阅读说明：本技术 一种用于乙炔氢氯化反应的碳纳米管无汞催化剂 (Carbon nano tube mercury-free catalyst for acetylene hydrochlorination ) 是由 王璐 廉立臻 闫海军 刘金斗 王吉德 王丰 武凤娟 宋雯 曹艳 于 2019-03-28 设计创作，主要内容包括：本发明涉及一种可用于乙炔氢氯化反应的负载型非贵金属催化剂。催化剂的组成包括活性组分和载体。其中,催化剂的活性组分为负载量1%~30%的非贵金属,包括铜、锡、铋、镍、钴、锌等元素中的一种盐以及其配合物；催化剂的载体为无机酸碱(盐酸、硫酸、硝酸、磷酸、氢氧化钾、氨水等)和有机酸碱(己二酸、酒石酸、草酸、柠檬酸、乙胺、乙二胺、吡啶等)试剂中的一种或多种改性的碳纳米管材料,包括含羟基、羧基、环氧基等极性基团的多壁碳纳米管中的一种。所述催化剂采用湿浸渍法、一锅法等方法中的一种进行制备。本发明的优点在于,该催化剂环境友好,工艺简单,所制催化剂的乙炔转化率可达75%,氯乙烯选择性可达95%以上。(The invention relates to a supported non-noble metal catalyst for hydrochlorination of acetylene. The catalyst comprises an active component and a carrier. The active component of the catalyst is a non-noble metal with the load of 1-30%, and comprises one salt of elements such as copper, tin, bismuth, nickel, cobalt, zinc and the like and a complex thereof; the carrier of the catalyst is one or more modified carbon nanotube materials in inorganic acid-base (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, potassium hydroxide, ammonia water and the like) and organic acid-base (adipic acid, tartaric acid, oxalic acid, citric acid, ethylamine, ethylenediamine, pyridine and the like) reagents, and comprises one of multi-walled carbon nanotubes containing polar groups such as hydroxyl, carboxyl, epoxy and the like. The catalyst is prepared by one of wet impregnation method, one-pot method and the like. The invention has the advantages that the catalyst is environment-friendly, the process is simple, the acetylene conversion rate of the prepared catalyst can reach 75 percent, and the selectivity of chloroethylene can reach more than 95 percent.)

1. A load type mercury-free catalyst used for acetylene hydrochlorination.

2. The catalyst of claim 1, wherein the active component is a non-noble metal with a loading of 1% to 30%, and the non-noble metal comprises a salt of copper, tin, bismuth, nickel, cobalt, zinc, and the like, and a complex thereof.

3. The catalyst of claims 1 and 2, wherein the carrier of the catalyst is one of multi-walled carbon nanotubes containing polar groups such as hydroxyl, carboxyl, epoxy and the like.

4. The carrier of catalyst according to claim 3, characterized in that the carbon nanotubes are modified by one or more of the reagents of inorganic acid base (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, potassium hydroxide, ammonia water, etc.) and organic acid base (adipic acid, tartaric acid, oxalic acid, citric acid, ethylamine, ethylenediamine, pyridine, etc.).

5. The method of any one of claims 1, 2, 3 and 4 for the preparation of a non-noble metal catalyst for the hydrochlorination of acetylene, characterized in that one of a wet impregnation method and a one-pot method is used.

6. Use of the catalyst system according to claims 1, 2, 3, 4 and 5, characterized in that the reaction conditions are: normal pressure, the space velocity of the raw material gas is 30-300 h^-1The raw material gas proportion is V (HCl): v (C)₂H₂) And (c) the reaction temperature is 90-200 ℃, and the reaction rate is 1.1-1.3.

Technical Field

The invention relates to synthesis and application of a supported carbon nanotube non-noble metal catalyst for acetylene hydrochlorination, and belongs to the field of catalyst preparation technology and application in fine organic synthesis.

Background

Vinyl Chloride Monomer (VCM) is an important raw material that is not replaced for the synthesis of polyvinyl chloride (PVC). At present, 80% of VCM in China is produced by adopting an acetylene hydrochlorination method.

In the traditional process, the mercury catalyst is toxic and easy to sublimate, thereby not only harming the ecological environment, but also influencing the product quality and causing the shortage of mercury resources. Therefore, the development of an environmentally friendly, economical and efficient mercury-free catalyst becomes especially important.

At present, the research of acetylene hydrochlorination mercury-free catalysts at home and abroad mainly focuses on finding and matching suitable active components and catalyst carriers. Although noble metal catalysts have high activity and are favored by many researchers, the high cost limits the industrial application, so that non-noble metal catalysts with relatively rich resources and low cost are good choices.

The invention provides a supported carbon nano tube non-noble metal catalyst for acetylene hydrochlorination, which has important significance for the research of producing vinyl chloride by an acetylene hydrochlorination method.

Disclosure of Invention

The invention provides a supported carbon nano tube non-noble metal catalyst for acetylene hydrochlorination aiming at the problems of pollution and harm of mercury in a mercury-free catalyst for acetylene hydrochlorination.

The catalyst provided by the invention consists of an active component and a carrier. The active component of the catalyst is non-noble metal with the load of 1-30%, and comprises one salt of copper, tin, bismuth, nickel, cobalt, zinc and other elements and a complex thereof; the carrier of the catalyst is one or more modified carbon nanotube materials in inorganic acid-base (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, potassium hydroxide, ammonia water and the like) and organic acid-base (adipic acid, tartaric acid, oxalic acid, citric acid, ethylamine, ethylenediamine, pyridine and the like) reagents, and comprises one of multi-walled carbon nanotubes containing polar groups such as hydroxyl, carboxyl, epoxy and the like.

The invention also discloses a preparation method of the supported carbon nanotube non-noble metal catalyst for acetylene hydrogen chloride reaction, which is characterized by comprising the following steps: (A) the method adopts an ultrasonic-stirring/refluxing-washing-drying method to modify the carbon nano tube, and comprises the following specific steps: adding a certain amount of carbon nano tubes into the prepared modified solution, performing ultrasonic-assisted dispersion under a certain condition, magnetically stirring or refluxing the mixed solution, washing and drying for later use. (B) The method for preparing the carbon nano tube non-noble metal catalyst by adopting a wet impregnation method or a one-pot method comprises the following specific steps: wet dipping method, weighing a certain amount of non-noble metal salt, stirring at room temperature and dissolving in hydrochloric acid water solution, fully dipping the obtained solution on the modified carbon nano tube in A to obtain a solid-liquid mixture, and drying; ② a one-pot method, weighing a certain amount of non-noble metal salt, stirring and dissolving in hydrochloric acid aqueous solution at room temperature, placing the mixed solution and the modified carbon nano tube carrier in A in a hydrothermal kettle with a polytetrafluoroethylene lining according to a certain proportion, reacting for a period of time under a certain condition, washing and drying.

The catalyst prepared by the invention is applied to acetylene hydrochlorination and has certain catalytic activity. The activity test of the catalyst is carried out by using a fixed bed reactor. The reaction conditions are as follows: the airspeed of the raw material gas is 30-300 h^-1Ratio of raw material gasExamples are V (HCl): v (C)₂H₂) And (c) the reaction temperature is 90-200 ℃, and the reaction temperature is 1.1-1.3 at normal pressure.

The supported carbon nanotube non-noble metal catalyst prepared by the method has the acetylene conversion rate of more than 75 percent and the vinyl chloride selectivity of more than 95 percent.

The invention has the advantages that: the non-noble metal active component is cheap and easy to obtain, the modification of the carbon nano tube carrier and the synthesis process of the carbon nano tube non-noble metal catalyst are simple, and the prepared catalyst is environment-friendly and has low cost.

Example 1: A. weighing 5 g of dry hydroxyl-containing multiwalled carbon nanotube MWCNTs-OH, adding the mixture into a prepared nitric acid modified solution (the mass fraction of nitric acid is 1% -20%), performing ultrasonic-assisted dispersion in an environment with normal pressure and 35 ℃, performing magnetic stirring on the mixed solution under certain conditions, washing to be neutral, and drying for later use. B. Weighing a certain mass of copper chloride (the loading capacity of copper is 25%), stirring at room temperature, dissolving in a hydrochloric acid aqueous solution, fully soaking the obtained solution on the carbon nano tube modified in the step A to obtain a solid-liquid mixture, and drying to obtain the nitric acid modified carbon nano tube-copper-based catalyst.

3.5 g of the catalyst thus obtained was weighed and charged into a fixed bed reactor (made of quartz glass). Under the reaction conditions: the space velocity of the raw material gas is 110 h^-1The raw material gas proportion is V (HCl): v (C)₂H₂) The activity of acetylene hydrochlorination reaction is evaluated at the reaction temperature of 160 ℃ under normal pressure, the acetylene conversion rate is about 52%, and the vinyl chloride selectivity is about 95%.