CN115138380A - Preparation method and application of covalent organic framework loaded copper catalyst for acetylene hydrochlorination - Google Patents

Preparation method and application of covalent organic framework loaded copper catalyst for acetylene hydrochlorination Download PDF

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CN115138380A
CN115138380A CN202210337297.5A CN202210337297A CN115138380A CN 115138380 A CN115138380 A CN 115138380A CN 202210337297 A CN202210337297 A CN 202210337297A CN 115138380 A CN115138380 A CN 115138380A
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cofs
catalyst
acetylene
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CN115138380B (en
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赵佳
冯涛
金春晓
王涛
蔡海婷
李小年
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Zhejiang University of Technology ZJUT
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
    • 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
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a preparation method and application of a Cu/COFs catalyst for acetylene hydrochlorination. The preparation method comprises the following specific steps: (1) preparing a covalent organic framework; (2) preparing a P-doped COFs carrier material; (3) preparing a Cu-COFs catalyst: dissolving a divalent copper-containing precursor in a solvent to prepare an active component solution; and (3) loading a precursor containing divalent copper onto the P-doped COFs carrier material prepared in the step (2) by a solution impregnation method, carrying out vacuum drying treatment, and then treating by adopting a glow discharge method to improve the dispersion of the Cu active component and inhibit the agglomeration of the Cu active component, thereby finally obtaining the Cu/COFs catalyst. The invention provides application of the Cu-COFs catalyst prepared by the preparation method in the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene. The Cu-COFs catalyst prepared by the invention is applied to acetylene hydrochlorination, can realize high conversion rate and high selectivity of the acetylene hydrochlorination, has good stability, and has good economic applicability and industrial application value.

Description

Preparation method and application of covalent organic framework loaded copper catalyst for acetylene hydrochlorination
(I) technical field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method and application of a supported copper-based covalent organic framework (Cu-COFs) catalyst for acetylene hydrochlorination.
(II) background of the invention
Polyvinyl chloride (PVC) is a widely used general purpose plastic, obtained by polymerisation of Vinyl Chloride Monomer (VCM). With the increasing demand of polyvinyl chloride in China, the production quantity of vinyl chloride monomer also increases year by year. Currently, the main world-wide processes for producing vinyl chloride are: acetylene hydrochlorination (calcium carbide acetylene process), ethylene oxychlorination and ethane oxychlorination processes. Based on the current situation of 'rich coal, lean oil and gas deficiency' in China, most enterprises in China mainly produce VCM by an acetylene hydrochlorination method. However, the method adopts a mercuric chloride catalyst as a catalyst, wherein the mercuric chloride is volatile and sublimated at the reaction temperature, so that a large amount of mercuric chloride is lost from the catalyst, the service life of the catalyst is greatly shortened, and the production is not facilitated. And the use of mercury in the production of polyvinyl chloride (PVC) has been prohibited since 2020 because of the extreme toxicity of mercury chloride, specified in the water guarantee for mercury. In order to solve the pollution problem caused by the mercury catalyst, the development of a novel mercury-free catalyst is an urgent problem to be solved in the whole industry for producing vinyl chloride by the calcium carbide method.
In the aspect of metal active components, the existing industrial mature non-mercury catalysts are mainly noble metal catalysts, such as gold, palladium, ruthenium and the like, although the reaction activity has certain advantages, the catalyst is difficult to regenerate after being deactivated, and the expensive price brings great cost pressure to the industrial production of vinyl chloride, so that the catalyst is limited by the problems of cost and the like, and no large-scale application report exists so far. Therefore, the development of non-noble metal catalysts represented by copper-based catalysts is imperative. Non-noble metal catalysts have the advantage of relatively low cost, but the activity and stability of the non-noble metal catalysts are far from those of noble metal catalysts, and further optimization and development are needed.
In the aspect of catalyst carriers, most acetylene hydrochlorination catalysts select activated carbon as the carrier, and the activated carbon has low mechanical strength and poor regeneration performance. For this purpose, molecular sieves, metal oxides, metal-organic framework compounds or Covalent Organic Frameworks (COFs) have been used as supports by researchers.
The Covalent Organic Frameworks (COFs) are organic porous polymers with periodicity and crystallinity, and organic building units of the covalent organic frameworks are connected through covalent bonds to form a porous crystalline covalent organic framework material with periodicity. Since the covalent organic framework materials are connected by light elements (H, B, C, N, O, etc.) through strong covalent bonds, they have many unique properties such as rigid structure (two-dimensional or three-dimensional), low density, high thermal stability and permanent porosity with large specific surface area, which makes them widely used in research fields such as gas adsorption, heterogeneous catalysis, photoconduction and energy storage. Meanwhile, a thought is provided for the development of the carrier in the hydrochlorination reaction of acetylene.
In the research at home and abroad, the patent CN201010248348.4 discloses a mercury-free catalyst, which takes a molecular sieve such as MCM-41 and the like as a carrier, and takes a noble metal ruthenium trichloride as an active component. The patent CN201110257696.2 discloses a mercury-free catalyst, which takes HZSM-5 type, naZSM-5 type, mordenite, H beta type and HY type molecular sieves as carriers, and halides and complexes of noble metal palladium as active components. The patent CN201310124706.4 discloses a mercury-free catalyst, which uses molecular sieve, silica or alumina as a carrier, pt and Cu as main active components, and alkaline earth metal as an auxiliary agent. The patent CN201910221548.1 discloses a mercury-free catalyst which uses a metal organic framework material with pyridine nitrogen as a carrier, and uses pyridine nitrogen and copper ions as active components.
Patent CN201110040369.1 reports that activated carbon is taken as a carrier and Cu is taken as 2 P-CuCl 2 Preparing solution of cupric chloride and hypophosphite with deionized water at room temperature, soaking the solution in activated carbon carrier, and dryingThe copper-based catalyst is prepared after roasting, but when the catalyst is used for acetylene hydrochlorination reaction at 170 ℃, the acetylene conversion rate is only 64 percent, and the vinyl chloride selectivity is 53 percent. The problems of low activity and selectivity are not solved.
Patent CN201711154986.8 reports that FAU type silicon-aluminum molecular sieve is used as a carrier, and an active component is CuCl 2 . Dissolving copper chloride by using deionized water or absolute ethyl alcohol; soaking the copper chloride solution on the molecular sieve according to the calculated proportion; and then the prepared catalyst is placed in an oven at 100-150 ℃ to be dried to obtain the catalyst. But stannous chloride is very easy to volatilize and lose in the reaction process, so that the stability of the catalyst is not strong, and the industrial requirement cannot be met.
In conclusion, the activity and stability of the mercury-free catalyst applied to the hydrochlorination of acetylene still hardly meet the industrial requirements. Although the activity can be improved by adding a metal additive, a stabilizer, or using an ionic liquid as an impregnation liquid, the problem of stability is difficult to solve. In addition, most acetylene hydrochlorination catalysts select activated carbon as a carrier, and the activated carbon has low mechanical strength and poor regeneration performance. Leading to the condition that catalyst pore channel collapses and sinters in the process of long-term use of the catalyst, causing the loss of the catalyst and serious pollution to the environment. Therefore, there is a great industrial application value in developing a cheap, effective, durable and environment-friendly non-metal catalyst to replace the existing acetylene hydrochlorination catalyst.
Disclosure of the invention
The first purpose of the invention is to solve the problems of poor acetylene conversion rate and poor catalyst stability of a copper catalyst in acetylene hydrochlorination reaction, and provide a preparation method of a Cu/COFs catalyst.
The second purpose of the invention is to provide the application of the Cu/COFs catalyst in the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene, and the Cu/COFs catalyst shows good catalytic activity and stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a Cu/COFs catalyst for acetylene hydrochlorination, which comprises the following specific steps:
(1) Preparation of Covalent Organic Frameworks (COFs): firstly, stirring an amino compound, a carbonyl compound and a non-aqueous organic solvent at the temperature of 20-30 ℃ for 3-6h; then adding the mixture into a heat-resistant glass tube (Pyrex), freezing the mixture by using liquid nitrogen, vacuumizing the mixture, thawing the mixture, and repeating freezing, vacuumizing and thawing operations to fully remove oxygen in the system; sealing the heat-resistant glass tube by using a flame spray gun, placing the sealed heat-resistant glass tube in a constant-temperature oven, controlling the temperature to be 100-200 ℃ and reacting for 1-9 days, and washing and drying the obtained reactant to obtain a Covalent Organic Frameworks (COFs) product; the amino compound is at least one of biphenyldiamine, o-phenylenediamine, 3-nitro-o-phenylenediamine, 3, 5-dimethyl-1, 2-phenylenediamine and 2,4, 6-trimethyl-1, 3-phenylenediamine; the carbonyl compound is at least one of 4,4' -biphenylphthalaldehyde, terephthalaldehyde, o-phthalaldehyde, trimesic aldehyde and trialdehyde phloroglucinol;
(2) Preparing a P-doped COFs carrier material: soaking the covalent organic framework product prepared in the step (1) in a phosphorus source solution at room temperature for 12-36h, taking out and drying the product, and roasting the product at 300-500 ℃ for 4-6h in a nitrogen atmosphere to obtain a P-doped covalent organic framework carrier material; p doping can be coordinated with copper to improve the activity and stability of the catalyst;
(3) Preparing a Cu-COFs catalyst: dissolving a divalent copper-containing precursor in a solvent to prepare an active component solution; loading a precursor containing divalent copper onto the P-doped COFs carrier material prepared in the step (2) by a solution impregnation method, carrying out vacuum drying treatment, and then treating by a glow discharge method to improve the dispersion of Cu active components and inhibit the agglomeration of the Cu active components, thereby finally obtaining the Cu/COFs catalyst.
Preferably, in step (1), the molar ratio of amino compound to carbonyl compound is 1:1-1:3; further preferably 1:1.
preferably, in the step (1), the non-aqueous organic solvent is at least one of ethanol, methanol and acetonitrile; methanol is more preferable.
Preferably, in the step (1), the stirring temperature is 25 ℃; the stirring time is 4-6h, most preferably 5h.
Preferably, in step (1), the reaction temperature is controlled to be in the range of 100 to 200 ℃, more preferably 110 to 130 ℃, and most preferably 120 ℃.
Preferably, in step (1), the reaction time is controlled to be 1 to 9 days, more preferably 2 to 4 days, and most preferably 3 days.
Preferably, in the step (1), the washing reagent is a mixed solvent of anhydrous N, N-dimethylacetamide and anhydrous acetone, and more preferably, the volume ratio of the anhydrous N, N-dimethylacetamide to the anhydrous acetone is 1:1.
preferably, in the step (2), the phosphorus source is phosphoric acid or sodium hypophosphite monohydrate, the solvent of the phosphorus source solution is deionized water, the volume concentration of the phosphoric acid solution is 60-90%, and the molar concentration of the aqueous solution of the sodium hypophosphite monohydrate is 0.9-4.8mol/L.
Preferably, in the step (2), the room-temperature immersion time is 18 to 30 hours.
Preferably, in the step (2), the drying conditions are as follows: the drying temperature is 120-300 ℃, and more preferably 120-180 ℃; the drying time is 4-12 hours.
Preferably, in the step (2), the roasting temperature is 400 ℃, and the roasting time is 4h.
Preferably, in the step (3), the loading amount (mass percentage relative to the carrier) of the copper in the Cu/COF catalyst is controlled to be 0.2-10 wt%.
Preferably, in the step (3), the divalent copper-containing precursor is selected from Cu (BF) 4 ) 2 、Cu(NO 3 ) 2 、Cu(C 5 H 7 O 2 ) 2 、 CuSO 4 Or CuCl 2 To (3) is provided. Preferably, the solvent is one or a mixture of more of deionized water, absolute ethyl alcohol, tetrahydrofuran, methanol, acetone, diethyl ether, cyclohexane, carbon tetrachloride and benzene. Preferably, the concentration of the active component solution is 0.0625-3.125mol/L.
Preferably, in the step (3), the solution dipping method is a solution dipping method, and specifically comprises the following steps: and mixing the active component solution and the carrier, stirring for 1-2h, centrifuging to remove supernatant, and loading the precursor containing the divalent copper onto the carrier. The dipping method is a known technology in the field, namely, the dripped dipping solution is matched with the pore volume of the porous solid carrier, and the dripped dipping solution completely enters the pore channel of the porous solid carrier.
Preferably, in the step (3), the vacuum drying treatment conditions are as follows: the temperature is 120-300 deg.C, and the time is 8-12 hr.
Preferably, in step (3), the glow discharge plasma treatment conditions are: the system is maintained in a vacuum state by using a vacuum pump with power of 250-500W, the pressure of the plasma chamber is maintained at 100Pa by adjusting the air flow, the plasma treatment intensity is adjusted by adjusting the discharge voltage value, the applied voltage is 80-300V, and the treatment time is 0.5-2 h.
In a second aspect, the invention provides the application of the Cu-COFs catalyst in the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene.
The application specifically comprises the following steps: the Cu/COFs catalyst is filled in a fixed bed reactor, and raw material gases HCl and C are introduced 2 H 2 The reaction temperature is 120-200 ℃, the reaction pressure is 0.01-2 MPa, and chloroethylene is obtained through reaction.
Preferably, the raw gas material mass ratio is n (HCl): n (C) 2 H 2 ) 1-1.2, and the volume air speed of acetylene is 5-500 h -1 。
Compared with the prior art, the invention has the following innovation points and technical advantages:
(1) According to the invention, the Cu catalyst is prepared by using covalent organic framework materials COFs instead of traditional active carbon as a catalyst carrier, and the catalyst is applied to acetylene hydrochlorination reaction, so that the catalytic activity and stability are improved. With the gradual maturity of the preparation technology of the COFs materials and the gradual reduction of the cost, the invention has a very strong industrial application prospect.
(2) The invention adopts glow discharge plasma technology to replace the traditional roasting treatment, greatly enhances the dispersibility of copper, is beneficial to reducing agglomeration, enables more active sites to be exposed on the inner surface and the outer surface of the catalyst, exerts higher activity and can keep stable in the long-time reaction process.
(3) According to the invention, the COFs carrier is P-doped and is further coordinated with Cu, so that the activity and stability of the Cu-based catalyst are enhanced; and can increase the dispersion of the Cu active component and the anti-carbon deposition capability.
(4) The Cu-COFs catalyst prepared by the invention is applied to acetylene hydrochlorination, can realize high conversion rate and high selectivity of the acetylene hydrochlorination, has good stability, and has good economic applicability and industrial application value.
(IV) detailed description of the preferred embodiments
The present invention will be described with reference to specific examples. It should be noted that the examples are only for further illustration of the present invention, but should not be construed as limiting the scope of the present invention, which is not limited thereto in any way. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.
Example 1
(1) Synthesis of covalent organic frameworks: firstly, mixing the components in a molar ratio of 1:1 of 0.0367mol of 3, 5-dimethyl-1, 2-phenylenediamine, 0.0367mol of 4,4' -biphenyldicarboxaldehyde and 30mL of methanol solvent were mixed, stirred at 25 ℃ for 5 hours, and then the mixture was put into a heat-resistant glass tube (Pyrex), frozen using liquid nitrogen, evacuated, and thawed. And repeating the operations of freezing, vacuumizing and unfreezing for three times to remove oxygen in the system, sealing a Pyrex tube by using a flame spray gun, placing the Pyrex tube in a constant-temperature oven at 120 ℃, reacting for 3 days, washing the obtained reactant for 1 hour by using a mixed solvent (volume ratio is 1: 1) of anhydrous N, N-Dimethylacetamide (DMAC) and anhydrous acetone, and performing vacuum drying at 80 ℃ for 4 hours to obtain the covalent organic framework products (COFs). Soaking the COFs in 35mL of 85% phosphoric acid solution with volume concentration for 24h at room temperature, drying the COFs in a constant-temperature oven at 150 ℃ for 8h until the COFs are dried, and roasting the COFs for 4h at 400 ℃ in nitrogen atmosphere to obtain the P-doped COFs carrier material.
(2) Preparation of Cu-COFs catalyst: taking 10g of P-doped COF obtained in the step (1)The s support material is added to the vessel. Then 20mL of Cu (BF) with a molar concentration of 0.1664mol/L is added 4 ) 2 Stirring the solution for 2 hours, centrifuging the solution, removing supernatant, carrying out vacuum drying at 120 ℃ for 10 hours, then carrying out glow discharge treatment, keeping a system in a vacuum state by using a vacuum pump with the power of 250-500W, keeping the pressure of a plasma chamber at 100Pa by adjusting the air flow, adjusting the plasma treatment intensity by adjusting the discharge voltage value, applying the voltage of 80V, and treating the time of 1.5 hours to obtain the COFs catalyst with the Cu (II) loading of 2.13 wt%.
(3) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 99.32%, and the selectivity of chloroethylene is 100%; after 500 hours of reaction time, the acetylene conversion was 99.08% and the vinyl chloride selectivity was 99.82%.
Example 2
(1) The same as in example 1. ( The molar ratio of reactants is 1:1 of 3-nitrophthalenediamine and 4,4' -biphenyldicarboxaldehyde )
(2) Preparation of Cu-COFs catalyst: and (2) adding 10g of the P-doped COFs carrier material obtained in the step (1) into a container. Then 20mL of Cu with the molar concentration of 0.2055mol/L is added 2 P 2 O 7 Stirring the solution for 2 hours, centrifuging the solution, removing supernatant, carrying out vacuum drying at 120 ℃ for 10 hours, then carrying out glow discharge treatment, keeping a system in a vacuum state by using a vacuum pump with the power of 250-500W, keeping the pressure of a plasma chamber at 100Pa by adjusting the air flow, adjusting the discharge voltage value to adjust the plasma treatment strength, applying the voltage of 100V, and treating the solution for 1.5 hours to obtain the COFs catalyst with the Cu (II) loading of 5.26 wt%.
(3) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl): n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . Initial stage of reactionThe acetylene conversion rate is 99.61 percent, and the chloroethylene selectivity is 100 percent; after 500 hours of reaction, the acetylene conversion was 99.13% and the vinyl chloride selectivity was 99.44%.
Example 3
(1) The same as in example 1. ( The molar ratio of reactants is 1:1 biphenyldiammine, 4' -biphenyldicarboxaldehyde )
(2) Preparation of Cu-COFs catalyst: and (2) adding 10g of the P-doped COFs carrier material obtained in the step (1) into a container. Then 20mL of Cu with the molar concentration of 0.1182mol/L is added 3 (PO 4 ) 2 Stirring for 2 hours, centrifuging, removing supernatant, vacuum drying at 120 ℃ for 10 hours, then performing glow discharge treatment, keeping the system in a vacuum state by using a vacuum pump with the power of 250-500W, keeping the pressure of a plasma chamber at 100Pa by adjusting the air flow, adjusting the plasma treatment intensity by adjusting the discharge voltage value, wherein the applied voltage is 120V, and the treatment time is 1.5 hours. Thus obtaining the COFs catalyst with the Cu (II) loading of 4.54 wt%.
(3) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) =1: acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 99.54 percent, and the selectivity of chloroethylene is 100 percent; after 500 hours of reaction, the acetylene conversion was 99.22% and the vinyl chloride selectivity was 99.51%.
Example 4
(1) The same as in example 1. ( The molar ratio of reactants is 1:1 of 2,4, 6-trimethyl-1, 3-phenylenediamine, 4' -biphenyldicarboxaldehyde )
(2) Preparation of Cu-COFs catalyst: and (2) adding 10g of the P-doped COFs carrier material obtained in the step (1) into a container. Then 20mL of CuCl with the molar concentration of 0.2508mol/L is added 2 Stirring for 2 hr, centrifuging, removing supernatant, vacuum drying at 120 deg.C for 10 hr, performing glow discharge treatment, maintaining the system in vacuum state with vacuum pump of 250-500W power, regulating air flow to maintain plasma chamber pressure at 100Pa, and regulating discharge voltageThe plasma treatment intensity was adjusted, the applied voltage was 140V, and the treatment time was 1.5h. Thus obtaining the COFs catalyst with the Cu (II) loading of 3.21 wt%.
(3) Tests prove that the catalyst is applied to the hydrochlorination reaction of acetylene in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 99.68 percent, and the selectivity of chloroethylene is 100 percent; after 500 hours of reaction, the acetylene conversion was 99.40% and the vinyl chloride selectivity was 99.27%.
Example 5
(1) The same as in example 1. ( The molar ratio of reactants is 1:1 o-phenylenediamine, 4' -biphenyldicarboxaldehyde )
(2) Preparation of Cu-COFs catalyst: and (2) adding 10g of the P-doped COFs carrier material obtained in the step (1) into a container. 20mL of Cu (BF) with a molar concentration of 0.2375mol/L was added 4 ) 2 Stirring for 2 hours, centrifuging, removing supernatant, vacuum drying at 120 ℃ for 10 hours, then performing glow discharge treatment, keeping the system in a vacuum state by using a vacuum pump with the power of 250-500W, keeping the pressure of a plasma chamber at 100Pa by adjusting the air flow, adjusting the plasma treatment intensity by adjusting the discharge voltage value, wherein the applied voltage is 160V, and the treatment time is 1.5 hours. Thus obtaining the COFs catalyst with the Cu (II) load of 3.04 wt%.
(3) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 99.43 percent, and the selectivity of chloroethylene is 100 percent; after 500 hours of reaction, the acetylene conversion was 99.19% and the vinyl chloride selectivity was 99.21%.
Example 6
(1) The same as in example 1. ( The molar ratio of reactants is 1:1 o-phenylenediamine and terephthalaldehyde )
(2) Preparation of Cu-COFs catalyst: adding 10g of the P-doped COFs carrier material obtained in the step (1) into a containerIn the device. 20mL of Cu (BF) with a molar concentration of 0.1664mol/L is added 4 ) 2 Stirring for 2 hours, centrifuging, removing supernatant, vacuum drying at 120 ℃ for 10 hours, then performing glow discharge treatment, keeping the system in a vacuum state by using a vacuum pump with the power of 250-500W, keeping the pressure of a plasma chamber at 100Pa by adjusting the air flow, adjusting the plasma treatment intensity by adjusting the discharge voltage value, wherein the applied voltage is 180V, and the treatment time is 1.5 hours. Thus obtaining the COFs catalyst with the Cu (II) loading of 2.13 wt%.
(3) Tests prove that the catalyst is applied to the hydrochlorination reaction of acetylene in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 99.22 percent, and the selectivity of chloroethylene is 100 percent; after 500 hours of reaction, the acetylene conversion was 98.89% and the vinyl chloride selectivity was 99.14%.
Example 7
(1) The same as in example 1. ( The molar ratio of reactants is 1:1 o-phenylenediamine, o-phthalaldehyde )
(2) Preparation of Cu-COFs catalyst: and (2) adding 10g of the P-doped COFs carrier material obtained in the step (1) into a container. Then 20mL of Cu with the molar concentration of 0.2055mol/L is added 2 P 2 O 7 Stirring for 2 hours, centrifuging, removing supernatant, vacuum drying at 120 ℃ for 10 hours, then performing glow discharge treatment, keeping the system in a vacuum state by using a vacuum pump with the power of 250-500W, keeping the pressure of a plasma chamber at 100Pa by adjusting the air flow, adjusting the discharge voltage value to adjust the plasma treatment intensity, wherein the applied voltage is 200V, and the treatment time is 1.5 hours. Thus obtaining the COFs catalyst with the Cu (II) loading of 5.26 wt%.
(3) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the acetylene conversion is 99.38%, and the chloroethyleneThe alkene selectivity is 100 percent; after 500 hours of reaction, the acetylene conversion was 99.24% and the vinyl chloride selectivity was 99.38%.
Example 8
(1) The same as in example 1. ( The molar ratio of reactants is 1:1 o-phenylenediamine and trimesic aldehyde )
(2) Preparation of Cu-COFs catalyst: and (2) adding 10g of the P-doped COFs carrier material obtained in the step (1) into a container. Then 20mL of Cu with the molar concentration of 0.1182mol/L is added 3 (PO 4 ) 2 Stirring for 2 hours, centrifuging, removing supernatant, vacuum drying at 120 ℃ for 10 hours, then performing glow discharge treatment, keeping the system in a vacuum state by using a vacuum pump with the power of 250-500W, keeping the pressure of a plasma chamber at 100Pa by adjusting the air flow, adjusting the plasma treatment intensity by adjusting the discharge voltage value, wherein the applied voltage is 180V, and the treatment time is 1.5 hours. Thus obtaining the COFs catalyst with the Cu (II) loading of 4.54 wt%.
(3) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl): n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 99.71 percent, and the selectivity of chloroethylene is 100 percent; after 500 hours of reaction, the acetylene conversion was 99.47% and the vinyl chloride selectivity was 99.79%.
Example 9
(1) The same as in example 1. ( The molar ratio of reactants is 1:1 o-phenylenediamine and trialdehyde phloroglucinol )
(2) Preparation of Cu-COFs catalyst: and (2) adding 10g of the P-doped COFs carrier material obtained in the step (1) into a container. Then 20mL of CuCl with the molar concentration of 0.2508mol/L is added 2 Stirring for 2 hr, centrifuging, removing supernatant, vacuum drying at 120 deg.C for 10 hr, performing glow discharge treatment, maintaining the system in vacuum state with vacuum pump with power of 250-500W, regulating air flow to maintain the pressure of the plasma chamber at 100Pa, regulating discharge voltage to regulate plasma treatment intensity, and applying voltage of 180VThe time is 1.5h. Thus obtaining the COFs catalyst with the Cu (II) loading of 3.21 wt%.
(3) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 99.57 percent, and the selectivity of chloroethylene is 100 percent; after 500 hours of reaction, the acetylene conversion was 99.28% and the vinyl chloride selectivity was 99.72%.
Example 10
(1) The same as in example 1. ( The molar ratio of reactants is 1:1 of 2,4, 6-trimethyl-1, 3-phenylenediamine, trialdehyde phloroglucinol )
(2) Preparation of Cu-COFs catalyst: and (2) taking 10g of the P-doped COFs carrier material obtained in the step (1) and adding the carrier material into a container. 20mL of Cu (BF) with a molar concentration of 0.2375mol/L was added 4 ) 2 Stirring for 2 hours, centrifuging, removing supernatant, vacuum drying at 120 ℃ for 10 hours, then performing glow discharge treatment, keeping the system in a vacuum state by using a vacuum pump with the power of 250-500W, keeping the pressure of a plasma chamber at 100Pa by adjusting the air flow, adjusting the plasma treatment intensity by adjusting the discharge voltage value, and applying the voltage of 150V for 1.5 hours. Thus obtaining the COFs catalyst with the Cu (II) load of 3.04 wt%.
(3) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 120 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 99.03 percent, and the selectivity of chloroethylene is 100 percent; after 500 hours of reaction, the acetylene conversion was 98.46% and the vinyl chloride selectivity was 99.23%.
Comparative example 1
Comparative example 1 illustrates the superiority of a covalent organic framework support material in terms of catalytic stability by comparison with example 1.
(1) Taking 10g of commercially available specific surface area of 500-1500 m 2 G, pore volume of 0.25-1.5 mL/gThe spherical activated carbon of (a) is added to the vessel. 20mL of Cu (BF) with a molar concentration of 0.1664mol/L is added 4 ) 2 Stirring for 2 hours, centrifuging, removing supernatant, vacuum drying for 10 hours at 120 ℃, then performing glow discharge treatment, keeping a system in a vacuum state by using a vacuum pump with the power of 250-500W, keeping the pressure of a plasma chamber at 100Pa by adjusting the air flow, adjusting the plasma treatment intensity by adjusting the discharge voltage value, applying the voltage of 80V, and treating for 1.5 hours to obtain the copper-based catalyst with the Cu (II) loading of 2.13 wt%.
(2) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl): n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 78.56%, and the selectivity of vinyl chloride is 93.61%; after 500 hours of reaction time, the acetylene conversion was 45.33% and the vinyl chloride selectivity was 87.64%.
Comparative example 2
Comparative example 2 illustrates the superiority of the covalent organic framework support material in terms of catalytic stability by comparison with example 2.
(1) Taking 10g of commercial specific surface area 1000-3000m 2 Activated carbon fiber with a pore diameter of 1.0-4.0 nm/g is added into the container. Then 20mL of Cu with the molar concentration of 0.2055mol/L is added 2 P 2 O 7 Stirring for 2 hours, centrifuging, removing supernatant, vacuum drying for 10 hours at 120 ℃, then performing glow discharge treatment, keeping a system in a vacuum state by using a vacuum pump with the power of 250-500W, keeping the pressure of a plasma chamber at 100Pa by adjusting the air flow, adjusting the plasma treatment intensity by adjusting the discharge voltage value, applying the voltage of 100V, and treating for 1.5 hours to obtain the copper-based catalyst with the Cu (II) loading of 5.26 wt%.
(2) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 76.39%, and the selectivity of vinyl chloride is 91.62%; after 500 hours of reaction time, the acetylene conversion was 42.28% and the vinyl chloride selectivity was 84.87%.
Comparative example 3
Comparative example 3 illustrates the irreplaceability of glow discharge plasma in the catalyst preparation process by comparison with example 3.
(1) The same as in example 1. ( The molar ratio of reactants is 1:1 biphenyldiammine, 4' -biphenyldicarboxaldehyde )
(2) Preparation of Cu-COFs catalyst: and (2) adding 10g of the P-doped COFs carrier material obtained in the step (1) into a container. Then 20mL of Cu with the molar concentration of 0.1182mol/L is added 3 (PO 4 ) 2 Stirring for 2 hours, centrifuging, removing supernatant, and vacuum drying at 120 ℃ for 10 hours to obtain the COFs catalyst with the Cu (II) load of 4.54 wt%.
(3) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the conversion rate of acetylene is 80.66%, and the selectivity of vinyl chloride is 94.74%; after 500 hours of reaction time, the acetylene conversion was 61.54% and the vinyl chloride selectivity was 88.49%.
Comparative example 4
Comparative example 4 illustrates the superiority of P doping in improving the activity and stability of Cu-based catalysts by comparison with example 4.
(1) In the same manner as in example 1, COFs carriers without P-doping treatment were obtained. ( The molar ratio of reactants is 1:1 of 2,4, 6-trimethyl-1, 3-phenylenediamine, 4' -biphenyldicarboxaldehyde )
(2) Preparation of Cu-COFs catalyst: and (2) taking 10g of the P-doped COFs carrier material obtained in the step (1) and adding the carrier material into a container. Then 20mL of CuCl with the molar concentration of 0.2508mol/L is added 2 Stirring for 2 hr, centrifuging, removing supernatant, vacuum drying at 120 deg.C for 10 hr, and glow discharge treating at 250-50% powerThe vacuum pump of 0W is kept in a vacuum state, the pressure of the plasma chamber is kept at 100Pa by adjusting the air flow, the plasma treatment intensity is adjusted by adjusting the discharge voltage value, the applied voltage is 140V, and the treatment time is 1.5h. Thus obtaining the COFs catalyst with the Cu (II) loading of 3.21 wt%.
(3) Tests show that the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C) 2 H 2 ) 1 and acetylene space velocity of 30h -1 . At the initial stage of the reaction, the acetylene conversion rate is 81.52 percent, and the vinyl chloride selectivity is 91.63 percent; after 500 hours of reaction time, the acetylene conversion was 68.31% and the vinyl chloride selectivity was 87.63%.
TABLE 1 evaluation of catalytic Performance of Cu-COF catalyst for acetylene hydrochlorination
Figure BDA0003574835270000101
Figure BDA0003574835270000111

Claims (10)

1. A preparation method of Cu/COFs catalyst for acetylene hydrochlorination is characterized by comprising the following steps: the preparation method comprises the following specific steps:
(1) Preparation of a covalent organic framework: firstly, stirring an amino compound, a carbonyl compound and a non-aqueous organic solvent at the temperature of 20-30 ℃ for 3-6h; then adding the mixture into a heat-resistant glass tube, freezing the mixture by using liquid nitrogen, vacuumizing the heat-resistant glass tube, unfreezing the heat-resistant glass tube, and repeating freezing-vacuumizing-unfreezing operations to fully remove oxygen in the system; sealing the heat-resistant glass tube by using a flame spray gun, placing the heat-resistant glass tube in a constant-temperature oven, controlling the temperature to be 100-200 ℃ and reacting for 1-9 days, and washing and drying the obtained reactant to obtain a covalent organic framework product; the amino compound is at least one of biphenyldiamine, o-phenylenediamine, 3-nitro-o-phenylenediamine, 3, 5-dimethyl-1, 2-phenylenediamine and 2,4, 6-trimethyl-1, 3-phenylenediamine; the carbonyl compound is 4,4' -biphenyldicarboxaldehyde, terephthalaldehyde, o-phthalaldehyde at least one of mesitylene-triformol and trialdehyde phloroglucinol;
(2) Preparing a P-doped COFs carrier material: soaking the covalent organic framework product prepared in the step (1) in a phosphorus source solution at room temperature for 12-36h, taking out and drying the product, and roasting the product at 300-500 ℃ for 4-6h in a nitrogen atmosphere to obtain a P-doped covalent organic framework carrier material;
(3) Preparing a Cu-COFs catalyst: dissolving a divalent copper-containing precursor in a solvent to prepare an active component solution; loading a precursor containing divalent copper onto the P-doped COFs carrier material prepared in the step (2) by a solution impregnation method, carrying out vacuum drying treatment, and then treating by a glow discharge method to improve the dispersion of Cu active components and inhibit the agglomeration of the Cu active components, thereby finally obtaining the Cu/COFs catalyst.
2. The method of claim 1, wherein: in the step (1), the molar ratio of the amino compound to the carbonyl compound is 1:1-1:3.
3. the method of claim 1, wherein: in the step (1), the non-aqueous organic solvent is at least one of ethanol, methanol and acetonitrile.
4. The method of claim 1, wherein: in the step (1), the reaction temperature is controlled to be 110-130 ℃, and the most preferable temperature is 120 ℃; the reaction time is controlled to be 2 to 4 days, most preferably 3 days.
5. The method of claim 1, wherein: in the step (1), the washing reagent is a mixed solvent of anhydrous N, N-dimethylacetamide and anhydrous acetone.
6. The method of claim 1, wherein: in the step (2), the phosphorus source is phosphoric acid or sodium hypophosphite monohydrate, the solvent of the phosphorus source solution is deionized water, the volume concentration of the phosphoric acid solution is 60% -90%, and the molar concentration of the aqueous solution of the sodium hypophosphite monohydrate is 0.9-4.8mol/L.
7. The method of claim 1, wherein: in the step (2), the room-temperature dipping time is 18-30h.
8. The method of claim 1, wherein: in the step (3), the loading amount of the copper in the Cu/COF catalyst is controlled to be 0.2-10 wt%.
9. The method of claim 1, wherein: in the step (3), the glow discharge plasma treatment conditions are as follows: the vacuum pump with power of 250-500W is used to maintain the system in vacuum state, the pressure of the plasma chamber is maintained at 100Pa by adjusting the air flow, the plasma treatment intensity is adjusted by adjusting the discharge voltage value, the applied voltage is 80-300V, and the treatment time is 0.5-2 h.
10. The use of the Cu-COFs catalyst prepared by the preparation method according to claim 1 in the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene.
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