CN107442169B - Catalyst loaded with chlorine-containing organotin and nitrogen-containing compound and preparation method and application thereof - Google Patents

Catalyst loaded with chlorine-containing organotin and nitrogen-containing compound and preparation method and application thereof Download PDF

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CN107442169B
CN107442169B CN201710696202.8A CN201710696202A CN107442169B CN 107442169 B CN107442169 B CN 107442169B CN 201710696202 A CN201710696202 A CN 201710696202A CN 107442169 B CN107442169 B CN 107442169B
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catalyst
nitrogen
chlorine
organotin
chloride
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CN107442169A (en
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李福祥
吴懿波
李博文
薛建伟
吕志平
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Taiyuan University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a catalyst loaded with chlorine-containing organotin and nitrogen-containing compounds, a preparation method and application thereof. The catalyst takes chlorine-containing organotin and nitrogen-containing compound as active components; under the condition of water bath, mixing chlorine-containing organotin and nitrogen-containing compound, dissolving the mixture in a solvent to prepare an impregnation solution, and stirring the carrier and the impregnation solution with equal volumes to obtain a sample, drying and roasting the sample to finally obtain a catalyst; the catalyst is applied to the acetylene hydrochlorination method to prepare the chloroethylene. The active component of the catalyst is non-noble metal, and does not contain mercury element, the synthesis process of the catalyst is simple and environment-friendly, and the synthesis cost is low. The catalyst is used for catalyzing the reaction of preparing the chloroethylene by the one-step method of acetylene and hydrogen chloride, and the catalyst has excellent reaction activity, selectivity and stability: at 200 ℃, the space velocity of acetylene is 15h‑1‑120 h‑1The molar ratio of the raw material gas is as follows: HCl/C2H2Under the condition of 1.05-1.1, the acetylene conversion rate is up to 99.5%.

Description

Catalyst loaded with chlorine-containing organotin and nitrogen-containing compound and preparation method and application thereof
Technical Field
The invention relates to a catalyst loaded with chlorine-containing organotin and nitrogen-containing compounds, a preparation method and application thereof, belonging to the technical field of catalysts and preparation thereof.
Background
The demand and the yield of the polyvinyl chloride are in the top of five synthetic resins, and the polyvinyl chloride resin has the characteristics of chemical corrosion resistance, electrical insulation, high quality, low price and the like, and is widely applied to important fields of agriculture, buildings, chemical industry, machinery, electronics, daily necessities and the like.
With the rapid development of economy, the living standard of people is increasingly improved, and the demand of polyvinyl chloride is continuously increased. Polyvinyl chloride is produced by polymerizing vinyl chloride. The production areas of the top three parts of the world vinyl chloride yield are Asia, North America and Western Europe in sequence, wherein the Asia yield accounts for more than 50% of the world total yield. In 2009 chinese yield of vinyl chloride accounted for 56.3% of asian yield. The current processes for the production of vinyl chloride are classified into three processes, including acetylene hydrochlorination, ethylene oxychlorination and ethane processes. Because China has abundant coal resourcesRich, oil and natural gas resources are relatively poor, so that the acetylene hydrochlorination method is rapidly developed in China, and the acetylene method is used for producing vinyl chloride by about 1.3 multiplied by 10 every year in China8t, the yield of polyvinyl chloride produced by the hydrochlorination of acetylene in china in 2015 accounts for 80.7% of the total yield. The traditional acetylene hydrochlorination method for preparing vinyl chloride adopts activated carbon loaded mercuric chloride as a catalyst, because the mercuric chloride is easy to run off in the reaction process, the stability of the catalyst is influenced, the running-off mercury causes serious damage to the environment and can also harm the life health of people, and meanwhile, the mercury resource is gradually poor and the international convention mercury limit exists, so that the research and synthesis of the catalyst which is low in cost, environment-friendly and excellent in activity is urgent.
Hutchings et al published a paper "Discovery, Development, and polymerization of Gold Catalysts for acetic hydrogenation" (journal of the American Chemical Society, 2015, 137(46): 14548.) and concluded that noble metals such as Au and Pd have strong catalytic activity in the preparation of vinyl chloride by the Acetylene process. The activity was verified in the experiment. Noble metals such as gold, palladium, etc. are used as catalysts. Although the noble metal catalyst has higher catalytic activity and vinyl chloride selectivity, the cost is too high, and the large-scale industrialization cannot be realized. The Dang national talent of the university of south Kokai and the like published a paper "development of a solid-phase non-mercury catalyst for synthesizing vinyl chloride by an acetylene method" (polyvinyl chloride, 1994, 6: 5-9.), three components of stannous chloride-bismuth trichloride-cuprous chloride composite non-catalyst are screened for the first time, and show excellent catalytic activity in the process of synthesizing vinyl chloride by acetylene hydrochlorination, and meanwhile, the stannous chloride component is found to be easy to lose in the reaction process in the research process. The method for preparing vinyl chloride by using activated carbon-loaded stannic chloride or stannous chloride as a catalyst in an acetylene hydrochlorination method has some defects. On one hand: stannic chloride has strong toxicity, is easy to pollute the environment, has strong corrosivity and can destroy the ecological environment. On the other hand, the boiling point of the stannic chloride is 114 ℃, and the reaction temperature for industrially producing vinyl chloride by hydrochlorinating acetylene is 150-200 ℃, so that the stannic chloride cannot exist stably. The catalytic activity of stannous chloride is general. The results show that inorganic tin shows certain catalytic activity in hydrochlorination of acetylene, but the key problems are to further improve the catalytic activity, improve the stability and reduce the pollution.
Disclosure of Invention
The invention aims to provide a catalyst loaded with chlorine-containing organotin and nitrogen-containing compounds, which has the characteristics of non-noble metal, no mercury, low cost, simple synthesis process and environmental protection. The invention provides a preparation method of the catalyst loaded with chlorine-containing organotin and nitrogen-containing compounds. The invention also provides the application of the catalyst loaded with chlorine-containing organotin and nitrogen-containing compound in preparing vinyl chloride by an acetylene hydrochlorination method, the catalyst has no adverse effect on the vinyl chloride polymerization process, and the catalyst activity and selectivity in the vinyl chloride synthesis process are excellent.
The invention provides a catalyst loaded with chlorine-containing organotin and nitrogen-containing compounds, which is prepared from the following raw materials:
the mass ratio of the chlorine-containing organotin, the nitrogen-containing compound and the carrier is as follows: 1-35:1-35:70.
The general formula of the chlorine-containing organotin is one of a formula I, a formula II or a formula III:
wherein the carbon atoms in R1, R2 and R3 are 1-20, and R1, R2 and R3 respectively represent one of alkyl, cycloalkyl, aromatic hydrocarbon, ester group and acyl;
the nitrogen-containing compound includes: one or more of dicyandiamide, melamine, urotropine and urea;
the carrier comprises: one of coconut shell activated carbon, coal-based activated carbon, pitch-based spherical activated carbon, columnar activated carbon, carbon nanotubes, silicon dioxide and zeolite molecular sieves.
Further, the chlorine-containing organotin is one of triphenyltin chloride, diphenyltin dichloride, phenyltin trichloride, monooctyltin trichloride, dioctyltin dichloride, trioctyltin chloride, tribenzyltin chloride, dibenzyltin chloride, monobenzyltin chloride, tricyclohexyltin chloride, dicyclohexyltin dichloride, cyclohexyltin trichloride, butyltin chloride dilaurate, octyltin chloride maleate, tributyltin chloride, dibutyltin dichloride and monobutyltin trichloride.
The invention provides a preparation method of the catalyst loaded with chlorine-containing organotin and nitrogen-containing compounds, which comprises the following steps:
(1) under the condition of water bath at 60-90 ℃, chlorine-containing organic tin and nitrogen-containing compounds are mixed and dissolved in a solvent, and the mixture is stirred in an open container for 5-60 min to prepare a steeping liquor, wherein the mass percentage concentration of the chlorine-containing organic tin is 1-55%, and the mass percentage concentration of the nitrogen-containing compounds is 1-40%;
(2) and stirring the carrier and the impregnation liquid in the same volume in an open container to obtain a sample, and drying and roasting the sample to finally obtain the catalyst.
The solvent comprises: one of methanol, ethanol and acetone.
The equal volume open stirring of the carrier and the steeping liquor refers to that: under the condition of 60-90 ℃, the soaking solution and the carrier are exposed to the atmosphere with the same volume and are stirred and soaked for 1-24 h; wherein the mass ratio of the chlorine-containing organotin to the carrier is 1-35:70, and the mass ratio of the nitrogen-containing compound to the carrier is 1-35: 70.
The drying is that: placing the impregnated carrier in an oven at 90-120 ℃ for drying for 6-24 h; the roasting is as follows: under the nitrogen atmosphere, heating to 150-650 ℃ at a heating rate of 1-15 ℃/min, keeping for more than 4h, and naturally cooling to room temperature to finally obtain the catalyst.
The invention provides application of the catalyst loaded with chlorine-containing organotin and nitrogen-containing compound in preparing vinyl chloride by an acetylene hydrochlorination method.
In the application, the temperature is controlled by electric heating to be raised to the reaction temperature of 150-200 ℃, the mass of the catalyst is 1.8-17.5 g, the space velocity of acetylene is 15/h-120/h, and the molar ratio of the raw material gas is as follows: HCl/C2H21.05-1.1:1, the reaction pressure is normal pressure; removing unreacted hydrogen chloride gas from the reaction tail gas by medical soda lime, sampling, and purifying in gas phaseThe analysis was performed in the spectra.
In the method for preparing vinyl chloride by using the catalyst in the acetylene hydrochlorination method, the highest conversion rate of acetylene can reach 99.5 percent, and the highest selectivity of vinyl chloride can reach 99.8 percent.
The invention has the beneficial effects that:
the active component of the catalyst provided by the invention is non-noble metal, does not contain mercury element, and has simple and environment-friendly synthesis process and low synthesis cost. Chlorinated organotin is generally used as a heat stabilizer and does not require removal during the subsequent polymerization of vinyl chloride. In the acetylene method vinyl chloride synthesis process, the catalyst activity and selectivity are excellent.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
firstly, 18ml of dioctyl tin dichloride solution with the mass percent concentration of 11 percent and 18ml of dicyandiamide solution with the mass percent concentration of 11 percent are mixed, methanol is used as a solvent, the mixture is subjected to open stirring for 30min under the water bath condition of 65 ℃, then 16g of 20-40 mesh active carbon is added, and the same-volume open stirring impregnation is carried out for 2h under the water bath condition of 65 ℃; drying the impregnated catalyst in a drying oven at 80 ℃ for 12 h; after drying, putting the catalyst into a tubular furnace in a nitrogen atmosphere, roasting the catalyst for 4 hours at 500 ℃, and naturally cooling the catalyst to room temperature to obtain the catalyst A.
The catalyst is used in the process of synthesizing chloroethylene by acetylene hydrochlorination: 17.5g of the catalyst was charged into a fixed bed reactor (made of glass) having an inner diameter of 16mm at a gas space velocity of 15 hours-1The reaction temperature is 200 ℃, and the molar ratio of raw material gas is HCl/C2H2=1.05:1, analyzing reaction tail gas, wherein the acetylene conversion rate of the catalyst is 99.5%, and the selectivity of chloroethylene is 98.6%.
The catalyst evaluation is shown in Table 1.
Example 2
Firstly, mixing 20ml of 10 percent by mass of a monooctyl tin trichloride solution and 16ml of 12.5 percent by mass of a melamine solution, taking ethanol as a solvent, stirring for 15min under the condition of 80 ℃ water bath, then adding 18g of 20-40 mesh active carbon, and carrying out isometric open stirring impregnation for 4h under the condition of 80 ℃ water bath; drying the impregnated catalyst in a drying oven at 100 ℃ for 15 h; after drying, placing the catalyst into a tubular furnace in a nitrogen atmosphere, roasting the catalyst for 6 hours at 450 ℃, and naturally cooling the catalyst to room temperature to obtain a catalyst B.
The catalyst is used in the process of synthesizing chloroethylene by acetylene hydrochlorination: 8.8g of the catalyst was charged into a fixed bed reactor (made of glass) having an inner diameter of 16mm at a gas space velocity of 30 hours-1The reaction temperature is 200 ℃, and the molar ratio of raw material gas is HCl/C2H2The catalyst is subjected to an acetylene hydrochlorination test under the condition of 1.05:1, and the catalyst has acetylene conversion rate of 96.6% and vinyl chloride selectivity of 98.9% by analyzing reaction tail gas.
The catalyst evaluation is shown in Table 1.
Example 3
Firstly, mixing 20ml of diphenyl tin dichloride solution with the mass percentage concentration of 10% and 16ml of melamine solution with the mass percentage concentration of 12.5%, taking ethanol as a solvent, stirring for 5min at the temperature of 80 ℃, then adding 15g of 20-40 mesh active carbon, and carrying out isometric open stirring impregnation for 4h under the water bath condition at the temperature of 80 ℃; drying the impregnated catalyst in a drying oven at 100 ℃ for 12 h; and after drying, putting the catalyst into a tubular furnace, roasting the catalyst for more than 4 hours at the temperature of 400 ℃, and naturally cooling the catalyst to room temperature to obtain a catalyst C.
The catalyst is used in the process of synthesizing chloroethylene by acetylene hydrochlorination: 10.3g of the above catalyst were charged into a reactor at a gas space velocity of 30h-1The reaction temperature is 200 ℃, and the molar ratio of raw material gas is HCl/C2H2The catalyst is subjected to an acetylene hydrochlorination test under the condition of 1.05:1, and the catalyst has acetylene conversion rate of 94.5% and vinyl chloride selectivity of 98.4% by analyzing reaction tail gas.
The catalyst evaluation is shown in Table 1.
Example 4
Firstly, mixing 25ml of monophenyl tin trichloride solution with the mass percentage concentration of 8% and 11ml of dicyandiamide solution with the mass percentage concentration of 18.2%, taking ethanol as a solvent, stirring for 25min under the condition of 80 ℃ water bath, then adding 18g of 20-40 mesh active carbon, carrying out isometric open stirring impregnation under the condition of 80 ℃ water bath, and evaporating to dryness; drying the impregnated catalyst in a drying oven at 100 ℃ for 12 h; after drying, putting the catalyst into a tube furnace in the atmosphere, roasting the catalyst for 5 hours at 500 ℃, and naturally cooling the catalyst to room temperature to obtain a catalyst D.
The catalyst is used in the process of synthesizing chloroethylene by acetylene hydrochlorination: 4.4g of the catalyst was charged into a fixed bed reactor (made of glass) having an inner diameter of 16mm at a gas space velocity of 60 hours-1The reaction temperature is 190 ℃, and the molar ratio of raw material gas is HCl/C2H2The catalyst is subjected to an acetylene hydrochlorination test under the condition of 1.05:1, and the catalyst has acetylene conversion rate of 81.6% and vinyl chloride selectivity of 99.1% by analyzing reaction tail gas.
The catalyst evaluation is shown in Table 1.
Example 5
Firstly, 18ml of dicyclohexyltin dichloride solution with the mass percentage concentration of 11 percent and 18ml of urotropine solution with the mass percentage concentration of 11 percent are mixed, ethanol is used as a solvent, the mixture is stirred for 30min under the condition of 80 ℃ water bath, then 18g of 20-40 mesh silicon dioxide microspheres are added, the equal-volume open stirring impregnation is carried out under the condition of 80 ℃ water bath, and the mixture is evaporated to dryness; drying the impregnated catalyst in a drying oven at 100 ℃ for 12 h; after drying, the catalyst is put into a tube furnace, roasted for 6 hours at the temperature of 200 ℃, and naturally cooled to room temperature to obtain a catalyst E.
The catalyst is used in the process of synthesizing chloroethylene by acetylene hydrochlorination: 6.7g of the above catalyst were charged into a reactor at a gas space velocity of 30h-1The reaction temperature is 200 ℃, and the molar ratio of raw material gas is HCl/C2H2=1.05:1, analyzing reaction tail gas, wherein the acetylene conversion rate of the catalyst is 94.9%, and the selectivity of vinyl chloride is 98.7%.
The catalyst evaluation is shown in Table 1.
Example 6
Firstly, mixing 20ml of 10 percent by mass of a mono-octyl tin trichloride solution and 16ml of 12.5 percent by mass of a dicyandiamide solution, taking ethanol as a solvent, stirring for 30min under the condition of 80 ℃ water bath, then adding 18g of 20-40 mesh active carbon, carrying out equal-volume open stirring impregnation under the condition of 80 ℃ water bath, and carrying out impregnation for 4 h; drying the impregnated catalyst in a drying oven at 100 ℃ for 12 h; after drying, the catalyst is put into a tube furnace, roasted for 4 hours at the temperature of 450 ℃, and naturally cooled to the room temperature to obtain a catalyst F.
The catalyst is used in the process of synthesizing chloroethylene by acetylene hydrochlorination: 6.1g of the above catalyst was charged into a reactor at a gas space velocity of 20h-1The reaction temperature is 200 ℃, and the molar ratio of raw material gas is HCl/C2H2=1.05:1, analyzing reaction tail gas, wherein the acetylene conversion rate of the catalyst is 98.9%, and the selectivity of vinyl chloride is 98.1%.
The catalyst evaluation is shown in Table 1.
Example 7
Firstly, mixing 15ml of dibutyltin dichloride solution with the mass percentage concentration of 13.3 percent and 15ml of dicyandiamide solution with the mass percentage concentration of 13.3 percent, taking ethanol as a solvent, stirring for 30min under the condition of 78 ℃ water bath, then adding 18g of 20-40 mesh ZSM-5, carrying out isometric open stirring impregnation under the condition of 80 ℃ water bath, and carrying out impregnation for 4 h; drying the impregnated catalyst in a drying oven at 100 ℃ for 12 h; after drying, the catalyst is put into a tube furnace, roasted for 12 hours at the temperature of 150 ℃, and naturally cooled to room temperature to obtain a catalyst G.
The catalyst is used in the process of synthesizing chloroethylene by acetylene hydrochlorination: 9.6g of the above catalyst was charged into a reactor at a gas space velocity of 30h-1The reaction temperature is 170 ℃, and the molar ratio of raw material gas is HCl/C2H2=1.1:1, analyzing reaction tail gas, wherein the acetylene conversion rate of the catalyst is 41.8 percent, and the selectivity of chloroethylene is 98.9 percent.
The catalyst evaluation is shown in Table 1.
Example 8
Firstly, mixing 20ml of 10 mass percent tin stearate solution and 16ml of 1.5 mass percent dicyandiamide solution, taking ethanol as a solvent, stirring for 30min under the condition of water bath at 79 ℃, then adding 18g of 20-40 mesh active carbon, carrying out isometric open stirring impregnation under the condition of water bath at 79 ℃, and carrying out impregnation for 4 h; drying the impregnated catalyst in a drying oven at 100 ℃ for 12 h; after drying, the catalyst is put into a tube furnace, roasted for 4 hours at the temperature of 200 ℃, and naturally cooled to room temperature to obtain a catalyst H.
The catalyst is used in the process of synthesizing chloroethylene by acetylene hydrochlorination: 7.9g of the above catalyst were charged into a reactor at a gas space velocity of 30h-1The reaction temperature is 150 ℃, and the molar ratio of raw material gas is HCl/C2H2The catalyst is subjected to an acetylene hydrochlorination test under the condition of 1.05:1, and the catalyst has the acetylene conversion rate of 15.7% and the vinyl chloride selectivity of 99.0% by analyzing reaction tail gas.
The catalyst evaluation is shown in Table 1.
Example 9
Firstly, mixing 20ml of 10 mass percent maleic acid octyl tin chloride solution and 16ml of 12.5 mass percent urea solution, taking ethanol as a solvent, stirring for 30min under the condition of water bath at 79 ℃, then adding 18g of 20-40 mesh active carbon, carrying out isometric open stirring impregnation under the condition of water bath at 60 ℃, and carrying out impregnation for 4 h; drying the impregnated catalyst in a drying oven at 100 ℃ for 12 h; after drying, the catalyst is put into a tube furnace, roasted for 4 hours at 650 ℃, and naturally cooled to room temperature to obtain a catalyst I.
The catalyst is used in the process of synthesizing chloroethylene by acetylene hydrochlorination: 14.7g of the above catalyst were charged into a reactor at a gas space velocity of 120h-1The reaction temperature is 160 ℃, and the molar ratio of raw material gas is HCl/C2H2The catalyst is subjected to an acetylene hydrochlorination test under the condition of 1.1:1, and the catalyst has the acetylene conversion rate of 22.53% and the vinyl chloride selectivity of 99.8% by analyzing reaction tail gas.
The catalyst evaluation is shown in Table 1.
Example 10
Firstly, mixing 30ml of 9.0 mass percent dioctyl tin dichloride solution, 10ml of 11.3 mass percent dicyandiamide and 12ml of 11.3 mass percent urea solution, taking ethanol as a solvent, stirring for 30min under the condition of 80 ℃ water bath, then adding 18g of 20-40 mesh active carbon, carrying out isometric open stirring impregnation under the condition of 90 ℃ water bath, and carrying out impregnation for 4 h; drying the impregnated catalyst in a drying oven at 100 ℃ for 12 h; after drying, the catalyst is put into a tube furnace, roasted for 4 hours at 550 ℃, and naturally cooled to room temperature to obtain a catalyst J.
The catalyst is used in the process of synthesizing chloroethylene by acetylene hydrochlorination: 1.8g of the above catalyst was charged into a reactor at a gas space velocity of 30h-1The reaction temperature is 180 ℃, and the molar ratio of raw material gas is HCl/C2H2The catalyst is tested by an acetylene hydrochlorination method under the condition of 1.1:1, and the catalyst has the acetylene conversion rate of 79.1% and the selectivity of vinyl chloride of 98.5% by analyzing reaction tail gas.
The catalyst evaluation is shown in Table 1.
Table 1 evaluation of catalysts
Figure 782986DEST_PATH_IMAGE002

Claims (9)

1. The catalyst for loading chlorine-containing organotin and nitrogen-containing compound is characterized by being prepared from the following raw materials:
the mass ratio of the chlorine-containing organotin, the nitrogen-containing compound and the carrier is as follows: 1-35:1-35: 70;
the general formula of the chlorine-containing organotin is one of a formula I, a formula II or a formula III:
Figure 943580DEST_PATH_IMAGE001
Figure 31622DEST_PATH_IMAGE002
formula I, formula II, formula III
Wherein the carbon atoms in R1, R2 and R3 are 1-20, and R1, R2 and R3 respectively represent one of alkyl, cycloalkyl, aromatic hydrocarbon, ester group and acyl;
the nitrogen-containing compound includes: one or more of dicyandiamide, melamine, urotropine and urea;
the carrier comprises: one of coconut shell activated carbon, coal-based activated carbon, pitch-based spherical activated carbon, columnar activated carbon, carbon nanotubes, silicon dioxide and zeolite molecular sieves;
the preparation method of the catalyst loaded with chlorine-containing organotin and nitrogen-containing compound comprises the following steps:
(1) under the condition of water bath at 60-90 ℃, chlorine-containing organic tin and nitrogen-containing compounds are mixed and dissolved in a solvent, and the mixture is stirred in an open container for 5-60 min to prepare a steeping liquor, wherein the mass percentage concentration of the chlorine-containing organic tin is 1-55%, and the mass percentage concentration of the nitrogen-containing compounds is 1-40%;
(2) stirring the carrier and the impregnation liquid in the same volume in an open container to obtain a sample, and drying and roasting the sample to finally obtain the catalyst;
the roasting is as follows: under the nitrogen atmosphere, heating to 150-650 ℃ at a heating rate of 1-15 ℃/min, keeping for more than 4h, and naturally cooling to room temperature to finally obtain the catalyst.
2. The organotin-containing and nitrogen compound-containing supported catalyst according to claim 1, characterized in that: the chlorine-containing organotin is one of triphenyltin chloride, diphenyltin dichloride, phenyltin trichloride, monooctyltin trichloride, dioctyltin dichloride, trioctyltin chloride, tribenzyltin chloride, dibenzyltin chloride, monobenzyltin chloride, tricyclohexyltin chloride, dicyclohexyltin dichloride, monocyclohexyltin trichloride, butyltin chloride dilaurate, octyltin chloride maleate, tributyltin chloride, dibutyltin dichloride and monobutyltin trichloride.
3. The organotin-containing and nitrogen compound-containing supported catalyst according to claim 1, characterized in that: the solvent is one of methanol, ethanol and acetone.
4. The organotin-containing and nitrogen compound-containing supported catalyst according to claim 1, characterized in that: the equal volume open stirring of the carrier and the steeping liquor refers to that: under the condition of 60-90 ℃, the soaking solution and the carrier are exposed to the atmosphere with the same volume and are stirred and soaked for 1-24 h; the mass ratio of the chlorine-containing organotin to the carrier is 1-35:70, and the mass ratio of the nitrogen-containing compound to the carrier is 1-35: 70.
5. The organotin-containing and nitrogen compound-containing supported catalyst according to claim 1, characterized in that: the drying is that: and (3) drying the impregnated carrier in an oven at 90-120 ℃ for 6-24 h.
6. Use of the catalyst supporting organotin containing chlorine and nitrogen-containing compound as claimed in claim 1 or 2 in the preparation of vinyl chloride by hydrochlorination of acetylene.
7. Use according to claim 6, characterized in that: the temperature is controlled by electrical heating to be raised to the reaction temperature of 150-200 ℃, the mass of the catalyst is 1.8-17.5 g, the space velocity of acetylene is 15/h-120/h, and the molar ratio of raw material gas is as follows: HCl/C2H21.05-1.1:1, the reaction pressure is normal pressure; and removing unreacted hydrogen chloride gas in the mixed gas by using the reaction tail gas through medical soda lime, then sampling, and analyzing in a gas chromatography.
8. Use according to claim 7, characterized in that: the highest conversion rate of acetylene can reach 99.5 percent.
9. Use according to claim 7, characterized in that: the highest selectivity of vinyl chloride can reach 99.8%.
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CN104588112A (en) * 2015-01-21 2015-05-06 四川花语精细化工有限公司 Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof

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JPS5083303A (en) * 1973-11-27 1975-07-05
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