CN107008465B - Copper-based catalyst with high activity and stability for hydrochlorination of acetylene - Google Patents

Copper-based catalyst with high activity and stability for hydrochlorination of acetylene Download PDF

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CN107008465B
CN107008465B CN201710208643.9A CN201710208643A CN107008465B CN 107008465 B CN107008465 B CN 107008465B CN 201710208643 A CN201710208643 A CN 201710208643A CN 107008465 B CN107008465 B CN 107008465B
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copper
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chloride
acetylene
stability
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CN107008465A (en
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罗国华
徐浩
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Tsinghua University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/122—Halides of copper
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons

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Abstract

The invention relates to a copper-based catalyst with high activity and stability for acetylene hydrochlorination, which takes copper salt as an active component; the copper salt is selected from one or more of copper chloride, copper nitrate, copper sulfate and copper phosphate, and is characterized in that a stabilizer is introduced into a copper-based catalyst; the stabilizer is selected from one or more of guanidine hydrochloride, tetramethylethylenediamine hydrochloride, tetramethylammonium chloride, tetraethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, methyltriphenylphosphonium chloride and 1-butyltriphenylphosphonium chloride. The stabilizer with the advantages of low cost, low toxicity, good thermal stability, small vapor pressure and the like is introduced into the catalyst, so that the stability of the copper acetylene hydrochlorination catalyst is obviously improved.

Description

Copper-based catalyst with high activity and stability for hydrochlorination of acetylene
Technical Field
The invention belongs to the technical field of preparing vinyl chloride by hydrochlorinating acetylene, and particularly relates to a copper-based catalyst for hydrochlorination of acetylene, which has high activity and stability.
Background
China is the first major country for the production of polyvinyl chloride (PVC) in the world, and accounts for more than 50% of the total production energy of the world. The production of Vinyl Chloride Monomer (VCM) is carried out by two major industrial routes, the petroleum-ethylene process and the coal-acetylene process. In China, the industrial route of the acetylene method (also called calcium carbide method) has abundant coal resources, high atom economy and cost advantage, so that the process for synthesizing vinyl chloride by hydrochlorination of the acetylene method in the production of polyvinyl chloride in China occupies over 70 percent of specific gravity and is still increased year by year. The core reaction is as follows:
Figure BDA0001260479610000011
in recent decades of industrial use, the main active component of the catalyst for this reaction is mercuric chloride. Mercury chloride has good activity for this reaction, but also has fatal problems. First, mercuric chloride is highly toxic and volatile. According to statistics and estimation, about 800 tons of mercury are used in the production process of vinyl chloride in China each year, about 200 tons of mercury cannot be recovered and directly enters the environment, and serious personal injury and environmental pollution are easily caused. Secondly, the mercury resource is exhausted due to the annual exploitation, and the catalyst cost is further increased. More importantly, mercury contamination has become a global problem and international organizations have increasingly placed restrictions on mercury use. At the same time, however, the calcium carbide process of chloroethylene will be the mainstream of the polyvinyl chloride industry for a long time. Therefore, the search for a synthetic vinyl chloride catalyst which has good performance and low price and can replace mercury is an imperative and urgent task for the green sustainable development of the PVC industry in China.
Currently, the noble metal gold is predicted and demonstrated to have the best acetylene hydrochlorination activity. The gold has the advantages of stability, high efficiency, cleanness, recoverability and the like, but the price of the gold is still relatively high, and the gold is difficult to be accepted by the PVC industry with low added value. Therefore, gold catalysts are still a distance from industrialization.
In contrast, non-noble metals have the characteristics of wide reserves and low price. The catalyst prepared from non-noble metal has more obvious cost advantage when applied to industry. Therefore, at present, a certain amount of research is carried out on non-noble metal acetylene hydrochlorination catalysts, wherein the catalyst taking copper as a main active component has excellent performance. The Duncao et al uses non-noble metal chlorides including copper as active components to prepare the low-cost catalyst, and the optimized catalyst formula can be used for 30 hours-1Acetylene volumetric space velocity operating conditions show greater than 98% conversion but the catalyst stability is poor. In CN101670293A, silica is used as a carrier, a composite metal including copper is used as a catalyst active component for loading, and a ligand is introduced to improve the activity of the catalyst, which is deactivated quickly, and a circulating fluidized bed is used for regeneration.
The most common problem in the current research of copper-based acetylene hydrochlorination catalysts is that the stability of the catalyst is not ideal enough. To achieve long-term industrial application of the catalyst, improving the stability of the catalyst is a problem that must be solved. The method for effectively improving the stability of the copper-based catalyst for acetylene hydrochlorination is a key point for accelerating the practical application of the catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a copper-based catalyst with high activity and stability for acetylene hydrochlorination.
Copper salt is used as an active component, and a stabilizing agent is introduced into the copper-based catalyst; the copper salt is selected from one or more of copper chloride, copper nitrate, copper sulfate and copper phosphate; the stabilizer is selected from one or more of guanidine hydrochloride, tetramethylethylenediamine hydrochloride, tetramethylammonium chloride, tetraethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, methyltriphenylphosphonium chloride and 1-butyltriphenylphosphonium chloride.
In one embodiment, the mass fraction of the stabilizer in the catalyst is 1 to 10 wt%.
In one embodiment, the mass fraction of the copper element in the catalyst is 1 to 15 wt%.
In one embodiment, the copper-based catalyst uses activated carbon as a carrier, and the activated carbon is selected from one or more of coconut shell carbon, wood carbon and coal carbon.
In one embodiment, the activated carbon has a particle size of 30 to 200 mesh and a specific surface area of 200 to 1200m2A density of 300 to 1000kg/m3The pore volume is 0.4 to 0.8 mL/g.
The invention has the beneficial effects that:
the stabilizer with the advantages of low cost, low toxicity, good thermal stability, small vapor pressure and the like is introduced into the catalyst, so that the stability of the copper acetylene hydrochlorination catalyst is obviously improved. The prepared catalyst can keep high selectivity (more than 99 percent), and the conversion rate is basically not reduced after the catalyst is continuously used for a long time, so that the catalyst can better meet the requirement of industrialized long-period operation. The catalyst has the characteristics of low cost, high safety and good performance, and has sufficient development potential.
Drawings
FIG. 1 is a graph showing the change of the acetylene conversion rate with the reaction time in examples 1 and 2 and comparative examples 1 and 2.
FIG. 2 is a graph of acetylene conversion versus reaction time for example 10.
Detailed Description
The invention is further described with reference to the following figures and detailed description. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
The preparation method of the catalyst comprises the following steps: and calculating the use amount of the copper salt and the stabilizing agent according to the set mass fraction, adding the weighed copper salt and the stabilizing agent into deionized water according to the use amount, and violently stirring to dissolve the components. After complete dissolution, the weighed activated carbon support was added with vigorous stirring. And (3) keeping the obtained product in a room-temperature normal-pressure environment for 6 hours, and then drying the product at 110 ℃ for 12 hours to obtain a catalyst finished product.
The following list shows the coconut shell carbon used in the examples and comparative examples: the particle size is 40-100 meshes and the specific surface area is 800m2A density of 500kg/m3The pore volume is 0.7 mL/g; the wood-based carbon used was: commercially available, particle size 30 mesh, specific surface area 500m2A density of 500kg/m3The pore volume was 0.5 mL/g.
The prepared catalyst was evaluated by a reaction evaluation apparatus composed of a flow control system, a reactor, a heating kettle, a condensing device, a drying device, a gas chromatograph for determining the conversion and selectivity of acetylene, and a tail gas absorbing device, with the recording frequency being once every 15 minutes.
The reaction conditions common to examples 1 to 9 and comparative examples 1 to 2 are listed below: the reaction temperature is 180 ℃, the reaction pressure is normal pressure, and the volume space velocity of acetylene is 180h-1The catalyst loading was 1.0g, and the volume flow ratio of acetylene to hydrogen chloride gas was 1: 1.1.
Example 1
The catalyst is prepared by using coconut shell carbon as a carrier and copper chloride dihydrate and trimethyl benzyl ammonium chloride, so that the mass fraction of copper element in the catalyst is 5%, and the mass fraction of trimethyl benzyl ammonium chloride is 2.5%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 1, and the curve of the conversion of the catalyst with the reaction time is shown in FIG. 1.
Comparative example 1
The catalyst is prepared by using coconut shell carbon as a carrier and copper chloride dihydrate, so that the mass fraction of copper element in the catalyst is 5%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 1, and the curve of the conversion of the catalyst with the reaction time is shown in FIG. 1.
Example 2
The catalyst is prepared by using coconut shell carbon as a carrier and using copper phosphate and trimethyl benzyl ammonium chloride, so that the mass fraction of copper element in the catalyst is 5%, and the mass fraction of trimethyl benzyl ammonium chloride is 2.5%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 1, and the curve of the conversion of the catalyst with the reaction time is shown in FIG. 1.
Comparative example 2
The coconut shell carbon is used as a carrier, and the copper phosphate is used for preparing the catalyst, so that the mass fraction of copper element in the catalyst is 5%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 1, and the curve of the conversion of the catalyst with the reaction time is shown in FIG. 1.
Example 3
The catalyst is prepared by using wood carbon as a carrier and copper chloride dihydrate and trimethyl benzyl ammonium chloride, so that the mass fraction of copper element in the catalyst is 5%, and the mass fraction of trimethyl benzyl ammonium chloride is 2.5%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 2.
Example 4
The catalyst is prepared by using coconut shell carbon as a carrier and copper chloride dihydrate and trimethyl benzyl ammonium chloride, so that the mass fraction of copper element in the catalyst is 5%, and the mass fraction of trimethyl benzyl ammonium chloride is 10%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 2.
Example 5
The catalyst is prepared by using coconut shell carbon as a carrier and using copper chloride dihydrate and tetramethylammonium chloride, so that the mass fraction of copper element in the catalyst is 10%, and the mass fraction of tetramethylammonium chloride is 2.5%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 2.
Example 6
The catalyst is prepared by using coconut shell carbon as a carrier and using copper chloride dihydrate and tetramethyl phosphonium chloride, so that the mass fraction of copper element in the catalyst is 5%, and the mass fraction of the tetramethyl phosphonium chloride is 2.5%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 2.
Example 7
The catalyst is prepared by using coconut shell carbon as a carrier and using copper chloride dihydrate and tetrabutyl phosphonium chloride, so that the mass fraction of copper element in the catalyst is 5%, and the mass fraction of tetrabutyl phosphonium chloride is 2.5%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 2.
Example 8
The catalyst is prepared by using coconut shell carbon as a carrier and using copper chloride dihydrate and tetramethylethylenediamine hydrochloride, so that the mass fraction of copper element in the catalyst is 5%, and the mass fraction of tetramethylethylenediamine hydrochloride is 2.5%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 2.
Example 9
The catalyst is prepared by using coconut shell carbon as a carrier and copper chloride dihydrate and guanidine hydrochloride, so that the mass fraction of copper element in the catalyst is 5%, and the mass fraction of guanidine hydrochloride is 2.5%. The reaction was carried out under the above reaction conditions, and the initial conversion of the catalyst and the data of the decrease in conversion after 12 hours are shown in Table 2.
In each of examples 1-9 and comparative examples 1-2 above, the selectivity to vinyl chloride was greater than 99%.
Example 10
The catalyst is prepared by using coconut shell carbon as a carrier and copper chloride dihydrate and trimethyl benzyl ammonium chloride, so that the mass fraction of copper element in the catalyst is 5%, and the mass fraction of trimethyl benzyl ammonium chloride is 2.5%. At the reaction temperature of 180 ℃, the reaction pressure of normal pressure and the volume space velocity of acetylene of 75h-1The catalyst load was 2.4g, the volume flow ratio of acetylene to hydrogen chloride gas was 1:1.1, the selectivity of vinyl chloride was maintained at 99% or more, the curve of change in catalyst conversion with reaction time over 90 hours is shown in fig. 2, the initial conversion of the catalyst was 74.0%, and the conversion of the catalyst after 90 hours was 83.68%, indicating that the catalyst had high activity stability.
TABLE 1 comparison of catalyst Performance before and after introduction of stabilizer
Figure BDA0001260479610000081
TABLE 2 Properties of the catalysts after introduction of the stabilizers
Figure BDA0001260479610000082

Claims (6)

1. The copper-based catalyst for the hydrochlorination of acetylene has high activity stability, and copper salt is used as an active component; the copper salt is selected from one or more of copper chloride, copper nitrate, copper sulfate and copper phosphate, and is characterized in that a stabilizer is introduced into a copper-based catalyst; the stabilizer is selected from one or more of tetramethylethylenediamine hydrochloride, tetramethylammonium chloride, tetraethylammonium chloride, trimethylbenzylammonium chloride and triethylbenzylammonium chloride.
2. The catalyst according to claim 1, wherein the mass fraction of the stabilizer in the catalyst is 1 to 10 wt%.
3. The catalyst according to claim 1, wherein the mass fraction of the copper element in the catalyst is 1 to 15 wt%.
4. The catalyst according to claim 1, wherein the copper-based catalyst is supported by activated carbon, and the activated carbon is selected from one or more of coconut shell carbon, wood carbon and coal carbon.
5. The catalyst according to claim 4, wherein the particle size of the activated carbon is 30 to 200 mesh and the specific surface area is 200 to 1200m2A density of 300 to 1000kg/m3The pore volume is 0.4 to 0.8 mL/g.
6. Use of the catalyst of any one of claims 1 to 5 in the hydrochlorination of acetylene.
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CN109847802A (en) * 2019-02-13 2019-06-07 石河子大学 A kind of Au hetero atom composition catalyst and its preparation method and application for acetylene hydrochlorination reaction
CN110694653A (en) * 2019-10-23 2020-01-17 那珊 Catalyst for vinyl chloride synthesis and preparation method and application thereof
CN112961027B (en) * 2021-02-24 2023-08-01 石河子大学 Insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof
CN115945216A (en) * 2022-09-01 2023-04-11 贵州重力科技环保股份有限公司 Copper-tetramethylguanidine hydrochloride catalyst for hydrochlorination of acetylene, preparation method and application
CN115430425B (en) * 2022-09-21 2023-09-19 清华大学 High-stability copper-based catalyst for catalyzing hydrochlorination of acetylene, preparation and application thereof

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CN104549522B (en) * 2013-10-16 2018-04-27 阳永荣 A kind of non-mercury catalyst and application method for acetylene hydrochlorination preparing chloroethylene
CN104326865B (en) * 2014-10-11 2016-03-23 中国科学院上海高等研究院 A kind of catalyzing acetylene ethylene dichloride prepares the method for vinylchlorid
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