阅读说明：本技术 一种钝化型超低含量金催化剂 (Passivation type ultralow-content gold catalyst ) 是由 宋晓玲 周军 郑伟玲 赵忠峰 张万鹏 万振国 庞晓东 李静 陈万银 刘飞 任军义 于 2021-07-28 设计创作，主要内容包括：本发明公开了一种钝化型超低含量金催化剂,特别是一种适用于乙炔氢氯化反应合成氯乙烯的非汞催化剂,该催化剂采用单酰胺为金基催化剂的钝化剂,以单质金、氯金酸、金的卤化物、金的氧化物中的一种或几种为主活性组分,再复配铁、钴、镍、铜、铯、镧、铈、锡的化合物的一种以上为辅活性组分；本发明所制备金复配催化剂显著的降低了贵金属催化剂的成本,解决了贵金属催化剂热点高、热点集中,容易发生副反应、积炭、失活了的缺点,大大改善了催化剂的性能。(The invention discloses a passivated ultra-low content gold catalyst, in particular to a non-mercury catalyst suitable for synthesizing chloroethylene by acetylene hydrochlorination, which adopts monoamide as a passivating agent of a gold-based catalyst, takes one or more of simple substance gold, chloroauric acid, gold halide and gold oxide as main active components, and then compounds of more than one of iron, cobalt, nickel, copper, cesium, lanthanum, cerium and tin as auxiliary active components; the prepared gold compound catalyst remarkably reduces the cost of the noble metal catalyst, overcomes the defects of high heat point, concentrated hot points, easy occurrence of side reaction, carbon deposit and inactivation of the noble metal catalyst, and greatly improves the performance of the catalyst.)

1. A passivated ultra-low gold catalyst is characterized in that the catalyst comprises a main active component and a noble metal gold compound; auxiliary active component, one or mixture of any more of iron, cobalt, nickel, copper, cesium, lanthanum, cerium and tin compounds; a catalyst deactivator, a monoamide compound; the carrier is active carbon.

2. A passivated ultra low gold catalyst according to claim 1 wherein the noble metal gold compound is one or both of chloroauric acid and gold chloride.

3. A passivated ultra low gold catalyst according to claim 1 wherein the gold is present in an amount of one to five ten thousandths of an activated carbon.

4. A passivated ultra low gold catalyst as claimed in claim 1 wherein the ancillary active components are chlorides and nitrates of one or any of the compounds of iron, cobalt, nickel, copper, cesium, lanthanum, cerium, tin.

5. The passivated ultra-low gold catalyst of claim 1 wherein the auxiliary active component element content is 1-50% of the activated carbon.

6. The passivated ultra low gold catalyst according to claim 1 wherein said mono-amide compound is one or more of formamide, acetamide, propionamide, N dimethylformamide, benzamide, tetracyclic amide, pentacyclic amide, hexacyclic amide, tetracyclic amide derivatives, pentacyclic amide derivatives, hexacyclic amide derivatives.

7. The passivated ultra-low gold catalyst according to claim 6 wherein the mass ratio of passivating agent to activated carbon is 0.01 to 0.3.

8. A passivated ultra low gold catalyst according to claim 1 wherein the catalyst is prepared by impregnating the secondary active component of the catalyst followed by the primary active component of the catalyst and the passivating agent.

9. The passivated ultra-low gold catalyst of claim 1 wherein the drying conditions are 30-80 ℃ for 8-72 hours and 105-125 ℃ for 8-48 hours.

10. The passivated ultra low gold catalyst of claim 1 wherein said catalyst is used in the reaction of acetylene hydrochlorination to vinyl chloride.

Technical Field

The invention belongs to the field of gold-based catalysts for synthesizing vinyl chloride by hydrochlorinating acetylene, and particularly relates to a passivated ultralow-content gold catalyst.

Background

The vinyl chloride monomer is an important synthetic raw material of polyvinyl chloride, the polyvinyl chloride is one of synthetic resins with the largest consumption and yield in China, and the basic national situation of more coal and less oil in China determines that the vinyl chloride produced by the acetylene hydrochlorination method still occupies the leading position in China. The main problems faced by the acetylene hydrochlorination method for synthesizing vinyl chloride are environmental pollution caused by the use of mercury catalyst and large consumption of mercury resources. With the increasing enhancement of environmental awareness and the increasing tension of international mercury-limiting treaties, the development of mercury-free catalysts is imperative for maintaining the living space of calcium carbide-process PVC.

At present, the research focus of the mercury-free catalyst focuses on the research and development of non-noble metal and noble metal mercury-free catalysts. Research and development of non-noble metal catalysts have also made certain research progress, for example, CN101497046, CN101671293, and CN102151581A are catalytic systems using non-noble metals such as Cu, Bi, and MoP as main active components, respectively, but the non-noble metal mercury-free catalysts still have major problems of low activity and short lifetime.

The development participation units of the noble metal mercury-free catalyst comprise development units of Sichuan university, Tianjin staphyla, Huadong university, Ak technology Limited, south China university, Qinghua university, Xinjiang celestial group, Dalian institute, Shihui university, Tianjin university, Xinjiang university, Zhejiang university and the like, so that the development of the noble metal mercury-free catalyst is greatly researched and developed, but the noble metal mercury-free catalyst has high conversion rate, but one of the main problems of the noble metal mercury-free catalyst is that the conversion rate of the catalyst is too high, the reaction of the catalyst is concentrated, the hot spot is too high, the local reaction heat transfer is not carried out, the catalyst sintering, carbon accumulation and side reaction are increased, the active component is inactivated and the like, and the one-time investment cost of the catalyst is high, so that the popularization and the application of the noble metal mercury-free catalyst are limited.

Aiming at the problems of the noble metal mercury-free catalyst, the invention firstly greatly reduces the content of the noble metal catalyst and the first investment and use cost of the noble metal catalyst, but aims at solving the problems of sintering, carbon deposit, side reaction increase, active component inactivation and the like of the catalyst caused by high reaction heat point, concentrated reaction and partial reaction heat transfer which still exist in the ultra-low content noble metal gold catalyst, thereby reducing the service life of the catalyst. The invention develops a passivator of a noble metal gold catalyst, which reduces the initial activity of the noble metal catalyst and prolongs the induction period of the catalyst by adding the passivator, and gradually releases the activity of the catalyst along with the progress of catalytic reaction, thereby reducing the hot spot temperature of the catalyst, prolonging the reaction bandwidth of the catalyst, reducing the side reaction of the catalyst, lightening the carbon deposit and the sintering condition of the catalyst, and prolonging the service life of the catalyst.

Disclosure of Invention

The invention aims to solve the problems that the high-toxicity mercury catalyst is used in the production of polyvinyl chloride by a calcium carbide acetylene method, the mercury consumption in the production is high, the environmental pollution is serious, the reaction heat point of the existing noble metal catalyst is high, the reaction is concentrated, the local reaction heat is not transferred, the catalyst sintering, carbon deposition and side reaction are increased, the active component is inactivated, and the one-time investment cost is high.

The passivated ultra-low gold catalyst has the advantages that the main active component of the catalyst is a noble metal gold compound; the auxiliary active component is one or a mixture of any more of iron, cobalt, nickel, copper, cesium, lanthanum, cerium and tin compounds, the catalyst passivator is a monoamide compound, and the carrier is activated carbon.

In the passivated ultra-low gold catalyst, the gold compound is one or two of chloroauric acid and gold chloride.

The passivated ultra-low gold catalyst has gold content of one ten-thousandth to five ten-thousandth of the activated carbon.

The passivated ultra-low gold catalyst has the auxiliary active components of chlorides and nitrates of compounds of iron, cobalt, nickel, copper, cesium, lanthanum, cerium and tin.

The content of the auxiliary active component simple substance is 1-50% of the active carbon.

In the above-mentioned passivated ultra-low gold catalyst, the monoamide compound is one or more of formamide, acetamide, propionamide, N-dimethylformamide, benzamide, tetracyclic amide, pentacyclic amide, hexacyclic amide, tetracyclic amide derivative, pentacyclic amide derivative and hexacyclic amide derivative.

The mass ratio of the passivating agent to the active carbon of the passivated ultralow-content gold catalyst is 0.01-0.3.

The preparation method of the passivated ultra-low gold catalyst comprises the steps of firstly impregnating the auxiliary active component of the catalyst, then impregnating the main active component of the catalyst and the passivating agent.

The drying condition of the passivated ultra-low content gold catalyst is drying for 8-72 hours at the temperature of 30-80 ℃, and drying for 8-48 hours at the temperature of 105-125 ℃.

The passivated catalyst with ultralow gold content is used in the reaction process of synthesizing vinyl chloride by hydrochlorinating acetylene and is used for producing vinyl chloride by acetylene and hydrogen chloride.

The preparation method of the high-dispersity gold-loaded catalyst provided by the invention is carried out for 30-360 h^-1When the space velocity reaction is carried out, the initial conversion rate reaches 80-100%, the conversion rate is kept stable after the reaction is carried out for 8-1000 h, and the selectivity of chloroethylene reaches more than 98%, so that the problems that the high-toxicity mercury catalyst is used in the production of polyvinyl chloride by a calcium carbide acetylene method, the mercury consumption in the production is high, the environmental pollution is serious, the hot spots of the existing noble metal catalyst are concentrated, the hot spot temperature is high, the reaction is concentrated, the local reaction heat is not transferred, the catalyst sintering, carbon deposition, side reaction increase, the active component inactivation and the one-time investment cost are high are solved.

Detailed Description

To better illustrate the present invention, the following examples are given. The scope of the invention is not to be limited by the examples, but rather is to be defined by the claims appended hereto.

Firstly, preparing a chloroauric acid solution, namely dissolving 1g of chloroauric acid in 100ml of deionized water to prepare the chloroauric acid solution, and preparing for subsequent sample preparation. Secondly, pretreatment of the carrier: 200g of activated carbon is weighed and repeatedly washed by deionized water until the supernatant of the water solution of the activated carbon is clear and bright, and then dried at 120 ℃ for later use.

Example 1

0.6224g of chloroauric acid solution and 0.2904g of ferric chloride were weighed into a beaker, and then diluted with 26ml of deionized water. Adding 0.2ml of formamide into the solution, stirring uniformly, adding 10g of activated carbon, stirring uniformly, soaking at normal temperature for 24h, drying at 50 ℃ for 12h, and drying at 125 ℃ for 24 h. The initial conversion of this catalyst reached 75%.

Example 2

0.6224g of chloroauric acid solution and 0.2203g of cobalt chloride are weighed in a beaker, 26ml of deionized water is added for dilution, 0.2ml of formamide is added into the solution, 10g of activated carbon is added after the mixture is uniformly stirred, the mixture is uniformly stirred and dipped for 24 hours at normal temperature, and then the mixture is dried for 12 hours at the temperature of 50 ℃ and 24 hours at the temperature of 125 ℃. 0.6224g of chloroauric acid solution was weighed out and added to 20ml of water, and the above dried catalyst was added to carry out secondary impregnation, followed by impregnation and drying under the above conditions. The initial conversion of this catalyst reached 78%.

Example 3

1.2448g of chloroauric acid solution and 0.4416g of nickel chloride were weighed into a beaker, followed by dilution with 26ml of deionized water. And then 2g of acetamide is taken and added into the solution, after the mixture is uniformly stirred, 10g of activated carbon is added, the mixture is uniformly stirred, the mixture is immersed for 24 hours at normal temperature, and then the mixture is dried for 12 hours at 50 ℃ and 24 hours at 125 ℃. The initial conversion of this catalyst reached 83%.

Example 4

1.8672g of chloroauric acid solution and 0.7991g of copper chloride were weighed into a beaker, and then diluted with 26ml of deionized water. And adding 3g of propionamide into the solution, uniformly stirring, adding 10g of activated carbon, uniformly stirring, soaking at normal temperature for 24 hours, drying at 50 ℃ for 12 hours, and drying at 125 ℃ for 24 hours. The initial conversion of this catalyst reached 80%.

Example 5

2.4896g of chloroauric acid solution and cesium chloride 1.0141 were weighed into a beaker and then diluted by adding 26ml of deionized water. And then adding 2ml of N, N-dimethylformamide into the solution, stirring uniformly, adding 10g of activated carbon, stirring uniformly, soaking at normal temperature for 24h, then drying at 50 ℃ for 12h, and drying at 125 ℃ for 24 h. The initial conversion of this catalyst reached 85%.

Example 6

3.1112g of chloroauric acid solution and 3.1171 g of lanthanum nitrate were weighed into a beaker, and then diluted with 26ml of deionized water. And then 0.6g of benzamide is added into the solution, after the stirring is uniform, 10g of activated carbon is added, the stirring is uniform, the impregnation is carried out for 24h at the normal temperature, then the drying is carried out for 12h at the temperature of 50 ℃, and the drying is carried out for 24h at the temperature of 125 ℃. The initial conversion of this catalyst reached 95%.

Example 7

0.6224g of chloroauric acid solution and 3.4912 g of cerium nitrate were weighed into a beaker, followed by dilution with 26ml of deionized water. And then 2ml of 2-pyrrolidone is added into the solution, after the mixture is uniformly stirred, 10g of activated carbon is added, the mixture is uniformly stirred, the mixture is soaked for 24 hours at normal temperature, and then the mixture is dried for 12 hours at the temperature of 50 ℃ and 24 hours at the temperature of 125 ℃. The initial conversion of this catalyst reached 76%.

Example 8

1.2448g of chloroauric acid solution and stannous chloride 3.8017 were weighed into a beaker and then diluted with 26ml of deionized water. And then 0.5ml of 2-piperidone is added into the solution, after the mixture is uniformly stirred, 10g of activated carbon is added, the mixture is uniformly stirred, the mixture is soaked for 24 hours at normal temperature, and then the mixture is dried for 12 hours at the temperature of 50 ℃ and dried for 24 hours at the temperature of 125 ℃. The initial conversion of this catalyst reached 90%.

Example 9

1.8672g of chloroauric acid solution and 1.2599 g of silver nitrate were weighed into a beaker, and then diluted by adding 26ml of deionized water. And then adding 0.5g of caprolactam into the solution, stirring uniformly, adding 10g of activated carbon, stirring uniformly, soaking at normal temperature for 24 hours, then drying at 50 ℃ for 12 hours, and drying at 125 ℃ for 24 hours. The initial conversion of this catalyst reached 86%.