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CN110743615B - A kind of multi-component metal catalyst for synthesizing vinyl chloride monomer and preparation method thereof - Google Patents

A kind of multi-component metal catalyst for synthesizing vinyl chloride monomer and preparation method thereof Download PDF

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CN110743615B
CN110743615B CN201910940506.3A CN201910940506A CN110743615B CN 110743615 B CN110743615 B CN 110743615B CN 201910940506 A CN201910940506 A CN 201910940506A CN 110743615 B CN110743615 B CN 110743615B
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metal
chloride
ionic liquid
solvent
mixture
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CN110743615A (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

一种用于合成氯乙烯单体的多组分金属催化剂及其制备方法A kind of multi-component metal catalyst for synthesizing vinyl chloride monomer and preparation method thereof

(一)技术领域(1) Technical field

本发明涉及一种用于合成氯乙烯单体的多组分金属催化剂及其制备方法。The invention relates to a multi-component metal catalyst for synthesizing vinyl chloride monomer and a preparation method thereof.

(二)背景技术(2) Background technology

氯乙烯是世界五大合成树脂之一聚氯乙烯(PVC)的单体，主要由电石乙炔法和石油乙烯法工艺生产。中国富煤、贫油、少气的能源赋存决定了将在未来相当长时间内，电石乙炔法将继续是我国氯乙烯生产的主要工艺，即氯化汞催化乙炔和氯化氢反应生成氯乙烯。但是，高毒性氯化汞催化剂严重地污染了环境和危害人体健康。因此，非汞催化剂的开发对于电石乙炔法合成氯乙烯工业可持续发展十分必要。Vinyl chloride is the monomer of polyvinyl chloride (PVC), one of the five major synthetic resins in the world, and is mainly produced by the calcium carbide acetylene method and the petroleum ethylene method. China's coal-rich, oil-poor, and gas-less energy resources determine that for a long time in the future, the calcium carbide acetylene process will continue to be the main process for the production of vinyl chloride in my country, that is, mercury chloride catalyzes the reaction of acetylene and hydrogen chloride to generate vinyl chloride. However, highly toxic mercuric chloride catalysts seriously pollute the environment and endanger human health. Therefore, the development of non-mercury catalysts is necessary for the sustainable development of vinyl chloride synthesis by calcium carbide acetylene method.

金、钌、铑、铜催化剂被认为是电石法制备氯乙烯产业中非汞催化剂的潜在替代者。负载离子液体的金属基催化剂被广泛的应用在乙炔氢氯化法制备氯乙烯工艺中。如中国专利CN104703953 A公开了一种固体负载离子液体和金属并应用于乙炔氢氯化反应的方法，所选用的固体载体为比表面积大于0.1m2/g、孔容大于0.02mL/g的固体，所选择离子液体的阳离子为咪唑鎓阳离子、吡啶鎓阳离子或吡咯烷鎓阳离子，阴离子可以选择任意阴离子，所选择的金属主要是以Au、Pd为代表的贵金属等。该专利申请中，金属分散在离子液体层中，尽管催化活性较高，但是评价结果显示反应500h后乙炔转化率只有60％左右。中国专利CN104936933 A公开了一种催化剂的制备方法。该专利申请中，金属首先锚定在碳载体表面，随后再在金属表面覆盖了一层离子液体层。但是该催化剂催化寿命较短，尚无工业化应用实例。Gold, ruthenium, rhodium, and copper catalysts are considered as potential substitutes for non-mercury catalysts in the production of vinyl chloride by calcium carbide. Metal-based catalysts supported by ionic liquids are widely used in the preparation of vinyl chloride by acetylene hydrochlorination. For example, Chinese patent CN104703953 A discloses a method for solid supporting ionic liquid and metal and applying it to acetylene hydrochlorination. The selected solid carrier is a solid with a specific surface area greater than 0.1m 2 /g and a pore volume greater than 0.02mL/g , the cation of the selected ionic liquid is imidazolium cation, pyridinium cation or pyrrolidinium cation, the anion can be any anion, and the selected metals are mainly noble metals represented by Au and Pd. In this patent application, the metal is dispersed in the ionic liquid layer. Although the catalytic activity is high, the evaluation results show that the acetylene conversion rate is only about 60% after 500 hours of reaction. Chinese patent CN104936933 A discloses a preparation method of a catalyst. In this patent application, the metal is first anchored on the surface of the carbon support, and then the metal surface is covered with an ionic liquid layer. However, the catalytic life of this catalyst is short, and there is no industrial application example.

综上所述，在负载离子液体的金属基催化剂体系中将金属分散在离子液体层中(图1a)所引发的金属团聚以及将金属锚定在碳载体表面再负载离子液体层(图1b)所引发的金属分散及传质的影响可能是导致上述两种负载离子液体的金属基催化剂体系中催化寿命不佳的重要原因。中国专利CN104936933 A强调了金属分散在离子液体层中(图1a)或者载体表面(图1b)主要是因为离子液体层和金属两者以物理吸附的方式限制在载体上，没有任何化学键联。In summary, the metal agglomeration induced by the dispersion of metals in the ionic liquid layer (Fig. 1a) and the anchoring of metals on the carbon support surface and the loading of the ionic liquid layer (Fig. 1b) in the ionic liquid-supported metal-based catalyst system (Fig. 1b) The effect of the induced metal dispersion and mass transfer may be an important reason for the poor catalytic lifetime of the above two metal-based catalyst systems supported by ionic liquids. Chinese patent CN104936933 A emphasizes that the metal is dispersed in the ionic liquid layer (Fig. 1a) or on the surface of the carrier (Fig. 1b) mainly because both the ionic liquid layer and the metal are confined on the carrier by physical adsorption without any chemical bonding.

本专利申请中，提出一种新的负载离子液体催化剂体系制备策略。将金属活性中心在外加静态电场的作用下以化学键的形式富集到催化剂外表面即离子液体外表层(图2)，显著的降低了底物传质对催化性能的影响，同时，通过金属活性中心与表层离子液体化学配位的形式提高了金属在离子液体层中的分散度。在电石法生产氯乙烯工艺中可能具有潜在的应用价值。In this patent application, a new preparation strategy of a supported ionic liquid catalyst system is proposed. The metal active centers are enriched to the outer surface of the catalyst in the form of chemical bonds under the action of an external static electric field, that is, the outer surface of the ionic liquid (Fig. 2), which significantly reduces the influence of substrate mass transfer on the catalytic performance. The form of chemical coordination between the center and the surface ionic liquid improves the dispersion of metals in the ionic liquid layer. It may have potential application value in the process of producing vinyl chloride by calcium carbide method.

(三)发明内容(3) Contents of the invention

本发明的目的是提供一种用于合成氯乙烯单体的多组分金属催化剂及其制备方法，本发明从根本上解决负载离子液体催化剂体系中气体金属分散性不高、传质低的缺点。The purpose of the present invention is to provide a multi-component metal catalyst for synthesizing vinyl chloride monomer and a preparation method thereof, and the present invention fundamentally solves the shortcomings of low gas metal dispersibility and low mass transfer in the supported ionic liquid catalyst system .

本发明的技术方案如下：The technical scheme of the present invention is as follows:

一种多组分金属催化剂，按如下方法制备得到：A multi-component metal catalyst is prepared as follows:

(1)将金属助剂溶于溶剂中，搅拌均匀，得到金属助剂溶液；(1) dissolving the metal auxiliary agent in the solvent, stirring uniformly, to obtain a metal auxiliary agent solution;

所述金属助剂可记作MsXs，其中，Ms为金属阳离子，选自锂、钠、钾、铝、锌、钙、锆、钡、铁钴中的一种或多种混合，Xs为非金属阴离子，选自硝酸根、硫酸根、氯、溴、双氰胺根、硫代硫酸根、亚硫酸根、吡咯烷酮根、吡啶烷酮根、铵根、磷酸根、焦磷酸根、三苯基膦、聚酞菁根、苯硫酚、酞菁、二氯(1,10-菲咯啉)根、乙酰丙酮酸中的一种或多种混合；The metal additive can be denoted as M s X s , wherein, M s is a metal cation, selected from one or more mixtures of lithium, sodium, potassium, aluminum, zinc, calcium, zirconium, barium, iron and cobalt, X s is a non-metal anion selected from nitrate, sulfate, chlorine, bromine, dicyandiamide, thiosulfate, sulfite, pyrrolidone, pyridinone, ammonium, phosphate, pyrophosphate , one or more mixtures of triphenylphosphine, polyphthalocyanine, thiophenol, phthalocyanine, dichloro(1,10-phenanthroline), and acetylacetonate;

所述溶剂为甲苯、氮氮二甲基甲酰胺、氮烷基吡咯烷酮、二氯亚砜、丙酮中的一种或两种以上任意比例的混合溶剂；The solvent is one or more mixed solvents in arbitrary proportions among toluene, nitrogen nitrogen dimethyl formamide, nitrogen alkyl pyrrolidone, thionyl chloride, and acetone;

所述溶剂的体积用量以金属助剂的质量计为0.5～10mL/g；The volume dosage of the solvent is 0.5-10 mL/g in terms of the mass of the metal auxiliary;

(2)将载体分散在步骤(1)得到的金属助剂溶液中，然后加入二甲基二氯硅烷、三乙胺，在惰性气体(例如氮气)保护、50～70℃的条件下搅拌0.5～3h，之后过滤、洗涤、烘干(180℃)，得到固体产物；(2) Disperse the carrier in the metal auxiliary agent solution obtained in step (1), then add dimethyldichlorosilane and triethylamine, and stir under the protection of inert gas (such as nitrogen) at 50-70° C. for 0.5 ~3h, then filtered, washed and dried (180°C) to obtain solid product;

所述载体为硼化锆、硼化硅、硼化钛、硼化钨中的一种或两种以上任意比例的混合物；The carrier is a mixture of one or more of zirconium boride, silicon boride, titanium boride and tungsten boride in any proportion;

所述金属助剂所含金属元素与载体的质量比为0.1～10：100，该步操作下，金属元素可认为是全部负载；The mass ratio of the metal element contained in the metal auxiliary agent to the carrier is 0.1-10:100, and in this step, the metal element can be considered to be fully loaded;

所述载体与二甲基二氯硅烷、三乙胺的质量比为100：1～7：2～8；The mass ratio of the carrier to dimethyldichlorosilane and triethylamine is 100:1-7:2-8;

(3)将离子液体溶于溶剂中，搅拌均匀，然后加入步骤(2)所得固体产物，浸渍2～10h，之后烘干(180℃)，得到离子液体负载的固体产物；(3) dissolving the ionic liquid in the solvent, stirring evenly, then adding the solid product obtained in step (2), soaking for 2-10 h, and then drying (180° C.) to obtain the solid product supported by the ionic liquid;

所述离子液体与载体的质量比为1～20：100，该步操作下，离子液体可认为是全部负载；The mass ratio of the ionic liquid to the carrier is 1 to 20:100, and in this step, the ionic liquid can be considered as the full load;

该步所用的溶剂与步骤(1)中的溶剂相同，该步溶剂的体积用量以离子液体的质量计为5～100mL/g；The solvent used in this step is the same as the solvent in step (1), and the volumetric consumption of the solvent in this step is 5 to 100 mL/g in terms of the mass of the ionic liquid;

所述离子液体选自如下式(I)～式(V)中的一种或两种以上任意比例的混合物；The ionic liquid is selected from the following formula (I) to formula (V) in one or a mixture of two or more arbitrary proportions;

Figure BDA0002222732840000021
Figure BDA0002222732840000021

式(I)中，In formula (I),

R1为H、CH3或C2H5；R 1 is H, CH 3 or C 2 H 5 ;

R2为CnH2n+1、硫、氧或氮原子，n为整数且1≤n≤14；R 2 is C n H 2n+1 , sulfur, oxygen or nitrogen atom, n is an integer and 1≤n≤14;

R3为CkH2k+1，k为整数且1≤k≤4；R 3 is C k H 2k+1 , k is an integer and 1≤k≤4;

X-为氯离子、溴离子、六氟磷酸根、四氟磷酸根、双三氟甲磺酰亚胺根、四氟硼酸根或亚胺根；X - is chloride, bromide, hexafluorophosphate, tetrafluorophosphate, bis-trifluoromethanesulfonimide, tetrafluoroborate or imide;

Figure BDA0002222732840000022
Figure BDA0002222732840000022

式(II)中，In formula (II),

R1、R2、R3、R4各自独立为CnH2n+1、硫、氧或氮原子，n为整数且1≤n≤6；R 1 , R 2 , R 3 and R 4 are each independently C n H 2n+1 , sulfur, oxygen or nitrogen atom, n is an integer and 1≤n≤6;

X-为氯离子、溴离子、六氟磷酸根、四氟磷酸根、双三氟甲磺酰亚胺根、四氟硼酸根或亚胺根；X - is chloride, bromide, hexafluorophosphate, tetrafluorophosphate, bis-trifluoromethanesulfonimide, tetrafluoroborate or imide;

Figure BDA0002222732840000023
Figure BDA0002222732840000023

式(III)中，In formula (III),

R1、R2、R3、R4各自独立为CnH2n+1、硫、氧或氮原子，n为整数且1≤n≤6；R 1 , R 2 , R 3 and R 4 are each independently C n H 2n+1 , sulfur, oxygen or nitrogen atom, n is an integer and 1≤n≤6;

X-为氯离子、溴离子、六氟磷酸根、四氟磷酸根、双三氟甲磺酰亚胺根、四氟硼酸根或亚胺根；X - is chloride, bromide, hexafluorophosphate, tetrafluorophosphate, bis-trifluoromethanesulfonimide, tetrafluoroborate or imide;

Figure BDA0002222732840000024
Figure BDA0002222732840000024

式(IV)中，In formula (IV),

R1、R2各自独立为CnH2n+1，n为整数且1≤n≤6；R 1 and R 2 are independently C n H 2n+1 , n is an integer and 1≤n≤6;

R3为CnH2n+1、硫、氧或氮原子，n为整数且1≤n≤6；R 3 is C n H 2n+1 , sulfur, oxygen or nitrogen atom, n is an integer and 1≤n≤6;

X-为氯离子、溴离子、六氟磷酸根、四氟磷酸根、三氟甲磺酰亚胺根、四氟硼酸根或亚胺根；X - is chloride, bromide, hexafluorophosphate, tetrafluorophosphate, trifluoromethanesulfonimide, tetrafluoroborate or imide;

Figure BDA0002222732840000031
Figure BDA0002222732840000031

式(V)中，In formula (V),

R1、R2各自独立为CnH2n+1，n为整数且1≤n≤6；R 1 and R 2 are independently C n H 2n+1 , n is an integer and 1≤n≤6;

R3为CnH2n+1、硫、氧或氮原子，n为整数且1≤n≤6；R 3 is C n H 2n+1 , sulfur, oxygen or nitrogen atom, n is an integer and 1≤n≤6;

X-为氯离子、溴离子、六氟磷酸根、四氟磷酸根、双三氟甲磺酰亚胺根、四氟硼酸根或亚胺根；X - is chloride, bromide, hexafluorophosphate, tetrafluorophosphate, bis-trifluoromethanesulfonimide, tetrafluoroborate or imide;

优选的，所述离子液体选自如下之一：Preferably, the ionic liquid is selected from one of the following:

1-丁基-3-甲基咪唑氯盐和1-丙基-3-丁基咪唑四氟磷酸根盐质量比1：4的混合物；A mixture of 1-butyl-3-methylimidazolium chloride and 1-propyl-3-butylimidazolium tetrafluorophosphate in a mass ratio of 1:4;

1-丁基-3-甲基咪唑六氟磷酸盐和氮甲基吡咯烷酮盐酸盐质量比3：7的混合物；A mixture of 1-butyl-3-methylimidazolium hexafluorophosphate and nitrogen methylpyrrolidone hydrochloride in a mass ratio of 3:7;

1-丁基-2，3-二甲基咪唑四氟磷酸盐和N-戊基-乙基哌啶氯盐质量比1：1的混合物；A mixture of 1-butyl-2,3-dimethylimidazolium tetrafluorophosphate and N-pentyl-ethylpiperidine chloride in a mass ratio of 1:1;

三苯基甲基膦双三氟甲磺酰亚胺盐和三苯基乙基溴化膦质量比3：1的混合物；A mixture of triphenylmethylphosphine bis-trifluoromethanesulfonimide salt and triphenylethylphosphine bromide in a mass ratio of 3:1;

1-丁基-3-甲基咪唑氯盐和三苯基乙基溴化膦质量比1：1的混合物；A mixture of 1-butyl-3-methylimidazolium chloride and triphenylethylphosphine bromide in a mass ratio of 1:1;

1-丙基-2，3-二甲基咪唑双三氟甲磺酰亚胺盐和1-丙基-3-丁基咪唑四氟磷酸根盐质量比1：1的混合物；A mixture of 1-propyl-2,3-dimethylimidazole bis-trifluoromethanesulfonimide salt and 1-propyl-3-butylimidazole tetrafluorophosphate salt in mass ratio of 1:1;

(4)将金属盐溶于溶剂，搅拌均匀，然后加入步骤(3)所得离子液体负载的固体产物，在外加静态电场中浸渍2～8h，之后烘干(180℃)，备用；(4) Dissolving the metal salt in the solvent, stirring evenly, then adding the solid product supported by the ionic liquid obtained in step (3), immersing it in an external static electric field for 2-8 hours, then drying (180° C.) for use;

所述金属盐所含金属元素与载体的质量比为0.05～20：100，该步操作下，金属元素可认为是全部负载；The mass ratio of the metal element contained in the metal salt to the carrier is 0.05 to 20:100, and in this step, the metal element can be considered to be fully loaded;

该步所用的溶剂与步骤(1)中的溶剂相同，该步溶剂的体积用量以金属盐的质量计为0.5～10mL/g；The solvent used in this step is the same as the solvent in step (1), and the volume consumption of the solvent in this step is 0.5 to 10 mL/g in terms of the mass of the metal salt;

所述金属盐可记作MX，其中，M为金属阳离子，选自金、钌、铑、铜中的一种或多种混合，X为非金属阴离子，选自硝酸根、硫酸根、氯、溴、双氰胺根、硫代硫酸根、亚硫酸根、吡咯烷酮根、吡啶烷酮根、铵根、磷酸根、焦磷酸根、三苯基膦、聚酞菁根、苯硫酚、酞菁、二氯(1,10-菲咯啉)根、乙酰丙酮酸中的一种或多种混合；The metal salt can be denoted as MX, wherein, M is a metal cation, selected from one or more mixtures of gold, ruthenium, rhodium, and copper, and X is a non-metal anion, selected from nitrate, sulfate, chlorine, Bromine, Dicyandiamide, Thiosulfate, Sulfite, Pyrrolidone, Pyrididone, Ammonium, Phosphate, Pyrophosphate, Triphenylphosphine, Polyphthalocyanine, Thiophenol, Phthalocyanine , one or more mixtures in dichloro (1,10-phenanthroline) root and acetylacetonate;

所述外加静态电场电压为0.2～4kV；The applied static electric field voltage is 0.2～4kV;

(5)将步骤(4)所得产物分散于溶剂和二甲基二氯硅烷的混合溶液中，然后置于旋转混合仪上40～60℃旋转处理10～14h，随后在外加静态电场中浸渍2～4h，并在特定气氛下烘干(烘干温度为180℃)，得到所述多组分金属催化剂；(5) Disperse the product obtained in step (4) in a mixed solution of solvent and dimethyldichlorosilane, then place it on a rotary mixer at 40-60°C for 10-14 hours of rotation, and then immerse it in an external static electric field for 2 ~4h, and drying in a specific atmosphere (drying temperature is 180°C) to obtain the multi-component metal catalyst;

所述溶剂和二甲基二氯硅烷的混合溶液中，所用的溶剂与步骤(1)中的溶剂相同，该处溶剂与二甲基二氯硅烷的比例为50～100：1(mL：g)；In the mixed solution of the solvent and dimethyldichlorosilane, the solvent used is the same as the solvent in step (1), and the ratio of the solvent to dimethyldichlorosilane here is 50-100:1 (mL: g );

所述溶剂和二甲基二氯硅烷的混合溶液的体积用量以步骤(4)所得产物的质量计为20～60mL/g；The volume dosage of the mixed solution of the solvent and dimethyldichlorosilane is 20-60 mL/g in terms of the mass of the product obtained in step (4);

所述特定气氛可选自氮气、氩气、空气、氧气、氢气、乙炔、氯化氢、甲烷、氧气、氯气中的一种或几种混合；The specific atmosphere can be selected from one or more mixtures of nitrogen, argon, air, oxygen, hydrogen, acetylene, hydrogen chloride, methane, oxygen, and chlorine;

所述外加静态电场电压为0.2～4kV。The applied static electric field voltage is 0.2-4kV.

本发明制得的多组分金属催化剂可应用于电石法合成氯乙烯的反应中。The multi-component metal catalyst prepared by the invention can be used in the reaction of synthesizing vinyl chloride by calcium carbide method.

具体的，所述应用的方法为：Specifically, the application method is:

在固定床反应器内，装入制备好的催化剂，反应温度为100～200℃，反应压力0.1～0.5MPa，通入原料气体HCl、C2H2，即可反应获得氯乙烯；In the fixed bed reactor, the prepared catalyst is loaded, the reaction temperature is 100～200°C, the reaction pressure is 0.1～0.5MPa, and the raw materials gas HCl and C 2 H 2 are introduced, and the vinyl chloride can be obtained by the reaction;

进一步，所述原料气体HCl、C2H2物质的量之比n(HCl)/n(C2H2)＝0.9～1.2/1；乙炔体积空速10～100h-1。Further, the ratio of the amount of the raw material gas HCl and C 2 H 2 is n(HCl)/n(C 2 H 2 )=0.9-1.2/1; the acetylene volume space velocity is 10-100 h −1 .

本发明所述的催化剂在上述合成氯乙烯反应中具有很高的稳定性，长时间运行2000h后，未表现出催化剂失活现象。The catalyst of the present invention has high stability in the above-mentioned vinyl chloride synthesis reaction, and does not show the phenomenon of catalyst deactivation after running for 2000 hours for a long time.

与现有技术相比，本发明存在以下优势：Compared with the prior art, the present invention has the following advantages:

1、载体的特殊性。本发明所提供的制备方法在所述的载体中金属的分散效果更高，催化活性更高，稳定性更好。1. The particularity of the carrier. The preparation method provided by the present invention has higher metal dispersion effect, higher catalytic activity and better stability in the carrier.

2、载体表面离子液体的稳定机制不同。本申请中的离子液体是通过硅羟基(Si-OH)稳定在载体表面，采用本申请中的制备方法，离子液体具有更高的稳定性，不易于从载体表面流失。2. The stabilization mechanisms of ionic liquids on the carrier surface are different. The ionic liquid in the present application is stabilized on the surface of the carrier by silyl hydroxyl groups (Si-OH). Using the preparation method in the present application, the ionic liquid has higher stability and is not easy to be lost from the surface of the carrier.

3、金属活性中心存在的位置不同。在公开报道的文献和专利中金属分散在离子液体中心(图1a)或者锚定。而本申请中的金属通过与离子液体配位的形式，稳定在催化剂的外表层(图2)，减少了传质的影响，同时提高了金属的分散度。3. The positions of metal active centers are different. Metals are dispersed in ionic liquid centers (Fig. 1a) or anchored in published literature and patents. The metal in the present application is stabilized on the outer surface of the catalyst in the form of coordination with the ionic liquid (Fig. 2), which reduces the influence of mass transfer and improves the dispersity of the metal at the same time.

4、首次将外加静态电场引入到负载离子液体的金属基催化剂制备中，促进了金属活性中心在离子液体表层的富集。4. For the first time, an external static electric field was introduced into the preparation of metal-based catalysts supported by ionic liquids, which promoted the enrichment of metal active centers on the surface of ionic liquids.

5、消除诱导期。由于本发明所述的催化剂金属活性中心分布在离子液体表层，减少了底物扩散的影响，在所评价的反应条件下，催化剂的诱导期消失。而公开报道的文献和专利中催化剂的诱导期为2-10h。5. Eliminate the induction period. Since the metal active centers of the catalyst described in the present invention are distributed in the surface layer of the ionic liquid, the influence of the substrate diffusion is reduced, and the induction period of the catalyst disappears under the evaluated reaction conditions. The induction period of the catalyst in the published literature and patents is 2-10h.

(四)附图说明(4) Description of drawings

图1：公开报道的专利中负载离子液体的金属基催化剂体系示意图：a)金属分散在离子液体层中间；b)金属分在催化剂载体的表面；Fig. 1: Schematic diagram of the metal-based catalyst system supporting ionic liquid 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;

图2：本发明中负载离子液体的金属基催化剂体系示意图。Figure 2: Schematic diagram of the metal-based catalyst system supporting the ionic liquid in the present invention.

(五)具体实施方式(5) Specific implementation methods

下面用具体实施例来说明本发明。有必要指出的是，实施例只用于对本发明进行的进一步说明，但不能理解为对本发明保护范围的限制，本发明不以任何方式局限于此。该领域的技术熟练人员可以根据上述发明的内容做出一些非本质的改进和调整。The present invention will be described below with specific examples. It is necessary to point out that the embodiments are only used to further illustrate the present invention, but should not be construed as limiting the protection scope of the present invention, and the present invention is not limited thereto in any way. Those skilled in the art can make some non-essential improvements and adjustments based on the content of the above invention.

以下实施例中，硼化锆购自上海超威纳米，比表面积500～1000m2 g-1；硼化硅购自辽宁中色新材料科技有限公司，比表面积500～100m2 g-1；硼化钛购自上海超威纳米，比表面积200～800m2 g-1；硼化钨购自辽宁中色新材料科技有限公司，比表面积500～1000m2 g-1。In the following examples, zirconium boride was purchased from Shanghai Chaowei Nano, with a specific surface area of 500 to 1000 m 2 g -1 ; silicon boride was purchased from Liaoning CNMC New Material Technology Co., Ltd. with a specific surface area of 500 to 100 m 2 g -1 ; boron Titanium was purchased from Shanghai Chaowei Nano, with a specific surface area of 200-800 m 2 g -1 ; tungsten boride was purchased from Liaoning CNMC New Material Technology Co., Ltd. with a specific surface area of 500-1000 m 2 g -1 .

旋转仪生产厂家为新芝生物，DH-II。The manufacturer of the rotator is Xinzhi Bio, DH-II.

实施例1Example 1

催化剂的制备：Preparation of catalyst:

1)选取金属助剂氯化钠0.13g，将其溶解在1.3mL甲苯中搅拌至完全溶解，得到金属助剂的溶液，备用。1) Select 0.13 g of metal auxiliary agent sodium chloride, dissolve it in 1.3 mL of toluene and stir until completely dissolved to obtain a solution of metal auxiliary agent, which is for later use.

2)选取硼化锆为载体10g，分散于步骤1)得到的溶液中，搅拌30min后加入0.1g二甲基二氯硅烷，0.8g三乙胺。上述混合物在氮气，50℃条件下热处理3小时。之后过滤，滤饼用甲苯和乙醇洗涤，在180℃条件下烘干，得到的固体样品备用。钠元素的质量负载量为0.5％。2) Select 10 g of zirconium boride as a carrier, disperse in the solution obtained in step 1), stir for 30 min, and add 0.1 g of dimethyldichlorosilane and 0.8 g of triethylamine. The above mixture was heat treated under nitrogen at 50°C for 3 hours. After filtering, the filter cake was washed with toluene and ethanol, dried at 180°C, and the obtained solid sample was used for later use. The mass loading of sodium element is 0.5%.

3)取0.02g 1-丁基-3-甲基咪唑氯盐和0.08g 1-丙基-3-丁基咪唑六氟磷酸盐离子液体溶于10mL甲苯中，搅拌均匀后，加入步骤2)中所得的固体样品，浸渍2h，并在180℃条件下烘干备用。其中离子液体的质量负载量为1％。3) Dissolve 0.02g of 1-butyl-3-methylimidazolium chloride and 0.08g of 1-propyl-3-butylimidazolium hexafluorophosphate ionic liquid in 10 mL of toluene, stir evenly, and add step 2) The solid samples obtained in 2 h were soaked for 2 h and dried at 180°C for use. The mass loading of the ionic liquid is 1%.

4)将0.009g氯金酸溶于0.09mL甲苯中，搅拌均匀后加入步骤3)所得到的样品，在外加0.2kV静态电场中浸渍2h后，并在180℃条件下烘干备用。其中金元素的质量负载量为0.05％。4) Dissolve 0.009 g of chloroauric acid in 0.09 mL of toluene, stir evenly, add the sample obtained in step 3), immerse it in an external 0.2 kV static electric field for 2 hours, and dry it at 180°C for later use. The mass loading of gold element is 0.05%.

5)上述得到的固体样品11.14g重新在668.4mL甲苯和6.68g二甲基二氯硅烷的混合溶液中再次分散。并将上述得到的混合物在旋转仪上50℃旋转处理12h。随后在外加3.6kV静态电场中浸渍3h后，180℃条件下在氮气气氛下烘干即得所需要的固体催化剂。5) 11.14 g of the solid sample obtained above was dispersed again in a mixed solution of 668.4 mL of toluene and 6.68 g of dimethyldichlorosilane. The mixture obtained above was rotated at 50°C on a rotator for 12 h. Then, after being immersed in a static electric field of 3.6kV for 3 hours, the solid catalyst was obtained by drying at 180°C in a nitrogen atmosphere.

催化剂性能评价：Catalyst performance evaluation:

此催化剂1.5g应用于固定床反应器内的乙炔氢氯化反应中，在反应条件为：温度100℃，压力0.1MPa，原料气体物质的量之比n(HCl)/n(C2H2)＝0.9/1，乙炔体积空速50h-1的条件下，诱导期为0h，反应2000h后，乙炔转化率为97％，氯乙烯选择性为99.5％。1.5g of this catalyst is used in the hydrochlorination of acetylene in a fixed-bed reactor. The reaction conditions are: temperature 100°C, pressure 0.1MPa, and the ratio of the amount of raw gas substances n(HCl)/n(C 2 H 2 )=0.9/1, under the condition of acetylene volume space velocity 50h -1 , the induction period is 0h, after 2000h reaction, the acetylene conversion rate is 97%, and the vinyl chloride selectivity is 99.5%.

实施例2Example 2

催化剂的制备：Preparation of catalyst:

1)选取金属助剂氯化钡0.03g，将其溶解在0.24mL氮氮二甲基甲酰胺中搅拌至完全溶解，得到金属助剂的溶液，备用。1) Select 0.03 g of metal auxiliary barium chloride, dissolve it in 0.24 mL of nitrogen-nitrogen dimethylformamide and stir until completely dissolved, to obtain a solution of metal auxiliary, for subsequent use.

2)选取硼化硅为载体10g，分散于步骤1)得到的溶液中，搅拌60min后加入0.3g二甲基二氯硅烷，0.6g三乙胺。上述混合物在氮气，55℃条件下热处理3小时。之后过滤，滤饼用甲苯和乙醇洗涤，在180℃条件下烘干，得到的固体样品备用。钡元素的质量负载量为0.2％。2) Select 10 g of silicon boride as a carrier, disperse it in the solution obtained in step 1), stir for 60 min, and add 0.3 g of dimethyldichlorosilane and 0.6 g of triethylamine. The above mixture was heat treated under nitrogen at 55°C for 3 hours. After filtering, the filter cake was washed with toluene and ethanol, dried at 180°C, and the obtained solid sample was used for later use. The mass loading of barium element is 0.2%.

3)取0.6g1-丁基-3-甲基咪唑六氟磷酸盐离子液体和1.4g氮甲基吡咯烷酮盐酸盐离子液体溶于10mL氮氮二甲基甲酰胺中，搅拌均匀后，加入步骤2)中所得的固体样品，浸渍4h，并在180℃条件下烘干备用。其中离子液体的质量负载量为20％。3) Dissolve 0.6 g of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid and 1.4 g of nitrogen methyl pyrrolidone hydrochloride ionic liquid in 10 mL of nitrogen nitrogen dimethyl formamide, stir evenly, and add the steps The solid sample obtained in 2) was immersed for 4 hours, and dried at 180°C for later use. The mass loading of the ionic liquid is 20%.

4)将4.23g氯化铜溶于2.12mL氮氮二甲基甲酰胺中，搅拌均匀后加入步骤3)所得到的样品，在外加4kV静态电场中浸渍4h后，并在180℃条件下烘干备用。其中铜元素的质量负载量为20％。4) Dissolve 4.23 g of cupric chloride in 2.12 mL of nitrosodimethylformamide, stir evenly, add the sample obtained in step 3), immerse it in an external 4kV static electric field for 4 hours, and bake it at 180°C Dry spare. The mass loading of copper element is 20%.

5)上述得到的固体样品17.16g重新在343.2mL氮氮二甲基甲酰胺和6.86g二甲基二氯硅烷的混合溶液中再次分散。并将上述得到的混合物在旋转仪上50℃旋转处理12h。随后在外加4kV静态电场中浸渍2h后，180℃条件下在氩气氛下烘干即得所需要的固体催化剂。5) 17.16 g of the solid sample obtained above was re-dispersed in a mixed solution of 343.2 mL of nitrogen dimethylformamide and 6.86 g of dimethyldichlorosilane. The mixture obtained above was rotated at 50°C on a rotator for 12 h. Then, after being immersed in an external static electric field of 4kV for 2 hours, the solid catalyst was obtained by drying at 180°C in an argon atmosphere.

催化剂性能评价：Catalyst performance evaluation:

此催化剂4.5g应用于固定床反应器内的乙炔氢氯化反应中，在反应条件为：温度100℃，压力0.1MPa，原料气体物质的量之比n(HCl)/n(C2H2)＝1.0/1，乙炔体积空速10h-1的条件下，诱导期为0h，反应2000h后，乙炔转化率为94％，氯乙烯选择性为99.5％。4.5g of this catalyst was used in the hydrochlorination of acetylene in a fixed-bed reactor. The reaction conditions were: temperature 100°C, pressure 0.1MPa, and the ratio of the amount of raw gas substances n(HCl)/n(C 2 H 2 )=1.0/1, under the condition of acetylene volume space velocity 10h -1 , the induction period is 0h, after 2000h reaction, the acetylene conversion rate is 94%, and the vinyl chloride selectivity is 99.5%.

实施例3Example 3

催化剂的制备：Preparation of catalyst:

1)选取金属助剂氯化锌1.67g，将其溶解在8.4mL丙酮中搅拌至完全溶解，得到金属助剂的溶液，备用。1) Select 1.67 g of metal auxiliary zinc chloride, dissolve it in 8.4 mL of acetone, and stir until completely dissolved to obtain a solution of metal auxiliary, which is for later use.

2)选取硼化钛为载体10g，分散于步骤1)得到的溶液中，搅拌90min后加入0.5g二甲基二氯硅烷，0.4g三乙胺。上述混合物在氮气，60℃条件下热处理3小时。之后过滤，滤饼用丙酮和乙醇洗涤，在180℃条件下烘干，得到的固体样品备用。锌元素的质量负载量为8％。2) Select 10 g of titanium boride as a carrier, disperse it in the solution obtained in step 1), stir for 90 min, and add 0.5 g of dimethyldichlorosilane and 0.4 g of triethylamine. The above mixture was heat treated under nitrogen at 60°C for 3 hours. After filtering, the filter cake was washed with acetone and ethanol, dried at 180°C, and the obtained solid sample was used for later use. The mass loading of zinc element is 8%.

3)取0.5g 1-丁基-3-甲基咪唑六氟磷酸盐和0.5g N-戊基-乙基哌啶氯盐溶于20mL丙酮中，搅拌均匀后，加入步骤2)中所得的固体样品，浸渍6h，并在180℃条件下烘干备用。其中离子液体的质量负载量为10％。3) Dissolve 0.5 g of 1-butyl-3-methylimidazolium hexafluorophosphate and 0.5 g of N-pentyl-ethylpiperidine chloride in 20 mL of acetone, stir evenly, and add the obtained solution in step 2). The solid samples were soaked for 6 hours and dried at 180°C for later use. The mass loading of the ionic liquid is 10%.

4)将0.2g氯化铑溶于1mL丙酮中，搅拌均匀后加入步骤3)所得到的样品，在外加0.5kV静态电场中浸渍8h后，并在180℃条件下烘干备用。其中铑元素的质量负载量为1.0％。4) Dissolve 0.2 g of rhodium chloride in 1 mL of acetone, stir evenly, add the sample obtained in step 3), immerse it in a static electric field of 0.5 kV for 8 hours, and then dry it at 180°C for use. The mass loading of rhodium element is 1.0%.

5)上述得到的固体样品13.8g重新在414mL丙酮和6.9g二甲基二氯硅烷的混合溶液中再次分散。并将上述得到的混合物在旋转仪上60℃旋转处理12h。随后在外加3.2kV静态电场中浸渍4h后，180℃条件下在氮、空气气氛下烘干即得所需要的固体催化剂。5) 13.8 g of the solid sample obtained above was redispersed in a mixed solution of 414 mL of acetone and 6.9 g of dimethyldichlorosilane. The mixture obtained above was rotated at 60° C. for 12 h on a rotator. Then, after being immersed in a static electric field of 3.2kV for 4 hours, the solid catalyst was obtained by drying at 180°C under nitrogen and air atmosphere.

催化剂性能评价：Catalyst performance evaluation:

此催化剂3.0g应用于固定床反应器内的乙炔氢氯化反应中，在反应条件为：温度100℃，压力0.1MPa，原料气体物质的量之比n(HCl)/n(C2H2)＝1.1/1，乙炔体积空速100h-1的条件下，诱导期为0h，反应2000h后，乙炔转化率为96％，氯乙烯选择性为98.5％。3.0 g of this catalyst was used in the hydrochlorination of acetylene in a fixed bed reactor. The reaction conditions were: temperature 100°C, pressure 0.1 MPa, and the ratio of the amount of raw gas to n(HCl)/n(C 2 H 2 )=1.1/1, under the condition of acetylene volume space velocity 100h -1 , the induction period is 0h, after 2000h reaction, the acetylene conversion rate is 96%, and the vinyl chloride selectivity is 98.5%.

实施例4Example 4

催化剂的制备：Preparation of catalyst:

1)选取金属助剂氯化铁0.73g，将其溶解在4.4mL二氯亚砜中搅拌至完全溶解，得到金属助剂的溶液，备用。1) Select 0.73 g of metal auxiliary agent ferric chloride, dissolve it in 4.4 mL of thionyl chloride and stir until completely dissolved to obtain a solution of metal auxiliary agent, which is for later use.

2)选取硼化钨为载体10g，分散于步骤1)得到的溶液中，搅拌120min后加入0.7g二甲基二氯硅烷，0.3g三乙胺。上述混合物在氮气，65℃条件下热处理3小时。之后过滤，滤饼用二氯亚砜和乙醇洗涤，在180℃条件下烘干，得到的固体样品备用。铁元素的质量负载量为2.5％。2) Select 10 g of tungsten boride as a carrier, disperse it in the solution obtained in step 1), stir for 120 min, and add 0.7 g of dimethyldichlorosilane and 0.3 g of triethylamine. The above mixture was heat treated under nitrogen at 65°C for 3 hours. After filtering, the filter cake was washed with thionyl chloride and ethanol, dried at 180°C, and the obtained solid sample was used for later use. The mass loading of iron element is 2.5%.

3)取0.6g三苯基甲基膦双三氟甲磺酰亚胺盐和0.2g三苯基乙基溴化膦溶于10mL二氯亚砜中，搅拌均匀后，加入步骤2)中所得的固体样品，浸渍10h，并在180℃条件下烘干备用。其中离子液体的质量负载量为8％。3) Dissolve 0.6 g of triphenylmethylphosphine bis-trifluoromethanesulfonimide salt and 0.2 g of triphenylethyl phosphine bromide in 10 mL of thionyl chloride, stir evenly, and add the obtained in step 2). The solid samples were immersed for 10 h and dried at 180 °C for use. The mass loading of the ionic liquid is 8%.

4)将0.103g氯化钌溶于0.5mL二氯亚砜中，搅拌均匀后加入步骤3)所得到的样品，在外加0.9kV静态电场中浸渍3.5h后，并在180℃条件下烘干备用。其中钌元素的质量负载量为0.5％。4) Dissolve 0.103 g of ruthenium chloride in 0.5 mL of thionyl chloride, stir evenly, add the sample obtained in step 3), immerse it in a static electric field of 0.9 kV for 3.5 hours, and dry it at 180°C spare. The mass loading of ruthenium element is 0.5%.

5)上述得到的固体样品12.63g重新在315.8mL二氯亚砜和4.86g二甲基二氯硅烷的混合溶液中再次分散。并将上述得到的混合物在旋转仪上40℃旋转处理10h。随后在外加2.1kV静态电场中浸渍2h后，180℃条件下在氢气气氛下烘干即得所需要的固体催化剂。5) 12.63 g of the solid sample obtained above was dispersed again in a mixed solution of 315.8 mL of thionyl chloride and 4.86 g of dimethyldichlorosilane. The mixture obtained above was rotated at 40°C for 10 h on a rotator. After immersion in an external static electric field of 2.1kV for 2 hours, the solid catalyst was obtained by drying in a hydrogen atmosphere at 180°C.

催化剂性能评价：Catalyst performance evaluation:

此催化剂1.6g应用于固定床反应器内的乙炔氢氯化反应中，在反应条件为：温度100℃，压力0.1MPa，原料气体物质的量之比n(HCl)/n(C2H2)＝1.2/1，乙炔体积空速80h-1的条件下，诱导期为0h，反应2000h后，乙炔转化率为99.3％，氯乙烯选择性为98.5％。1.6g of this catalyst was used in the hydrochlorination of acetylene in a fixed-bed reactor. The reaction conditions were: temperature 100°C, pressure 0.1MPa, and the ratio of the amount of raw gas substances n(HCl)/n(C 2 H 2 )=1.2/1, under the condition that the volume space velocity of acetylene is 80h -1 , the induction period is 0h, after 2000h reaction, the conversion rate of acetylene is 99.3%, and the selectivity of vinyl chloride is 98.5%.

实施例5Example 5

催化剂的制备：Preparation of catalyst:

1)选取金属助剂氯化铝0.49g，将其溶解在4.4mL氮甲基吡咯烷酮中搅拌至完全溶解，得到金属助剂的溶液，备用。1) Select 0.49 g of metal auxiliary aluminum chloride, dissolve it in 4.4 mL of nitrogen methyl pyrrolidone, and stir until completely dissolved to obtain a solution of metal auxiliary, which is for later use.

2)选取硼化锆为载体10g，分散于步骤1)得到的溶液中，搅拌180min后加入0.6g二甲基二氯硅烷，0.2g三乙胺。上述混合物在氮气，70℃条件下热处理3小时。之后过滤，滤饼用和乙醇洗涤，在180℃条件下烘干，得到的固体样品备用。铝元素的质量负载量为1％。2) Select 10 g of zirconium boride as a carrier, disperse in the solution obtained in step 1), stir for 180 min, and add 0.6 g of dimethyldichlorosilane and 0.2 g of triethylamine. The above mixture was heat treated under nitrogen at 70°C for 3 hours. After filtering, the filter cake was washed with ethanol and dried at 180°C, and the obtained solid sample was used for later use. The mass loading of aluminum element is 1%.

3)取0.5g1-丁基-3-甲基咪唑氯盐和0.5g三苯基乙基溴化膦溶于5mL氮甲基吡咯烷酮中，搅拌均匀后，加入步骤2)中所得的固体样品，浸渍10h，并在180℃条件下烘干备用。其中离子液体的质量负载量为10％。3) Dissolve 0.5 g of 1-butyl-3-methylimidazolium chloride and 0.5 g of triphenylethyl phosphine bromide in 5 mL of nitrogen methylpyrrolidone, stir evenly, add the solid sample obtained in step 2), Immersion for 10h and drying at 180°C for later use. The mass loading of the ionic liquid is 10%.

4)将4.53g酞菁铜溶于9.1mL氮甲基吡咯烷酮中，搅拌均匀后加入步骤3)所得到的样品，在外加3.6kV静态电场中浸渍3h后，并在180℃条件下烘干备用。其中铜元素的质量负载量为5％。4) Dissolve 4.53 g of copper phthalocyanine in 9.1 mL of nitrogen methyl pyrrolidone, stir evenly, add the sample obtained in step 3), immerse it in a static electric field of 3.6 kV for 3 hours, and dry it at 180 °C for later use . The mass loading of copper element is 5%.

5)上述得到的固体样品16.82g重新在420.5mL氮甲基吡咯烷酮和5.26g二甲基二氯硅烷的混合溶液中再次分散。并将上述得到的混合物在旋转仪上60℃旋转处理14h。随后在外加2.8kV静态电场中浸渍4h后，180℃条件下在乙炔气氛下烘干即得所需要的固体催化剂。5) 16.82 g of the solid sample obtained above was dispersed again in a mixed solution of 420.5 mL of nitrogen methylpyrrolidone and 5.26 g of dimethyldichlorosilane. The mixture obtained above was rotated at 60°C on a rotator for 14 h. After immersion in an external static electric field of 2.8kV for 4 hours, the solid catalyst was obtained by drying in an acetylene atmosphere at 180°C.

催化剂性能评价：Catalyst performance evaluation:

此催化剂3.0g应用于固定床反应器内的乙炔氢氯化反应中，在反应条件为：温度100℃，压力0.1MPa，原料气体物质的量之比n(HCl)/n(C2H2)＝0.9/1，乙炔体积空速20h-1的条件下，诱导期为0h，反应2000h后，乙炔转化率为98％，氯乙烯选择性为99.5％。3.0 g of this catalyst was used in the hydrochlorination of acetylene in a fixed bed reactor. The reaction conditions were: temperature 100°C, pressure 0.1 MPa, and the ratio of the amount of raw gas to n(HCl)/n(C 2 H 2 )=0.9/1, under the condition of acetylene volume space velocity 20h -1 , the induction period is 0h, after 2000h reaction, the acetylene conversion rate is 98%, and the vinyl chloride selectivity is 99.5%.

实施例6Example 6

催化剂的制备：Preparation of catalyst:

1)选取金属助剂磷酸钙2.58g，将其溶解在15.5mL丙酮中搅拌至完全溶解，得到金属助剂的溶液，备用。1) Select 2.58 g of metal auxiliary agent calcium phosphate, dissolve it in 15.5 mL of acetone, and stir until completely dissolved to obtain a solution of metal auxiliary agent, which is for later use.

2)选取硼化硅为载体10g，分散于步骤1)得到的溶液中，搅拌30min后加入0.4g二甲基二氯硅烷，0.2g三乙胺。上述混合物在氮气，60℃条件下热处理3小时。之后过滤，滤饼用丙酮和乙醇洗涤，在180℃条件下烘干，得到的固体样品备用。钙元素的质量负载量为10％。2) Select 10 g of silicon boride as a carrier, disperse it in the solution obtained in step 1), stir for 30 min, and add 0.4 g of dimethyldichlorosilane and 0.2 g of triethylamine. The above mixture was heat treated under nitrogen at 60°C for 3 hours. After filtering, the filter cake was washed with acetone and ethanol, dried at 180°C, and the obtained solid sample was used for later use. The mass loading of calcium element is 10%.

3)取0.7g1-丙基-2，3-二甲基咪唑双三氟甲磺酰亚胺盐和0.7g 1-丙基-3-丁基咪唑四氟磷酸根盐溶于10mL丙酮中，搅拌均匀后，加入步骤2)中所得的固体样品，浸渍2h，并在180℃条件下烘干备用。其中离子液体的质量负载量为14％。3) Dissolve 0.7g of 1-propyl-2,3-dimethylimidazole bis-trifluoromethanesulfonimide salt and 0.7g of 1-propyl-3-butylimidazole tetrafluorophosphate in 10 mL of acetone, After stirring evenly, the solid sample obtained in step 2) was added, immersed for 2 h, and dried at 180°C for use. The mass loading of ionic liquid is 14%.

4)将2.0g磷酸铜溶于12mL丙酮中，搅拌均匀后加入步骤3)所得到的样品，在外加0.2kV静态电场中浸渍2h后，并在180℃条件下烘干备用。其中铜元素的质量负载量为10％。4) Dissolve 2.0 g of copper phosphate in 12 mL of acetone, stir evenly, add the sample obtained in step 3), immerse it in an externally applied 0.2 kV static electric field for 2 hours, and dry it at 180°C for later use. The mass loading of copper element is 10%.

5)上述得到的固体样品16.58g重新在497.4mL丙酮和5.85g二甲基二氯硅烷的混合溶液中再次分散。并将上述得到的混合物在旋转仪上40℃旋转处理10h。随后在外加04kV静态电场中浸渍3h后，180℃条件下在氯化氢气氛下烘干即得所需要的固体催化剂。5) 16.58 g of the solid sample obtained above was redispersed in a mixed solution of 497.4 mL of acetone and 5.85 g of dimethyldichlorosilane. The mixture obtained above was rotated at 40°C for 10 h on a rotator. Then, after being immersed in a static electric field of 04kV for 3 hours, the solid catalyst was obtained by drying in a hydrogen chloride atmosphere at 180°C.

催化剂性能评价：Catalyst performance evaluation:

此催化剂1.5g应用于固定床反应器内的乙炔氢氯化反应中，在反应条件为：温度100℃，压力0.1MPa，原料气体物质的量之比n(HCl)/n(C2H2)＝1.0/1，乙炔体积空速30h-1的条件下，诱导期为0h，反应2000h后，乙炔转化率为98％，氯乙烯选择性为97.5％。1.5g of this catalyst is used in the hydrochlorination of acetylene in a fixed-bed reactor. The reaction conditions are: temperature 100°C, pressure 0.1MPa, and the ratio of the amount of raw gas substances n(HCl)/n(C 2 H 2 )=1.0/1, under the condition of acetylene volume space velocity 30h -1 , induction period is 0h, after 2000h reaction, acetylene conversion rate is 98%, vinyl chloride selectivity is 97.5%.

对比例1Comparative Example 1

本对比例通过与实施例1对比，研究金属分散在离子液体层中对催化性能的影响。In this comparative example, by comparing with Example 1, the effect of metal dispersion in the ionic liquid layer on the catalytic performance was studied.

催化剂的制备：Preparation of catalyst:

取0.02g 1-丁基-3-甲基咪唑氯盐和0.08g 1-丙基-3-丁基咪唑六氟磷酸盐离子液体溶于20mL去离子水溶液中，加入10g硼化锆，搅拌均匀后，加入一定含量的氯金酸溶液。浸渍3h后，并在110℃条件下烘干备用。其中金元素和离子液体的质量负载量分别为0.05％及1％。Dissolve 0.02g 1-butyl-3-methylimidazolium chloride and 0.08g 1-propyl-3-butylimidazolium hexafluorophosphate ionic liquid in 20mL deionized aqueous solution, add 10g zirconium boride, stir well Then, add a certain amount of chloroauric acid solution. After immersion for 3 hours, it was dried at 110°C for later use. The mass loadings of gold element and ionic liquid were 0.05% and 1%, respectively.

催化剂性能评价：Catalyst performance evaluation:

此催化剂应用于固定床反应器内的乙炔氢氯化反应中，在反应条件为：温度140℃，压力0.3MPa，原料气体物质的量之比n(HCl)/n(C2H2)＝1.2/1,乙炔体积空速50h-1的条件下，诱导期为3h，反应2000h后，乙炔转化率为77％，氯乙烯选择性为98.9％。This catalyst is used in the hydrochlorination of acetylene in a fixed-bed reactor. The reaction conditions are: temperature 140°C, pressure 0.3MPa, and the ratio of the amount of raw gas substances n(HCl)/n(C 2 H 2 )= Under the condition of 1.2/1, the volume space velocity of acetylene is 50h -1 , the induction period is 3h, after 2000h of reaction, the conversion rate of acetylene is 77%, and the selectivity of vinyl chloride is 98.9%.

对比例2Comparative Example 2

本对比例通过与实施例1对比，研究金属锚定在载体表面后再覆盖离子液体层对催化性能的影响。This comparative example is compared with Example 1 to study the effect of metal anchoring on the surface of the carrier and then covering the ionic liquid layer on the catalytic performance.

取10g硼化锆，加入一定含量的氯金酸溶液。浸渍3h后，并在110℃条件下烘干备用。其中金元素的质量负载量为0.05％。向上述烘干好的备用用品中，加入0.02g 1-丁基-3-甲基咪唑氯盐和0.08g 1-丙基-3-丁基咪唑六氟磷酸盐离子液体和20mL去离子水。搅拌均匀后，110℃条件下烘干备用。其中金元素和离子液体的质量负载量分别为0.05％及1％。Take 10g of zirconium boride, add a certain content of chloroauric acid solution. After immersion for 3 hours, it was dried at 110°C for later use. The mass loading of gold element is 0.05%. To the above-mentioned dried standby products, add 0.02g of 1-butyl-3-methylimidazolium chloride, 0.08g of 1-propyl-3-butylimidazolium hexafluorophosphate ionic liquid and 20mL of deionized water. After stirring evenly, it was dried at 110°C for later use. The mass loadings of gold element and ionic liquid were 0.05% and 1%, respectively.

催化剂性能评价：Catalyst performance evaluation:

此催化剂应用于固定床反应器内的乙炔氢氯化反应中，在反应条件为：温度140℃，压力0.3MPa，原料气体物质的量之比n(HCl)/n(C2H2)＝1.2/1,乙炔体积空速50h-1的条件下，诱导期为10h，反应2000h后，乙炔转化率为61％，氯乙烯选择性为99.1％。This catalyst is used in the hydrochlorination of acetylene in a fixed-bed reactor. The reaction conditions are: temperature 140°C, pressure 0.3MPa, and the ratio of the amount of raw gas substances n(HCl)/n(C 2 H 2 )= Under the condition of 1.2/1, the volume space velocity of acetylene is 50h -1 , the induction period is 10h, after 2000h of reaction, the conversion rate of acetylene is 61%, and the selectivity of vinyl chloride is 99.1%.

Claims (10)

1.一种多组分金属催化剂，其特征在于，按如下方法制备得到：1. a multicomponent metal catalyst is characterized in that, is prepared as follows: (1)将金属助剂溶于溶剂中，搅拌均匀，得到金属助剂溶液；(1) dissolving the metal auxiliary agent in the solvent, stirring uniformly, to obtain a metal auxiliary agent solution; 所述金属助剂可记作MsXs，其中，Ms为金属阳离子，选自锂、钠、钾、铝、锌、钙、锆、钡、铁钴中的一种或多种混合，Xs为非金属阴离子，选自硝酸根、硫酸根、氯、溴、双氰胺根、硫代硫酸根、亚硫酸根、吡咯烷酮根、吡啶烷酮根、铵根、磷酸根、焦磷酸根、三苯基膦、聚酞菁根、苯硫酚、酞菁、二氯(1,10-菲咯啉)根、乙酰丙酮酸中的一种或多种混合；The metal additive can be denoted as M s X s , wherein, M s is a metal cation, selected from one or more mixtures of lithium, sodium, potassium, aluminum, zinc, calcium, zirconium, barium, iron and cobalt, X s is a non-metal anion selected from nitrate, sulfate, chlorine, bromine, dicyandiamide, thiosulfate, sulfite, pyrrolidone, pyridinone, ammonium, phosphate, pyrophosphate , one or more mixtures of triphenylphosphine, polyphthalocyanine, thiophenol, phthalocyanine, dichloro(1,10-phenanthroline), and acetylacetonate; (2)将载体分散在步骤(1)得到的金属助剂溶液中，然后加入二甲基二氯硅烷、三乙胺，在惰性气体保护、50～70℃的条件下搅拌0.5～3h，之后过滤、洗涤、烘干，得到固体产物；(2) Disperse the carrier in the metal auxiliary agent solution obtained in step (1), then add dimethyldichlorosilane and triethylamine, and stir for 0.5 to 3 hours under the protection of inert gas at 50 to 70° C., and then Filter, wash, and dry to obtain solid product; 所述载体为硼化锆、硼化硅、硼化钛、硼化钨中的一种或两种以上任意比例的混合物；The carrier is a mixture of one or more of zirconium boride, silicon boride, titanium boride and tungsten boride in any proportion; 所述金属助剂所含金属元素与载体的质量比为0.1～10：100；The mass ratio of the metal element contained in the metal auxiliary to the carrier is 0.1-10:100; 所述载体与二甲基二氯硅烷、三乙胺的质量比为100：1～7：2～8；The mass ratio of the carrier to dimethyldichlorosilane and triethylamine is 100:1-7:2-8; (3)将离子液体溶于溶剂中，搅拌均匀，然后加入步骤(2)所得固体产物，浸渍2～10h，之后烘干，得到离子液体负载的固体产物；(3) dissolving the ionic liquid in the solvent, stirring uniformly, then adding the solid product obtained in step (2), soaking for 2-10 h, and then drying to obtain the solid product supported by the ionic liquid; 所述离子液体与载体的质量比为1～20：100；The mass ratio of the ionic liquid to the carrier is 1-20:100; 所述离子液体选自如下式(I)～式(V)中的一种或两种以上任意比例的混合物；The ionic liquid is selected from the following formula (I) to formula (V) in one or a mixture of two or more arbitrary proportions;
Figure FDA0003506877000000011
Figure FDA0003506877000000011
 式(I)中，In formula (I), R1为H、CH3或C2H5；R 1 is H, CH 3 or C 2 H 5 ; R2为CnH2n+1、硫、氧或氮原子，n为整数且1≤n≤14；R 2 is C n H 2n+1 , sulfur, oxygen or nitrogen atom, n is an integer and 1≤n≤14; R3为CkH2k+1，k为整数且1≤k≤4；R 3 is C k H 2k+1 , k is an integer and 1≤k≤4; X-为氯离子、溴离子、六氟磷酸根、四氟磷酸根、双三氟甲磺酰亚胺根、四氟硼酸根或亚胺根；X - is chloride, bromide, hexafluorophosphate, tetrafluorophosphate, bis-trifluoromethanesulfonimide, tetrafluoroborate or imide;
Figure FDA0003506877000000012
Figure FDA0003506877000000012
 式(II)中，In formula (II), R1、R2、R3、R4各自独立为CnH2n+1、硫、氧或氮原子，n为整数且1≤n≤6；R 1 , R 2 , R 3 and R 4 are each independently C n H 2n+1 , sulfur, oxygen or nitrogen atom, n is an integer and 1≤n≤6; X-为氯离子、溴离子、六氟磷酸根、四氟磷酸根、双三氟甲磺酰亚胺根、四氟硼酸根或亚胺根；X - is chloride, bromide, hexafluorophosphate, tetrafluorophosphate, bis-trifluoromethanesulfonimide, tetrafluoroborate or imide;
Figure FDA0003506877000000013
Figure FDA0003506877000000013
 式(III)中，In formula (III), R1、R2、R3、R4各自独立为CnH2n+1、硫、氧或氮原子，n为整数且1≤n≤6；R 1 , R 2 , R 3 and R 4 are each independently C n H 2n+1 , sulfur, oxygen or nitrogen atom, n is an integer and 1≤n≤6; X-为氯离子、溴离子、六氟磷酸根、四氟磷酸根、双三氟甲磺酰亚胺根、四氟硼酸根或亚胺根；X - is chloride, bromide, hexafluorophosphate, tetrafluorophosphate, bis-trifluoromethanesulfonimide, tetrafluoroborate or imide;
Figure FDA0003506877000000021
Figure FDA0003506877000000021
 式(IV)中，In formula (IV), R1、R2各自独立为CnH2n+1，n为整数且1≤n≤6；R 1 and R 2 are each independently C n H 2n+1 , n is an integer and 1≤n≤6; R3为CnH2n+1、硫、氧或氮原子，n为整数且1≤n≤6；R 3 is C n H 2n+1 , sulfur, oxygen or nitrogen atom, n is an integer and 1≤n≤6; X-为氯离子、溴离子、六氟磷酸根、四氟磷酸根、三氟甲磺酰亚胺根、四氟硼酸根或亚胺根；X - is chloride, bromide, hexafluorophosphate, tetrafluorophosphate, trifluoromethanesulfonimide, tetrafluoroborate or imide;
Figure FDA0003506877000000022
Figure FDA0003506877000000022
 式(V)中，In formula (V), R1、R2各自独立为CnH2n+1，n为整数且1≤n≤6；R 1 and R 2 are independently C n H 2n+1 , n is an integer and 1≤n≤6; R3为CnH2n+1、硫、氧或氮原子，n为整数且1≤n≤6；R 3 is C n H 2n+1 , sulfur, oxygen or nitrogen atom, n is an integer and 1≤n≤6; X-为氯离子、溴离子、六氟磷酸根、四氟磷酸根、双三氟甲磺酰亚胺根、四氟硼酸根或亚胺根；X - is chloride, bromide, hexafluorophosphate, tetrafluorophosphate, bis-trifluoromethanesulfonimide, tetrafluoroborate or imide; (4)将金属盐溶于溶剂，搅拌均匀，然后加入步骤(3)所得离子液体负载的固体产物，在外加静态电场中浸渍2～8h，之后烘干，备用；(4) dissolving the metal salt in the solvent, stirring evenly, then adding the solid product supported by the ionic liquid obtained in step (3), immersing it in an external static electric field for 2-8 hours, then drying it for later use; 所述金属盐所含金属元素与载体的质量比为0.05～20：100；The mass ratio of the metal element contained in the metal salt to the carrier is 0.05-20:100; 所述金属盐可记作MX，其中，M为金属阳离子，选自金、钌、铑、铜中的一种或多种混合，X为非金属阴离子，选自硝酸根、硫酸根、氯、溴、双氰胺根、硫代硫酸根、亚硫酸根、吡咯烷酮根、吡啶烷酮根、铵根、磷酸根、焦磷酸根、三苯基膦、聚酞菁根、苯硫酚、酞菁、二氯(1,10-菲咯啉)根、乙酰丙酮酸中的一种或多种混合；The metal salt can be denoted as MX, wherein, M is a metal cation, selected from one or more mixtures of gold, ruthenium, rhodium, and copper, and X is a non-metal anion, selected from nitrate, sulfate, chlorine, Bromine, Dicyandiamide, Thiosulfate, Sulfite, Pyrrolidone, Pyrididone, Ammonium, Phosphate, Pyrophosphate, Triphenylphosphine, Polyphthalocyanine, Thiophenol, Phthalocyanine , one or more mixtures in dichloro (1,10-phenanthroline) root and acetylacetonate; (5)将步骤(4)所得产物分散于溶剂和二甲基二氯硅烷的混合溶液中，然后置于旋转混合仪上40～60℃旋转处理10～14h，随后在外加静态电场中浸渍2～4h，并在特定气氛下烘干，得到所述多组分金属催化剂；(5) Disperse the product obtained in step (4) in a mixed solution of solvent and dimethyldichlorosilane, then place it on a rotary mixer at 40-60°C for 10-14 hours of rotation, and then immerse it in an external static electric field for 2 ~4h, and drying in a specific atmosphere to obtain the multi-component metal catalyst; 所述溶剂和二甲基二氯硅烷的混合溶液中，溶剂与二甲基二氯硅烷的比例为50～100：1；In the mixed solution of the solvent and dimethyldichlorosilane, the ratio of the solvent to the dimethyldichlorosilane is 50-100:1; 所述特定气氛选自氮气、氩气、空气、氧气、氢气、乙炔、氯化氢、甲烷、氯气中的一种或几种混合。The specific atmosphere is selected from one or a mixture of nitrogen, argon, air, oxygen, hydrogen, acetylene, hydrogen chloride, methane and chlorine. 2.如权利要求1所述的多组分金属催化剂，其特征在于，步骤(1)中，所述溶剂为甲苯、氮氮二甲基甲酰胺、氮烷基吡咯烷酮、二氯亚砜、丙酮中的一种或两种以上任意比例的混合溶剂，步骤(3)、(4)、(5)中用到的溶剂与步骤(1)中的相同。2. The multi-component metal catalyst according to claim 1, wherein in step (1), the solvent is toluene, nitrogen nitrogen dimethyl formamide, nitrogen alkyl pyrrolidone, thionyl chloride, acetone One or two or more mixed solvents in arbitrary proportions, and the solvents used in steps (3), (4), and (5) are the same as those in step (1). 3.如权利要求1所述的多组分金属催化剂，其特征在于，步骤(1)中，溶剂的体积用量以金属助剂的质量计为0.5～10mL/g。3 . The multi-component metal catalyst according to claim 1 , wherein, in step (1), the volume dosage of the solvent is 0.5-10 mL/g in terms of the mass of the metal auxiliary. 4 . 4.如权利要求1所述的多组分金属催化剂，其特征在于，步骤(3)中，溶剂的体积用量以离子液体的质量计为5～100mL/g。4 . The multi-component metal catalyst according to claim 1 , wherein, in step (3), the volume dosage of the solvent is 5-100 mL/g in terms of the mass of the ionic liquid. 5 . 5.如权利要求1所述的多组分金属催化剂，其特征在于，步骤(3)中，所述离子液体选自如下之一：5. The multicomponent metal catalyst of claim 1, wherein in step (3), the ionic liquid is selected from one of the following: 1-丁基-3-甲基咪唑氯盐和1-丙基-3-丁基咪唑四氟磷酸根盐质量比1：4的混合物；A mixture of 1-butyl-3-methylimidazolium chloride and 1-propyl-3-butylimidazolium tetrafluorophosphate in a mass ratio of 1:4; 1-丁基-3-甲基咪唑六氟磷酸盐和氮甲基吡咯烷酮盐酸盐质量比3：7的混合物；A mixture of 1-butyl-3-methylimidazolium hexafluorophosphate and nitrogen methylpyrrolidone hydrochloride in a mass ratio of 3:7; 1-丁基-2，3-二甲基咪唑四氟磷酸盐和N-戊基-乙基哌啶氯盐质量比1：1的混合物；A mixture of 1-butyl-2,3-dimethylimidazolium tetrafluorophosphate and N-pentyl-ethylpiperidine chloride in a mass ratio of 1:1; 三苯基甲基膦双三氟甲磺酰亚胺盐和三苯基乙基溴化膦质量比3：1的混合物；A mixture of triphenylmethylphosphine bis-trifluoromethanesulfonimide salt and triphenylethylphosphine bromide in a mass ratio of 3:1; 1-丁基-3-甲基咪唑氯盐和三苯基乙基溴化膦质量比1：1的混合物；A mixture of 1-butyl-3-methylimidazolium chloride and triphenylethylphosphine bromide in a mass ratio of 1:1; 1-丙基-2，3-二甲基咪唑双三氟甲磺酰亚胺盐和1-丙基-3-丁基咪唑四氟磷酸根盐质量比1：1的混合物。A mixture of 1-propyl-2,3-dimethylimidazole bis-trifluoromethanesulfonimide salt and 1-propyl-3-butylimidazole tetrafluorophosphate salt in a mass ratio of 1:1. 6.如权利要求1所述的多组分金属催化剂，其特征在于，步骤(4)中，溶剂的体积用量以金属盐的质量计为0.5～10mL/g。6 . The multi-component metal catalyst according to claim 1 , wherein, in step (4), the volume dosage of the solvent is 0.5-10 mL/g in terms of the mass of the metal salt. 7 . 7.如权利要求1所述的多组分金属催化剂，其特征在于，步骤(5)中，溶剂和二甲基二氯硅烷的混合溶液的体积用量以步骤(4)所得产物的质量计为20～60mL/g。7. multicomponent metal catalyst as claimed in claim 1, is characterized in that, in step (5), the volume consumption of the mixed solution of solvent and dimethyldichlorosilane is calculated as the mass of the product obtained in step (4) 20～60mL/g. 8.如权利要求1所述的多组分金属催化剂，其特征在于，步骤(4)或(5)中，所述外加静态电场电压为0.2～4kV。8 . The multi-component metal catalyst according to claim 1 , wherein in step (4) or (5), the applied static electric field voltage is 0.2-4 kV. 9 . 9.如权利要求1所述的多组分金属催化剂在电石法合成氯乙烯的反应中的应用。9. The application of the multi-component metal catalyst as claimed in claim 1 in the reaction of synthesizing vinyl chloride by calcium carbide method. 10.如权利要求9所述的应用，其特征在于，所述应用的方法为：10. application as claimed in claim 9, is characterized in that, the method of described application is: 在固定床反应器内，装入制备好的催化剂，反应温度为100～200℃，反应压力0.1～0.5MPa，通入原料气体HCl、C2H2，即可反应获得氯乙烯；In the fixed bed reactor, the prepared catalyst is loaded, the reaction temperature is 100～200°C, the reaction pressure is 0.1～0.5MPa, and the raw materials gas HCl and C 2 H 2 are introduced, and the vinyl chloride can be obtained by the reaction; 所述原料气体HCl、C2H2物质的量之比n(HCl)/n(C2H2)＝0.9～1.2/1；乙炔体积空速10～100h-1。The ratio of the amount of the raw material gas HCl and C 2 H 2 is n(HCl)/n(C 2 H 2 )=0.9-1.2/1; the volume space velocity of acetylene is 10-100 h -1 .
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