CN112961027B - Insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof - Google Patents
Insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof Download PDFInfo
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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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
- B01J31/18—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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- 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
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses an insoluble copper complex catalyst for catalyzing acetylene hydrochlorination and a preparation method thereof, and relates to the technical field of catalyst preparation. The preparation method comprises the following steps: firstly, uniformly mixing two components of a carrier, a copper precursor and a surfactant, adding a third component, and then soaking and thermally activating to obtain the copper-based catalyst. Due to Cu n+ The complex formed by the three components has poor solubility and even insoluble matters, and the preparation method can change the addition sequence of the three components to effectively improve the dispersibility of the active components on the carrier; the active components in the copper-based catalyst of the invention are in a high dispersion state, thereby greatly improving the catalytic activity and stability of the catalyst.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to an insoluble copper complex catalyst for catalyzing acetylene hydrochlorination, and a preparation method and application thereof.
Background
Polyvinyl chloride (PVC) is polymerized by Vinyl Chloride Monomer (VCM), and has the advantages of low price, durability, wide application and the like as one of five general-purpose resins. In coal resourceVCM is produced mainly by hydrochlorination of acetylene in relatively rich source regions, however, hgCl is highly toxic and volatile 2 The AC catalyst may seriously harm the environment and human health. Therefore, there is an urgent need to develop efficient, mercury-free alternative catalysts to ensure sustainable development of the PVC industry. Many non-mercury metal catalysts currently studied in acetylene hydrochlorination reactions comprise noble metal catalysts such as Au, pt, pd, ru and the like and non-noble metal catalysts such as Cu, sn and the like, and many researchers in Hutchings and China consider that gold-based catalysts are the best candidates in the reactions. Nevertheless, the high cost of gold-based catalysts is likely to be limited in the face of large-scale low-cost PVC industrial production. Thus, researchers have been striving to explore more economical, efficient non-noble metal-based catalysts in recent years. Copper is used as an important research object, and has the advantages of abundant reserves, low price, wide application in the catalysis field and the like.
Aiming at the preparation of copper-based catalysts, a plurality of different improvements appear in the prior art, for example, chinese patent (CN 107008465A) discloses an acetylene hydrochlorination copper-based catalyst with high activity stability, which takes copper salt supported on a carbon-based carrier as a main active component, and improves the catalytic activity and stability of the catalyst by adding a stabilizer; chinese patent (CN 108993585A) discloses a copper-based catalyst for synthesizing chloroethylene by hydrochlorination of acetylene, a preparation method and application thereof, wherein copper salt and a five-membered ring compound are mixed, immersed, filtered and dried to obtain the copper-based catalyst with higher conversion rate and selectivity; chinese patent (CN 108993596A) discloses a copper complex catalyst for hydrochlorination of acetylene and a preparation method, wherein the copper complex in the catalyst is formed by complexing copper salt and an organic phosphoric acid ligand, and the preparation method is simple, low in cost and high in conversion rate and selectivity; chinese patent (CN 106944151A) discloses a mercury-free catalyst for synthesizing chloroethylene by hydrochlorination of acetylene, and a preparation method and application thereof, wherein the preparation method comprises the steps of dissolving base metal salt (selected from copper salt) and amide solvents in water to prepare a mixed solution, adding activated carbon into the mixed solution, filtering and drying to obtain the catalyst, and further improving the reaction efficiency through the synergistic effect of the base metal salt and the amide solvents, so that the catalyst has high low-temperature activity and good selectivity and stability.
However, the current common preparation method of the supported copper-based catalyst in the hydrochlorination of acetylene is to load a copper precursor and an additive on a carrier through an impregnation method under certain conditions. However Cu is 2+ The lack of solubility or even insolubles of the complexes formed with certain ionic liquids or ligands will result in an uneven dispersion of the active ingredient onto the support during impregnation. We therefore propose a method of uniformly supporting an insoluble copper complex on an Activated Carbon (AC) support and using it to catalyze acetylene hydrochlorination. For this purpose, we propose an insoluble copper complex catalyst for catalyzing acetylene hydrochlorination and a method for preparing the same.
Disclosure of Invention
The invention mainly aims to provide an insoluble copper complex catalyst for catalyzing acetylene hydrochlorination and a preparation method thereof, so as to solve the problems in the background art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: an insoluble copper complex catalyst for catalyzing acetylene hydrochlorination reaction uses active carbon as a carrier, copper precursors of different types as main active components, and nitrogen-containing ligand or ionic liquid as a surfactant.
Preferably, the surfactant is selected from one of dodecyl trimethyl ammonium chloride, 2, 3-epoxypropyl trimethyl ammonium chloride, acetylcholine chloride and tetramethyl ammonium chloride, preferably tetramethyl ammonium chloride.
Preferably, the copper precursor is one of copper sulfate, copper chloride and copper pyrophosphate, preferably copper chloride.
A method of preparing an insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene, the method comprising three;
the method one comprises the following steps:
step one: firstly, adding an active carbon carrier into a prepared copper precursor solution, and uniformly mixing to obtain a mixed solution;
step two: slowly dripping the surfactant solution into the mixed solution;
step three: the required copper-based catalyst is obtained through impregnation and thermal activation.
The second method comprises the following steps:
step one: firstly, adding an active carbon carrier into a prepared surfactant solution, and uniformly mixing to obtain a mixed solution;
step two: slowly dripping the copper precursor solution into the mixed solution;
step three: the required copper-based catalyst is obtained through impregnation and thermal activation.
The third method comprises the following steps:
step one: slowly dripping the surfactant solution into the prepared copper precursor solution for mixing reaction to obtain a mixed solution;
step two: adding an active carbon carrier into the mixed solution;
step three: the required copper-based catalyst is obtained through impregnation and thermal activation.
Preferably, the loading of Cu is 3 to 15wt%, preferably 5 to 10wt%, based on the total weight of the catalyst.
Preferably, the molar ratio of the metal precursor to the surfactant is 1:0.1-5, preferably 1:0.5-2.
Preferably, the impregnation temperature of the first, second and third steps is 25-100 ℃, the impregnation time is 2-24h, preferably the impregnation temperature is 50-80 ℃, and the impregnation time is 4-12h.
Preferably, the acetylene hydrochlorination reaction is carried out under the catalysis of an insoluble copper complex catalyst according to any one of claims 1 to 3.
Preferably, the acetylene hydrochlorination reaction is a gas phase reaction, and the gas phase reaction temperature is 110-300 ℃.
Preferably, the insoluble copper complex catalyst is used as a catalyst in acetylene hydrochlorination, wherein the acetylene hydrochlorination is to react acetylene with hydrogen chloride to generate vinyl chloride.
The invention has the following beneficial effects:
the invention is due to Cu 2+ The complex formed with some ligands has poor solubility and even presents insoluble matters, and the preparation method can change the adding sequence of the three components to effectively improve the dispersibility of the active components on the carrier.
The active components in the copper-based catalyst of the invention are in a high dispersion state, so that the catalytic activity and stability of the existing metal catalyst are greatly improved.
Compared with the existing metal catalyst for hydrochlorination of acetylene, the insoluble copper complex catalyst provided by the invention has the advantages that the active components in the insoluble copper complex catalyst are in a high dispersion state, are not easy to run off and agglomerate, and meanwhile, the acetylene and hydrogen chloride reactants are activated, so that the catalytic activity and stability of the existing metal catalyst are improved.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a graph (a) of acetylene conversion versus reaction time and a graph (b) of vinyl chloride selectivity versus reaction time for catalysts (examples 1-4 and comparative example 1);
FIG. 2 is a graph (a) of acetylene conversion versus reaction time and a graph (b) of vinyl chloride selectivity versus reaction time for catalysts (example 1 and comparative examples 1-3);
fig. 3 is a TEM image of fresh (left) and deactivated (right) Cu-based catalyst of the invention: comparative example 1 (a, b), comparative example 2 (c, d) and example 1 (e, f);
FIG. 4 is a TPD curve of the metal complex catalyst of the invention (example 1) and the comparative catalysts (comparative examples 1-3) versus the reactants hydrogen chloride and acetylene.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
An insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene uses active carbon as a carrier, copper precursors of different types as main active components, and nitrogen-containing ligand or ionic liquid as a surfactant.
Wherein the surfactant is selected from one of dodecyl trimethyl ammonium chloride, 2, 3-epoxypropyl trimethyl ammonium chloride, acetylcholine chloride and tetramethyl ammonium chloride, preferably tetramethyl ammonium chloride.
Among them, one of copper sulfate, copper chloride and copper pyrophosphate, copper chloride is preferable.
A preparation method of an insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene, which comprises three preparation methods;
the method one comprises the following steps:
step one: firstly, adding an active carbon carrier into a prepared copper precursor solution, and uniformly mixing to obtain a mixed solution;
step two: slowly dripping the surfactant solution into the mixed solution;
step three: the required copper-based catalyst is obtained through impregnation and thermal activation.
The second method comprises the following steps:
step one: firstly, adding an active carbon carrier into a prepared surfactant solution, and uniformly mixing to obtain a mixed solution;
step two: slowly dripping the copper precursor solution into the mixed solution;
step three: the required copper-based catalyst is obtained through impregnation and thermal activation.
The method III comprises the following steps:
step one: slowly dripping the surfactant solution into the prepared copper precursor solution for mixing reaction to obtain a mixed solution;
step two: adding an active carbon carrier into the mixed solution;
step three: the required copper-based catalyst is obtained through impregnation and thermal activation.
Wherein the loading of Cu is 3-15wt%, preferably 5-10wt%, based on the total weight of the catalyst.
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 Surface active agent 。
For example: in example 1, the load amount was calculated by: m is m Cu /(m Carrier body +m Steady state metal precursors +m Surface active agent )＝0.1998g/(3.2319g+0.4231g+0.3449g)＝5.0wt％。
Wherein, the mol ratio of the metal precursor to the surfactant is 1:0.1-5, and the preferable mol ratio is 1:0.5-2.
Wherein the dipping temperature of the first, second and third steps is 25-100 ℃, the dipping time is 2-24h, the dipping temperature is 50-80 ℃ and the dipping time is 4-12h.
Wherein the hydrochlorination of acetylene is carried out under the catalysis of an insoluble copper complex catalyst according to any one of claims 1 to 3.
Wherein, the hydrochlorination of acetylene is a gas phase reaction, the temperature of the gas phase reaction is 110-300 ℃, the gas phase reaction is carried out in a fixed bed reactor, and the catalyst is filled in the fixed bed reactor. The control range of the acetylene airspeed adopts the control range commonly used in the field, specifically 30-1000h -1 Preferably, the space velocity of acetylene is controlled between 30 and 180 hours -1 。
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-CH 3
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 both exothermic reactions, but the thermal effect of the polymerization side reaction is larger than that of the main reaction, and the higher temperature is more favorable for inhibiting the polymerization side reaction (the polymerization product can be deposited on the surface of the catalyst to form carbon deposit), so that the selectivity of the main reaction is improved, the carbon deposit is reduced, and the metal catalyst has the problem of valence variation and 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 ℃, and most preferably 180-260 ℃.
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 insoluble copper complex catalyst is used as a catalyst in the hydrochlorination of acetylene, wherein the hydrochlorination of acetylene is that acetylene reacts with hydrogen chloride to generate chloroethylene.
In the present invention,
1. the preparation method of the catalyst comprises the following steps:
according to the different adding sequences of the components, three preparation methods are divided, firstly, an active carbon carrier is added into a prepared copper precursor ethanol solution, stirring is carried out for 2-10h at normal temperature, and then a surfactant solution is slowly added into the mixed solution in a dropwise manner, and stirring is continued for 6h. The mixture was allowed to stand at 70℃for 6-12 hours and then dried at 120℃for 12 hours to give a copper-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 copper complex on the support.
And II: hydrochlorination of acetylene:
filling the metal 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 30-1000h -1 And reacting for 24 hours under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1-2.
Preferably, the reaction temperature is controlled between 140 and 280 ℃, and most preferably, the reaction temperature is controlled between 180 and 260 ℃.
Example 1
The preparation method of the insoluble copper complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
0.4231g of CuCl was placed in a 50mL beaker 2 After dissolving in 15mL of ethanol, adding 3.2319g of AC and stirring for 2h, the prepared 10mL of tetramethyl ammonium chloride (0.3449 g) ethanol solution is slowly added dropwise to the mixture and stirring is continued for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried and is thermally activated for 12 hours at 120 ℃. The prepared catalyst is named Cu@IL 1 /AC。
Example 2
The preparation method of the insoluble copper complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
0.4231g of CuCl was placed in a 50mL beaker 2 After dissolving in 15mL of ethanol, adding 3.2319g of AC and stirring for 2h, 10mL of a prepared 2, 3-epoxypropyltrimethylammonium chloride (0.4772 g) ethanol solution was slowly added dropwise to the mixture and stirring was continued for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried and is thermally activated for 12 hours at 120 ℃. The prepared catalyst is named Cu@IL 2 /AC。
Example 3
The preparation method of the insoluble copper complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
0.4231g of CuCl was placed in a 50mL beaker 2 After dissolving in 15mL of ethanol and adding 3.2319g of AC and stirring for 2h, the prepared 10mL of acetylcholine chloride (0.5717 g) ethanol solution was slowly added dropwise to the mixture with continued stirring for 2hh, performing H; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried and is thermally activated for 12 hours at 120 ℃. The prepared catalyst is named Cu@IL 3 /AC。
Example 4
The preparation method of the insoluble copper complex catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
0.4231g of CuCl was placed in a 50mL beaker 2 After dissolving in 15mL of ethanol, adding 3.2319g of AC and stirring for 2h, 10mL of a solution of dodecyltrimethylammonium chloride (0.8305 g) ethanol was slowly added dropwise to the mixture and stirring was continued for 2h; the beaker is sealed by a preservative film and kept stand for 6 hours at 60 ℃, then the solvent is slowly dried and is thermally activated for 12 hours at 120 ℃. The prepared catalyst is named Cu@IL 4 /AC。
Comparative example 1
The preparation method of the copper-based catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
0.4231g of CuCl was placed in a 50mL beaker 2 Dissolving in 15mL of ethanol, adding 3.2319g of AC, stirring for 2h, sealing with a preservative film, standing for 6h at 60 ℃, slowly drying the solvent, and thermally activating at 120 ℃ for 12h. The catalyst prepared was designated Cu/AC.
Comparative example 2
The preparation method of the copper-based catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
0.4231g of CuCl was placed in a 50mL beaker 2 Dissolving in 15mL of ethanol, adding 10mL of prepared tetramethyl ammonium chloride (0.3449 g) ethanol solution, stirring for 2h, adding 3.2319g of AC after the reaction is completed, 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 and is thermally activated for 12 hours at 120 ℃. The prepared catalyst is named Cu-IL 1 /AC。
Comparative example 3
The preparation method of the copper-based catalyst for catalyzing the hydrochlorination of acetylene comprises the following steps:
0.3449g of tetramethyl ammonium chloride was dissolved in 15mL of ethanol in a 50mL beaker, 3.2319g of AC was added and stirred for 2 hours, and 10mL of CuCl was prepared 2 (0.4231 g) ethanol solution was slowly added dropwise to the mixtureContinuing stirring the compound 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 and is thermally activated for 12 hours at 120 ℃. The catalyst prepared was named IL 1 @Cu/AC。
Example 5
5mL of the catalyst prepared in examples 1 to 4 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 90 hours -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.
FIG. 1 is a graph (a) showing the acetylene conversion versus reaction time and a graph (b) showing the vinyl chloride selectivity versus reaction time for the catalysts (examples 1-4 and comparative example 1).
Example 6
5mL of the catalyst prepared in example 1 and comparative examples 1 to 3 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 90 hours -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. 2.
FIG. 2 is a graph (a) showing the acetylene conversion versus reaction time and a graph (b) showing the vinyl chloride selectivity versus reaction time for the catalysts (example 1 and comparative examples 1-3).
Table 1 shows the conversion and selectivity of acetylene hydrochlorination catalyzed by different catalysts:
as can be seen from the results of the catalytic test of the catalyst on the hydrochlorination of acetylene, the stability of the catalyst is obviously improved after the surfactant is added (figures 1-2), and the insoluble copper complex compound cannot be uniformly dispersed on the carrier in the impregnation process, so that the catalytic performance of the catalyst can be possibly influenced. The catalyst prepared by the selection method (1) is uniformly dispersed on the carrier (figure 3) by comparison with the comparative example, more active sites are exposed to strengthen the adsorption capacity of reactants hydrogen chloride and acetylene (figure 4), and the catalytic activity and stability of the catalyst are improved.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (7)
1. The insoluble copper complex catalyst for catalyzing acetylene hydrochlorination is characterized in that active carbon is used as a carrier, copper precursors of different types are used as main active components, and one of dodecyl trimethyl ammonium chloride, 2, 3-epoxypropyl trimethyl ammonium chloride, acetylcholine chloride and tetramethyl ammonium chloride is used as a surfactant;
the copper precursor is one of copper sulfate, copper chloride and copper pyrophosphate;
the preparation method of the insoluble copper complex catalyst comprises the following steps:
step one: firstly, adding an active carbon carrier into a prepared copper precursor solution, and uniformly mixing to obtain a mixed solution;
step two: slowly dripping the surfactant solution into the mixed solution;
step three: the required insoluble copper complex catalyst is obtained through standing and thermal activation.
2. An insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene according to claim 1, wherein the loading of Cu is from 3 to 15wt% by weight of the total catalyst.
3. An insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene according to claim 1, wherein the molar ratio of copper precursor to surfactant is from 1:0.1 to 5.
4. An insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene according to claim 1, wherein the standing temperature is 25-100 ℃ and the standing time period is 2-24 h.
5. The use of the insoluble copper complex catalyst according to any one of claims 1 to 4 for catalyzing hydrochlorination of acetylene.
6. The use according to claim 5, wherein the acetylene hydrochlorination is a gas phase reaction at a temperature of from 110 to 300 ℃.
7. The use according to claim 5, wherein the hydrochlorination of acetylene is the reaction of acetylene with hydrogen chloride to form vinyl chloride.
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