CN110743615A - Multi-component metal catalyst for synthesizing vinyl chloride monomer and preparation method thereof - Google Patents

Multi-component metal catalyst for synthesizing vinyl chloride monomer and preparation method thereof Download PDF

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CN110743615A
CN110743615A CN201910940506.3A CN201910940506A CN110743615A CN 110743615 A CN110743615 A CN 110743615A CN 201910940506 A CN201910940506 A CN 201910940506A CN 110743615 A CN110743615 A CN 110743615A
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radical
metal
ionic liquid
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chloride
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CN110743615B (en
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李小年
赵佳
卢春山
许孝良
岳玉学
金春晓
王赛赛
方正
陆金跃
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Zhejiang University of Technology ZJUT
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Abstract

The invention provides a multi-component metal catalyst for synthesizing vinyl chloride monomer and a preparation method thereof, which fundamentally solves the defects of low gas metal dispersibility and low mass transfer in a supported ionic liquid catalyst system; the ionic liquid in the catalyst is stabilized on the surface of the carrier through silicon hydroxyl and is not easy to flow out of the surface of the carrier, the metal is stabilized on the outer surface layer of the catalyst in a form of coordination with the ionic liquid, the influence of mass transfer is reduced, and meanwhile, the dispersion degree of the metal is improved.

Description

Multi-component metal catalyst for synthesizing vinyl chloride monomer and preparation method thereof
(I) technical field
The invention relates to a multi-component metal catalyst for synthesizing vinyl chloride monomer and a preparation method thereof.
(II) background of the invention
Chloroethylene is a monomer of polyvinyl chloride (PVC) which is one of five synthetic resins in the world, and is mainly produced by a calcium carbide acetylene method and a petroleum ethylene method. The existence of energy sources rich in coal, lean oil and little gas in China determines that the calcium carbide acetylene method will continue to be the main process for producing vinyl chloride in China in a long time in the future, namely mercury chloride catalyzes the reaction of acetylene and hydrogen chloride to generate vinyl chloride. However, highly toxic mercuric chloride catalysts severely pollute the environment and harm human health. Therefore, the development of the non-mercury catalyst is necessary for the sustainable development of the industry for synthesizing vinyl chloride by the acetylene method of calcium carbide.
Gold, ruthenium, rhodium, copper catalysts are considered as potential substitutes for non-mercury catalysts in the industry of preparing vinyl chloride by the calcium carbide process. The metal-based catalyst loaded with ionic liquid is widely applied to the process for preparing vinyl chloride by acetylene hydrochlorination. For example, Chinese patent CN 104703953A discloses a method for loading ionic liquid and metal on solid and applying the ionic liquid and metal to hydrochlorination of acetylene, wherein the selected solid carrier has a specific surface area of more than 0.1m2The solid has a pore volume of more than 0.02mL/g, the cation of the selected ionic liquid is an imidazolium cation, a pyridinium cation or a pyrrolidinium cation, the anion can be any anion, and the selected metal is mainly noble metal represented by Au and Pd. In this patent application, the metal is dispersed in the ionic liquid layer, and although the catalytic activity is high, the evaluation results show that the acetylene conversion rate after 500 hours of reaction is only about 60%. Chinese patent CN 104936933A discloses a preparation method of a catalyst. In this patent application, the metal is first anchored to the carbon support surface and then the metal surface is covered with a layer of ionic liquid. However, the catalyst has short catalytic life and no industrial application example.
In summary, the metal agglomeration caused by the metal dispersed in the ionic liquid layer (fig. 1a) and the metal dispersion and mass transfer caused by the metal anchored on the surface of the carbon carrier and the ionic liquid layer (fig. 1b) loaded in the ionic liquid-loaded metal-based catalyst system may be important reasons for the poor catalytic life of the two ionic liquid-loaded metal-based catalyst systems. Chinese patent CN 104936933A emphasizes that the metal is dispersed in the ionic liquid layer (fig. 1a) or the surface of the support (fig. 1b) mainly because both the ionic liquid layer and the metal are physically bound to the support without any chemical linkage.
In the present patent application, a new preparation strategy of supported ionic liquid catalyst systems is proposed. The metal active center is enriched to the outer surface of the catalyst, namely the ionic liquid outer surface layer (figure 2), in a chemical bond mode under the action of an external static electric field, so that the influence of substrate transmission on the catalytic performance is remarkably reduced, and meanwhile, the dispersion degree of metal in the ionic liquid layer is improved in a mode of chemical coordination of the metal active center and the ionic liquid of the surface layer. The method has potential application value in the process of producing vinyl chloride by the calcium carbide method.
Disclosure of the invention
The invention aims to provide a multi-component metal catalyst for synthesizing vinyl chloride monomer and a preparation method thereof, which fundamentally solve the defects of low gas metal dispersibility and low mass transfer in a supported ionic liquid catalyst system.
The technical scheme of the invention is as follows:
a multi-component metal catalyst is prepared by the following method:
(1) dissolving a metal additive in a solvent, and uniformly stirring to obtain a metal additive solution;
the metal promoter may be designated as MsXsWherein M issIs a metal cation selected from one or more of lithium, sodium, potassium, aluminum, zinc, calcium, zirconium, barium and iron cobalt, and XsIs a non-metal anion selected from one or more of nitrate radical, sulfate radical, chlorine, bromine, dicyandiamide radical, thiosulfate radical, sulfite radical, pyrrolidone radical, pyridine radical, ammonium radical, phosphate radical, pyrophosphate radical, triphenylphosphine, poly-phthalocyanine radical, thiophenol, phthalocyanine, dichloro (1, 10-phenanthroline) radical and acetyl pyruvic acid;
the solvent is one or a mixed solvent of more than two of toluene, nitrogen-nitrogen dimethylformamide, nitrogen alkyl pyrrolidone, thionyl chloride and acetone in any proportion;
the volume dosage of the solvent is 0.5-10 mL/g based on the mass of the metal auxiliary agent;
(2) dispersing a carrier in the metal auxiliary solution obtained in the step (1), adding dimethyldichlorosilane and triethylamine, stirring for 0.5-3 h under the protection of inert gas (such as nitrogen) at 50-70 ℃, filtering, washing, and drying (180 ℃) to obtain a solid product;
the carrier is one or a mixture of more than two of zirconium boride, silicon boride, titanium boride and tungsten boride in any proportion;
the mass ratio of the metal elements contained in the metal auxiliary agent to the carrier is 0.1-10: 100, under the operation of the step, the metal elements can be regarded as full load;
the mass ratio of the carrier to the dimethyldichlorosilane to the triethylamine is 100: 1-7: 2-8;
(3) dissolving ionic liquid in a solvent, uniformly stirring, adding the solid product obtained in the step (2), soaking for 2-10h, and drying (180 ℃) to obtain an ionic liquid loaded solid product;
the mass ratio of the ionic liquid to the carrier is 1-20: 100, under this step of operation, the ionic liquid can be considered as being fully loaded;
the solvent used in the step is the same as the solvent in the step (1), and the volume consumption of the solvent in the step is 5-100 mL/g based on the mass of the ionic liquid;
the ionic liquid is selected from one or a mixture of more than two of the following formulas (I) to (V) in any proportion;
Figure BDA0002222732840000021
in the formula (I), the compound is shown in the specification,
R1is H, CH3Or C2H5；
R2Is CnH2n+1Sulfur, oxygen or nitrogen atoms, n is an integer and n is more than or equal to 1 and less than or equal to 14;
R3is CkH2k+1K is an integer and is not less than 1 and not more than 4;
X-is chloride ion, bromide ion, hexafluorophosphate radical, tetrafluorophosphate radical, bis (trifluoromethanesulfonyl) imide radical, tetrafluoroborate radical or imide radical;
Figure BDA0002222732840000022
in the formula (II), the compound is shown in the specification,
R1、R2、R3、R4each independently is CnH2n+1Sulfur, oxygen or nitrogen atoms, n is an integer and n is more than or equal to 1 and less than or equal to 6;
X-is chloride ion, bromide ion, hexafluorophosphate radical, tetrafluorophosphate radical, bis (trifluoromethanesulfonyl) imide radical, tetrafluoroborate radical or imide radical;
in the formula (III), the compound represented by the formula (III),
R1、R2、R3、R4each independently is CnH2n+1Sulfur, oxygen or nitrogen atoms, n is an integer and n is more than or equal to 1 and less than or equal to 6;
X-is chloride ion, bromide ion, hexafluorophosphate radical, tetrafluorophosphate radical, bis (trifluoromethanesulfonyl) imide radical, tetrafluoroborate radical or imide radical;
Figure BDA0002222732840000024
in the formula (IV), the compound is shown in the specification,
R1、R2each independently is CnH2n+1N is an integer and n is not less than 1 and not more than 6;
R3is CnH2n+1Sulfur, oxygen or nitrogen atoms, n is an integer and n is more than or equal to 1 and less than or equal to 6;
X-is chloride ion, bromide ion, hexafluorophosphate radical, tetrafluorophosphate radical, trifluoromethanesulfonimide radical, tetrafluoroborate radical or iminate radical;
Figure BDA0002222732840000031
in the formula (V), the compound represented by the formula (V),
R1、R2each independently is CnH2n+1N is an integer and n is not less than 1 and not more than 6;
R3is CnH2n+1Sulfur, oxygen or nitrogen atoms, n is an integer and n is more than or equal to 1 and less than or equal to 6;
X-is chloride ion, bromide ion, hexafluorophosphate radical, tetrafluorophosphate radical, bis (trifluoromethanesulfonyl) imide radical, tetrafluoroborate radical or imide radical;
preferably, the ionic liquid is selected from one of the following:
the mass ratio of the 1-butyl-3-methylimidazole chloride salt to the 1-propyl-3-butylimidazole tetrafluorophosphate salt is 1: 4;
the mass ratio of 1-butyl-3-methylimidazole hexafluorophosphate to azomethylpyrrolidone hydrochloride is 3: 7;
the mass ratio of 1-butyl-2, 3-dimethyl imidazole tetrafluorophosphate to N-amyl-ethyl piperidine chloride salt is 1: 1;
the mass ratio of the triphenylphosphine bistrifluoromethanesulfonimide salt to the triphenylphosphine ethyl bromide is 3: 1;
the mass ratio of the 1-butyl-3-methylimidazole chloride salt to the triphenyl ethyl phosphine bromide is 1: 1;
the mass ratio of the 1-propyl-2, 3-dimethyl imidazole bis (trifluoromethyl) sulfonyl imide salt to the 1-propyl-3-butyl imidazole tetrafluoro phosphate salt is 1: 1;
(4) dissolving metal salt in a solvent, uniformly stirring, adding the ionic liquid loaded solid product obtained in the step (3), soaking in an external static electric field for 2-8 h, and then drying (180 ℃) for later use;
the mass ratio of metal elements contained in the metal salt to the carrier is 0.05-20: 100, under the operation of the step, the metal elements can be regarded as full load;
the solvent used in the step is the same as the solvent in the step (1), and the volume consumption of the solvent in the step is 0.5-10 mL/g based on the mass of the metal salt;
the metal salt can be recorded as MX, wherein M is a metal cation and is selected from one or more of gold, ruthenium, rhodium and copper, and X is a non-metal anion and is selected from one or more of nitrate, sulfate, chlorine, bromine, dicyandiamide radical, thiosulfate radical, sulfite radical, pyrrolidone radical, pyridine radical, ammonium radical, phosphate radical, pyrophosphate radical, triphenylphosphine, poly phthalocyanine radical, thiophenol, phthalocyanine, dichloro (1, 10-phenanthroline) radical and acetyl pyruvic acid;
the voltage of the external static electric field is 0.2-4 kV;
(5) dispersing the product obtained in the step (4) in a mixed solution of a solvent and dimethyldichlorosilane, then placing the mixture on a rotary mixer for rotary treatment at 40-60 ℃ for 10-14 h, then soaking the mixture in an external static electric field for 2-4 h, and drying the mixture in a specific atmosphere (the drying temperature is 180 ℃) to obtain the multi-component metal catalyst;
in the mixed solution of the solvent and the dimethyldichlorosilane, the used solvent is the same as the solvent in the step (1), and the ratio of the solvent to the dimethyldichlorosilane is 50-100: 1 (mL: g);
the volume usage of the mixed solution of the solvent and the dimethyldichlorosilane is 20-60 mL/g based on the mass of the product obtained in the step (4);
the specific atmosphere can be selected from one or a mixture of several of nitrogen, argon, air, oxygen, hydrogen, acetylene, hydrogen chloride, methane, oxygen and chlorine;
the voltage of the external static electric field is 0.2-4 kV.
The multi-component metal catalyst prepared by the invention can be applied to the reaction of synthesizing chloroethylene by a calcium carbide method.
Specifically, the application method comprises the following steps:
the prepared catalyst is filled in a fixed bed reactor, the reaction temperature is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and raw material gases HCl and C are introduced2H2Then vinyl chloride can be obtained through reaction;
further, the raw material gases HCl and C2H2The ratio of the amounts of substances n (HCl)/n (C)2H2) 0.9-1.2/1; the volume space velocity of acetylene is 10-100 h-1。
The catalyst of the invention has high stability in the reaction of synthesizing chloroethylene, and does not show the phenomenon of catalyst deactivation after running for 2000 hours for a long time.
Compared with the prior art, the invention has the following advantages:
1. specificity of the vector. The preparation method provided by the invention has the advantages of higher metal dispersion effect, higher catalytic activity and better stability in the carrier.
2. The stability mechanism of ionic liquid on the surface of the carrier is different. The ionic liquid is stabilized on the surface of the carrier through silicon hydroxyl (Si-OH), and by adopting the preparation method, the ionic liquid has higher stability and is not easy to flow out of the surface of the carrier.
3. The metal active centers are present in different positions. In the publicly reported literature and patents, metals are dispersed in the center of the ionic liquid (fig. 1a) or anchored. The metal in the application is stabilized on the outer surface layer of the catalyst (figure 2) in a form of coordination with the ionic liquid, so that the influence of mass transfer is reduced, and meanwhile, the dispersion degree of the metal is improved.
4. The external static electric field is introduced into the preparation of the metal-based catalyst loaded with the ionic liquid for the first time, so that the enrichment of metal active centers on the surface layer of the ionic liquid is promoted.
5. The induction period was eliminated. Because the active center of the catalyst metal is distributed on the surface layer of the ionic liquid, the influence of substrate diffusion is reduced, and the induction period of the catalyst disappears under the evaluated reaction condition. The induction period of the catalyst in the publicly reported literature and patent is 2-10 h.
(IV) description of the drawings
FIG. 1: schematic diagram of the ionic liquid supported metal-based catalyst system in the published patent: a) the metal is dispersed in the middle of the ionic liquid layer; b) the metal is distributed on the surface of the catalyst carrier;
FIG. 2: the invention discloses a schematic diagram of a metal-based catalyst system for loading ionic liquid.
(V) detailed description of the preferred embodiments
The present invention will be described with reference to specific examples. It should be noted that the examples are only intended to illustrate the invention further, but should not be construed as limiting the scope of the invention, which is in no way limited thereto. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.
In the following examples, zirconium boride is obtained from Shanghai Chaowei nanometer, and the specific surface area is 500-1000 m2g-1(ii) a The silicon boride is purchased from Liaoning Medium-color New Material science and technology Limited company, and the specific surface area is 500-100 m2g-1(ii) a Titanium boride is purchased from Shanghai super-Wei nanometer, and the specific surface area is 200-800 m2g-1(ii) a Technology for preparing new material with middle color from Liaoning tungsten borideLimited company, specific surface area 500-1000 m2g-1。
The rotometer manufacturer is a New Ganoderma organism, DH-II.
Example 1
Preparation of the catalyst:
1) 0.13g of metal additive sodium chloride is selected and dissolved in 1.3mL of toluene and stirred until the metal additive sodium chloride is completely dissolved, and a solution of the metal additive is obtained for later use.
2) Selecting 10g of zirconium boride as a carrier, dispersing the zirconium boride in the solution obtained in the step 1), stirring for 30min, and adding 0.1g of dimethyldichlorosilane and 0.8g of triethylamine. The mixture was heat treated under nitrogen at 50 ℃ for 3 hours. And then filtering, washing a filter cake by using toluene and ethanol, and drying at 180 ℃ to obtain a solid sample for later use. The mass loading of sodium element is 0.5%.
3) Dissolving 0.02g of 1-butyl-3-methylimidazole chloride salt and 0.08g of 1-propyl-3-butylimidazolium hexafluorophosphate ionic liquid in 10mL of toluene, stirring uniformly, adding the solid sample obtained in the step 2), soaking for 2h, and drying at 180 ℃ for later use. Wherein the mass loading of the ionic liquid is 1%.
4) Dissolving 0.009g chloroauric acid in 0.09mL toluene, stirring uniformly, adding the sample obtained in the step 3), immersing in an external 0.2kV static electric field for 2h, and drying at 180 ℃ for later use. Wherein the mass loading of the gold element is 0.05 percent.
5) 11.14g of the solid sample obtained above was redispersed in 668.4mL of a mixed solution of toluene and 6.68g of dimethyldichlorosilane. And the mixture obtained above was subjected to a spinning treatment for 12h at 50 ℃ on a spinner. And then dipping the catalyst in an externally-added 3.6kV static electric field for 3h, and drying the catalyst at 180 ℃ in a nitrogen atmosphere to obtain the required solid catalyst.
Evaluation of catalyst Performance:
1.5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 100 ℃, the pressure is 0.1MPa, and the mass ratio of the raw material gas substances n (HCl)/n (C)2H2) 0.9/1, and the space velocity of acetylene volume is 50h-1Under the conditions of (a) under (b),the induction period is 0h, and after 2000h of reaction, the acetylene conversion rate is 97 percent and the chloroethylene selectivity is 99.5 percent.
Example 2
Preparation of the catalyst:
1) selecting 0.03g of metal auxiliary agent barium chloride, dissolving the metal auxiliary agent barium chloride in 0.24mL of nitrogen-nitrogen dimethyl formamide, and stirring until the metal auxiliary agent barium chloride is completely dissolved to obtain a metal auxiliary agent solution for later use.
2) Selecting 10g of silicon boride as a carrier, dispersing the carrier in the solution obtained in the step 1), stirring for 60min, and adding 0.3g of dimethyldichlorosilane and 0.6g of triethylamine. The mixture was heat treated under nitrogen at 55 ℃ for 3 hours. And then filtering, washing a filter cake by using toluene and ethanol, and drying at 180 ℃ to obtain a solid sample for later use. The mass loading of barium element was 0.2%.
3) 0.6g of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid and 1.4g of azomethylpyrrolidone hydrochloride ionic liquid are dissolved in 10mL of azodicarbonamide, and after uniform stirring, the solid sample obtained in the step 2) is added, soaked for 4h and dried at 180 ℃ for later use. Wherein the mass loading of the ionic liquid is 20%.
4) Dissolving 4.23g of copper chloride in 2.12mL of nitrogen-nitrogen dimethylformamide, stirring uniformly, adding the sample obtained in the step 3), soaking in an external 4kV static electric field for 4 hours, and drying at 180 ℃ for later use. Wherein the mass loading of the copper element is 20 percent.
5) 17.16g of the solid sample obtained above was redispersed in 343.2mL of a mixed solution of N-dimethylformamide and 6.86g of dimethyldichlorosilane. And the mixture obtained above was subjected to a spinning treatment for 12h at 50 ℃ on a spinner. And then soaking in an additional 4kV static electric field for 2h, and drying at 180 ℃ in an argon atmosphere to obtain the required solid catalyst.
Evaluation of catalyst Performance:
4.5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 100 ℃, the pressure is 0.1MPa, and the mass ratio of the raw material gas substances n (HCl)/n (C)2H2) 1.0/1, acetylene volume space velocity of 10h-1Under the condition of (1), the induction period is 0h, and after the reaction is 2000h, the acetylene conversion rate is 94% and the vinyl chloride selectivity is 99.5%.
Example 3
Preparation of the catalyst:
1) 1.67g of metal additive zinc chloride is selected and dissolved in 8.4mL of acetone and stirred until the metal additive is completely dissolved, so as to obtain a solution of the metal additive for later use.
2) Selecting 10g of titanium boride as a carrier, dispersing the carrier in the solution obtained in the step 1), stirring for 90min, and adding 0.5g of dimethyldichlorosilane and 0.4g of triethylamine. The mixture was heat treated under nitrogen at 60 ℃ for 3 hours. And then filtering, washing a filter cake by using acetone and ethanol, and drying at 180 ℃ to obtain a solid sample for later use. The mass loading of the zinc element is 8 percent.
3) Dissolving 0.5g of 1-butyl-3-methylimidazolium hexafluorophosphate and 0.5g N-amyl-ethylpiperidine chloride in 20mL of acetone, stirring uniformly, adding the solid sample obtained in the step 2), soaking for 6h, and drying at 180 ℃ for later use. Wherein the mass loading of the ionic liquid is 10%.
4) Dissolving 0.2g of rhodium chloride in 1mL of acetone, stirring uniformly, adding the sample obtained in the step 3), soaking in an external 0.5kV static electric field for 8 hours, and drying at 180 ℃ for later use. Wherein the mass loading of rhodium element is 1.0%.
5) 13.8g of the solid sample obtained above was redispersed in 414mL of a mixed solution of acetone and 6.9g of dimethyldichlorosilane. And the mixture obtained above was subjected to a spinning treatment for 12h at 60 ℃ on a spinner. And then soaking in an externally-added 3.2kV static electric field for 4h, and drying at 180 ℃ in a nitrogen and air atmosphere to obtain the required solid catalyst.
Evaluation of catalyst Performance:
the catalyst 3.0g is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 100 ℃, the pressure is 0.1MPa, and the mass ratio of the raw material gas substances n (HCl)/n (C)2H2) 1.1/1, acetylene volume space velocity of 100h-1Under the condition of (1), the induction period is 0h, and after the reaction time is 2000h, the acetylene conversion rate is 96 percentThe selectivity to vinyl chloride was 98.5%.
Example 4
Preparation of the catalyst:
1) selecting 0.73g of metal auxiliary agent ferric chloride, dissolving the metal auxiliary agent ferric chloride in 4.4mL of thionyl chloride, and stirring until the metal auxiliary agent ferric chloride is completely dissolved to obtain a solution of the metal auxiliary agent for later use.
2) Selecting 10g of tungsten boride as a carrier, dispersing the tungsten boride into the solution obtained in the step 1), stirring for 120min, and adding 0.7g of dimethyldichlorosilane and 0.3g of triethylamine. The mixture was heat treated under nitrogen at 65 ℃ for 3 hours. And then filtering, washing a filter cake by using thionyl chloride and ethanol, and drying at 180 ℃ to obtain a solid sample for later use. The mass loading of the iron element is 2.5%.
3) Dissolving 0.6g of triphenylphosphine bistrifluoromethanesulfonimide salt and 0.2g of triphenylphosphine ethylbromide in 10mL of thionyl chloride, stirring uniformly, adding the solid sample obtained in the step 2), soaking for 10h, and drying at 180 ℃ for later use. Wherein the mass loading of the ionic liquid is 8%.
4) Dissolving 0.103g of ruthenium chloride in 0.5mL of thionyl chloride, stirring uniformly, adding the sample obtained in the step 3), soaking in an externally-applied 0.9kV static electric field for 3.5h, and drying at 180 ℃ for later use. Wherein the mass loading of the ruthenium element is 0.5 percent.
5) A12.63 g portion of the solid sample obtained above was redispersed in 315.8mL of a mixed solution of thionyl chloride and 4.86g of dimethyldichlorosilane. And the mixture obtained above was subjected to a spinning treatment for 10h at 40 ℃ on a spinner. And then dipping the catalyst in an additional 2.1kV static electric field for 2h, and drying the catalyst at 180 ℃ in a hydrogen atmosphere to obtain the required solid catalyst.
Evaluation of catalyst Performance:
1.6g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 100 ℃, the pressure is 0.1MPa, and the mass ratio of the raw material gas substances n (HCl)/n (C)2H2) 1.2/1, acetylene volume space velocity of 80h-1Under the condition of (1), the induction period is 0h, and after the reaction is 2000h, the acetylene conversion rate is 99.3 percent and the chloroethylene selectivity is 98.5 percent.
Example 5
Preparation of the catalyst:
1) 0.49g of metal auxiliary agent aluminum chloride is selected and dissolved in 4.4mL of nitrogen methyl pyrrolidone, and the mixture is stirred until the metal auxiliary agent aluminum chloride is completely dissolved to obtain a solution of the metal auxiliary agent for later use.
2) Selecting 10g of zirconium boride as a carrier, dispersing the zirconium boride in the solution obtained in the step 1), stirring for 180min, and adding 0.6g of dimethyldichlorosilane and 0.2g of triethylamine. The mixture was heat treated under nitrogen at 70 ℃ for 3 hours. And then filtering, washing a filter cake with ethanol, and drying at 180 ℃ to obtain a solid sample for later use. The mass loading of the aluminum element is 1%.
3) 0.5g of 1-butyl-3-methylimidazolium chloride salt and 0.5g of triphenyl ethyl phosphine bromide are dissolved in 5mL of nitrogen methyl pyrrolidone, and after uniform stirring, the solid sample obtained in the step 2) is added, soaked for 10h and dried at 180 ℃ for later use. Wherein the mass loading of the ionic liquid is 10%.
4) 4.53g of copper phthalocyanine is dissolved in 9.1mL of azomethyl pyrrolidone, the mixture is uniformly stirred and then added into the sample obtained in the step 3), and the sample is immersed in an external 3.6kV static electric field for 3 hours and then dried at 180 ℃ for standby. Wherein the mass loading of the copper element is 5 percent.
5) A16.82 g portion of the solid sample obtained above was redispersed in 420.5mL of a mixed solution of N-methylpyrrolidone and 5.26g of dimethyldichlorosilane. And the mixture obtained above was subjected to a spinning treatment for 14h at 60 ℃ on a spinner. And then dipping the catalyst in an additional 2.8kV static electric field for 4h, and drying the catalyst at 180 ℃ in an acetylene atmosphere to obtain the required solid catalyst.
Evaluation of catalyst Performance:
the catalyst 3.0g is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 100 ℃, the pressure is 0.1MPa, and the mass ratio of the raw material gas substances n (HCl)/n (C)2H2) 0.9/1, and the acetylene volume space velocity is 20h-1Under the condition of (1), the induction period is 0h, and after the reaction is 2000h, the acetylene conversion rate is 98 percent and the chloroethylene selectivity is 99.5 percent.
Example 6
Preparation of the catalyst:
1) 2.58g of metal assistant calcium phosphate is selected and dissolved in 15.5mL of acetone, and the mixture is stirred until the metal assistant calcium phosphate is completely dissolved to obtain a metal assistant solution for later use.
2) Selecting 10g of silicon boride as a carrier, dispersing the carrier in the solution obtained in the step 1), stirring for 30min, and adding 0.4g of dimethyldichlorosilane and 0.2g of triethylamine. The mixture was heat treated under nitrogen at 60 ℃ for 3 hours. And then filtering, washing a filter cake by using acetone and ethanol, and drying at 180 ℃ to obtain a solid sample for later use. The mass loading of the calcium element is 10%.
3) Dissolving 1g of propyl-2, 3-dimethyl imidazole bis (trifluoromethanesulfonimide) salt and 0.7g of 1-propyl-3-butyl imidazole tetrafluorophosphate salt in 10mL of acetone, stirring uniformly, adding the solid sample obtained in the step 2), soaking for 2h, and drying at 180 ℃ for later use. Wherein the mass loading of the ionic liquid is 14%.
4) Dissolving 2.0g of copper phosphate in 12mL of acetone, stirring uniformly, adding the sample obtained in the step 3), soaking in an external 0.2kV static electric field for 2 hours, and drying at 180 ℃ for later use. Wherein the mass loading of the copper element is 10 percent.
5) A16.58 g portion of the solid sample obtained above was redispersed in 497.4mL of a mixed solution of acetone and 5.85g of dimethyldichlorosilane. And the mixture obtained above was subjected to a spinning treatment for 10h at 40 ℃ on a spinner. And then soaking in an external 04kV static electric field for 3h, and drying at 180 ℃ in hydrogen chloride atmosphere to obtain the required solid catalyst.
Evaluation of catalyst Performance:
1.5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 100 ℃, the pressure is 0.1MPa, and the mass ratio of the raw material gas substances n (HCl)/n (C)2H2) 1.0/1, acetylene volume space velocity of 30h-1Under the condition of (1), the induction period is 0h, and after 2000h of reaction, the acetylene conversion rate is 98% and the vinyl chloride selectivity is 97.5%.
Comparative example 1
This comparative example investigated the effect of metal dispersion in the ionic liquid layer on catalytic performance by comparison with example 1.
Preparation of the catalyst:
0.02g of 1-butyl-3-methylimidazole chloride salt and 0.08g of 1-propyl-3-butylimidazole hexafluorophosphate ionic liquid are dissolved in 20mL of deionized water solution, 10g of zirconium boride is added, and after uniform stirring, a chloroauric acid solution with a certain content is added. After dipping for 3h, drying at 110 ℃ for standby. Wherein the mass loading amounts of the gold element and the ionic liquid are respectively 0.05 percent and 1 percent.
Evaluation of catalyst Performance:
the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 140 ℃, the pressure is 0.3MPa, and the mass ratio of the raw material gas substances n (HCl)/n (C)2H2) 1.2/1, acetylene volume space velocity of 50h-1Under the condition of (1), the induction period is 3h, and after 2000h of reaction, the acetylene conversion rate is 77 percent and the vinyl chloride selectivity is 98.9 percent.
Comparative example 2
This comparative example studies the effect of metal anchoring to the support surface and then covering with a layer of ionic liquid on the catalytic performance by comparison with example 1.
10g of zirconium boride is taken and added into a chloroauric acid solution with a certain content. After dipping for 3h, drying at 110 ℃ for standby. Wherein the mass loading of the gold element is 0.05 percent. To the dried ready-to-use product, 0.02g of 1-butyl-3-methylimidazolium chloride, 0.08g of 1-propyl-3-butylimidazolium hexafluorophosphate ionic liquid and 20mL of deionized water were added. After being stirred evenly, the mixture is dried for standby at the temperature of 110 ℃. Wherein the mass loading amounts of the gold element and the ionic liquid are respectively 0.05 percent and 1 percent.
Evaluation of catalyst Performance:
the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 140 ℃, the pressure is 0.3MPa, and the mass ratio of the raw material gas substances n (HCl)/n (C)2H2) 1.2/1, acetylene volume space velocity of 50h-1Under the condition of (1), the induction period is 10h, and the acetylene conversion rate is 61 percent after the reaction is 2000hThe selectivity to vinyl chloride was 99.1%.

Claims (10)

1. A multi-component metal catalyst is characterized by being prepared by the following method:
(1) dissolving a metal additive in a solvent, and uniformly stirring to obtain a metal additive solution;
the metal promoter may be designated as MsXsWherein M issIs a metal cation selected from one or more of lithium, sodium, potassium, aluminum, zinc, calcium, zirconium, barium and iron cobalt, and XsIs a non-metal anion selected from one or more of nitrate radical, sulfate radical, chlorine, bromine, dicyandiamide radical, thiosulfate radical, sulfite radical, pyrrolidone radical, pyridine radical, ammonium radical, phosphate radical, pyrophosphate radical, triphenylphosphine, poly-phthalocyanine radical, thiophenol, phthalocyanine, dichloro (1, 10-phenanthroline) radical and acetyl pyruvic acid;
(2) dispersing a carrier in the metal auxiliary solution obtained in the step (1), adding dimethyldichlorosilane and triethylamine, stirring for 0.5-3 h under the protection of inert gas at 50-70 ℃, and then filtering, washing and drying to obtain a solid product;
the carrier is one or a mixture of more than two of zirconium boride, silicon boride, titanium boride and tungsten boride in any proportion;
the mass ratio of the metal elements contained in the metal auxiliary agent to the carrier is 0.1-10: 100, respectively;
the mass ratio of the carrier to the dimethyldichlorosilane to the triethylamine is 100: 1-7: 2-8;
(3) dissolving ionic liquid in a solvent, uniformly stirring, adding the solid product obtained in the step (2), soaking for 2-10 hours, and drying to obtain an ionic liquid loaded solid product;
the mass ratio of the ionic liquid to the carrier is 1-20: 100, respectively;
the ionic liquid is selected from one or a mixture of more than two of the following formulas (I) to (V) in any proportion;
Figure FDA0002222732830000011
in the formula (I), the compound is shown in the specification,
R1is H, CH3Or C2H5；
R2Is CnH2n+1Sulfur, oxygen or nitrogen atoms, n is an integer and n is more than or equal to 1 and less than or equal to 14;
R3is CkH2k+1K is an integer and is not less than 1 and not more than 4;
X-is chloride ion, bromide ion, hexafluorophosphate radical, tetrafluorophosphate radical, bis (trifluoromethanesulfonyl) imide radical, tetrafluoroborate radical or imide radical;
in the formula (II), the compound is shown in the specification,
R1、R2、R3、R4each independently is CnH2n+1Sulfur, oxygen or nitrogen atoms, n is an integer and n is more than or equal to 1 and less than or equal to 6;
X-is chloride ion, bromide ion, hexafluorophosphate radical, tetrafluorophosphate radical, bis (trifluoromethanesulfonyl) imide radical, tetrafluoroborate radical or imide radical;
Figure FDA0002222732830000013
in the formula (III), the compound represented by the formula (III),
R1、R2、R3、R4each independently is CnH2n+1Sulfur, oxygen or nitrogen atoms, n is an integer and n is more than or equal to 1 and less than or equal to 6;
X-is chloride ion, bromide ion, hexafluorophosphate radical, tetrafluorophosphate radical, bis (trifluoromethanesulfonyl) imide radical, tetrafluoroborate radical or imide radical;
Figure FDA0002222732830000021
in the formula (IV), the compound is shown in the specification,
R1、R2each independently is CnH2n+1N is an integer and n is not less than 1 and not more than 6;
R3is CnH2n+1Sulfur, oxygen or nitrogen atoms, n is an integer and n is more than or equal to 1 and less than or equal to 6;
X-is chloride ion, bromide ion, hexafluorophosphate radical, tetrafluorophosphate radical, trifluoromethanesulfonimide radical, tetrafluoroborate radical or iminate radical;
Figure FDA0002222732830000022
in the formula (V), the compound represented by the formula (V),
R1、R2each independently is CnH2n+1N is an integer and n is not less than 1 and not more than 6;
R3is CnH2n+1Sulfur, oxygen or nitrogen atoms, n is an integer and n is more than or equal to 1 and less than or equal to 6;
X-is chloride ion, bromide ion, hexafluorophosphate radical, tetrafluorophosphate radical, bis (trifluoromethanesulfonyl) imide radical, tetrafluoroborate radical or imide radical;
(4) dissolving metal salt in a solvent, uniformly stirring, adding the ionic liquid loaded solid product obtained in the step (3), soaking in an external static electric field for 2-8 hours, and then drying for later use;
the mass ratio of metal elements contained in the metal salt to the carrier is 0.05-20: 100, respectively;
the metal salt can be recorded as MX, wherein M is a metal cation and is selected from one or more of gold, ruthenium, rhodium and copper, and X is a non-metal anion and is selected from one or more of nitrate, sulfate, chlorine, bromine, dicyandiamide radical, thiosulfate radical, sulfite radical, pyrrolidone radical, pyridine radical, ammonium radical, phosphate radical, pyrophosphate radical, triphenylphosphine, poly phthalocyanine radical, thiophenol, phthalocyanine, dichloro (1, 10-phenanthroline) radical and acetyl pyruvic acid;
(5) dispersing the product obtained in the step (4) in a mixed solution of a solvent and dimethyldichlorosilane, then placing the mixture on a rotary mixer for rotary treatment for 10-14 h at 40-60 ℃, then dipping the mixture in an external static electric field for 2-4 h, and drying the mixture in a specific atmosphere to obtain the multi-component metal catalyst;
in the mixed solution of the solvent and the dimethyldichlorosilane, the ratio of the solvent to the dimethyldichlorosilane is 50-100: 1;
the specific atmosphere is selected from one or a mixture of several of nitrogen, argon, air, oxygen, hydrogen, acetylene, hydrogen chloride, methane, oxygen and chlorine.
2. A multicomponent metallic catalyst as in claim 1, wherein in step (1), the solvent is one or a mixture of two or more of toluene, nitrogen-nitrogen dimethylformamide, nitrogen-alkyl pyrrolidone, thionyl chloride and acetone at any ratio, and the solvents used in steps (3), (4) and (5) are the same as those used in step (1).
3. The multi-component metal catalyst according to claim 1, wherein in the step (1), the volume usage amount of the solvent is 0.5 to 10mL/g based on the mass of the metal promoter.
4. The multi-component metal catalyst according to claim 1, wherein in the step (3), the volume usage amount of the solvent is 5 to 100mL/g based on the mass of the ionic liquid.
5. A multi-component metal catalyst according to claim 1, wherein in step (3), the ionic liquid is selected from one of:
the mass ratio of the 1-butyl-3-methylimidazole chloride salt to the 1-propyl-3-butylimidazole tetrafluorophosphate salt is 1: 4;
the mass ratio of 1-butyl-3-methylimidazole hexafluorophosphate to azomethylpyrrolidone hydrochloride is 3: 7;
the mass ratio of 1-butyl-2, 3-dimethyl imidazole tetrafluorophosphate to N-amyl-ethyl piperidine chloride salt is 1: 1;
the mass ratio of the triphenylphosphine bistrifluoromethanesulfonimide salt to the triphenylphosphine ethyl bromide is 3: 1;
the mass ratio of the 1-butyl-3-methylimidazole chloride salt to the triphenyl ethyl phosphine bromide is 1: 1;
the mass ratio of the 1-propyl-2, 3-dimethyl imidazole bis (trifluoromethyl) sulfonyl imide salt to the 1-propyl-3-butyl imidazole tetrafluoro phosphate salt is 1: 1.
6. The multi-component metal catalyst according to claim 1, wherein in the step (4), the volume usage amount of the solvent is 0.5 to 10mL/g based on the mass of the metal salt.
7. The multi-component metal catalyst according to claim 1, wherein in the step (5), the volume usage of the mixed solution of the solvent and the dimethyldichlorosilane is 20 to 60mL/g based on the mass of the product obtained in the step (4).
8. A multicomponent metallic catalyst according to claim 1, wherein in step (4) or (5), the applied static electric field voltage is 0.2 to 4 kV.
9. The use of the multi-component metal catalyst of claim 1 in the reaction of synthesizing vinyl chloride by the calcium carbide process.
10. The application of claim 9, wherein the method of applying is:
the prepared catalyst is filled in a fixed bed reactor, the reaction temperature is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and raw material gases HCl and C are introduced2H2Then vinyl chloride can be obtained through reaction;
the raw material gases are HCl and C2H2The ratio of the amounts of substances n (HCl)/n (C)2H2) 0.9-1.2/1; the volume space velocity of acetylene is 10-100 h-1。
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CN114146728A (en) * 2021-11-29 2022-03-08 内蒙古鄂尔多斯电力冶金集团股份有限公司 Composite carrier Cu-based acetylene hydrochlorination catalyst and preparation method thereof

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