CN117463400A - Insoluble platinum-ion solution complex catalyst, preparation method and application thereof, and method for preparing vinyl chloride by hydrochlorination of acetylene - Google Patents

Insoluble platinum-ion solution complex catalyst, preparation method and application thereof, and method for preparing vinyl chloride by hydrochlorination of acetylene Download PDF

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CN117463400A
CN117463400A CN202311146167.4A CN202311146167A CN117463400A CN 117463400 A CN117463400 A CN 117463400A CN 202311146167 A CN202311146167 A CN 202311146167A CN 117463400 A CN117463400 A CN 117463400A
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platinum
ion solution
complex catalyst
acetylene
insoluble
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李建
戴云生
安霓虹
左川
侯文明
冯洋洋
刘俊
王金营
杨文超
蒋金科
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Kunming Sino Platinum Metals Catalyst Co ltd
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Kunming Sino Platinum Metals Catalyst Co ltd
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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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • B01J33/00—Protection of catalysts, e.g. by coating
    • 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
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of catalysts, and provides an insoluble platinum-ion solution complex catalyst which is used for solving the problem that the stability and the catalytic activity of the existing catalyst are not high enough, wherein the carrier of the catalyst comprises active carbon; the auxiliary agent of the catalyst comprises an ionic solution containing at least one atom of N, O, S and P as a heteroatom; the active component of the catalyst comprises a platinum precursor. Compared with the existing metal catalyst for hydrochlorination of acetylene, the insoluble platinum-ion solution complex catalyst provided by the invention has the advantages that active components in the insoluble platinum-ion solution complex catalyst are in a high dispersion state, are not easy to run off and agglomerate, acetylene and hydrogen chloride reactants are activated, and the catalytic activity and stability of the existing metal catalyst are improved.

Description

Insoluble platinum-ion solution complex catalyst, preparation method and application thereof, and method for preparing vinyl chloride by hydrochlorination of acetylene
Technical Field
The invention relates to the field of catalysts, in particular to an insoluble platinum-ion solution complex catalyst, a preparation method and application thereof, and a method for preparing vinyl chloride by hydrochlorination of acetylene.
Background
Polyvinyl chloride (PVC) is a high polymer material polymerized by Vinyl Chloride (VCM), and the global usage amount thereof is the third position of the high polymer material, and is widely applied to the fields of industry, agriculture, daily life and the like. The production method of VCM is mainly divided into acetylene method and ethylene method, the proportion (more than 80%) of the production process of acetylene method based on coal is far superior to that of ethylene method based on oil gas, and the PVC productivity of China is rapidly improved along with the rapid development of national economy. In 2007, PVC productivity in China generally tends to increase. According to China chlorine-alkali industry association data, 2021, the total production capacity of Chinese polyvinyl chloride (PVC) reaches 2713 ten thousand tons/year, and 49 ten thousand tons/year is improved compared with 2020. However, hgCl is still adopted in actual industrial production at present 2 As industrial catalyst for the hydrochlorination of acetylene, 1.02-1.41kg of catalyst per ton of PVC are statistically consumed, of which about 25% of HgCl 2 The components are lost during the recycling process. The service life of the catalyst is estimated according to 10000 hours, at present, the annual consumption of mercury chloride in China reaches 8000t, the consumption of mercury resources is reduced to 500t, the annual consumption of mercury in VCM production is about 70% of the mercury consumption in China, and the global mercury demand is realized20% of the measured value; our country has signed the water convention for limiting mercury usage and emissions, requiring that production processes using mercury or mercury compounds be eliminated by 2025. Mercury is used as a rare resource and heavy metal with high sensitivity to the environment, the supply amount is reduced year by year, the consumption of the mercury resource in the calcium carbide process polyvinyl chloride industry is increased day by day, the excessive consumption and dependence of the mercury resource are huge barriers to the development of the calcium carbide process polyvinyl chloride, and meanwhile, the mercury-containing waste discharged in the production process of the calcium carbide process polyvinyl chloride seriously threatens the physical health and ecological balance of human beings. The reduction of mercury consumption and mercury pollution is an urgent task related to the development of the PVC industry, and is also a key link for realizing sustainable and healthy development of the PVC industry.
Under the double constraints of 'water protocol' and 'double carbon target', a higher requirement is put forward on the green sustainable development of the polyvinyl chloride industry, so that the project aims at the problem to develop a non-mercury noble metal catalyst with high catalytic efficiency and green economy, lays a foundation for the application of the mercury-free catalyst in the VCM production process, and has a clear national condition characteristic. The current common preparation method of the supported catalyst in the hydrochlorination of acetylene is that a metal precursor and an auxiliary agent are supported on a carrier by an impregnation method under certain conditions.
The patent with publication number of CN116408151A discloses a noble metal catalyst for hydrochlorination of acetylene, a preparation method and application thereof, wherein the catalyst comprises active carbon, ionic liquid and ruthenium species, and the ionic liquid is one or more of 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazolium salt, 1-butyl-3-methylimidazolium bromide, N-ethylpyridine bromide, tributyl methyl ammonium diimmonium salt, tributylhexyl phosphorus bromide, N-butyl-N-methylpyrrolidine bromide and N-butyl-N-methylpiperidine bromide ionic liquid.
Patent publication No. CN113649057A discloses a platinum catalyst for preparing vinyl chloride by hydrochlorination of acetylene, a preparation method and application thereof, wherein a carrier of the catalyst is carbon nitride, an active component is platinum, and the platinum exists in an ionic form on the carrier. The catalyst is applied to an acetylene hydrochlorination process, and can obtain higher chloroethylene yield; compared with the mercury-free catalyst reported in the prior literature, the catalyst provided by the invention has excellent stability and good service life.
Disclosure of Invention
The invention aims to provide an insoluble platinum-ion solution complex catalyst, which solves the problem that the stability and catalytic activity of the existing mercury-free catalyst are not high enough.
The embodiment of the invention is realized by the following technical scheme:
an insoluble platinum-ion solution complex catalyst, the carrier of which comprises activated carbon; the auxiliary agent of the catalyst comprises an ionic solution containing at least one atom of N, O, S and P as a heteroatom; the active component of the catalyst comprises a platinum precursor. The preferred support is coal-based columnar activated carbon.
Further, the auxiliary agent at least comprises one of 1-ethyl-3-methylimidazole diethyl phosphate, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole nitrate, 1-ethyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole ethyl sulfate, 1-ethyl-3-methylimidazole perchlorate, 1-amyl-3-methylimidazole chloride and 1-amyl-3-methylimidazole triflate. Preferably, the auxiliary agent is 1-ethyl-3-methylimidazole nitrate.
Further, the platinum precursor at least comprises PtCl 4 、H 2 PtCl 6 、(NH 4 ) 2 PtCl 6 And C 8 H 12 Cl 2 One of Pt. Preferably, the platinum precursor is H 2 PtCl 6 。
Further, the Pt loading is 0.2-1wt% based on the total weight of the catalyst. Preferably 0.2 to 0.4wt%.
Wherein, the total weight of the catalyst is calculated by the following steps: m is m Total (S) ＝m Carrier body +m Steady state metal precursors +m Auxiliary agent 。
For example: in example 1, the load amount was calculated by: m is m Pt /(m Carrier body +m Steady state metal precursors +m Auxiliary agent )＝0.02g/(0.0421g+0.0271g+9.9308g)＝0.2wt％。
The preparation method of the insoluble platinum-ion solution complex catalyst comprises the steps of slowly dropwise adding an auxiliary agent solution into a prepared platinum precursor solution for mixing reaction, adding a carrier into the mixed solution, and finally obtaining the platinum-based catalyst through dipping and drying.
Further, the molar ratio of the platinum precursor to the auxiliary agent is 1:0.1-5.
Further, the molar ratio of the platinum precursor to the auxiliary agent is 1:1-2.
Further, the dipping temperature is 50-150 ℃; the soaking time is 6-12h. Preferably, the dipping temperature is 70-120 ℃ and the dipping time is 8-10h.
Further, the particle size of the carrier is 1.5-5mm. Preferably, the particle size of the carrier is 2-4mm.
The method for preparing vinyl chloride by hydrochlorination of acetylene comprises the steps of taking acetylene and hydrogen chloride as raw materials, mixing and reacting to obtain vinyl chloride, wherein the reaction is carried out under the catalysis of the insoluble platinum-ion solution complex catalyst.
The reaction is a gas phase reaction.
The reactions mainly involved in the hydrochlorination of acetylene include:
the main reaction: c (C) 2 H 2 +HCl→CH 2 ＝CHCl
Non-polymerization side reactions:
CH 2 ＝CHCl+HCl→CH 3 CHCl 2
CH 2 ＝CHCl+HCl→CH 2 ClCH 2 Cl
polymerization side reaction:
2CH 2 ＝CHCl→CH 2 ClCH＝CCl-CH3
2C 2 H 2 →CH 2 ＝CH-C≡CH
the prior thermodynamic research shows that the main reaction is greatly influenced by polymerization side reaction, the influence of non-polymerization side reaction on the main reaction is small, the main reaction and the side reaction are exothermic reaction, but the thermal effect of the polymerization side reaction is larger than that of the main reaction, the higher temperature is more favorable for inhibiting the polymerization side reaction, reducing the deposition of a polymerization product on the surface of a catalyst, improving the selectivity of the main reaction and reducing carbon deposit, but the metal catalyst has the problem of valence-changing inactivation at high temperature. Taking into consideration the influence of temperature on polymerization side reaction and catalyst reduction deactivation, the reaction temperature is controlled to be 110-300 ℃, more preferably 140-280 ℃, most preferably 170-240 ℃.
The volume ratio of acetylene to hydrogen chloride is generally used in the art, specifically 1:1-2, more preferably, the volume ratio of acetylene to hydrogen chloride is 1:1-1.5, and most preferably, the volume ratio of acetylene to hydrogen chloride is 1:1.02-1.2.
The gas phase reaction is carried out in a fixed bed reactor in which the catalyst is packed. The control range of the acetylene volume airspeed adopts the control range commonly used in the field, and is particularly 30-1200h -1 Preferably, the volume space velocity of acetylene is controlled between 30 and 900 hours -1 。
The application of the insoluble platinum-ion solution complex catalyst in preparing vinyl chloride by mixing acetylene and hydrogen chloride. The reaction is a gas phase reaction, and the reaction temperature is 110-300 ℃.
The invention has at least the following beneficial effects:
compared with the existing metal catalyst for hydrochlorination of acetylene, the insoluble platinum-ion solution complex catalyst provided by the invention has the advantages that active components in the insoluble platinum-ion solution complex catalyst are in a high dispersion state, are not easy to run off and agglomerate, acetylene and hydrogen chloride reactants are activated, and the catalytic activity and stability of the existing metal catalyst are improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing acetylene conversion versus reaction time for the catalysts prepared in examples 1-8 and comparative example 1.
FIG. 2 is a TPD curve of catalyst vs. reactant acetylene for the preparation of examples 1-8 and comparative example 1.
FIG. 3 shows TPD curves of the catalysts prepared in examples 1-8 and comparative example 1 versus the reaction product vinyl chloride.
FIG. 4 shows the acetylene conversion curves for the catalyst prepared in examples 9-11 and example 3 for 24h.
Detailed Description
For the purposes of making the objects, method aspects and advantages of the embodiments of the present invention clear, a method aspect of the embodiments of the present invention will be clearly and completely described, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments.
1. The preparation method of the catalyst comprises the following steps:
according to different addition sequences of the carrier, the auxiliary agent and the active ingredient, the preparation method can be divided into three preparation methods, and the preferred selection method is as follows: slowly dripping the auxiliary agent solution into the prepared platinum precursor ethanol solution, stirring for 2-10h at normal temperature, and then adding the active carbon carrier into the mixed solution for continuous stirring for 2-10h. The mixture was allowed to stand at 70℃for 6-12 hours and then dried at 120℃for 12 hours to give a platinum-based catalyst.
The above limitations on temperature or time are due to the need to react at the above temperatures for a period of time to allow for a more uniform dispersion of the insoluble complex on the support.
2. Hydrochlorination of acetylene
Filling the insoluble platinum-ion solution complex catalyst prepared in the first step into a fixed bed reactor as a catalyst, introducing acetylene and hydrogen chloride reaction gas, and controlling the acetylene space velocity (GHSV) at 110-300 ℃ for 30-1200h -1 And reacting for 24 hours under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1-2.
The reaction temperature is controlled between 110 and 300 ℃, more preferably between 140 and 280 ℃, and most preferably between 170 and 240 ℃.
Example 1:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0421g H in a 50mL beaker 2 PtCl 6 Dissolving in 15mL of ethanol, slowly dripping 15mL of 1-ethyl-3-methylimidazole diethyl phosphate (0.0271 g) ethanol solution into the solution, continuously stirring for 2h, adding 9.9308g CAC with the particle size of 2mm, and stirring for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt-L 1 /CAC。
Example 2:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0421g H in a 50mL beaker 2 PtCl 6 Dissolving in 15mL of ethanol, slowly dripping 15mL of 1-ethyl-3-methylimidazole acetate (0.0174 g) ethanol solution into the solution, continuously stirring for 2h, adding 9.9405g CAC with the particle size of 2mm, and stirring for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt-L 2 /CAC。
Example 3:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0421g H in a 50mL beaker 2 PtCl 6 Dissolving in 15mL of ethanol, slowly dripping 15mL of 1-ethyl-3-methylimidazole nitrate (0.0178 g) ethanol solution into the solution, continuously stirring for 2h, adding 9.9402g CAC with the particle size of 2mm, and stirring for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt-L 3 /CAC。
Example 4:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0421g H in a 50mL beaker 2 PtCl 6 Dissolving in 15mL of ethanol, and slowly dissolving 15mL of 1-ethyl-3-methylimidazole chloride (0.0150 g) in ethanolDropwise adding the mixture into the mixture, continuously stirring for 2 hours, adding 9.9429g of CAC with the particle size of 2mm, and stirring for 2 hours; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt-L 4 /CAC。
Example 5:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0421g H in a 50mL beaker 2 PtCl 6 Dissolving in 15mL of ethanol, slowly dripping 15mL of 1-ethyl-3-methylimidazole ethyl sulfate (0.0242 g) ethanol solution into the solution, continuously stirring for 2h, adding 9.9337g CAC with the particle size of 2mm, and stirring for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt-L 5 /CAC。
Example 6:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0421g H in a 50mL beaker 2 PtCl 6 Dissolving in 15mL of ethanol, slowly dripping the prepared 15mL of 1-ethyl-3-methylimidazole perchlorate (0.0216 g) ethanol solution into the ethanol solution, continuously stirring for 2h, adding 9.9363g of CAC with the particle size of 2mm, and stirring for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt-L 6 /CAC。
Example 7:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0421g H in a 50mL beaker 2 PtCl 6 Dissolving in 15mL of ethanol, slowly dripping 15mL of 1-amyl-3-methylimidazole chloride (0.0193 g) ethanol solution into the solution, continuously stirring for 2h, adding 9.9386g CAC with the particle size of 2mm, and stirring for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt-L 7 /CAC。
Example 8:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0421g H in a 50mL beaker 2 PtCl 6 Dissolving in 15mL of ethanol, slowly dripping 15mL of 1-amyl-3-methylimidazole trifluoro methanesulfonate (0.0310 g) ethanol solution into the ethanol solution, continuously stirring for 2h, adding 9.9269g CAC with the particle size of 2mm, and stirring for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt-L 8 /CAC。
Example 9:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0345g PtCl was placed in a 50mL beaker 4 Dissolving in 15mL of ethanol, slowly dripping 15mL of 1-ethyl-3-methylimidazole nitrate (0.0178 g) ethanol solution into the solution, continuously stirring for 2h, adding 9.9477g CAC with the particle size of 2mm, and stirring for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt 1 -L 3 /CAC。
Example 10:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0455g (NH) was placed in a 50mL beaker 4 ) 2 PtCl 6 Dissolving in 15mL of ethanol, slowly dripping 15mL of 1-ethyl-3-methylimidazole nitrate (0.0178 g) ethanol solution into the solution, continuously stirring for 2h, adding 9.9367g CAC with the particle size of 2mm, and stirring for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt 2 -L 3 /CAC。
Example 11:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
will 0.0384g C in a 50mL beaker 8 H 12 Cl 2 Pt was dissolved in 15mL of ethanol, and 15mL of 1-ethyl-3-A was preparedAn ethanol solution of imidazole nitrate (0.0178 g) was slowly added dropwise thereto, and after stirring was continued for 2 hours, 9.9439g of CAC having a particle size of 2mm was added thereto and stirred for 2 hours; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt 3 -L 3 /CAC。
Comparative example 1:
the preparation method of the insoluble platinum-ion solution complex catalyst comprises the following steps:
0.0421g H in a 50mL beaker 2 PtCl 6 Dissolving in 15mL of ethanol, slowly dripping the prepared 15mL of ethanol solution into the solution, continuously stirring for 2 hours, adding 9.9579g of CAC with the particle size of 2mm, and stirring for 2 hours; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried by punching, and then the beaker is dried for 12 hours at 120 ℃. The catalyst prepared was designated Pt/CAC.
Example 12
5mL of the catalyst prepared in examples 1 to 8 and comparative example 1 were packed in a fixed bed reactor, and acetylene and hydrogen chloride reaction gas were introduced at 180℃with a space velocity of acetylene (GHSV) of 600h -1 And (3) reacting for 24 hours under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1.15, and detecting the conversion rate of acetylene and the selectivity of vinyl chloride. The test results of the hydrochlorination of acetylene catalyzed by each catalyst are shown in Table 1 and FIG. 1.
Example 10
5mL of the catalyst prepared in examples 9 to 11 and example 1 were packed in a fixed bed reactor, and acetylene and hydrogen chloride reaction gas were introduced at 180℃with a space velocity of acetylene (GHSV) of 600h -1 And (3) reacting for 24 hours under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1.15, and detecting the conversion rate of acetylene and the selectivity of vinyl chloride. The test results of the hydrochlorination of acetylene catalyzed by each catalyst are shown in Table 2 and FIG. 4.
TABLE 1 conversion of acetylene hydrochlorination catalyzed by different catalysts
TABLE 2 conversion of acetylene hydrochlorination catalyzed by different precursor catalysts
The catalytic test result of the catalyst on the hydrochlorination of acetylene shows that the stability of the catalyst is obviously improved after the addition of the auxiliary agent, and the catalyst added with the auxiliary agent containing nitrogen-oxygen double bonds has higher activity and higher stability compared with other auxiliary agents. The chloroplatinic acid precursor has better reactivity than the other three precursors.
The above is only a preferred embodiment of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. An insoluble platinum-ion solution complex catalyst, characterized in that the carrier of the catalyst comprises activated carbon; the auxiliary agent of the catalyst comprises an ionic solution containing at least one atom of N, O, S and P as a heteroatom; the active component of the catalyst comprises a platinum precursor.
2. The insoluble platinum-ion solution complex catalyst according to claim 1, wherein the auxiliary comprises at least one of 1-ethyl-3-methylimidazole diethyl phosphate, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole nitrate, 1-ethyl-3-methylimidazole chloride, ethyl 1-ethyl-3-methylimidazole sulfate, 1-ethyl-3-methylimidazole perchlorate, 1-pentyl-3-methylimidazole chloride, and 1-pentyl-3-methylimidazole triflate.
3. The insoluble platinum-ion solution complex catalyst according to claim 1 or 2, wherein said platinum precursor comprises at least PtCl 4 、H 2 PtCl 6 、(NH 4 ) 2 PtCl 6 And C 8 H 12 Cl 2 One of Pt.
4. An insoluble platinum-ion solution complex catalyst according to claim 3, wherein the loading of Pt is from 0.2 to 1wt% based on the total weight of the catalyst.
5. A process for preparing an insoluble platinum-ion solution complex catalyst according to any one of claims 1 to 4, wherein the additive solution is slowly dropped into the prepared platinum precursor solution to carry out a mixing reaction, then the carrier is added into the above-mentioned mixed solution, and finally the insoluble platinum-ion solution complex catalyst is obtained by dipping and drying.
6. The method for preparing an insoluble platinum-ion solution complex catalyst according to claim 5, wherein the molar ratio of platinum precursor to auxiliary agent is 1:0.1-5.
7. The method for preparing an insoluble platinum-ion solution complex catalyst according to claim 5, wherein the molar ratio of said platinum precursor to said promoter is 1:1-2.
8. The method for preparing an insoluble platinum ion solution complex catalyst according to claim 5, wherein the impregnation temperature is 50 to 150 ℃; the soaking time is 6-12h.
9. The method for preparing an insoluble platinum ion solution complex catalyst according to claim 5, wherein the particle size of said carrier is 1 to 5mm.
10. The method for preparing vinyl chloride by hydrochlorination of acetylene comprises the steps of taking acetylene and hydrogen chloride as raw materials, and mixing and reacting to obtain the vinyl chloride, and is characterized in that: the reaction is carried out under the catalysis of the insoluble platinum-ion solution complex catalyst according to any one of claims 1 to 5.
11. Use of an insoluble platinum-ion solution complex catalyst according to any one of claims 1 to 5 in the preparation of vinyl chloride by mixing acetylene with hydrogen chloride.
CN202311146167.4A 2023-09-06 2023-09-06 Insoluble platinum-ion solution complex catalyst, preparation method and application thereof, and method for preparing vinyl chloride by hydrochlorination of acetylene Pending CN117463400A (en)

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