CN116764685A - Copper-based catalyst, preparation method and application - Google Patents

Copper-based catalyst, preparation method and application Download PDF

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CN116764685A
CN116764685A CN202310669862.2A CN202310669862A CN116764685A CN 116764685 A CN116764685 A CN 116764685A CN 202310669862 A CN202310669862 A CN 202310669862A CN 116764685 A CN116764685 A CN 116764685A
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copper
based catalyst
ligand
cucl
catalyst according
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李建
戴云生
侯文明
刘桂华
蒋金科
左川
沈亚峰
杨文超
唐振艳
尹召锦
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Guiyan Chemical Materials Yunnan Co ltd
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Guiyan Chemical Materials Yunnan 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
    • B01J31/1845—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 phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • 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
    • B01J31/1845—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 phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/186—Mono- or diamide derivatives thereof
    • 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
    • B01J31/1845—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 phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • 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
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper

Abstract

The invention discloses a copper-based catalyst, a preparation method and application thereof, and relates to a copper-based catalyst for catalyzing hydrochlorination of acetylene, which has the technical scheme that: a copper-based catalyst formulation comprising coal-based activated carbon, a copper precursor, and a ligand; the copper element loading in the copper-based catalyst formula is 8-16wt%; the molar ratio of the metallic copper precursor to the ligand is 10-25:1; the rest is coal-based activated carbon. The copper-based catalyst has good dispersibility and high activity.

Description

Copper-based catalyst, preparation method and application
Technical Field
The invention relates to a copper-based catalyst for catalyzing hydrochlorination of acetylene, in particular to a copper-based catalyst, a preparation method and application.
Background
Vinyl chloride is a monomer for producing polyvinyl chloride (PVC), the main vinyl chloride production process adopted in China is acetylene hydrochlorination, and the catalyst adopted in the traditional process is load type HgCl 2 The disadvantage of the AC catalyst, which is prone to evaporation, is that not only does the active components run off, but the mercury that is lost is also harmful to human health and the environment. In the prediction of Hutchings, the electrode potential is positively correlated with the hydrochlorination catalytic performance of acetylene, cu 2 + has a higher electrode potential and thus may have better catalytic performance for hydrochlorination of acetylene. Compared with noble metals such as Au, ru and the like, cu has good thermal stability, is cheap and easy to obtain, so that Cu has important research significance in the PVC industrial production process as a substitute of the noble metals.
There are many different improvements to the copper-based catalysts for hydrochlorination of acetylene, such as composite supported Cu-based catalysts, which are prepared by precipitation of CeO 2 The active carbon is loaded on the active carbon to form composite active carbon, so that on one hand, the generation of carbon deposition in the reaction process can be inhibited, on the other hand, the interaction between the active component and the carrier can be improved, and the loss of the active component can be prevented; the copper-based composite catalyst is prepared by adopting a Schiff base pretreatment active carbon carrier and combining an amino acid complexation impregnation technology, so that the nano-loading of Cu on the surface of the carrier is realized, the loss of Cu in the reaction is reduced, and the growth of crystal grains is slowed down; activated carbon is taken asThe carrier is subjected to nitrogen doping treatment, and the ionic liquid is added as an auxiliary agent, so that the ionic liquid and the metal copper salt are prepared into an impregnating solution, and the impregnating solution is loaded on the activated carbon by adopting an isovolumetric impregnation method, so that the catalytic activity of the catalyst can be effectively improved, and the industrial preparation cost of the catalyst is reduced; the traditional isovolumetric impregnation method is combined with the high-voltage pulse electric field technology, and the high-voltage pulse electric field with proper strength interacts with charged particles in a preparation system, so that the highly dispersed catalyst can be prepared, and has the advantages of high activity and good stability; the fluorine-containing weakly coordinated anion modified copper-based catalyst introduces the weakly coordinated anion into the copper-based catalyst, so that the electronic structure of an active center is regulated, and the activity and stability of the copper-based catalyst are improved.
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. Although researchers have a certain effect on the improvement of copper-based catalysts in recent years, the problems of catalyst deactivation caused by weak interaction force between an active component and a carrier, uneven Cu dispersion and easy agglomeration of active species of the copper-based catalysts, reduction of active species of high-valence copper and the like still exist.
Disclosure of Invention
In order to solve the problems of uneven dispersion, easy agglomeration and easy deactivation of a copper-based catalyst in the background art, the patent firstly provides a copper-based catalyst.
The technical aim of the invention is realized by the following technical scheme: a copper-based catalyst formulation comprising coal-based activated carbon, a copper precursor, and a ligand; the copper element loading in the copper-based catalyst formula is 8-16wt%; the molar ratio of the metallic copper precursor to the ligand is 10-25:1; the rest is active carbon.
Further, the copper precursor is CuCl 2 、CuCl、CuSO 4 And Cu (NO) 3 ) 2 One of the following; or CuCl 2 、CuCl、CuSO 4 And Cu (NO) 3 ) 2 Is a hydrate of one of the above.
Further, the copper precursor isCuCl 2 ·2H 2 O。
Further, the ligand is a compound containing a phosphorus-oxygen double bond and a cyclic molecular structure.
Further, the ligand is one of phenylphosphonic dichloride, 1-ethyl-3-methylimidazole diethyl phosphate, O- (diphenylphosphorus) hydroxylamine, bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride and 2-chloro-2-oxo-1, 3, 2-dioxaphospholane.
Further, the ligand is bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride.
Secondly, the invention provides a production method of the copper-based catalyst, which adopts the formula as described above and comprises the following steps: mixing a copper precursor, a ligand and absolute ethyl alcohol, and uniformly stirring; adding coal-based activated carbon and then continuously and uniformly stirring; and (5) drying after soaking and heat activation to obtain the copper-based catalyst.
Further, the method also comprises a pretreatment method for the coal-based activated carbon, wherein the pretreatment method comprises the following steps: reflux stirring the prepared 0.5-1.5 mol/L hydrochloric acid and 40-60 meshes of coal-based active carbon for 6-10 h at 70 ℃, washing with deionized water to be neutral, and drying in a baking oven at 100-120 ℃ for 10-12 h.
Further, the dipping heat activation mode is water bath heating, and the water bath temperature is.
And the activation time is 5-7 h at 60-70 ℃.
Finally, the invention provides application of the copper-based catalyst in preparing vinyl chloride by hydrochlorination of acetylene.
In summary, the invention has the following beneficial effects: the invention provides a method for preparing CuCl by taking coal-based activated carbon as a carrier 2 ·2H 2 O is a steady state metal precursor, and several compounds containing phosphorus-oxygen double bonds and a cyclic molecular structure are copper-based catalysts of ligands. The added ligand can help anchor the copper active species to the support and inhibit agglomeration or loss of the highly dispersed metallic copper. In addition, the Cu active species with high valence is stabilized by the electron transfer between the ligand with strong electron donating ability and the metal precursor, thereby improving the catalysisThe adsorption capacity of the catalyst to reactants of hydrogen chloride and acetylene is achieved, and meanwhile, carbon deposition in the reaction process is inhibited, so that the activity and stability of the catalyst are obviously improved. The prepared catalyst is applied to acetylene hydrochlorination reaction, has the characteristics of low cost, high activity, good stability and the like, and has good economical efficiency and industrial application value.
Drawings
FIG. 1 is a graph showing the acetylene conversion versus reaction time in the case of example 6 using the catalysts provided in examples 1 to 5 and comparative example 1.
FIG. 2 is a graph showing the relationship between vinyl chloride selectivity and reaction time in the state of example 6 using the catalysts provided in examples 1 to 5 and comparative example 1.
FIG. 3 is a TPD curve for reactant hydrogen chloride for the copper-based catalysts provided in examples 1-5 and comparative example 1.
Fig. 4 is a TPD curve of the copper-based catalysts provided in examples 1 to 5 and comparative example 1 for the reactant acetylene.
FIG. 5 is a Transmission Electron Microscope (TEM) image of the copper-based catalyst provided in example 1
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
The present example first provides a formulation for a copper-based catalyst comprising a support, a copper precursor, and a ligand.
The carrier is coal-based activated carbon (CAC).
The copper precursor is CuCl 2 、CuCl、CuSO 4 And Cu (NO) 3 ) 2 One of the following; or CuCl 2 、CuCl、CuSO 4 And Cu (NO) 3 ) 2 Is one of the hydrates of (2); preferably, the copper precursor is CuCl 2 ·2H 2 O。
The ligand is one of phenylphosphonic dichloride, 1-ethyl-3-methylimidazole diethyl phosphate, O- (diphenylphosphorus) hydroxylamine, bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride and 2-chloro-2-oxo-1, 3, 2-dioxaphospholane; preferably, the ligand is bis (2-oxo-3-oxazolidinyl) phosphinic chloride.
The copper-based catalyst formulation has a loading of copper element of 8 to 16wt.%, preferably 12wt.%. The copper element load is calculated by the following steps: the load capacity is calculated in the following way: m is m Cu /(m Carrier body +m Copper precursor +m Ligand )；m Cu Is the mass of copper element, m Carrier body The quality of the carrier is that of the carrier; m is m Copper precursor The mass of the copper precursor is as follows; m is m Ligand Is ligand quality.
The molar ratio of the copper precursor to the ligand is 10-25:1; preferably, the molar ratio of copper precursor to ligand is 15:1.
Secondly, the embodiment provides a preparation method of the copper-based catalyst by utilizing the formula, which comprises the following steps:
pretreatment of coal-based activated carbon (CAC): firstly, taking activated carbon (CAC) as a carrier, purchasing coal, pretreating, using, refluxing and stirring prepared 1mol/L hydrochloric acid and 40-60 meshes of coal-based activated carbon at 70 ℃ for 6 hours, washing with deionized water to be neutral, and drying in a baking oven at 120 ℃ for 12 hours. Firstly, acid solution (0.01-0.1 mol/L) is used for acid washing, and after the acid solution is dried at 140 ℃, the acid is one or a mixed solution of hydrochloric acid, nitric acid and phosphoric acid, and then potassium salt and/or tin salt are used for modification, and the drying is carried out at 120 ℃, wherein the potassium salt is one of potassium chloride, potassium bromide, potassium sulfide and potassium azide; the tin salt is one of tin chloride, tin sulfate and tin nitrate. Preferably, the treatment is carried out by the second method.
Mixing the raw materials: mixing the coordination compound and the copper precursor with absolute ethyl alcohol, uniformly stirring, adding coal-based activated carbon (CAC), and stirring for 2 hours at room temperature.
Catalyst activation: after fully stirring the raw materials, putting the raw materials into a water bath kettle with the temperature of 60-70 ℃ to be closed and kept at the constant temperature for 4-7 hours, and carrying out dipping activation.
And (3) drying: and drying the activated catalyst at 70 ℃ for 12 hours to obtain the copper-based complex catalyst containing the phosphorus complex.
Finally, the embodiment also provides a method for preparing vinyl chloride by utilizing the copper-based catalyst to carry out acetylene hydrochlorination. The reaction method comprises the following steps: filling the prepared copper-based catalyst into a fixed bed reactor, introducing acetylene and hydrogen chloride reaction gas, and controlling the acetylene space velocity (GHSV) to be 160h at 160 DEG C -1 And reacting for 24 hours under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1.12.
The reaction mainly involved in the hydrochlorination of acetylene comprises the following steps:
the main reaction: c (C) 2 H 2 +HCl→CH 2 ＝CHCl
Non-polymerization side reactions:
CH 2 ＝CHCl+HCl→CH3CHCl 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 reaction temperature is overhigh, polymerization products can be deposited on the surface of a catalyst to form carbon deposition, so that the catalyst is deactivated), the selectivity of the main reaction is improved, the carbon deposition is reduced, and the metal catalyst has the problem of valence change and deactivation at high temperature. After comprehensively considering the influence of temperature on polymerization side reaction and catalyst reduction deactivation, the reaction temperature should be controlled at about 160 ℃.
The volume ratio of acetylene to hydrogen chloride is 1:1-2, preferably the volume ratio of acetylene to hydrogen chloride is 1:1.12.
The gas phase reaction is carried out in a fixed bed reactor, and the copper-based catalyst is packed in the fixed bed reactor. The control range of the acetylene airspeed is 90-720h -1 Preferably at 160h -1 。
Example 1
2.2536g (0.01322 mol) of CuCl are placed in a 50mL beaker 2 ·2H 2 O is dissolved in 15mL absolute ethanol, then 0.2243g of bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride (0.00088 mol) is added at room temperature, after stirring for 30min, 4.5221g of CAC is slowly added into the mixture to continue stirring for 2h, then the mixture is put into a 70 ℃ water bath kettle to be sealed and kept at constant temperature for 6h, finally the mixture is dried in a 70 ℃ blast drying box for 12h, thus obtaining the copper-based catalyst, named Cu-L 1 /CAC。
Example 2
2.2536g (0.01322 mol) of CuCl are placed in a 50mL beaker 2 ·2H 2 O is dissolved in 15mL absolute ethanol, then 0.2329g of 1-ethyl-3-methylimidazole diethyl phosphate (0.00088 mol) is added at room temperature, after stirring for 30min, 4.5135g of CAC is slowly added into the mixture to continue stirring for 2h, then the mixture is put into a water bath kettle with the temperature of 70 ℃ to be sealed and kept constant for 6h, finally the mixture is dried in a blast drying box with the temperature of 70 ℃ for 12h, thus obtaining the copper-based catalyst named Cu-L 2 /CAC。
Example 3
2.2536g (0.01322 mol) of CuCl are placed in a 50mL beaker 2 ·2H 2 O is dissolved in 15mL absolute ethanol, then 0.1756g O- (diphenylphosphorus) hydroxylamine (0.00088 mol) is added at room temperature, after stirring for 30min, 4.5708g CAC is slowly added into the mixture to continue stirring for 2h, then the mixture is put into a 70 ℃ water bath kettle to be sealed and kept at constant temperature for 6h, finally the mixture is dried for 12h in a 70 ℃ blast drying box, thus obtaining the copper-based catalyst, named Cu-L 3 /CAC。
Example 4
2.2536g (0.01322 mol) of CuCl are placed in a 50mL beaker 2 ·2H 2 O is dissolved in 15mL absolute ethanol, then 0.1718g of phenylphosphonic dichloride (0.00088 mol) is added at room temperature, after stirring for 30min, 4.5746g of CAC is slowly added into the mixture to continue stirring for 2h, then the mixture is put into a water bath kettle with the temperature of 70 ℃ to be sealed and kept constant for 6h, finally the mixture is dried for 12h in a blast drying box with the temperature of 70 ℃ to obtain a copper-based catalyst, which is named Cu-L 4 /CAC。
Example 5
2.2536g (0.01322 mol) of CuCl are placed in a 50mL beaker 2 ·2H 2 O is dissolved in 15mLAdding 0.1256g of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (0.00088 mol) into absolute ethyl alcohol at room temperature, stirring for 30min, slowly adding 4.6208g of CAC into the mixture, continuously stirring for 2h, placing into a 70 ℃ water bath, sealing and keeping the temperature for 6h, and finally drying in a 70 ℃ blast drying oven for 12h to obtain the copper-based catalyst named Cu-L 5 /CAC。
Comparative example 1
2.2536g (0.01322 mol) of CuCl are placed in a 50mL beaker 2 ·2H 2 O is dissolved in 15mL absolute ethanol, after stirring for 30min, 4.7464g of CAC is slowly added into the mixture to continue stirring for 2h, then the mixture is put into a 70 ℃ water bath kettle to be sealed and kept at constant temperature for 6h, and finally the mixture is dried in a 70 ℃ blast drying oven for 12h, thus obtaining the copper-based catalyst, named Cu/CAC.
The effect of the above catalyst was verified using the following examples.
Example 6
5mL of the catalysts prepared in examples 1 to 5 and comparative examples 1 to 5 were respectively packed in a fixed bed reactor, mixed reaction gas of acetylene and hydrogen chloride was introduced, and the space velocity (GHSV) of acetylene was maintained at 160℃for 160 hours -1 Under the reaction condition that the volume ratio of acetylene to hydrogen chloride is 1:1.12, the reaction is carried out for 24 hours, and the highest conversion (%) of acetylene, the reduction in conversion (%) of the reaction for 24 hours and the selectivity of Vinyl Chloride (VCM) are detected.
The gas mixture entering the gas chromatograph is mainly acetylene and vinyl chloride, and sometimes generates trace 1, 1-dichloroethane impurity gas, which is calculated by a peak area normalization method. Since hydrogen chloride after the reaction is completely absorbed, the reaction volume in the system can be regarded as a constant value, the acetylene conversion (X A ) Vinyl chloride selectivity (S) VC ) The calculation method comprises the following steps:
the method for calculating the acetylene conversion rate comprises the following steps: x is X A ＝(Ψ A0 -Ψ A )/Ψ A0 *100%, taking the average of 3 determinations.
VCM selectivity calculation method: s is S VC ＝Ψ VC /(I-Ψ A ) 100%, taking the average of 3 determinations.
Wherein ψ is A0 、Ψ A And psi is VC Representing in sequence the volume fraction of acetylene in the feed gas, the volume fraction of acetylene remaining in the product, and the volume fraction of vinyl chloride in the product. The test results of the acetylene hydrochlorination reaction catalyzed by each catalyst are shown in table 1.
TABLE 1 Performance of different catalysts to catalyze hydrochlorination of acetylene
As can be seen from Table 1, when the ligand added was bis (2-oxo-3-oxazolidinyl) phosphinic chloride, the prepared copper-based catalyst Cu-L1/CAC with a loading of 12wt.% had a significantly better catalytic activity than the other catalysts, and the 24-hour conversion drop was relatively small. This is because the addition of the ligand can help anchor the copper active species to the support and inhibit agglomeration or loss of the highly dispersed metallic copper. In addition, the high-valence Cu active species are stabilized through electron transfer between the ligand with strong electron supply capability and the metal precursor, so that the adsorption capability of the catalyst on reactants hydrogen chloride and acetylene is improved, and meanwhile, the rapid deactivation caused by carbon deposition, copper active species agglomeration and loss in the reaction process is effectively inhibited, so that the activity and stability of the catalyst are obviously improved.
FIG. 1 is a graph showing the acetylene conversion versus reaction time in the case of example 6 using the catalysts provided in examples 1 to 5 and comparative example 1; from the figure, it can be seen that the catalyst with the addition of the auxiliary agent has higher acetylene conversion rate.
FIG. 2 is a graph showing the relationship between vinyl chloride selectivity and reaction time in the state of example 6 using the catalysts provided in examples 1 to 5 and comparative example 1; as can be seen from the graph, the vinyl chloride selectivity of the copper-based catalyst reaches more than 90%.
FIG. 3 is a TPD curve for reactant hydrogen chloride for the copper-based catalysts provided in examples 1-5 and comparative example 1. Fig. 4 is a TPD curve of the copper-based catalysts provided in examples 1 to 5 and comparative example 1 for the reactant acetylene. It can be seen that the catalyst has strong adsorption capacity to reactants of hydrogen chloride and acetylene, and is beneficial to improving the activity and stability of the catalyst.
The active components of the catalyst prepared by the method of the example 1 in fig. 5 are uniformly dispersed on the carrier, more active sites are exposed, the adsorption capacity of reactants hydrogen chloride and acetylene is enhanced, and the catalytic activity and stability of the catalyst are improved.
The present embodiment is only for explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.

Claims (10)

1. A copper-based catalyst, characterized by: the copper-based catalyst formulation comprises coal-based activated carbon, a copper precursor and a ligand;
the copper element loading in the copper-based catalyst formula is 8-16wt%; the molar ratio of the metallic copper precursor to the ligand is 10-25:1; the rest is coal-based activated carbon.
2. A copper-based catalyst according to claim 1, characterized in that: the copper precursor is CuCl 2 、CuCl、CuSO 4 And Cu (NO) 3 ) 2 One of the following; or CuCl 2 、CuCl、CuSO 4 And Cu (NO) 3 ) 2 Is a hydrate of one of the above.
3. A copper-based catalyst according to claim 2, characterized in that: the copper precursor is CuCl 2 ·2H 2 O。
4. A copper-based catalyst according to claim 1, characterized in that: the ligand is a compound containing phosphorus-oxygen double bond and a cyclic molecular structure.
5. A copper-based catalyst according to claim 3, characterized in that: the ligand is one of phenylphosphonic dichloride, 1-ethyl-3-methylimidazole diethyl phosphate, O- (diphenylphosphorus) hydroxylamine, bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride and 2-chloro-2-oxo-1, 3, 2-dioxaphospholane.
6. A copper-based catalyst according to claim 5, characterized in that: the ligand is bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride.
7. A method for producing a copper-based catalyst using the formulation of claim 1, comprising the steps of:
mixing a copper precursor, a ligand and absolute ethyl alcohol, and uniformly stirring;
adding coal-based activated carbon and then continuously and uniformly stirring;
and (5) drying after soaking and heat activation to obtain the copper-based catalyst.
8. The method for producing a copper-based catalyst according to claim 7, further comprising a pretreatment method for coal-based activated carbon, the pretreatment method comprising:
reflux stirring the prepared 0.5-1.5 mol/L hydrochloric acid and 40-60 meshes of coal-based active carbon for 6-10 h at 70 ℃, washing with deionized water to be neutral, and drying in a baking oven at 100-120 ℃ for 10-12 h.
9. The method for producing a copper-based catalyst according to claim 9, characterized in that: the dipping heat activation mode is water bath heating; the water bath temperature is 60-70 ℃; the activation time is 5-7 h.
10. Use of a copper-based catalyst according to claim 1 for the preparation of vinyl chloride by hydrochlorination of acetylene.
CN202310669862.2A 2023-06-07 2023-06-07 Copper-based catalyst, preparation method and application Pending CN116764685A (en)

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