阅读说明：本技术 一种氯乙烯合成用催化剂及其制备方法和应用 (Catalyst for vinyl chloride synthesis and preparation method and application thereof ) 是由 不公告发明人 于 2019-10-23 设计创作，主要内容包括：本发明属于氯乙烯合成用催化剂技术领域,尤其涉及一种氯乙烯合成用催化剂及其制备方法和应用。本发明提供的氯乙烯合成用催化剂的制备方法,包括以下步骤：将活性炭置于含氮化合物水溶液中,进行第一浸泡,将所得固体物料进行第一干燥,得到第一产物；将所述第一产物置于铜氯化物溶液中进行第二浸泡,将所得固体物料进行第二干燥,得到氯乙烯合成用催化剂。实施例的结果表明,本发明的氯乙烯合成用催化剂用于乙炔与氯化氢合成氯乙烯,现有汞催化剂HgCl<Sub>2</Sub>-活性炭催化剂的转化率比本发明的无汞催化剂的转化率低3个百分比；本发明的无汞催化剂具有转化率高、选择性好、使用寿命长的优点,使用寿命可达10000h。(The invention belongs to the technical field of catalysts for synthesizing vinyl chloride, and particularly relates to a catalyst for synthesizing vinyl chloride and a preparation method and application thereof. The preparation method of the catalyst for vinyl chloride synthesis provided by the invention comprises the following steps: placing the activated carbon in a nitrogen-containing compound aqueous solution, carrying out first soaking, and carrying out first drying on the obtained solid material to obtain a first product; and placing the first product in a copper chloride solution for secondary soaking, and performing secondary drying on the obtained solid material to obtain the catalyst for synthesizing the chloroethylene. The results of the examples show that the catalyst for vinyl chloride synthesis of the present invention is used for vinyl chloride synthesis from acetylene and hydrogen chloride, and the existing mercury catalyst HgCl 2 -livingThe conversion rate of the carbon catalyst is lower than that of the mercury-free catalyst by 3 percent; the mercury-free catalyst has the advantages of high conversion rate, good selectivity and long service life, and the service life can reach 10000 h.)

1. A method for preparing a catalyst for vinyl chloride synthesis is characterized by comprising the following steps:

placing the activated carbon in a nitrogen-containing compound aqueous solution, carrying out first soaking, and carrying out first drying on the obtained solid material to obtain a first product;

and placing the first product in a copper chloride solution for secondary soaking, and performing secondary drying on the obtained solid material to obtain the catalyst for synthesizing the chloroethylene.

2. The preparation method according to claim 1, wherein the activated carbon has a porosity of 45 to 85%; the diameter is 2.0-4.0 mm; the mechanical strength is 93-98%.

3. The method according to claim 1, wherein the nitrogen-containing compound in the aqueous solution of a nitrogen-containing compound is ethylenediamine, EDTA, melamine or ammonium chloride.

4. The production method according to claim 1 or 3, wherein the mass concentration of the aqueous solution of the nitrogen-containing compound is 5 to 30%.

5. The preparation method according to claim 1, wherein the temperature of the first soaking is 35-80 ℃, and the time of the first soaking is 0.5-8 h;

the temperature of the first drying is 60-145 ℃, and the time of the first drying is 6-24 hours.

6. The preparation method according to claim 1, wherein the copper chloride in the copper chloride solution is copper chloride or cuprous chloride, the copper chloride solution is a copper chloride acid solution or a copper chloride aqueous solution, the acid used in the copper chloride acid solution is hydrochloric acid, phosphoric acid or sulfuric acid, and the mass concentration of the copper chloride solution is 3.39-25%.

7. The production method according to claim 1 or 6, wherein the volume of the copper chloride solution is 0.2 to 2 times the volume of the activated carbon.

8. The preparation method according to claim 1, wherein the temperature of the second soaking is 35-80 ℃, and the time of the second soaking is 6-300 min; the temperature of the second drying is 60-200 ℃, and the time of the second drying is 6-24 hours.

9. The catalyst for vinyl chloride synthesis prepared by the preparation method according to any one of claims 1 to 8, wherein the nitrogen content of the catalyst for vinyl chloride synthesis is 0.5 to 6%; the copper content is 1-10%; the water content is less than or equal to 3 percent; the particle size is phi (2.0-4.0) mm multiplied by the length (3-6) mm; the mechanical strength is more than or equal to 95 percent; bulk density <700 g/L.

10. Use of the catalyst for vinyl chloride synthesis prepared by the preparation method according to any one of claims 1 to 8 or the catalyst for vinyl chloride synthesis according to claim 9 in the synthesis of vinyl chloride from acetylene and hydrogen chloride.

Technical Field

The invention relates to the technical field of catalysts for synthesizing vinyl chloride, in particular to a catalyst for synthesizing vinyl chloride and a preparation method and application thereof.

Background

The chloroethylene-based resin (including homopolymerization, copolymerization and grafting resin) has excellent performance and low price, and is widely applied to important fields of industry, agriculture, building materials and the like. With the development of socio-economy, the use of vinyl chloride-based resins is expanding and the demand is increasing. In 1930, after polyvinyl chloride was industrialized, acetylene was produced for a long time by using calcium carbide, and the acetylene and hydrogen chloride were in HgCl₂-ActivityVinyl chloride is produced under the action of the carbon catalyst, and then the vinyl chloride is polymerized to obtain the polyvinyl chloride. Wherein, HgCl₂The activated carbon catalyst has high catalytic activity, good selectivity to vinyl chloride, relatively abundant mercury resources and low price, so the HgCl₂Activated carbon catalyst has been used for a long time as the only catalyst for the hydrochlorination of acetylene to vinyl chloride.

However, HgCl₂The activated carbon catalyst is HgCl with the content of mercuric chloride of 4-12%₂Activated carbon, which contains elemental mercury that is a serious environmental pollution. Therefore, for healthy and stable development of the method for preparing polyvinyl chloride by using the calcium carbide acetylene, research and development of mercury-free and non-precious metal catalysts with high conversion rate and long service life are of great importance.

Disclosure of Invention

The invention aims to provide a catalyst for synthesizing vinyl chloride, a preparation method and application thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of a catalyst for vinyl chloride synthesis, which comprises the following steps:

placing the activated carbon in a nitrogen-containing compound aqueous solution, carrying out first soaking, and carrying out first drying on the obtained solid material to obtain a first product;

and placing the first product in a copper chloride solution for secondary soaking, and performing secondary drying on the obtained solid material to obtain the catalyst for synthesizing the chloroethylene.

Preferably, the porosity of the activated carbon is 45-85%; the diameter is 2.0-4.0 mm; the mechanical strength is 93-98%.

Preferably, the nitrogen-containing compound in the nitrogen-containing compound aqueous solution is ethylenediamine, EDTA, melamine or ammonium chloride.

Preferably, the mass concentration of the nitrogen-containing compound aqueous solution is 5-30%.

Preferably, the first soaking temperature is 35-80 ℃, and the first soaking time is 0.5-8 hours;

the temperature of the first drying is 60-145 ℃, and the time of the first drying is 6-24 hours.

Preferably, the copper chloride in the copper chloride solution is cupric chloride or cuprous chloride, the copper chloride solution is a copper chloride acid solution or a copper chloride aqueous solution, the acid used in the copper chloride acid solution is hydrochloric acid, phosphoric acid or sulfuric acid, and the mass concentration of the copper chloride solution is 3.39-25%.

Preferably, the volume of the copper chloride solution is 0.2-2 times of the volume of the activated carbon.

Preferably, the second soaking temperature is 35-80 ℃, and the second soaking time is 6-300 min; the temperature of the second drying is 60-200 ℃, and the time of the second drying is 6-24 hours.

The invention provides the catalyst for synthesizing the chloroethylene, which is prepared by the preparation method in the technical scheme, wherein the nitrogen content of the catalyst for synthesizing the chloroethylene is 0.5-6%; the copper content is 1-10%; the water content is less than or equal to 3 percent; the particle size is phi (2.0-4.0) mm multiplied by the length (3-6) mm; the mechanical strength is more than or equal to 95 percent; bulk density <700 g/L.

The invention provides the catalyst for synthesizing vinyl chloride prepared by the preparation method in the technical scheme or the application of the catalyst for synthesizing vinyl chloride in synthesizing vinyl chloride by acetylene and hydrogen chloride in the technical scheme.

The invention provides a preparation method of a catalyst for vinyl chloride synthesis, which comprises the following steps: placing the activated carbon in a nitrogen-containing compound aqueous solution, carrying out first soaking, and carrying out first drying on the obtained solid material to obtain a first product; and placing the first product in a copper salt solution for secondary soaking, and performing secondary drying on the obtained solid material to obtain the catalyst for synthesizing vinyl chloride.

The method comprises the steps of loading a nitrogen-containing compound on activated carbon to obtain an activated carbon carrier with ammonia nitrogen, and loading copper chloride on the activated carbon carrier with ammonia nitrogen to promote the ammonia nitrogen to be firm and stable on the activated carbon carrier so as to play a role in protecting volatilization; and the catalytic activity of the catalyst can be enhanced because the copper chloride has conversion activity.

The invention provides a catalyst for synthesizing chloroethylene, wherein the nitrogen content of the catalyst for synthesizing chloroethylene is 0.5-6%; the copper content is 1-10%; the water content is less than or equal to 3 percent; the particle size is phi (2.0-4.0) mm multiplied by the length (3-6) mm; the mechanical strength is more than or equal to 95 percent; bulk density <700 g/L. The copper chloride and the nitrogen-containing compound are loaded on the activated carbon of the catalyst for synthesizing the chloroethylene, wherein the ammonia nitrogen contained in the catalyst plays a main role, and the copper plays a composite role, so that the catalytic activity of the catalyst for synthesizing the chloroethylene can be enhanced.

The invention provides application of the catalyst for synthesizing vinyl chloride in synthesizing vinyl chloride from acetylene and hydrogen chloride. The results of examples in which the catalyst for vinyl chloride synthesis of the present invention was used for vinyl chloride synthesis from acetylene and hydrogen chloride showed that the existing mercury catalyst HgCl₂The conversion of the activated carbon catalyst is lower by 3 percent than the conversion of the mercury-free catalyst of the invention; the mercury-free catalyst has the advantages of high conversion rate, good selectivity and long service life, and the existing mercury catalyst HgCl₂The service time of the activated carbon catalyst is 6000-8000 h, and the service time of the catalyst for synthesizing the chloroethylene can reach 10000 h.

Detailed Description

The invention provides a preparation method of a catalyst for vinyl chloride synthesis, which comprises the following steps:

placing the activated carbon in a nitrogen-containing compound aqueous solution, carrying out first soaking, and carrying out first drying on the obtained solid material to obtain a first product;

and placing the first product in a copper chloride solution for secondary soaking, and performing secondary drying on the obtained solid material to obtain the catalyst for synthesizing the chloroethylene.

In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.

The method comprises the steps of placing the activated carbon in a nitrogen-containing compound aqueous solution, carrying out first soaking, and carrying out first drying on the obtained solid material to obtain a first product. In the invention, the porosity of the activated carbon is preferably 45-85%, and more preferably 50-65%; the diameter is preferably 2.0-4.0 mm; the mechanical strength is preferably 93-98%, and more preferably 95-98%; the parameters of the activated carbon are preferably determined by the carbon tetrachloride method.

In the present invention, before the activated carbon is placed in the aqueous solution of the nitrogen-containing compound, the activated carbon is preferably subjected to acid washing and drying. The pickling process of the present invention is not particularly limited, and a process known to those skilled in the art may be used. The invention removes the dust of the active carbon and trace mineral substances in the pore volume by acid washing. In the present invention, the drying is preferably performed under the condition that the moisture content of the activated carbon is preferably less than 0.3%. The invention enhances the adsorption effect of the activated carbon by drying, so that the activated carbon has large adsorption force and short adsorption time.

In the present invention, the nitrogen-containing compound in the aqueous solution of a nitrogen-containing compound is preferably ethylenediamine, EDTA, melamine or ammonium chloride; the mass concentration of the nitrogen-containing compound aqueous solution is preferably 5 to 30%, and more preferably 10 to 20%. In the present invention, the EDTA is preferably used in the form of EDTA disodium salt; when the nitrogen-containing compound is melamine, the melamine is preferably dissolved in an aqueous solution at 70 ℃ or higher and pH 4 or lower.

In the invention, the first soaking temperature is preferably 35-80 ℃, more preferably 45-65 ℃, and most preferably 50-60 ℃; the first soaking time is preferably 0.5-8 hours, more preferably 1-6 hours, and most preferably 3-5 hours. In the first soaking process, nitrogen-containing compounds are adsorbed and deposited on the activated carbon to obtain the activated carbon carrier containing ammonia nitrogen.

In the invention, the first drying temperature is preferably 60-145 ℃, more preferably 80-140 ℃, and most preferably 100-120 ℃, and the first drying time is preferably 6-24 hours, more preferably 7-20 hours, and most preferably 7-18 hours. The drying method is not particularly limited, and may be any method known to those skilled in the art.

After the first product is obtained, the first product is placed in a copper chloride solution for second soaking, and the obtained solid material is subjected to second drying to obtain the catalyst for synthesizing vinyl chloride.

In the invention, the copper chloride in the copper chloride solution is preferably copper chloride or cuprous chloride, the copper chloride solution is preferably a copper chloride acid solution or a copper chloride aqueous solution, the acid used in the copper chloride acid solution is preferably hydrochloric acid, phosphoric acid or sulfuric acid, more preferably hydrochloric acid, and the mass concentration of the copper chloride solution is preferably 3.39-25%, more preferably 5-10%. In the present invention, the volume of the copper chloride solution is preferably 0.2 to 2 times, and more preferably 0.5 to 1 time the volume of the activated carbon.

In the invention, the second soaking temperature is preferably 35-80 ℃, more preferably 45-65 ℃, and most preferably 50-60 ℃, and the second soaking time is preferably 6-300 min, more preferably 8-200 min, and most preferably 8-120 min. According to the invention, by controlling the temperature and time of the second soaking, desorption of ammonia nitrogen in the activated carbon can be avoided, and the ammonia nitrogen content and the copper content in the activated carbon are ensured. In the second soaking process, ammonia nitrogen is adsorbed in the inner hole of the activated carbon, and copper ions are loaded on the outer surface layer with the ammonia nitrogen activated carbon carrier and coexist on the activated carbon.

In the invention, the temperature of the second drying is preferably 60-200 ℃, more preferably 80-150 ℃, and most preferably 100-120 ℃, and the time of the second drying is preferably 6-24 hours, more preferably 8-15 hours, and most preferably 10-12 hours. The drying method is not particularly limited, and may be any method known to those skilled in the art.

The invention provides the catalyst for synthesizing the chloroethylene, which is prepared by the preparation method in the technical scheme, wherein the nitrogen content of the catalyst for synthesizing the chloroethylene is 0.5-6%; the copper content is 1-10%; the water content is less than or equal to 3 percent; the particle size is phi (2.0-4.0) mm multiplied by the length (3-6) mm; the mechanical strength is more than or equal to 95 percent; bulk density <700 g/L. The invention utilizes the synergistic effect of ammonia nitrogen and copper to enhance the catalytic activity of ammonia nitrogen, thereby enhancing the activity of the catalyst for synthesizing vinyl chloride.

The invention provides the catalyst for synthesizing vinyl chloride prepared by the preparation method in the technical scheme or the application of the catalyst for synthesizing vinyl chloride in synthesizing vinyl chloride by acetylene and hydrogen chloride in the technical scheme. The method for using the catalyst for vinyl chloride synthesis in the synthesis of vinyl chloride from acetylene and hydrogen chloride is not particularly limited, and a method known to those skilled in the art may be used. In the embodiment of the invention, the method is particularly applied to the production of vinyl chloride synthesized by acetylene and hydrogen chloride in the conventional industrialization.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.