CN114749215B - MXene-based catalyst carrier for hydrochlorination of acetylene and preparation method and application of catalyst - Google Patents

MXene-based catalyst carrier for hydrochlorination of acetylene and preparation method and application of catalyst Download PDF

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CN114749215B
CN114749215B CN202210338006.4A CN202210338006A CN114749215B CN 114749215 B CN114749215 B CN 114749215B CN 202210338006 A CN202210338006 A CN 202210338006A CN 114749215 B CN114749215 B CN 114749215B
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mxene
acetylene
hydrochlorination
catalyst
carrier
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CN114749215A (en
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赵佳
王涛
李小年
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Zhejiang University of Technology ZJUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • 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

Abstract

The invention discloses a catalyst carrier for acetylene hydrochlorination based on MXene, a preparation method and application of the catalyst carrier. The preparation method of the carrier comprises the following steps: (1) preparing a multi-layer MXene precipitate; (2) Re-dispersing the multi-layer MXene precipitate into an organic solvent to form a suspension, adding an ionic liquid into the suspension, and fully standing in a low-frequency electromagnetic field to obtain a mixture; (3) And (3) vacuum drying the mixture obtained in the step (3) to obtain the catalyst carrier for hydrochlorination of acetylene based on MXene. The invention also provides a method for preparing the catalyst by using the carrier-supported ruthenium. The carrier prepared by the invention has high stability, and the catalyst for hydrochlorination of acetylene based on MXene prepared by the invention has high catalytic activity and high stability.

Description

MXene-based catalyst carrier for hydrochlorination of acetylene and preparation method and application of catalyst
Field of the art
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of an acetylene hydrochlorination carrier with high stability and long service life based on MXene.
(II) background art
Vinyl Chloride (VCM) is used for producing polyvinyl chloride (PVC). Polyvinyl chloride is one of five general resins PVC, PE, PP, PS and ABS in the world), is an important plastic product, has the advantages of wear resistance, flame resistance, insulation, corrosion resistance, high mechanical strength and the like, and has wide application in the aspects of industry, agriculture, construction, daily necessities, packaging, electric power and the like. At present, the PVC production process mainly comprises an ethylene oxychlorination method and a calcium carbide glow method. Because of the special energy structure of rich coal and less oil in China, the ethylene raw material is deficient, but rich coal resources provide sufficient acetylene raw materials for the calcium carbide PVC process, and the process route for synthesizing the vinyl chloride by the acetylene hydrochlorination method is still dominant in China. The traditional acetylene hydrochlorination production process adopts HgCl/AC as a catalyst, has extremely toxic and volatile HgCl, and is easy to cause harm to human health and environment. Therefore, the problem to be solved by many researchers in the chemical industry at present is how to eliminate Hg pollution and realize a clean and low-consumption production process for synthesizing chloroethylene by an acetylene hydrochlorination method. Recently, scientists have proposed the best solution to solve the Hg pollution to develop and research mercury-free catalysts, and many scientists have conducted a great deal of research on the mercury-free catalysts, but the effect is not outstanding enough. At present, many researches show that the noble metal catalyst has ultrahigh activity and stability in the hydrochlorination of acetylene, but is limited by the influence of a carrier, and the activity and stability of the catalyst are reduced due to the fact that the carbon carrier is influenced by the property of the carbon carrier in the reaction process and the mechanical strength is not high, so that phenomena such as pore collapse and the like occur in the reaction process, and noble metal active substances are lost and stacked. At present, the better active carbon is monopolyed abroad, the carrier is wanted to be developed in China, the monopoly of the foreign technology is broken through, and the active carbon is not clamped in the neck. It is an important and promising task to find a carrier which is excellent in its own right and suitable for use in acetylene hydrochlorination systems.
MXene is a novel transition metal carbide or nitride, has the characteristics of unique two-dimensional structure, good stability, ultrahigh conductivity, excellent specific capacitance and the like, and therefore has great application prospects in the aspects of capacitors, catalysis, chemisorption and the like. But the MXene is extremely easy to oxidize in the air or under high temperature conditions, so that the conductivity of the MXene is greatly reduced, and the MXene is easy to stack and agglomerate similar to other two-dimensional materials, so that the exertion of the excellent characteristics of the MXene is greatly restricted, and the application of the MXene in the field of catalysis is severely limited. If the carrier based on MXene can be prepared, the unique two-dimensional structure of the carrier is considered, the exposed multi-defect point positions are considered, the carrier has higher stability and service life, the purposes of high activity and good stability are achieved, the application of the MXene material is greatly promoted, and the green and efficient development of acetylene hydrochlorination reaction is promoted.
Therefore, the development of the carrier for the hydrochlorination of acetylene based on MXene with high stability and long service life has great industrial application value.
(III) summary of the invention
The first object of the present invention is to provide a method for preparing a catalyst carrier for an MXene-based hydrochlorination of acetylene, which has high stability and long life.
The second object of the invention is to provide a method for preparing a catalyst for hydrochlorination of acetylene based on MXene.
It is a third object of the present invention to provide the use of said catalyst in hydrochlorination of acetylene.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a catalyst support for hydrochlorination of acetylene based on MXene, comprising the steps of:
step one: adding LiF powder into HCl solution, slowly adding MAX powder after full dissolution, stirring and etching by using ultrasonic auxiliary oil bath, and centrifugally washing by using deionized water to obtain multi-layer MXene precipitate;
step two: re-dispersing the multi-layer MXene precipitate obtained in the first step into an organic solvent to form a suspension, adding an ionic liquid into the suspension, and placing the suspension in a low-frequency electromagnetic field for full standing to obtain a mixture; the ionic liquid is one or more of 1-ethyl-2, 3-dimethyl imidazole hexafluorophosphate, 1-methyl-3-hexadecyl imidazole bistrifluoromethane sulfonic acid imine salt, trimethyl imidazole tetrafluoroborate and 1-methyl-3-octyl imidazole hexafluorophosphate; the mass ratio of the added ionic liquid to the MXene sediment is (1-3): 1;
step three: and (3) drying the mixture obtained in the step (II) in vacuum to obtain the catalyst carrier for hydrochlorination of acetylene based on MXene.
Further, in the first step, the mass-volume ratio of the LiF powder to the HCl solution is 1g: (5-60) mL, wherein the mass volume ratio of the MAX powder to the HCl solution is 1g (10-30) mL, and the concentration of the HCl solution is 8-9 mol/L.
Further, in step one, the MAX powder may be Ti 3 AlC 2 、Ti 2 AlC、TiNbAlC、V 2 AlC、Nb 2 AlC、Ti 3 AlCN、Ti 3 SiC 2 、Ti 2 SiC、TiNbSiC、V 2 SiC、Nb 2 SiC、Nb 4 SiC 3 、Ti 3 One or more of SiCN.
In the first step, the ultrasonic wave frequency used for ultrasonic auxiliary oil bath stirring etching is 20-80kHz, the stirring speed is 500-800r/min, the oil bath reaction temperature is 20-60 ℃, and the treatment time is 8-24 h.
Further, in the first step, centrifugal washing was repeated with deionized water until ph=6, to obtain a multi-layered MXene precipitate.
In the first step, the centrifugal washing rotating speed is 2000-5000 rpm.
Further, in the second step, the concentration of the formed MXene suspension is 0.3-0.6 g/mL.
In the second step, the organic solvent is at least one of methanol, ethanol, n-propanol, isopropanol, glycerol and acetonitrile.
In the second step, the frequency of the low-frequency electromagnetic field is 50-60 Hz, the magnetic field strength is 0.2-0.4 mu T, and the standing time is 8-24 h.
In the third step, the vacuum drying temperature is 100-120 ℃ and the drying time is 12-24 h.
In a second aspect, the present invention provides a method for preparing a catalyst for hydrochlorination of acetylene based on MXene, comprising: adding a ruthenium ion-containing solution into a reaction vessel, adding ethanol, fully stirring, adding a catalyst carrier for acetylene hydrochlorination based on MXene, fully soaking, and drying to obtain the catalyst for acetylene hydrochlorination based on MXene.
Preferably, the ruthenium loading (relative to the support) in the catalyst is controlled to be 0.2 to 3wt%.
Preferably, the ethanol is added in an amount of 0.3 to 1mL of ethanol per gram of carrier. The addition of ethanol allows for better mixing of the ruthenium solution and the ionic liquid.
Preferably, the impregnation time is 8-12 hours.
Preferably, the drying conditions are: baking at 100-120deg.C for 8-12 hr.
In a third aspect, the invention provides the use of the catalyst prepared by the preparation method described above in the hydrochlorination of acetylene to vinyl chloride.
The application is specifically as follows: charging a fixed bed reactor with the catalyst, and introducing raw material gases HCl and C 2 H 2 The reaction temperature is 120-200 ℃, the reaction pressure is 0.01-2 MPa, and the chloroethylene is obtained by reaction.
Further, the ratio of the raw material gas materials is n (HCl) to n (C) 2 H 2 ) The acetylene volume space velocity is 50-500 h, which is 1:1-1.2:1 -1 。
Compared with the prior art, the invention has the following innovation points and technical advantages:
(1) According to the invention, ultrasonic auxiliary oil bath etching is adopted, and under the action of ultrasonic waves, MAX powder can be more thoroughly stripped to form single-layer and multi-layer MXene;
(2) According to the invention, specific ionic liquid is combined with the MXene material, and the ionic liquid is firstly loaded on the surface of the MXene material, so that the MXene is protected, the effects of promoting the adsorption of reaction substrates and the desorption of products are simultaneously achieved, the phenomena that the MXene material is easy to oxidize at high temperature and is stacked and agglomerated are solved, and the high stability of the MXene material is realized;
(3) The low-frequency electromagnetic field is applied to the process of adsorbing the ionic liquid to the MXene material, so that the adsorption of the ionic liquid on the surface of the MXene material is promoted, the ionic liquid can enter between the multi-layer MXene interlayers which are difficult to enter originally, the adsorption effect of the carrier is enhanced, and the activity of the catalyst is further improved;
(4) The catalyst for hydrochlorination of acetylene based on MXene prepared by the invention has high catalytic activity and high stability.
(5) The method has the advantages of easily obtained reagent, no toxicity or harm, simple process, easy mass production and industrialization realization.
(IV) description of the drawings
FIG. 1 is an electron micrograph of a precursor MAX powder used in the examples;
FIG. 2 is an electron micrograph of the multilayer MXene prepared in step 1) of example 1;
FIG. 3 is an electron micrograph of the ionic liquid prepared in step 2) of example 1 after loading with an MXene material.
(fifth) detailed description of the invention
The invention is illustrated below by means of specific examples. It is to be noted that the examples are only for further explanation of the present invention and are not to be construed as limiting the scope of the present invention in any way. Those skilled in the art will be able to make numerous insubstantial modifications and adaptations in light of the above disclosure.
The MAX powder used in the embodiment of the invention is Ti 3 AlC 2 And (3) powder. In an embodiment, each drug is purchased from a reagent platform.
Example 1
A preparation method and application of an MXene acetylene hydrochlorination carrier with high stability and long service life comprise the following steps:
1) Adding 2g of LiF powder into 50ml of HCl solution with the concentration of 9mol/L, slowly adding 5g of MAX powder after full dissolution, carrying out oil bath at the temperature of 20 ℃ under the assistance of 20kHz ultrasonic wave, stirring at the speed of 500r/min, stirring and etching for 8h, repeatedly carrying out centrifugal washing with deionized water at the speed of 2000rpm for 30min, and washing to pH=6 to obtain multilayer MXene precipitate;
2) Re-dispersing 5g of the multi-layer MXene precipitate into 10ml of methanol to form a suspension, adding 10g of 1-ethyl-2, 3-dimethyl imidazole hexafluorophosphate into the suspension, and standing for 8 hours in a low-frequency electromagnetic field with the frequency of 50Hz and the intensity of 0.2 mu T;
3) The mixture after standing in step 2) was dried under vacuum at 100℃for 12 hours to obtain a catalyst support 1 for hydrochlorination of acetylene based on MXene.
4) Preparation of the catalyst: 5ml of RuCl at a concentration of 0.989M was added to a clean petri dish 3 Adding 10ml of ethanol into the solution, fully stirring, adding 20g of carrier 1, soaking for 8 hours, and then putting into a baking oven to dry at 110 ℃ for 8 hours to obtain a catalyst 1;
4) Use of catalyst 1 in hydrochlorination of acetylene: the evaluation of acetylene hydrochlorination was carried out on a fixed bed reactor apparatus under the following reaction conditions: the temperature is 150 ℃ and the acetylene airspeed is 50h -1 ，n(HCl):n(C 2 H 2 ) Carried out under the condition of =1.1:1. In the initial stage of the reaction, the conversion rate of acetylene is 99.71%, and the selectivity of chloroethylene is 99.96%; after 1000 hours of reaction, the conversion of acetylene was 97.43% and the selectivity to vinyl chloride was 99.85%.
Example 2
A preparation method and application of an MXene acetylene hydrochlorination carrier with high stability and long service life comprise the following steps:
1) Adding 8g LiF powder into 150ml of HCl solution with the concentration of 9mol/L, slowly adding 5g MAX powder after full dissolution, carrying out oil bath at the temperature of 30 ℃ under the assistance of 30kHz ultrasonic wave, stirring at the speed of 600r/min, stirring and etching for 8h, repeatedly carrying out centrifugal washing with deionized water at the rotating speed of 3000rpm, washing for 60min until the pH=6, and obtaining multilayer MXene precipitate;
2) Re-dispersing 5g of the multilayer MXene precipitate into 10ml of ethanol to form a suspension, adding 10g of 1-methyl-3-hexadecyl imidazole bistrifluoromethane sulfonic acid imine salt into the suspension, and standing for 24 hours in a low-frequency electromagnetic field with the frequency of 60Hz and the intensity of 0.4 mu T;
3) The mixture after standing in the step 2) was dried under vacuum at 120℃for 24 hours to obtain a catalyst support 2 for hydrochlorination of acetylene based on MXene.
4) Preparation of the catalyst: 5ml of RuCl at a concentration of 0.989M was added to a clean petri dish 3 Adding 10ml of ethanol into the solution, fully stirring, adding 20g of carrier 2, soaking for 8 hours, and then putting into a baking oven to dry at 110 ℃ for 8 hours to obtain a catalyst 2;
4) Use of catalyst 2 in hydrochlorination of acetylene: the evaluation of acetylene hydrochlorination was carried out on a fixed bed reactor apparatus under the following reaction conditions: the temperature is 150 ℃ and the acetylene airspeed is 50h -1 ，n(HCl):n(C 2 H 2 ) Carried out under the condition of =1.1:1. In the initial stage of the reaction, the conversion rate of acetylene is 99.32%, and the selectivity of chloroethylene is 99.92%; after 1000 hours of reaction, the conversion of acetylene was 97.82% and the selectivity to vinyl chloride was 99.76%.
Example 3
A preparation method and application of an MXene acetylene hydrochlorination carrier with high stability and long service life comprise the following steps:
1) Adding 6g LiF powder into 80ml of HCl solution with the concentration of 9mol/L, slowly adding the solution after full dissolution, then slowly adding 6g MAX powder, carrying out oil bath at 40 ℃ under the assistance of 40kHz ultrasonic wave, stirring at the speed of 500r/min, stirring and etching for 14h, and repeatedly carrying out centrifugal washing with deionized water at the rotating speed of 3000rpm for 60min until the pH=6 to obtain multilayer MXene precipitate;
2) Re-dispersing 5g of the multi-layer MXene precipitate into 10ml of n-propanol to form a suspension, adding 10g of trimethylimidazole tetrafluoroborate into the suspension, and standing for 8h in a low-frequency electromagnetic field with the frequency of 50Hz and the intensity of 0.2 mu T;
3) The mixture after standing in the step 2) was dried in vacuum at 100℃for 12 hours to obtain a catalyst support 3 for hydrochlorination of acetylene based on MXene.
4) Preparation of the catalyst: 5ml of RuCl at a concentration of 0.989M was added to a clean petri dish 3 Adding 10ml of ethanol into the solution, fully stirring, adding 20g of carrier 3, soaking for 8 hours, and then putting into a baking oven to dry at 110 ℃ for 8 hours to obtain a catalyst 3;
4) Use of catalyst 3 in hydrochlorination of acetylene: the evaluation of acetylene hydrochlorination was carried out on a fixed bed reactor apparatus under the following reaction conditions: the temperature is 150 ℃ and the acetylene airspeed is 100h -1 ，n(HCl):n(C 2 H 2 ) Carried out under the condition of =1.1:1. In the initial stage of the reaction, the conversion rate of acetylene is 99.09%, and the selectivity of chloroethylene is 99.94%; after 1000 hours of reaction, the conversion of acetylene was 97.98% and the selectivity to vinyl chloride was 99.86%.
Example 4
A preparation method and application of an MXene acetylene hydrochlorination carrier with high stability and long service life comprise the following steps:
1) Adding 10g of LiF powder into 160ml of HCl solution with the concentration of 9mol/L, slowly adding 6g of MAX powder after full dissolution, carrying out oil bath at 60 ℃ under the assistance of 60kHz ultrasonic wave, stirring at the speed of 700r/min, stirring and etching for 14h, repeatedly carrying out centrifugal washing with deionized water at the speed of 4000rpm for 80min, and washing to pH=6 to obtain multilayer MXene precipitate;
2) Re-dispersing 5g of the multi-layer MXene precipitate into 10ml of isopropanol to form a suspension, adding 10g of 1-methyl-3-octyl imidazole hexafluorophosphate into the suspension, and standing for 24 hours in a low-frequency electromagnetic field with the frequency of 60Hz and the intensity of 0.4 mu T;
3) The mixture after standing in the step 2) was dried under vacuum at 120 ℃ for 24 hours to obtain a catalyst support 4 for hydrochlorination of acetylene based on MXene.
4) Preparation of the catalyst: 5ml of RuCl at a concentration of 0.989M was added to a clean petri dish 3 Adding 10ml of ethanol into the solution, fully stirring, adding 20g of carrier 4, soaking for 8 hours, and then putting into a baking oven to dry at 110 ℃ for 8 hours to obtain a catalyst 4;
4) Use of catalyst 4 in hydrochlorination of acetylene: in a fixed bed reactor arrangementThe acetylene hydrochlorination reaction was evaluated above, and the reaction conditions were: the temperature is 150 ℃ and the acetylene airspeed is 100h -1 ，n(HCl):n(C 2 H 2 ) Carried out under the condition of =1.1:1. In the initial stage of the reaction, the conversion rate of acetylene is 99.36 percent, and the selectivity of chloroethylene is 99.95 percent; after 1000 hours of reaction, the conversion of acetylene was 97.46% and the selectivity to vinyl chloride was 99.66%.
Example 5
A preparation method and application of an MXene acetylene hydrochlorination carrier with high stability and long service life comprise the following steps:
1) Adding 6g LiF powder into 80ml of HCl solution with the concentration of 9mol/L, slowly adding the solution after full dissolution, then slowly adding 8g MAX powder, carrying out oil bath at 50 ℃ under the assistance of 80kHz ultrasonic wave, stirring at the speed of 700r/min, stirring and etching for 18h, and repeatedly carrying out centrifugal washing with deionized water at the speed of 4000rpm for 100min until the pH=6 to obtain multilayer MXene precipitate;
2) Re-dispersing 5g of the multilayer MXene precipitate into 10ml of glycerol to form a suspension, adding 10g of 1-ethyl-2, 3-dimethylimidazole hexafluorophosphate into the suspension, and standing for 8h in a low-frequency electromagnetic field with the frequency of 50Hz and the intensity of 0.4 mu T;
3) The mixture after standing in the step 2) was dried in vacuum at 100℃for 12 hours to obtain a catalyst support 5 for hydrochlorination of acetylene based on MXene.
4) Preparation of the catalyst: 5ml of RuCl at a concentration of 0.989M was added to a clean petri dish 3 Adding 10ml of ethanol into the solution, fully stirring, adding 20g of carrier 5, soaking for 8 hours, and then putting into a baking oven to dry at 110 ℃ for 8 hours to obtain catalyst 5;
4) Use of catalyst 5 in hydrochlorination of acetylene: the evaluation of acetylene hydrochlorination was carried out on a fixed bed reactor apparatus under the following reaction conditions: the temperature is 150 ℃ and the acetylene airspeed is 200h -1 ，n(HCl):n(C 2 H 2 ) Carried out under the condition of =1.1:1. In the initial stage of the reaction, the conversion rate of acetylene is 99.51 percent, and the selectivity of chloroethylene is 99.94 percent; after 1000 hours of reaction, the conversion of acetylene was 97.34% and the selectivity to vinyl chloride was 99.61%.
Example 6
A preparation method and application of an MXene acetylene hydrochlorination carrier with high stability and long service life comprise the following steps:
1) Adding 15g LiF powder into 200ml of HCl solution with the concentration of 9mol/L, slowly adding the solution after full dissolution, then slowly adding 8g MAX powder, carrying out oil bath at the temperature of 60 ℃ under the assistance of 80kHz ultrasonic wave, stirring at the speed of 800r/min, stirring and etching for 24h, repeatedly carrying out centrifugal washing with deionized water at the speed of 5000rpm, wherein the washing time is 120min, and washing until the pH=6, thus obtaining multilayer MXene precipitate;
2) Re-dispersing 5g of the multilayer MXene precipitate into 10ml of acetonitrile to form a suspension, adding 10g of 1-ethyl-2, 3-dimethylimidazole hexafluorophosphate into the suspension, and standing for 24 hours in a low-frequency electromagnetic field with the frequency of 60Hz and the intensity of 0.4 mu T;
3) The mixture after standing in step 2) was dried under vacuum at 120℃for 24 hours to obtain a catalyst support 6 for hydrochlorination of acetylene based on MXene.
4) Preparation of the catalyst: 5ml of RuCl at a concentration of 0.989M was added to a clean petri dish 3 Adding 10ml of ethanol into the solution, fully stirring, adding 20g of carrier 6, soaking for 8 hours, and then putting into a baking oven to dry at 110 ℃ for 8 hours to obtain a catalyst 6;
4) Use of catalyst 6 in hydrochlorination of acetylene: the evaluation of acetylene hydrochlorination was carried out on a fixed bed reactor apparatus under the following reaction conditions: the temperature is 150 ℃ and the acetylene airspeed is 200h -1 ，n(HCl):n(C 2 H 2 ) Carried out under the condition of =1.1:1. In the initial stage of the reaction, the conversion rate of acetylene is 99.71%, and the selectivity of chloroethylene is 99.97%; after 1000 hours of reaction, the conversion of acetylene was 97.13% and the selectivity to vinyl chloride was 99.65%.
Comparative example 1: the catalyst is AC
The reaction conditions are as follows: the temperature is 150 ℃ and the acetylene airspeed is 50h -1 ，n(HCl):n(C 2 H 2 ) Acetylene hydrochlorination test was performed on activated carbon material (activated carbon model NoritROX 0.8) under the condition of =1.1:1. In the initial stage of reaction, the conversion rate of acetylene is 10.67%, and vinyl chloride is selectedSex 40.23%; after 1000 hours of reaction, the conversion of acetylene was 2.26% and the selectivity to vinyl chloride was 20.43%.
Comparative example 2: the catalyst is MXene
The reaction conditions are as follows: the temperature is 150 ℃ and the acetylene airspeed is 30h -1 ，n(HCl):n(C 2 H 2 ) Acetylene hydrochlorination test was performed on Mxene material prepared in step 1) of example 1, under the condition of =1.1:1. In the initial stage of the reaction, the conversion rate of acetylene is 65.34%, and the selectivity of chloroethylene is 84.52%; after 1000 hours of reaction, the conversion of acetylene was 8.12% and the selectivity to vinyl chloride was 66.25%.
Comparative example 3: without using low-frequency electromagnetic fields
A preparation method and application of an MXene acetylene hydrochlorination carrier with high stability and long service life comprise the following steps:
1) Adding 4g of LiF powder into 60ml of HCl solution with the concentration of 9mol/L, slowly adding 3g of MAX powder after full dissolution, carrying out oil bath at the temperature of 60 ℃ under the assistance of 80kHz ultrasonic wave, stirring at the speed of 500r/min, stirring and etching for 24h, repeatedly carrying out centrifugal washing with deionized water at the speed of 5000rpm, wherein the washing time is 120min, and washing to pH=6, thereby obtaining multilayer MXene precipitate;
2) Re-dispersing 5g of the multi-layer MXene precipitate into 10ml of acetonitrile to form a suspension, adding 10g of 1-ethyl-2, 3-dimethyl imidazole hexafluorophosphate into the suspension, and soaking for 8 hours at room temperature;
3) Vacuum drying the mixture after standing in the step 2) for 24 hours at 120 ℃ to obtain a catalyst carrier 7 for hydrochlorination of acetylene based on MXene;
4) Preparation of the catalyst: 5ml of RuCl at a concentration of 0.989M was added to a clean petri dish 3 Adding 10ml of ethanol into the solution, fully stirring, adding 20g of carrier 7, soaking for 8 hours, putting into a baking oven, and drying at 110 ℃ for 8 hours to obtain catalyst 7;
5) Use of catalyst 7 in hydrochlorination of acetylene: the evaluation of acetylene hydrochlorination was carried out on a fixed bed reactor apparatus under the following reaction conditions: the temperature is 150 ℃ and the acetylene airspeed is 200h -1 ，n(HCl):n(C 2 H 2 )＝1.11, under the condition of. In the initial stage of the reaction, the conversion rate of acetylene is 96.35 percent, and the selectivity of chloroethylene is 99.2 percent; after 1000 hours of reaction, the conversion of acetylene was 90.16% and the selectivity to vinyl chloride was 98.62%.
Comparative example 4: without assistance of ultrasound
A preparation method and application of an MXene acetylene hydrochlorination carrier with high stability and long service life comprise the following steps:
1) Adding 4g of LiF powder into 60ml of HCl solution with the concentration of 9mol/L, slowly adding 3g of MAX powder after full dissolution, carrying out oil bath at 60 ℃, stirring at the speed of 500r/min, stirring and etching for 24h, repeatedly carrying out centrifugal washing with deionized water at the speed of 5000rpm, washing for 120min, and washing to pH=6 to obtain multilayer MXene precipitate;
2) Re-dispersing 5g of the multi-layer MXene precipitate into 10ml of acetonitrile to form a suspension, adding 10g of 1-ethyl-2, 3-dimethyl imidazole hexafluorophosphate into the suspension, and soaking for 8 hours at room temperature;
3) Vacuum drying the mixture after standing in the second step for 24 hours at 120 ℃ to obtain a catalyst carrier 8 for hydrochlorination of acetylene based on MXene;
4) Preparation of the catalyst: 5ml of RuCl at a concentration of 0.989M was added to a clean petri dish 3 Adding 10ml of ethanol into the solution, fully stirring, adding 20g of carrier 7, soaking for 8 hours, putting into a baking oven, and drying at 110 ℃ for 8 hours to obtain a catalyst 8;
5) Use of catalyst 8 in hydrochlorination of acetylene: the evaluation of acetylene hydrochlorination was carried out on a fixed bed reactor apparatus under the following reaction conditions: the temperature is 150 ℃ and the acetylene airspeed is 200h -1 ，n(HCl):n(C 2 H 2 ) Carried out under the condition of =1.1:1. In the initial stage of the reaction, the conversion rate of acetylene is 94.63 percent, and the selectivity of vinyl chloride is 98.89 percent; after 1000 hours of reaction, the conversion of acetylene was 87.62% and the selectivity to vinyl chloride was 97.62%.
Comparative example 5: using other ionic liquids
1) Adding 2g of LiF powder into 50ml of HCl solution with the concentration of 9mol/L, slowly adding 5g of MAX powder after full dissolution, carrying out oil bath at the temperature of 20 ℃ under the assistance of 20kHz ultrasonic wave, stirring at the speed of 500r/min, stirring and etching for 8h, repeatedly carrying out centrifugal washing with deionized water at the speed of 2000rpm for 30min, and washing to pH=6 to obtain multilayer MXene precipitate;
2) Re-dispersing 5g of the multi-layer MXene precipitate into 10ml of methanol to form a suspension, adding 10g of N-ethylpyridine hexafluorophosphate into the suspension, and standing for 8h in a low-frequency electromagnetic field with the frequency of 50Hz and the intensity of 0.2 mu T;
3) The mixture after standing in step 2) was dried under vacuum at 100℃for 12 hours to obtain a catalyst support 9 for hydrochlorination of acetylene based on MXene.
4) Preparation of the catalyst: 5ml of RuCl at a concentration of 0.989M was added to a clean petri dish 3 Adding 10ml of ethanol into the solution, fully stirring, adding 20g of carrier 9, soaking for 8 hours, and then putting into a baking oven to dry at 110 ℃ for 8 hours to obtain catalyst 9;
4) Use of catalyst 9 in hydrochlorination of acetylene: the evaluation of acetylene hydrochlorination was carried out on a fixed bed reactor apparatus under the following reaction conditions: the temperature is 150 ℃ and the acetylene airspeed is 50h -1 ，n(HCl):n(C 2 H 2 ) Carried out under the condition of =1.1:1. In the initial stage of the reaction, the conversion rate of acetylene is 70.28 percent, and the selectivity of chloroethylene is 86.53 percent; after 1000 hours of reaction, the conversion of acetylene was 10.21% and the selectivity to vinyl chloride was 68.94%.
Comparative example 6: without adding ionic liquid, only using multilayer MXene to load ruthenium
1) Adding 2g of LiF powder into 50ml of HCl solution with the concentration of 9mol/L, slowly adding 5g of MAX powder after full dissolution, carrying out oil bath at the temperature of 20 ℃ under the assistance of 20kHz ultrasonic wave, stirring at the speed of 500r/min, stirring and etching for 8h, repeatedly carrying out centrifugal washing with deionized water at the speed of 2000rpm for 30min, and washing to pH=6 to obtain multilayer MXene precipitate;
2) Redispersing 5g of the multilayered MXene precipitate in 10ml of methanol to form a suspension, and standing the suspension in a low-frequency electromagnetic field with the frequency of 50Hz and the intensity of 0.2 mu T for 8 hours;
3) The mixture after standing in step 2) was dried under vacuum at 100℃for 12 hours to obtain a catalyst carrier 10 for hydrochlorination of acetylene based on MXene.
4) Preparation of the catalyst: 5ml of RuCl at a concentration of 0.989M was added to a clean petri dish 3 Adding 10ml of ethanol into the solution, fully stirring, adding 20g of carrier 10, soaking for 8 hours, putting into a baking oven, and drying at 110 ℃ for 8 hours to obtain a catalyst 10;
4) Use of catalyst 10 in hydrochlorination of acetylene: the evaluation of acetylene hydrochlorination was carried out on a fixed bed reactor apparatus under the following reaction conditions: the temperature is 150 ℃ and the acetylene airspeed is 50h -1 ，n(HCl):n(C 2 H 2 ) Carried out under the condition of =1.1:1. In the initial stage of the reaction, the conversion rate of acetylene is 99.12%, and the selectivity of chloroethylene is 99.54%; after 1000 hours of reaction, the conversion of acetylene was 26.52% and the selectivity to vinyl chloride was 76.12%.

Claims (10)

1. A preparation method of a catalyst carrier for hydrochlorination of acetylene based on MXene comprises the following steps:
step one: adding LiF powder into HCl solution, slowly adding MAX powder after full dissolution, stirring and etching by using ultrasonic auxiliary oil bath, and centrifugally washing by using deionized water to obtain multi-layer MXene precipitate; the MAX powder is Ti 3 AlC 2 、Ti 2 AlC、TiNbAlC、V 2 AlC、Nb 2 AlC、Ti 3 AlCN、Ti 3 SiC 2 、Ti 2 SiC、TiNbSiC、V 2 SiC、Nb 2 SiC、Nb 4 SiC 3 、Ti 3 One or more of SiCN;
step two: re-dispersing the multi-layer MXene precipitate obtained in the first step into an organic solvent to form a suspension, adding an ionic liquid into the suspension, and placing the suspension in a low-frequency electromagnetic field for full standing to obtain a mixture; the ionic liquid is one or more of 1-ethyl-2, 3-dimethyl imidazole hexafluorophosphate, 1-methyl-3-hexadecyl imidazole bistrifluoromethane sulfonic acid imine salt, trimethyl imidazole tetrafluoroborate and 1-methyl-3-octyl imidazole hexafluorophosphate; the mass ratio of the added ionic liquid to the MXene precipitate is (1-3) 1;
step three: and (3) drying the mixture obtained in the step (II) in vacuum to obtain the catalyst carrier for hydrochlorination of acetylene based on MXene.
2. The method of manufacturing according to claim 1, wherein: in the first step, the frequency of ultrasonic waves used for ultrasonic-assisted oil bath stirring etching is 20-80kHz, the stirring speed is 500-800r/min, the oil bath reaction temperature is 20-60 ℃, and the treatment time is 8-24 h.
3. The method of manufacturing according to claim 1, wherein: in the second step, the frequency of the low-frequency electromagnetic field is 50-60 Hz, the magnetic field strength is 0.2-0.4 mu T, and the standing time is 8-24 h.
4. The method of manufacturing according to claim 1, wherein: and thirdly, performing vacuum drying at 100-120 ℃ for 12-24 hours.
5. A method for preparing a catalyst for hydrochlorination of acetylene based on MXene, comprising the following steps: adding a ruthenium ion-containing solution into a reaction vessel, adding ethanol, stirring thoroughly, adding the catalyst carrier for acetylene hydrochlorination based on MXene prepared by the preparation method according to claim 1, soaking thoroughly, and drying to obtain the catalyst for acetylene hydrochlorination based on MXene.
6. The method of manufacturing according to claim 5, wherein: the loading of ruthenium in the catalyst is controlled to be 0.2-3wt%.
7. The method of manufacturing according to claim 5, wherein: the addition amount of the ethanol is 0.3-1 mL of ethanol per gram of carrier.
8. The method of manufacturing according to claim 5, wherein: the soaking time is 8-12h.
9. The method of manufacturing according to claim 5, wherein: the drying conditions are as follows: baking at 100-120deg.C for 8-12h.
10. The use of the catalyst prepared by the preparation method according to claim 5 in the reaction of synthesizing chloroethylene by hydrochlorination of acetylene.
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