CN113145130A - Supported copper-containing high-entropy alloy activated carbon catalyst for acetylene hydrochlorination reaction and preparation method and application thereof - Google Patents

Supported copper-containing high-entropy alloy activated carbon catalyst for acetylene hydrochlorination reaction and preparation method and application thereof Download PDF

Info

Publication number
CN113145130A
CN113145130A CN202110352858.4A CN202110352858A CN113145130A CN 113145130 A CN113145130 A CN 113145130A CN 202110352858 A CN202110352858 A CN 202110352858A CN 113145130 A CN113145130 A CN 113145130A
Authority
CN
China
Prior art keywords
chloride
catalyst
acetylene
metal
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110352858.4A
Other languages
Chinese (zh)
Other versions
CN113145130B (en
Inventor
李小年
赵佳
丰枫
岳玉学
王涛
冯涛
于明德
王婷
王赛赛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN202110352858.4A priority Critical patent/CN113145130B/en
Publication of CN113145130A publication Critical patent/CN113145130A/en
Application granted granted Critical
Publication of CN113145130B publication Critical patent/CN113145130B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • 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
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a loaded copper-containing high-entropy alloy activated carbon catalyst for acetylene hydrochlorination and a preparation method and application thereof. The catalyst comprises an activated carbon carrier and a metal component loaded on the carrier, wherein the metal component consists of a Cu element, a metal element A and a metal element B, the metal element A represents one or two noble metal elements of Au, Ag, Pd, Pt and Ru, the metal element B is selected from two or three metal elements of Fe, Mn, Zn, K, Ca, Sn, Ni, Co, Cr, Al and In, and the types of the metal elements A and B are 4, wherein the loading capacity of the copper element is 10-30 wt%, the loading capacity of each metal element A is 0.01-0.05%, and the loading capacity of each metal element B is 10-30 wt%. The preparation method of the catalyst combines the traditional immersion method and the electromagnetic field stirring technology, and the prepared catalyst shows ultra-long stability and ultra-high activity in the reaction of preparing vinyl chloride by hydrochlorinating acetylene.

Description

Supported copper-containing high-entropy alloy activated carbon catalyst for acetylene hydrochlorination reaction and preparation method and application thereof
(I) technical field
The invention relates to a catalyst for acetylene hydrochlorination, a preparation method thereof and application thereof in acetylene hydrochlorination.
(II) background of the invention
Along with the increasing demand of polyvinyl chloride, the production of Vinyl Chloride Monomer (VCM) is increasing year by year in China. Vinyl chloride monomer is synthesized mainly by an ethylene process and an acetylene process. Based on the current situations of shortage of petroleum resources and relative abundance of coal resources in China, ethylene production by an acetylene method always occupies a leading position in domestic markets, mercury chloride catalyst is adopted in the method, but the mercury chloride is volatile, through statistical estimation, the loss amount of the mercury chloride in the synthesis process is 350-700 t every year, and liquid mercury metal reduced in the reaction is lost. The loss of mercury not only causes the inactivation of the catalyst, but also causes great harm to the ecological environment because the catalyst can not be regenerated due to the loss of the active components, and the quality of VCM products is also influenced. Although the composite catalyst is made by adding other metal chlorides or with NH3The methods of pretreating the carrier and the like can reduce the loading capacity of the mercury and the loss of the mercury,however, in the long term, the fundamental method for solving the above problems still needs to find a non-mercury catalyst which can replace mercury chloride for industrial production.
Most of the non-mercury catalysts known to be used in industry at present use noble metals as active components, such as gold, palladium, ruthenium, etc., and although there is a certain advantage in reaction activity, the catalysts are difficult to regenerate after deactivation, and the expensive price and instability thereof bring great cost pressure to the industrial production of vinyl chloride, so the development of high-stability and low-price catalysts is imperative.
Chinese patent publication No. CN107299362A discloses "a method for preparing an activated carbon-supported cobalt-nickel alloy material and its application", in which activated carbon is immersed in a precursor solution of a cobalt source and a carbon source and subjected to heat treatment under nitrogen to obtain the activated carbon-supported cobalt-nickel alloy material. However, the material prepared by the method is a bimetallic material and has limitations.
In summary, it remains a great challenge to improve the activity and stability of the catalyst in the hydrochlorination of acetylene. 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. The traditional noble metal catalyst has good activity, but high price, and can migrate and agglomerate in the reaction process, thereby seriously affecting the activity and stability of the catalyst. Therefore, it is significant to invent a catalyst containing trace noble metal to solve the instability of noble metal catalyst in the hydrochlorination reaction of acetylene and the high price, and the low price and the ultrahigh stability are the main advantages.
Disclosure of the invention
The technical problem to be solved by the invention is to provide a catalyst (CuAB) with ultrahigh stability and catalytic activity for acetylene hydrochlorination, a preparation method thereof and application thereof in acetylene hydrochlorination.
The technical solution adopted by the present invention is specifically explained below.
In a first aspect, the invention provides a catalyst for acetylene hydrochlorination, which comprises an activated carbon carrier and metal components loaded on the carrier, wherein the metal components consist of a Cu element, an A metal element and a B metal element, the A metal element represents one or two noble metal elements of Au, Ag, Pd, Pt and Ru, the B metal element is selected from two or three metal elements of Fe, Mn, Zn, K, Ca, Sn, Ni, Co, Cr, Al and In, and the A and B metal elements are 4 In types, wherein the loading amount (relative to the mass of the carrier) of the copper element is 10-30 wt%, the loading amount (relative to the mass of the carrier) of each of the A metal elements is 0.01-0.05%, and the loading amount (relative to the mass of the carrier) of each of the B metal elements is 10-30 wt%;
the preparation method of the catalyst comprises the following steps: preparing salt of each metal element into a precursor mixed solution, mixing the precursor mixed solution with an activated carbon carrier, adding the mixture into an electromagnetic stirring instrument, and performing electromagnetic stirring, wherein the magnetic field setting conditions are as follows: setting the intensity of the magnetic field to be 50-500T, and treating for 1-2 h; then the obtained mixture is processed by conventional dipping treatment, then is heated to 300-500 ℃ at the heating rate of 40-100 ℃/min under the air atmosphere, is naturally cooled to the room temperature, is slowly heated to 100-300 ℃ at the heating rate of 10-20 ℃/min under the nitrogen atmosphere, is kept for 3-10h, and is naturally cooled to the room temperature, thus obtaining the catalyst for the hydrochlorination reaction of acetylene.
Preferably, the activated carbon is columnar carbon or spherical activated carbon, the particle size is 20-100 meshes, and the specific surface area is 500-1500 m2The pore volume is 0.25 to 1.5 mL/g.
The invention combines the traditional impregnation method and the electromagnetic field stirring technology, the electromagnetic strength with proper strength enables each metal component to be better diffused to the carrier, and the loaded high-entropy alloy (namely, each metal element forms the high-entropy alloy) activated carbon catalyst with highly dispersed metal components and zero valence states of the metal elements can be prepared.
In a second aspect, the present invention provides a method for preparing a catalyst (CuAB) for acetylene hydrochlorination, specifically comprising the steps of;
(1) taking salt of each metal element, and adding the salt into a solvent to prepare a precursor mixed solution;
(2) mixing the precursor mixed solution with an activated carbon carrier, adding the mixture into an electromagnetic stirrer, and performing electromagnetic stirring, wherein the magnetic field setting conditions are as follows: setting the strength of the magnetic field to be 50-500T, treating for 1-2 h, and then taking out;
(3) soaking the mixture obtained in the step (2) for 10-48h, and then drying;
(4) and (3) putting the product obtained in the step (3) into an electromagnetic heating furnace, heating to 500 ℃ at the heating rate of 40-100 ℃/min under the air atmosphere, naturally cooling to room temperature, slowly heating to 300 ℃ at the temperature of 10-20 ℃/min under the nitrogen atmosphere, maintaining the pressure for 3-10h, and naturally cooling to room temperature to obtain the catalyst for the hydrochlorination of acetylene.
Preferably, the activated carbon is columnar carbon or spherical activated carbon, the particle size is 20-100 meshes, and the specific surface area is 500-1500 m2The pore volume is 0.25-1.5 mL/g.
Preferably, the copper salt is one of copper chloride, copper nitrate, copper sulfate, copper phosphate and copper pyrophosphate.
Preferably, the salt of the A metal component is one or two elements of silver nitrate, palladium chloride, ruthenium chloride and gold chloride.
Preferably, the salt of the metal element B is two or three selected from aluminum chloride, nickel chloride, cobalt chloride, zirconium chloride, ferric chloride, manganese chloride, potassium chloride, calcium chloride and tin chloride.
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 mixing ratio of the precursor mixed solution and the activated carbon carrier is determined according to the requirement of equal-volume impregnation. The preparation method of the isometric impregnation method is a conventional known technology, namely dropwise adding the mixed solution to be matched with the pore volume of the carrier, and completely introducing the dropwise adding impregnation solution into the pore channel of the activated carbon carrier.
Preferably, in the step (3), the drying conditions are as follows: drying at the temperature of 120 ℃ and 250 ℃ for 5-20 h.
In a third aspect, the invention provides the application of the catalyst in the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene.
The application specifically comprises the following steps: the copper catalyst is filled in a fixed bed reactor, and raw material gases HCl and C are introduced2H2The reaction temperature is 100-200 ℃, the reaction pressure is 0.01-2 MPa, and chloroethylene is obtained through reaction.
Preferably, the raw gas material mass ratio is n (HCl) to n (C)2H2) The volume space velocity of acetylene is 1: 1-1.2: 1, and the volume space velocity of acetylene is 20-500 h-1。
Compared with the existing catalyst, the invention has the following innovation points and technical advantages:
(1) the invention applies the electromagnetic field stirring technology to the catalyst preparation process, generates tangential electromagnetic force in the catalyst system by magnetic field stirring with certain strength, drives the metal component to generate rotary motion, ensures that the active component of the catalyst has high dispersion degree and is effectively anchored on the surface of the carrier, prevents the agglomeration of the active component, exposes more active sites on the inner and outer surfaces of the catalyst, and exerts higher activity.
(2) In the process of preparing the catalyst, the catalyst precursor is firstly placed in an electromagnetic heating furnace, and due to the electromagnetic induction principle and the heat effect generated by the induction current passing through a conductor, the temperature rise rate is extremely high, so that the active metal component can be quickly anchored on the surface of the carrier and is not easy to lose, and then the temperature is slowly raised in the nitrogen atmosphere, so that the active component of the catalyst is further anchored on the surface of the active carbon carrier, and the reaction activity of the catalyst is improved.
(3) Compared with a noble metal catalyst, the high-entropy alloy catalyst containing trace noble metals prepared by the invention has the advantage of low price. In addition, the high-entropy alloy catalyst is different from the conventional metal alloy, so that the phase structure is relatively stable due to the maximization of the entropy in the high-entropy alloy; mutual doping among metals in the alloy causes lattice distortion, so that active components in the alloy are not easy to lose. Therefore, the catalyst is applied to acetylene hydrochlorination, the active component can exert better activity due to the synergistic effect between the copper and the trace noble metal, and the catalyst shows overlong stability and ultrahigh activity in the reaction of preparing vinyl chloride because the ultrahigh stability of the alloy and the active component are not easy to lose, so that the problems of poor stability and high price of other noble metal catalysts are solved, and the catalyst has good economic applicability and industrial application value.
(IV) description of the drawings
FIGS. 1-a and 1-b are graphs showing the conversion and selectivity of the catalysts prepared in examples and comparative examples, respectively, in the hydrochlorination of acetylene as a function of time.
FIG. 2 is a TEM image of the copper-containing high-entropy alloy-supported activated carbon catalyst prepared in example 7, and the formation of the alloy can be seen from the Mapping image, and in addition, the metal components are dispersed more completely as can be seen from the content graph.
FIG. 3 is an XPS plot of the supported copper-containing high entropy alloy activated carbon catalyst prepared in example 7, and from the XPS peak separation results for various elements, the valence states of various metal elements are zero, which illustrates the formation of the alloy.
(V) 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 intended to illustrate the invention further, but should not be construed as limiting the scope of the invention, which is in no way limited thereto. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.
In all the examples and comparative examples of the present invention, the mixing ratio of the precursor mixed solution and the activated carbon support was determined according to the requirement of equal volume impregnation.
Example 1
Selecting columnar active carbon as carrier, with particle diameter of 20 mesh and specific surface area of 1000m2The pore volume is 1 mL/g.
Dissolving 41.92g of copper chloride, 0.015g of gold chloride, 22g of cobalt chloride, 50g of aluminum chloride and 25.54g of zirconium chloride in absolute ethyl alcohol, stirring to mix uniformly, then dripping the mixture onto 100g of dried activated carbon carrier at 30 ℃, putting the mixture into an electromagnetic stirrer, setting the magnetic field strength to be 50T, treating for 1h, taking the mixture out of the electromagnetic stirrer, soaking for 12h, and then drying for 10h at 120 ℃ to obtain a catalyst precursor containing five metals, wherein the copper loading is 20%, the gold loading is 0.01%, and the cobalt loading, the aluminum loading and the zirconium loading are all 10%.
And then putting the precursor into an electromagnetic heating furnace for rapid heating treatment, heating to 300 ℃ at the heating rate of 50 ℃/min, naturally cooling to room temperature, taking out, slowly heating to 200 ℃ at 10 ℃/min in the electromagnetic heating furnace in the nitrogen atmosphere, maintaining the pressure for 3h, and naturally cooling to room temperature to obtain the catalyst material.
Then 10g of the catalyst is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are set as follows: at 140 deg.C, the reaction pressure is 0.01MPa, the selectivity of vinyl chloride is n (HCl): n (C)2H2)1.2:1, and the space velocity of acetylene is 10h-1. The data for the vinyl chloride production reaction and the acetylene conversion are shown in figure 1.
Example 2
The same columnar activated carbon as in example 1 was selected as the carrier.
Dissolving 90g of copper nitrate, 0.03g of gold chloride, 22g of nickel chloride, 50g of aluminum chloride and 25.54g of zirconium chloride in absolute ethyl alcohol, stirring to mix uniformly, then dropwise adding the mixture onto 100g of dried activated carbon carrier at 30 ℃, then placing the mixture in an electromagnetic stirrer, setting the magnetic field strength to be 100T, treating for 1h, then taking the mixture out of the electromagnetic stirrer, soaking for 12h, and drying for 10h at 120 ℃ to obtain a catalyst precursor containing five metals, wherein the copper loading is 30%, the gold loading is 0.02%, and the nickel, aluminum and zirconium loadings are 10%.
And then placing the precursor into an electromagnetic heating furnace to carry out rapid heating treatment under an air atmosphere, heating to 300 ℃ at a heating rate of 60 ℃/min, naturally cooling to room temperature, taking out, slowly heating to 200 ℃ at 10 ℃/min in a nitrogen atmosphere in the electromagnetic heating furnace, maintaining the pressure for 5h, and naturally cooling to room temperature to obtain the catalyst material.
Then 10g of the catalyst is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are set as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C)2H2)1.2:1, and 20h of acetylene space velocity-1. The reaction data, acetylene conversion and vinyl chloride selectivity for the preparation of vinyl chloride are shown in FIGS. 1-a and 1-b.
Example 3
The same columnar activated carbon as in example 1 was selected as the carrier.
Dissolving 37.5g of copper sulfate, 0.017g of platinum chloride, 44g of nickel chloride, 100g of aluminum chloride and 51.08g of zirconium chloride in absolute ethyl alcohol, stirring to mix uniformly, then dripping the mixture onto 100g of dried activated carbon carrier at 30 ℃, then placing the mixture in an electromagnetic stirrer, setting the magnetic field intensity to be 200T, treating for 1h, then taking the mixture out of the electromagnetic stirrer, soaking for 12h, and then drying for 10h at 150 ℃ to obtain the catalyst precursor containing five metals, wherein the copper loading is 15%, the platinum loading is 0.01%, and the nickel, aluminum and zirconium loading is 20%.
And then putting the precursor into an electromagnetic heating furnace for rapid heating treatment, heating to 400 ℃ at the heating rate of 70 ℃/min, slowly cooling to room temperature, taking out, slowly heating to 200 ℃ at 10 ℃/min in the atmosphere of nitrogen in the electromagnetic heating furnace, keeping the pressure for 3h, and finally slowly cooling to room temperature to obtain the catalyst material.
Then 10g of the catalyst is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are set as follows: the temperature is 170 ℃, the reaction pressure is 0.01MPa, n (HCl) is n (C)2H2)1, and the space velocity of acetylene is 150h-1. The reaction data, acetylene conversion and vinyl chloride selectivity for the preparation of vinyl chloride are shown in FIGS. 1-a and 1-b.
Example 4
The same columnar activated carbon as in example 1 was selected as the carrier.
Dissolving 56.4g of copper pyrophosphate, 0.061g of ruthenium chloride, 36.6g of manganese chloride, 80g of aluminum chloride and 40.87g of zirconium chloride in absolute ethyl alcohol, stirring to mix uniformly, dripping the mixture onto 100g of dried activated carbon carrier at 30 ℃, putting the mixture into an electromagnetic stirrer, setting the magnetic field strength to be 250T, treating for 1h, taking the mixture out of the electromagnetic stirrer, soaking for 12h, and drying for 10h at 200 ℃ to obtain the catalyst precursor containing five metals, wherein the copper loading is 12%, the metal ruthenium loading is 0.02%, and the manganese, aluminum and zirconium loadings are 16%.
And then putting the precursor into an electromagnetic heating furnace for rapid heating treatment, heating to 500 ℃ at the heating rate of 80 ℃/min, slowly cooling to room temperature, taking out, slowly heating to 200 ℃ at 10 ℃/min in the atmosphere of nitrogen in the electromagnetic heating furnace, continuously maintaining the pressure for 6h, and finally slowly cooling to room temperature to obtain the catalyst material.
Then 10g of the catalyst is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are set as follows: the temperature is 180 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C)2H2)1, and the space velocity of acetylene is 200h-1. The reaction data, acetylene conversion and vinyl chloride selectivity for the preparation of vinyl chloride are shown in FIGS. 1-a and 1-b.
Example 5
The same columnar activated carbon as in example 1 was selected as the carrier.
78g of copper phosphate, 0.047g of silver nitrate, 35.25g of nickel chloride, 80g of aluminum chloride and 40.87g of zirconium chloride are dissolved in absolute ethyl alcohol, stirred and uniformly mixed, then the mixed solution is dripped onto 100g of dry activated carbon carrier at 30 ℃, the mixture is placed in an electromagnetic stirrer, the magnetic field intensity is set to 300T, the treatment time is 1h, then the mixture is taken out of the electromagnetic stirrer, soaked for 12h and dried for 10h at 120 ℃, and the catalyst precursor containing five metals can be obtained, wherein the copper loading capacity is 13%, the trace metal silver loading capacity is 0.03%, and the nickel, aluminum and zirconium loading capacities are 16%.
And then putting the precursor into an electromagnetic heating furnace for rapid heating treatment, heating to 450 ℃ at a heating rate of 90 ℃/min, slowly cooling to room temperature, taking out, slowly heating to 200 ℃ at 10 ℃/min in the electromagnetic heating furnace in a nitrogen atmosphere, continuously maintaining the pressure for 8h, and finally slowly cooling to room temperature to obtain the catalyst material.
Then 10g of the catalyst is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are set as follows: the temperature is 190 ℃, the reaction pressure is 0.01MPa, n (HCl) is n (C)2H2)1.2:1, and the space velocity of acetylene is 400h-1. The reaction data, acetylene conversion and vinyl chloride selectivity for the preparation of vinyl chloride are shown in FIGS. 1-a and 1-b.
Example 6
The same columnar activated carbon as in example 1 was selected as the carrier.
78g of copper phosphate, 0.06g of gold chloride, 30.7g of potassium chloride, 44.4g of calcium chloride and 40.87g of zirconium chloride are dissolved in tetrahydrofuran, stirred and uniformly mixed, then the mixed solution is dripped onto 100g of dry activated carbon carrier at 30 ℃, the mixture is placed in an electromagnetic stirrer, the magnetic field intensity is set to be 300T, the treatment time is 1h, then the mixture is taken out of the electromagnetic stirrer, soaked for 12h and dried for 10h at 150 ℃, and a catalyst precursor containing five metals can be obtained, wherein the copper loading capacity is 13%, the trace metal gold loading capacity is 0.04%, and the potassium loading capacity, the calcium loading capacity and the zirconium loading capacity are respectively 16%.
And then putting the precursor into an electromagnetic heating furnace for rapid heating treatment, heating to 450 ℃ at a heating rate of 90 ℃/min, slowly cooling to room temperature, taking out, slowly heating to 200 ℃ at 10 ℃/min in the electromagnetic heating furnace in a nitrogen atmosphere, continuously maintaining the pressure for 5h, and finally slowly cooling to room temperature to obtain the catalyst material.
Then 10g of the catalyst is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are set as follows: the temperature is 200 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C)2H2)1.2:1, and the space velocity of acetylene is 500h-1. The reaction data, acetylene conversion and vinyl chloride selectivity for the preparation of vinyl chloride are shown in FIGS. 1-a and 1-b.
Example 7
The same columnar activated carbon as in example 1 was selected as the carrier.
78g of copper phosphate, 0.06g of gold chloride, 0.066g of palladium chloride, 35.3g of tin chloride and 30.8g of indium chloride are dissolved in tetrahydrofuran, stirred and uniformly mixed, then the mixed solution is dripped onto 100g of dry activated carbon carrier at 30 ℃, the mixture is placed in an electromagnetic stirrer, the magnetic field intensity is set to be 300T, the treatment time is 1h, then the mixture is taken out of the electromagnetic stirrer, soaked for 12h and dried for 10h at 200 ℃, and the catalyst precursor containing five metals can be obtained, wherein the copper loading capacity is 13%, the micro-metal gold and palladium loading capacities are respectively 0.04%, and the tin and indium loading capacities are respectively 16%.
And then putting the precursor into an electromagnetic heating furnace for rapid heating treatment, heating to 450 ℃ at a heating rate of 90 ℃/min, slowly cooling to room temperature, taking out, slowly heating to 200 ℃ at 10 ℃/min in the electromagnetic heating furnace in a nitrogen atmosphere, continuously maintaining the pressure for 5h, and finally slowly cooling to room temperature to obtain the catalyst material.
Then 10g of the catalyst is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are set as follows: the temperature is 200 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C)2H2)1.2:1, and the space velocity of acetylene is 500h-1. The reaction data, acetylene conversion and vinyl chloride selectivity for the preparation of vinyl chloride are shown in FIGS. 1-a and 1-b. The synthesized high-entropy alloy catalyst is characterized by TEM and XPS, and is found to form a high-entropy alloy, and the valence states of various elements are zero, as shown in figures 2 and 3.
Comparative example 1
Comparative example 1 illustrates the non-substitutability of an electromagnetic stirrer during the preparation of this catalyst by comparison with example 1.
The columnar active carbon is selected as carrier, the particle diameter is 20 meshes, the specific surface area is 1000m2The pore volume is 1 mL/g.
41.92g of copper chloride, 0.015g of gold chloride, 22g of cobalt chloride, 50g of aluminum chloride and 25.54g of zirconium chloride are dissolved in absolute ethyl alcohol, stirred and uniformly mixed, then the mixed solution is dripped onto 100g of dry activated carbon carrier at 30 ℃, the mixture is immersed for 12 hours at room temperature, and then dried for 10 hours at 120 ℃, and a catalyst precursor containing five metals can be obtained, wherein the copper loading is 20%, the gold loading is 0.01%, and the cobalt loading, the aluminum loading and the zirconium loading are all 10%.
And then putting the precursor into an electromagnetic heating furnace for rapid heating treatment, heating to 300 ℃ at the heating rate of 50 ℃/min, slowly cooling to room temperature, taking out, slowly heating to 200 ℃ at 10 ℃/min in the atmosphere of nitrogen in the electromagnetic heating furnace, continuously maintaining the pressure for 3h, and finally slowly cooling to room temperature to obtain the catalyst material.
Then 10g of the catalyst is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are set as follows: the temperature is 140 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C)2H2)1.2:1, and the space velocity of acetylene is 10h-1. The reaction data, acetylene conversion and vinyl chloride selectivity for the preparation of vinyl chloride are shown in FIGS. 1-a and 1-b.
Comparative example 2
Comparative example 2 is a comparison with example 2 to illustrate the non-substitutability of catalyst precursors in an electromagnetic oven during catalyst preparation.
The same columnar activated carbon as in example 1 was selected as the carrier.
Dissolving 90g of copper nitrate, 0.03g of gold chloride, 22g of nickel chloride, 50g of aluminum chloride and 25.54g of zirconium chloride in absolute ethyl alcohol, stirring to mix uniformly, then dropwise adding the mixture onto 100g of dried activated carbon carrier at 30 ℃, then placing the mixture in an electromagnetic stirrer, setting the magnetic field strength to be 100T, treating for 1h, then taking the mixture out of the electromagnetic stirrer, soaking for 12h, and drying for 10h at 120 ℃ to obtain a catalyst precursor containing five metals, wherein the copper loading is 30%, the gold loading is 0.02%, and the aluminum and zirconium loadings are 10%.
And then putting the precursor into an electromagnetic heating furnace for rapid heating treatment, heating to 300 ℃ at the heating rate of 60 ℃/min, slowly cooling to room temperature, taking out, slowly heating to 200 ℃ at 10 ℃/min in the atmosphere of nitrogen in the electromagnetic heating furnace, keeping the pressure for 3h, and finally slowly cooling to room temperature to obtain the catalyst material.
Then 10g of the catalyst is applied to acetylene hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are set as follows: the temperature is 150 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C)2H2)1.2:1, and 20h of acetylene space velocity-1. The reaction data, acetylene conversion and vinyl chloride selectivity for the preparation of vinyl chloride are shown in FIGS. 1-a and 1-b.

Claims (9)

1. A catalyst for acetylene hydrochlorination comprises an active carbon carrier and metal components loaded on the carrier, wherein the metal components comprise a Cu element, an A metal element and a B metal element, the A metal element represents one or two noble metal elements of Au, Ag, Pd, Pt and Ru, the B metal element is selected from two or three metal elements of Fe, Mn, Zn, K, Ca, Sn, Ni, Co, Cr, Al and In, the types of the A and B metal elements are 4, the loading amount of the copper element is 10-30 wt%, the loading amount of each of the A metal elements is 0.01-0.05%, and the loading amount of each of the B metal elements is 10-30 wt%;
the preparation method of the catalyst comprises the following steps: preparing salt of each metal element into a precursor mixed solution, mixing the precursor mixed solution with an activated carbon carrier, adding the mixture into an electromagnetic stirring instrument, and performing electromagnetic stirring, wherein the magnetic field setting conditions are as follows: setting the intensity of the magnetic field to be 50-500T, and treating for 1-2 h; and then carrying out conventional impregnation treatment on the obtained mixture, heating to 300-500 ℃ at the heating rate of 40-100 ℃/min in the air atmosphere, naturally cooling to room temperature, heating to 100-300 ℃ at the heating rate of 10-20 ℃/min in the nitrogen atmosphere, maintaining the pressure for 3-10h, and naturally cooling to room temperature to obtain the catalyst for the acetylene hydrochlorination reaction.
2. The catalyst of claim 1, wherein: the active carbon is columnar carbon or spherical active carbon, the particle size is 20-100 meshes, and the specific surface area is 500-1500 m2The pore volume is 0.25 to 1.5 mL/g.
3. A production method of the catalyst for hydrochlorination of acetylene according to claim 1 or 2, which specifically comprises the steps of;
(1) taking salt of each metal element, and adding the salt into a solvent to prepare a precursor mixed solution;
(2) mixing the precursor mixed solution with an activated carbon carrier, adding the mixture into an electromagnetic stirrer, and performing electromagnetic stirring, wherein the magnetic field setting conditions are as follows: setting the strength of the magnetic field to be 50-500T, treating for 1-2 h, and then taking out;
(3) soaking the mixture obtained in the step (2) for 10-48h, and then drying;
(4) and (4) putting the product obtained in the step (3) into an electromagnetic heating furnace, heating to 500 ℃ at the heating rate of 40-100 ℃/min under the air atmosphere, naturally cooling to room temperature, heating to 300 ℃ at the heating rate of 10-20 ℃/min under the nitrogen atmosphere, maintaining the pressure for 3-10h, and naturally cooling to room temperature to obtain the catalyst for the hydrochlorination of acetylene.
4. The method of claim 3, wherein: the copper salt is one of copper chloride, copper nitrate, copper sulfate, copper phosphate and copper pyrophosphate;
the salt of the metal component A is one or two elements of silver nitrate, palladium chloride, ruthenium chloride and gold chloride;
the salt of the metal element B is two or three selected from aluminum chloride, nickel chloride, cobalt chloride, zirconium chloride, ferric chloride, manganese chloride, potassium chloride, calcium chloride and tin chloride;
the solvent is one or more of deionized water, absolute ethyl alcohol, tetrahydrofuran, methanol, acetone, diethyl ether, cyclohexane, carbon tetrachloride and benzene.
5. The method of claim 3, wherein: the mixing proportion of the precursor mixed solution and the activated carbon carrier is determined according to the requirement of equal-volume impregnation.
6. The method of claim 3, wherein: in the step (3), the drying conditions are as follows: drying at the temperature of 120 ℃ and 250 ℃ for 5-20 h.
7. Use of the catalyst of claim 1 in the reaction of hydrochlorination of acetylene to vinyl chloride.
8. The use of claim 7, wherein: the application specifically comprises the following steps: the copper catalyst is filled in a fixed bed reactor, and raw material gases HCl and C are introduced2H2The reaction temperature is 100-200 ℃, the reaction pressure is 0.01-2 MPa, and chloroethylene is obtained through reaction.
9. The use of claim 8, wherein: the mass ratio of the raw material gas is n (HCl) to n (C)2H2) The volume space velocity of acetylene is 1: 1-1.2: 1, and the volume space velocity of acetylene is 20-500 h-1。
CN202110352858.4A 2021-03-31 2021-03-31 Copper-bearing high-entropy alloy-loaded activated carbon catalyst for hydrochlorination of acetylene as well as preparation method and application thereof Active CN113145130B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110352858.4A CN113145130B (en) 2021-03-31 2021-03-31 Copper-bearing high-entropy alloy-loaded activated carbon catalyst for hydrochlorination of acetylene as well as preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110352858.4A CN113145130B (en) 2021-03-31 2021-03-31 Copper-bearing high-entropy alloy-loaded activated carbon catalyst for hydrochlorination of acetylene as well as preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113145130A true CN113145130A (en) 2021-07-23
CN113145130B CN113145130B (en) 2023-05-23

Family

ID=76886126

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110352858.4A Active CN113145130B (en) 2021-03-31 2021-03-31 Copper-bearing high-entropy alloy-loaded activated carbon catalyst for hydrochlorination of acetylene as well as preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113145130B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114950405A (en) * 2021-12-28 2022-08-30 安徽华塑股份有限公司 Polyvinyl chloride mercury-free catalyst and preparation method thereof
CN116139904A (en) * 2023-01-04 2023-05-23 上海交通大学 Ruthenium-indium composite catalyst and preparation method and application thereof
CN116159579A (en) * 2022-12-07 2023-05-26 内蒙古鄂尔多斯电力冶金集团股份有限公司 Acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101947465A (en) * 2010-09-03 2011-01-19 清华大学 Mercury-free catalyst with low bullion content for acetylene hydrochlorination and application thereof
CN102631947A (en) * 2012-04-01 2012-08-15 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) Gold complex catalyst for hydrochlorinating acetylene
CN107983375A (en) * 2016-10-27 2018-05-04 中国科学院大连化学物理研究所 A kind of three component acetylene hydrochlorination catalyst without mercury and preparation method thereof
CN110743556A (en) * 2019-09-29 2020-02-04 浙江工业大学 Copper-based alloy catalyst and preparation method and application thereof
CN113209971A (en) * 2021-03-31 2021-08-06 浙江工业大学 Loaded high-entropy alloy activated carbon catalyst for acetylene hydrochlorination reaction and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101947465A (en) * 2010-09-03 2011-01-19 清华大学 Mercury-free catalyst with low bullion content for acetylene hydrochlorination and application thereof
CN102631947A (en) * 2012-04-01 2012-08-15 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) Gold complex catalyst for hydrochlorinating acetylene
CN107983375A (en) * 2016-10-27 2018-05-04 中国科学院大连化学物理研究所 A kind of three component acetylene hydrochlorination catalyst without mercury and preparation method thereof
CN110743556A (en) * 2019-09-29 2020-02-04 浙江工业大学 Copper-based alloy catalyst and preparation method and application thereof
CN113209971A (en) * 2021-03-31 2021-08-06 浙江工业大学 Loaded high-entropy alloy activated carbon catalyst for acetylene hydrochlorination reaction and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114950405A (en) * 2021-12-28 2022-08-30 安徽华塑股份有限公司 Polyvinyl chloride mercury-free catalyst and preparation method thereof
CN116159579A (en) * 2022-12-07 2023-05-26 内蒙古鄂尔多斯电力冶金集团股份有限公司 Acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof
CN116139904A (en) * 2023-01-04 2023-05-23 上海交通大学 Ruthenium-indium composite catalyst and preparation method and application thereof

Also Published As

Publication number Publication date
CN113145130B (en) 2023-05-23

Similar Documents

Publication Publication Date Title
CN113145130A (en) Supported copper-containing high-entropy alloy activated carbon catalyst for acetylene hydrochlorination reaction and preparation method and application thereof
CN110302769A (en) A kind of catalyst carrier, loaded catalyst and its preparation method and application
CN112642448B (en) Preparation method and application of copper catalyst for acetylene hydrochlorination
CN101982236A (en) Hydrogenation catalyst and preparation method of 1,4-cyclohexanedimethanol
CN107362798B (en) Preparation method of Pd-M-based metal catalyst for preparing ethylene by hydrogenation of high-purity acetylene and method for preparing ethylene
CN105521801A (en) Catalyst for ethyne hydrochlorination for synthesis of chloroethylene and preparation method thereof
CN113210019A (en) Preparation method and application of Cu-MOF catalyst for acetylene hydrochlorination
CN109622000A (en) A kind of base metal selective hydrocatalyst of acetylene and its preparation method and application
CN111468163B (en) Two-dimensional iron monatomic catalyst, preparation thereof and application thereof in production of ethylene by reducing 1,2-dichloroethane
CN113713841B (en) Acetylene copper chloride-based catalyst and preparation method and application thereof
CN113209971A (en) Loaded high-entropy alloy activated carbon catalyst for acetylene hydrochlorination reaction and preparation method and application thereof
CN112007657B (en) Method for controlling metal atomic ratio in supported Cu-Pd/AC alloy catalyst
CN111039755A (en) Application of nickel boride catalyst in selective hydrogenation of alkynol
CN111013585A (en) Silver catalyst for ethylene epoxidation reaction and preparation method and application thereof
CN108067227B (en) Platinum-based catalyst highly dispersed in carrier aluminum oxide and preparation method and application thereof
CN108997266B (en) Method for preparing 2, 2-di (2-tetrahydrofuryl) propane by hydrogenating 2, 2-di (2-furyl) propane
CN113926458A (en) Preparation method of copper-based hydrogenation catalyst, catalyst prepared by preparation method and application of catalyst
CN115318296B (en) High-dispersion film-shaped carbon-coated nickel catalyst and preparation method and application thereof
CN114849694B (en) Catalyst for hydrogenation of nitroaromatic hydrocarbon based on metal-loaded tungsten oxide, preparation method and application thereof
CN109759085B (en) Activated carbon-loaded iron sulfide-based catalyst and preparation and application thereof
CN115970707A (en) Preparation method and application method of hydrogenation catalyst
CN113649030B (en) Hydrodehalogenation catalyst and preparation method of chlorotrifluoroethylene and trifluoroethylene
KR101678225B1 (en) Preparation of the catalysts Platinum System
CN114669294A (en) Composite catalyst for preparing 2, 2-di (2-tetrahydrofuryl) propane by hydrogenating 2, 2-di (2-furyl) propane
CN111617774B (en) Synthesis and application of quaternary platinum-iron-rhodium-ruthenium nano alloy with hierarchical structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant