the hydrogen phosphite diester comprises dimethyl hydrogen phosphite, diethyl hydrogen phosphite, dipropyl hydrogen phosphite, diisopropyl hydrogen phosphite, dibutyl hydrogen phosphite and the like, the addition amount of the stabilizer is 0.1-0.8% of the weight of sulfur dichloride, and the amount of the sulfur dichloride is calculated by the amount of sulfur in the ingredients according to a reaction equation.

The temperature control range of the temperature reduction treatment in the reaction is preferably-10 to 10 ℃.

A certain pressure is preferably applied in the reaction process, the reaction pressure is controlled to be within 0-0.2 Mpa of gauge pressure, and the gauge pressure is one atmosphere when the gauge pressure is zero.

The reaction process of the preparation method still needs to add the catalyst according to the conventional mode, and the Lewis acid catalyst is used, such as ferric trichloride, zinc chloride, copper chloride, aluminum chloride and the like, and the adding amount of the catalyst is 0.1-0.2% of the weight of sulfur dichloride.

The preparation method can refer to and refer to the aspects of the conventional preparation process, and can be carried out by referring to the common knowledge condition without being described repeatedly.

The preparation method of the sulfur dichloride has the advantages of high product yield, almost 100 percent conversion, good stability, high purity which can reach more than 98 percent, no less than 95 percent after being stored for three months, no raw material waste, no too much process consumption, low cost, simple and convenient operation, easy implementation, especially industrial implementation, no environmental pollution and contribution to popularization and application.

Detailed Description

The present invention will be further described with reference to the following examples.

Example 1

According to the preparation method of sulfur dichloride, the molar ratio of the chlorine to the sulfur is 2.05: 1. Adding sulfur and a ferric chloride catalyst which is equivalent to the sulfur dichloride and has the weight of 0.15 percent of the sulfur dichloride into a reaction kettle, and then introducing chlorine, wherein the reaction temperature is controlled to be 90-100 ℃, and the reaction pressure is controlled to be 0.1-0.15 Mpa of gauge pressure, so as to prepare disulfide dichloride;

cooling the disulfide dichloride to 2-8 ℃, and introducing chlorine gas into the disulfide dichloride to a set ventilation amount to obtain a sulfur dichloride product;

after standing, the ethyl phosphite stabilizer accounting for 0.2 percent of the weight of the sulfur dichloride is added to obtain a sulfur dichloride finished product with good stability, the purity of the sulfur dichloride finished product reaches more than 98 percent, the storage period can reach 3 months, the purity of the sulfur dichloride finished product is not lower than 95 percent, and the sulfur dichloride finished product is convenient to store and use.

Under the condition of identical other conditions, the results of different stabilizers used only for the product are shown in the table 1 compared with the use condition of the existing phosphorus trichloride stabilizer, and the stability of the product is obviously different.

Conditions are as follows: storing at normal temperature and normal pressure, and measuring the content of impurities (namely the decomposed disulfide dichloride) in the product in different time.

Example 2

According to the preparation method of sulfur dichloride, the molar ratio of the chlorine to the sulfur is 2.06: 1. Adding sulfur and a ferric trichloride catalyst which is 0.12 percent of the weight of sulfur dichloride equivalent to the sulfur dichloride into a reaction kettle, and then introducing chlorine, wherein the reaction temperature is controlled to be 80-90 ℃, and the reaction pressure is controlled to be 0.15-0.18 Mpa of gauge pressure, so as to prepare disulfide dichloride;

cooling the disulfide dichloride to-6 to-1 ℃, and introducing chlorine gas into the disulfide dichloride to obtain a sulfur dichloride product;

after standing, adding a phosphite ester stabilizer accounting for 0.4 percent of the weight of the sulfur dichloride to obtain a sulfur dichloride finished product.

Example 3

According to the preparation method of sulfur dichloride, the molar ratio of the chlorine to the sulfur is 2.03: 1. Adding sulfur and a zinc chloride catalyst which is 0.16 percent of the weight of sulfur dichloride and is equivalent to the sulfur dichloride into a reaction kettle, and then introducing chlorine, controlling the reaction temperature to be 110-120 ℃, and controlling the reaction pressure to be 0.1-0.12 Mpa of gauge pressure to prepare disulfide dichloride;

cooling the disulfide dichloride to-8 to-4 ℃, and introducing chlorine gas into the disulfide dichloride to obtain a sulfur dichloride product;

after standing, adding a dimethyl hydrogen phosphite stabilizer accounting for 0.5 percent of the weight of the sulfur dichloride to obtain a sulfur dichloride finished product.

Example 4

According to the preparation method of sulfur dichloride, the molar ratio of the chlorine to the sulfur is 2.05: 1. Adding sulfur and an aluminum chloride catalyst which is 0.18 percent of the weight of sulfur dichloride and is equivalent to the sulfur dichloride into a reaction kettle, and then introducing chlorine, wherein the reaction temperature is controlled to be 100-110 ℃, and the reaction pressure is controlled to be 0.05-0.08 MPa gauge pressure, so as to prepare disulfide dichloride;

cooling the disulfide dichloride to-2-3 ℃, and introducing chlorine gas into the disulfide dichloride to obtain a sulfur dichloride product;

after standing, adding a triethyl phosphite stabilizer accounting for 0.6 percent of the weight of the sulfur dichloride to obtain a sulfur dichloride finished product with good stability.

Example 5

According to the preparation method of sulfur dichloride, the molar ratio of the chlorine to the sulfur is 2.02: 1. Adding sulfur and a ferric chloride catalyst which is 0.13 percent of the weight of sulfur dichloride and is equivalent to the sulfur dichloride into a reaction kettle, and then introducing chlorine, wherein the reaction temperature is controlled to be 90-96 ℃, and the reaction pressure is controlled to be 0.11-0.13 Mpa of gauge pressure, so as to prepare disulfide dichloride;

cooling the disulfide dichloride to 2-6 ℃, and introducing chlorine gas into the disulfide dichloride to obtain a sulfur dichloride product;

after standing, adding triethyl phosphite accounting for 0.2 percent of the weight of the sulfur dichloride and trimethyl phosphite stabilizer accounting for 0.2 percent of the weight of the sulfur dichloride to obtain a sulfur dichloride finished product with good stability.

Example 6

According to the preparation method of sulfur dichloride, the molar ratio of the chlorine to the sulfur is 2.04: 1. Adding sulfur and a copper chloride catalyst which is equivalent to the sulfur dichloride and accounts for 0.11 percent of the weight of the sulfur dichloride into a reaction kettle, and then introducing chlorine, wherein the reaction temperature is controlled to be 85-95 ℃, and the reaction pressure is controlled to be 0.09-0.11 Mpa of gauge pressure, so as to prepare disulfide dichloride;

cooling the disulfide dichloride to-5-1 ℃, and introducing chlorine gas into the disulfide dichloride to obtain a sulfur dichloride product;

after standing, trimethyl phosphite accounting for 0.15 percent of the weight of the sulfur dichloride and dibutyl hydrogen phosphite stabilizer accounting for 0.35 percent of the weight of the sulfur dichloride are added to obtain a sulfur dichloride finished product with good stability.

Example 7

Stabilizers A stabilizer consisting of 0.2% tripropylene phosphite and 0.4% tributyl phosphite was used, otherwise the same as in example 5.

Example 8

The stabilizer used was 0.5% tripropylphosphite, otherwise the same as in example 2.

Example 9

The stabilizer used was 0.3% diethyl hydrogen phosphite, 0.2% diisopropyl hydrogen phosphite and 0.1% tripropyl hydrogen phosphite, the other examples being identical to example 3.

Example 10

The stabilizer used was a stabilizer composed of 0.2% triisopropyl phosphite and 0.3% dimethyl hydrogen phosphite, and the procedure was otherwise the same as in example 5.

Example 11

The stabilizer used was 0.4% trimethyl phosphite, otherwise the same as in example 6.

Example 12

The stabilizer used was 0.6% diethyl hydrogenphosphite, otherwise the same as in example 3.

Claims

1. A preparation method of sulfur dichloride is characterized in that under the conditions that the reaction temperature of chlorine and sulfur is 80-120 ℃ and the gauge pressure is 0-0.2 Mpa, one of ferric trichloride, zinc chloride, copper chloride and aluminum chloride is added as a catalyst, the amount of the catalyst accounts for 0.1-0.2% of the weight of the sulfur dichloride, after gas-solid reaction is carried out to generate disulfide dichloride, the temperature is reduced to-10 ℃, and the chlorine is continuously introduced for reaction to prepare the sulfur dichloride.

2. A process for preparing sulfur dichloride as claimed in claim 1, wherein a stabilizer is added after the reaction is completed to obtain a finished product.

3. The method for preparing sulfur dichloride according to claim 2, wherein the stabilizer is one or a combination of two of phosphite ester and hydrogen phosphite ester in any ratio.

4. The method for producing sulfur dichloride according to claim 3, wherein the amount of the stabilizer added is 0.1 to 0.8% by weight of the sulfur dichloride.