阅读说明：本技术 一种复合载体钌基催化剂在乙炔氢氯化反应中的应用 (Application of composite carrier ruthenium-based catalyst in acetylene hydrochlorination ) 是由 王小艳 宋晓玲 周军 李国栋 陈万银 李静 张学鲁 郑伟玲 庞晓东 赵忠峰 司江 于 2020-06-22 设计创作，主要内容包括：本发明公开了一种复合载体钌基催化剂在乙炔氢氯化反应中的应用,该催化剂的复合载体由磷/膦酸锆浸渍负载于活性炭上构成,其主要制备过程为用水溶解锆前驱体,加入除灰干燥的活性炭,充分搅拌浸渍,后滴加磷/膦酸溶液,充分搅拌静置,水洗干燥焙烧制备而成。将该载体浸渍负载三氯化钌、醋酸钌、三联吡啶氯化钌中任意一种制备得到乙炔氢氯化反应无汞钌基催化剂。本发明所制备的催化剂具有活性高、选择性好,生产方法简单、对环境友好等特点,为进一步电石法聚氯乙烯行业无汞化工业进程再添新动力。(The invention discloses an application of a composite carrier ruthenium-based catalyst in acetylene hydrochlorination, wherein the composite carrier of the catalyst is prepared by impregnating and loading phosphorus/zirconium phosphonate on active carbon, and the preparation process mainly comprises the steps of dissolving a zirconium precursor by water, adding ash-removed and dried active carbon, fully stirring and impregnating, then dropwise adding a phosphorus/phosphonic acid solution, fully stirring and standing, washing, drying and roasting. The carrier is dipped and loaded with any one of ruthenium trichloride, ruthenium acetate and ruthenium terpyridyl chloride to prepare the mercury-free ruthenium-based catalyst for acetylene hydrochlorination. The catalyst prepared by the invention has the characteristics of high activity, good selectivity, simple production method, environmental friendliness and the like, and is a new power for further adding a mercury-free industrial process in the calcium carbide process polyvinyl chloride industry.)

1. The application of the composite carrier ruthenium-based catalyst in the hydrochlorination of acetylene is characterized in that: comprises a composite carrier which loads phosphorus/zirconium phosphonate on active carbon and a main active component which contains any one of ruthenium trichloride, ruthenium acetate and ruthenium terpyridyl chloride loaded on the active carbon; the composite carrier is prepared by the following method: weighing a certain amount of zirconium precursor, adding water to dissolve the zirconium precursor, adding dried activated carbon, fully stirring and dipping for 2-4 h, then dropwise adding a phosphorus/phosphonic acid solution, fully stirring and reacting, standing for 4-8 h, washing with water, drying, and finally roasting to prepare the zirconium precursor.

2. The use of a composite supported ruthenium-based catalyst in the hydrochlorination of acetylene according to claim 1, wherein: the zirconium precursor contains at least one of soluble zirconium salts such as zirconium chloride, zirconium oxychloride, zirconium carbonate and zirconyl sulfate, and the mass of zirconium accounts for 0.02-2% of the mass of the activated carbon.

3. The use of a composite supported ruthenium-based catalyst according to any one of claims 1 and 2 in hydrochlorination of acetylene, characterized in that: the phosphorus/phosphonic acid comprises at least one of phosphoric acid, hydroxyethylidene diphosphonic acid, amino trimethylene phosphonic acid, ethylene diamine tetra methylene phosphonic acid, dihexene triamine pentamethylene phosphonic acid and phenyl phosphonic acid, and the molar weight ratio of the phosphorus/phosphonic acid to the zirconium salt is 1-10.

4. The use of a composite supported ruthenium-based catalyst in the hydrochlorination of acetylene according to claim 1, wherein: the main active component of the acetylene hydrochlorination catalyst comprises at least one of ruthenium trichloride, ruthenium acetate and terpyridyl ruthenium chloride, and the mass content of ruthenium is 0.01-1%.

5. The use of a composite supported ruthenium-based catalyst in the hydrochlorination of acetylene according to claim 1, wherein: and during roasting, inert gas is used for protection, the roasting temperature is 150-350 ℃, and the roasting time is 1-8 hours.

Technical Field

The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a phosphorus/zirconium phosphonate composite carrier ruthenium-based catalyst and application of the catalyst in acetylene hydrochlorination.

Background

Polyvinyl chloride is one of five synthetic resins in the world, and is widely applied to important fields of national economy such as industry, agriculture, building materials and the like. The synthesis method mainly comprises a calcium carbide acetylene method, an ethylene method, a dichloroethane cracking method, an ethane oxychlorination method and the like. The energy structure of China determines that the production process of the polyvinyl chloride by the calcium carbide method occupies a leading position for a long time.

Chloroethylene is prepared from acetylene and hydrogen chloride through reaction of HgCl₂the/AC is synthesized by the reaction of a catalyst. The mercuric chloride is volatile, belongs to a highly toxic substance, has negative effects on the environment and the health of operators, is difficult to treat and recycle mercury-containing pollutants, causes great harm to the sustainable development of the industry and the creation of environment-friendly economy, and leads to the international society to have a mercury regulation, the European union to comprehensively limit mercury transactions, the domestic mercury resource is deficient and the like, so that the calcium carbide method polyvinyl chloride industry faces the survival crisis.

The development of mercury-free catalysts is the fundamental approach to the problem. The research and development direction summary about the mercury-free catalyst for acetylene hydrochlorination in recent years is mainly divided into: noble metal mercury-free catalysts, non-metal mercury-free catalysts and the like. At present, the non-noble metal mercury-free catalyst mainly uses compounds such as Cu, Sn, Bi and the like as main active components in the research direction, but the catalyst has short service life due to the problems of easy agglomeration, easy loss, easy carbon deposition and the like, and cannot be applied to large-scale industrialization. The nonmetal mercury-free catalyst mainly performs optimized structure treatment on a carrier, mainly focuses on nitrogen-doped carbon materials, but has low activity and poor stability, and is far from industrial application. The noble metal catalyst is mainly researched by taking noble metals such as Au, Ru, Pd, Pt, Rh, Ir and the like as main active components, wherein the Au mercury-free catalyst has better activity and stability, is the non-mercury catalyst which is most hopeful to be industrially applied at present, but the gold-based catalyst is expensive, and has a plurality of problems which need to be solved in industrialization. The price of ruthenium is much lower than that of gold, and the excellent catalyst performance is receiving much attention and research. However, the low-content ruthenium catalyst has the problems of low activity, unstable ruthenium trichloride aqueous solution, easy agglomeration in the reaction process, easy reduction in high-concentration acetylene atmosphere, weak interaction with a carrier, narrow reaction temperature range and the like, and aiming at the problems of the ruthenium catalyst, more research institutes research the ruthenium catalyst from the aspects of changing ruthenium valence state and compounds, adding auxiliary agent compounding, ligand complexing and coordination, ionic liquid, preparation methods, carrier modification and the like.

The phosphorus/zirconium phosphonate is a cationic compound with a regular layered structure, has larger specific surface area and surface charge, has good ion exchange characteristic, and has more applications in the fields of chemistry, optics, electronics, polymer modification, composite materials, functional materials and the like. Can also be applied to the field of catalysts.

The composite carrier catalyst for acetylene hydrochlorination is prepared by depositing a nano inorganic oxide on active carbon, wherein the inorganic substances comprise cerium dioxide, titanium dioxide, zirconium dioxide and lanthanum oxide and account for 0.5-8.0 percent; the preparation method adopts a continuous two-step deposition-precipitation method. The inorganic oxide precursor is any one or two of cerium nitrate, titanyl sulfate, zirconium nitrate and lanthanum nitrate, potassium hydroxide or ammonia water is used as a precipitator to form hydroxide, the hydroxide is roasted at 350-650 ℃ in nitrogen atmosphere to obtain a carrier, and gold and ruthenium are used as main active components. The catalyst has better overall performance, but no industrial application report exists.

In 2017, Zhangchao and Wangxiang, a patent of a pillared layered zirconium phosphate supported nickel-based catalyst, a preparation method and application thereof, which is published by Dajun of Chinese academy of sciences, discloses that the catalyst is prepared by taking a silicon pillared layered a-zirconium phosphate mesoporous material as a carrier and loading transition metal on the carrier. The method comprises the steps of carrying out colloid modification on a-zirconium phosphate by using organic alcohol amine, introducing organic silicon by using long-chain quaternary ammonium salt as a guiding agent for self-assembly to obtain a silicon pillared layered zirconium phosphate precursor, soaking a soluble metal salt mixed solution on the precursor in an equal volume, drying, roasting, reducing and activating to obtain the nickel-based catalyst, and the nickel-based catalyst is mainly used for hydrodeoxygenation reaction of C-O bond or alkyl C-O bond organic compounds containing aromatic hydrocarbon.

Disclosure of Invention

In order to solve the problem of mercury pollution in the process of synthesizing vinyl chloride by acetylene hydrochlorination, the invention provides a composite carrier ruthenium-based catalyst which is applied to acetylene hydrochlorination and solves the problems of low activity and poor stability of low-content ruthenium-based catalysts.

The technical scheme of the invention is as follows: the application of composite carrier ruthenium-based catalyst in hydrochlorination of acetylene comprises a composite carrier which is loaded on active carbon after phosphorus/zirconium phosphonate is soaked, and a main active component which contains any one of ruthenium trichloride, ruthenium acetate and ruthenium terpyridyl chloride and is loaded on the active carbon. The composite carrier and the active components are dipped on the active carbon, and the active carbon is washed by water to remove ash.

The composite carrier is prepared by the following method: weighing a certain amount of zirconium precursor, adding water to dissolve the zirconium precursor, adding the ash-removed and dried activated carbon, fully stirring and dipping for 2-4 h, then dropwise adding a phosphorus/phosphonic acid solution, fully stirring and reacting, standing for 4-8 h, washing with water, drying, and finally roasting to prepare the zirconium precursor.

The excessive phosphorus/phosphonic acid is removed in the roasting process, so that the thermal property, the chemical property, the layered structure and the mechanical strength of the combined phosphorus/zirconium phosphonate and activated carbon are more stable and solidified; the finally prepared catalyst is applied to acetylene hydrogen chlorination reaction.

The zirconium precursor contains at least one soluble zirconium salt such as zirconium chloride, zirconium oxychloride, zirconium carbonate, zirconium sulfate, etc., and the mass percentage of zirconium to the mass of the activated carbon is 0.02 to 2%.

The phosphorus/phosphonic acid comprises at least one of phosphoric acid, hydroxyethylidene diphosphonic acid, aminotrimethylidenephosphonic acid, ethylenediamine tetramethylene phosphonic acid, dihexyltriamine pentamethylene phosphonic acid and phenylphosphonic acid, and the molar ratio of the phosphorus/phosphonic acid to the zirconium salt is 1-10.

The main active component of the acetylene hydrochlorination catalyst comprises at least one of ruthenium trichloride, ruthenium acetate and ruthenium terpyridyl chloride, and the mass content of ruthenium is 0.01-1%, and the optimal content is 0.05-0.3%.

The roasting is carried out under the protection of inert gas, the roasting temperature is 150-350 ℃, and the roasting time is 1-8 hours.

The composite carrier of the ruthenium-based catalyst is formed by impregnating and loading phosphorus/zirconium phosphonate on active carbon, wherein the phosphorus/zirconium phosphonate has a regular layered structure, is insoluble in water, can resist strong acidity and certain alkalinity, has the advantages of strong thermal stability and mechanical strength, high chemical stability and the like, is combined on the opposite outer surface of an active carbon porous structure, regulates the relatively disordered outer surface of the active carbon, increases the specific surface area, enhances the thermal stability and strength of the active carbon, and greatly reduces the phenomena of collapse and self-blockage of an active carbon pore channel structure caused by local overheating in reaction. The active components of the metal ruthenium base enter a relatively ordered layered pore channel structure in the dipping process, the distribution is more uniform, and stable ligands are formed by the interaction between ruthenium and phosphorus/zirconium phosphonate, so that the active sites are increased, the dispersibility and uniformity of the active sites are greatly improved, the agglomeration phenomenon of local reaction overheating and the occurrence of side reactions are avoided, the generation rate of carbon deposition is slowed down, and the content of ruthenium compounds in the catalyst is greatly reduced. The catalyst has excellent overall performance and high economy, is environment-friendly, and provides technical support for the sustainable development of the calcium carbide process polyvinyl chloride industry.

Detailed Description

In order to better illustrate the invention, the following examples are given. The scope of the invention is not limited to the examples, but rather the scope of protection is set forth in the claims.