CN112517085B - Non-noble metal catalyst and process for producing chloroethylene by using same - Google Patents

Non-noble metal catalyst and process for producing chloroethylene by using same Download PDF

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CN112517085B
CN112517085B CN202011607922.0A CN202011607922A CN112517085B CN 112517085 B CN112517085 B CN 112517085B CN 202011607922 A CN202011607922 A CN 202011607922A CN 112517085 B CN112517085 B CN 112517085B
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李通
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/344—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 electromagnetic wave energy
    • B01J37/346—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 electromagnetic wave energy of microwave 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention provides a non-noble metal catalyst, and a preparation method of the catalyst comprises the steps of active carbon pretreatment, carrier particle preparation, adsorption liquid configuration, adsorption, load, balancing and drying. The invention also provides a process for producing vinyl chloride by adopting the catalyst, which comprises the following steps: and (3) filling, activating and synthesizing the vinyl chloride by using the catalyst. The non-noble metal catalyst of the invention has the catalyst activation temperature of only 80-90 ℃ and the catalyst activation time of only 7-8 hours; the culture period only needs 7-9 days, and the culture temperature only needs 90-100 ℃, so that the consumption of production resource cost and time cost is effectively reduced. The non-noble metal catalyst has an acetylene airspeed of 130 at a reaction temperature of 105 DEG C ‑1 Under the condition, the initial conversion rate of acetylene is more than 99.0%, and the selectivity of chloroethylene is more than 99.1%.

Description

Non-noble metal catalyst and process for producing chloroethylene by using same
Technical Field
The invention relates to the field of vinyl chloride production, in particular to a non-noble metal catalyst and a process for producing vinyl chloride by adopting the catalyst.
Background
Vinyl chloride, a monomer for synthesizing polyvinyl chloride. The polyvinyl chloride resin is an important plastic raw material, is one of five general synthetic resins, has good physical and mechanical properties, and is widely applied to various fields in production and life. The production of vinyl chloride monomer is an important element in the polyvinyl chloride industry.
The synthesis process of vinyl chloride is divided into two main types, namely an ethylene oxychlorination method and an acetylene hydrochlorination method, wherein the acetylene hydrochlorination method is mainly adopted. Specifically, acetylene with certain purity and hydrogen chloride gas are taken as raw materials, mixed according to a certain proportion, added into a converter containing a catalyst, and heated for reaction to generate chloroethylene. The chemical reaction equation is as follows: c (C) 2 H 2 + HCl → C 2 H 3 Cl
The current research on catalysts for preparing vinyl chloride by hydrochlorination of acetylene mainly comprises a noble metal catalyst, a non-noble metal catalyst and a non-metal catalyst. The noble metal catalyst has higher catalytic activity and a stable system, and the professor Graham.J. Hutchings of the university of Carduff in British indicates that Au (gold) catalyzes the solid phase reaction of acetylene and hydrogen chloride, provides a catalytic mechanism and an deactivation mechanism of the Au catalyst, and carries out industrial tests, and the test result effect is superior to that of the harmful heavy metal catalyst, but the catalyst is high in price, greatly increases the production cost of polyvinyl chloride and has no economic feasibility.
Compared with a metal catalyst, the nonmetal catalyst has lower catalytic activity, higher energy consumption for preparation, complicated steps and incapability of meeting the requirement of large-scale industrial application.
The main research directions of the non-noble metal catalyst are tin, copper, barium, zinc, molybdenum, bismuth and the like, and compared with the noble metal catalyst, the non-noble metal catalyst has the advantages of low cost, less harm to the environment, higher catalytic activity and capability of achieving the condition of industrial application.
The applicant finds that when the existing non-noble metal catalyst is used in the process of producing vinyl chloride, the activation treatment is needed to be carried out on the non-noble metal catalyst in order to ensure better catalytic performance and more ideal catalytic life, but the time and the temperature needed for activating the non-noble metal catalyst are long in the activation treatment process, so that the production progress is influenced; meanwhile, in the early stage of vinyl chloride synthesis, the mixed gas of acetylene and hydrogen chloride is cultured in a converter for a long period, the optimal culture temperature often exceeds 110 ℃, and the time cost and the resource cost are consumed greatly. Meanwhile, the applicant also discovers that in the process of catalyst activation or culture period, incomplete activation or insufficient culture period can have adverse effect on the performance of the catalyst, and influence the performance and service life of the catalyst, so that the conversion rate and purity of the product are reduced, and the requirement of large-scale industrial production cannot be met.
Chinese patent CN110550997a discloses a process for producing vinyl chloride by mercury-free catalyst catalysis, which adopts a catalyst with specific components and proportions, and catalyzes the production of vinyl chloride by a specific process method. However, in the process of catalyzing the catalyst, the catalyst needs long activation time and high activation temperature; meanwhile, in the early stage of vinyl chloride synthesis, the culture period of the acetylene and hydrogen chloride mixed gas in a converter is as long as 10-30 days, and the optimal culture temperature is as high as 120 ℃.
Chinese patent CN106215977a discloses a mercury-free catalyst with high catalytic activity for synthesizing vinyl chloride and a preparation method thereof, which adopts specific raw material components and proportions, and the mercury-free catalyst prepared by the specific preparation method catalyzes the production of vinyl chloride. However, in the process of catalyzing the mercury-free catalyst, the mercury-free catalyst needs long time for preheating and activating and has high activation temperature; meanwhile, in the early stage of vinyl chloride synthesis, the mixed gas of acetylene and hydrogen chloride is cultured in a converter for 30 days, and the culture temperature is 105-115 ℃.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a non-noble metal catalyst and a process for producing vinyl chloride by adopting the catalyst, so as to realize the following aims:
(1) On the premise of ensuring the catalytic performance and the catalytic life of the catalyst, the time and temperature conditions required by the activation of the catalyst are reduced;
(2) On the premise of ensuring the catalytic performance and the catalytic life of the catalyst, the culture period of the mixed gas of acetylene and hydrogen chloride in the converter is shortened in the earlier stage of vinyl chloride synthesis, and the required culture temperature is reduced.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a non-noble metal catalyst for preparing chloroethylene by catalytic reaction of acetylene and chloroethylene has a reaction temp of 105 deg.C and acetylene space velocity of 130 -1 Under the condition that the initial conversion rate of acetylene exceeds 99.0%, and the selectivity of chloroethylene exceeds 99.1%;
the preparation method of the catalyst comprises the steps of active carbon pretreatment, carrier particle preparation, adsorption liquid configuration, adsorption, load, balancing and drying;
the preparation of the carrier particles comprises the steps of firstly mixing raw materials, reacting and shaping to prepare carrier particles, then carrying out microwave activation, modifying by mixing a modifying liquid, and controlling the nitrogen content of the carrier particles to be 2-5%, thus obtaining the carrier particles;
the mixed modified liquid is prepared by mixing the following raw materials: absolute ethanol, N-methylpyrrolidone, N-methyl-4-bromo-2-hydroxypyridine, and dimethyldichlorosilane.
Further, the activated carbon is pretreated;
the activated carbon pretreatment comprises activated carbon selection and impurity removal;
the activated carbon is selected, wherein the specific surface area is 800-1000 square meters per gram, the carbon tetrachloride adsorption rate is 70-80%, the bulk density is 320-370g/L, the average pore diameter is 80-120nm, and the nitrogen content is 1-3%;
the impurity is removed, the activated carbon is put into 0.5mol/L phosphoric acid, the temperature is increased to 50 ℃ at the heating rate of 1.5-2.0 ℃/min, and the mixture is stirred and kept for 1 hour; filtering out the activated carbon, and leaching the activated carbon by adopting a 5% hydroxylamine hydrochloride solution at 35 ℃ for 1-1.5h; and after leaching, washing the activated carbon by using enough deionized water until the PH of the activated carbon is 5-6.
Further, the carrier particles are prepared, including mixing, reacting, shaping, activating and modifying;
the mixing, namely adding predetermined parts of lutetium chloride and lanthanum chloride into deionized water to prepare mixed rare earth solution with the concentration of 0.2-0.3 mol/L; then mixing the mixed rare earth liquid with a predetermined part of n-heptane, n-amyl alcohol and hexadecyl trimethyl ammonium bromide, heating to 60 ℃, and stirring for 1-2 hours at 50-100RPM to prepare a mixed liquid; then, simultaneously dripping 0.2-0.3mol/L of disodium uridylate aqueous solution and 0.1mol/L of ammonium fluoride aqueous solution into the mixed solution, wherein the dripping speed is 5ml/min, preserving heat at 60 ℃, and stirring at 100-130RPM for 1-2 hours; then adding a predetermined part of disodium glutarate aqueous solution, preserving heat at 50 ℃ and stirring for 1-2h at 200-300 RPM.
Further, the lutetium chloride: the molar ratio of lanthanum chloride is 20-30:1.
The mixed rare earth liquid comprises the following components: n-heptane: n-amyl alcohol: the weight ratio of the cetyl trimethyl ammonium bromide to the mixture is 1:15:5:1.
The mixed rare earth liquid comprises the following components: disodium uridylate aqueous solution: aqueous ammonium fluoride solution: the volume ratio of the disodium glutarate aqueous solution is 1:1.2:1.5:1.
Further, the reaction is carried out, the mixed solution prepared in the mixing step is put into 18-22MPa and 160 ℃ for reaction molding for 7-8h;
the shaping is carried out, a predetermined part of acetone is added into the material after the shaping step, 7000-8000RPM is used for separating for 2-3min, and solid matters are taken; then, sequentially washing the solid by adopting acetone, absolute ethyl alcohol and deionized water with the volume of 3-5 times; drying at 60-70 ℃ for 1-2h under the condition of minus 0.07-minus 0.08MPa to prepare the carrier particles;
the activation is carried out under the nitrogen environment of 5-10MPa, intermittent microwave radiation is adopted, the temperature of the carrier is controlled to be kept within the range of 80-90 ℃, and the treatment time is 5-10min.
Further, the adsorption is carried out, the modified carrier particles are put into adsorption liquid with the volume of 5-6 times, the temperature is increased to 55 ℃ at the heating rate of 2 ℃/min, and the heat preservation and the adsorption are carried out for 1-2 hours; then heating to 70 ℃ at a heating rate of 3 ℃/min, and preserving heat and adsorbing for 1-2h;
the adsorption liquid is a mixed liquid of copper chloride and 6% ammonium chloride solution;
and (3) loading, namely putting the activated carbon prepared in the activated carbon pretreatment step into a mixed solution of carrier particles and adsorption liquid, naturally cooling to 45-50 ℃, preserving heat, pressurizing to 3-5MPa, and stirring at 30-60RPM for 3-5h to prepare the activated carbon loaded with the carrier particles.
Further, the activated carbon loaded with the carrier particles is placed under nitrogen atmosphere and pressurized to 1-2MPa, and kept stand for 5-8h in the environment of 30-40 ℃;
and (3) drying, namely placing the activated carbon loaded with the carrier particles in a vacuum environment, and drying at 90 ℃ for 6-8 hours to obtain the non-noble metal catalyst.
Further, the weight ratio of the absolute ethyl alcohol to the N-methyl pyrrolidone to the N-methyl-4-bromo-2-hydroxypyridine to the dimethyl dichlorosilane is 30-50:2-3:5-7:0.5-1.
A process for producing vinyl chloride by using a non-noble metal catalyst prepared by the preparation method comprises the following steps: catalyst filling, activating and synthesizing chloroethylene;
the catalyst is filled, the non-noble metal catalyst is filled into a reactor with clean inner wall and dried at the temperature of 30-35 ℃ for 20min;
after the catalyst is filled, introducing 80-90 ℃ dry hydrogen chloride gas into the reactor for activation treatment for 7-8 hours;
the flow rate of the hydrogen chloride gas is 5-6m/h.
The synthesis of vinyl chlorideAcetylene and hydrogen chloride gas with preheating temperature of 35-40 ℃ are introduced into the reactor, the temperature is controlled within the range of 90-100 ℃, and the culture period is 7-9 days; after the culture period is finished, the reaction period is started, and the reaction temperature is 105 ℃ and the acetylene airspeed is 130 -1 Reacting to synthesize chloroethylene under the condition that the reaction pressure is 0.02 MPa;
the incubation period, the acetylene: the molar ratio of the hydrogen chloride is 1:0.9;
the reaction period, the acetylene: the molar ratio of the hydrogen chloride is 1:1.05.
Compared with the prior art, the invention has the beneficial effects that:
(1) The non-noble metal catalyst has high activity on the premise of ensuring excellent catalytic performance and catalytic life, the catalyst activation temperature is only 80-90 ℃, the catalyst activation time is only 7-8 hours, and the optimal catalytic activity can be achieved, compared with the prior art, the catalyst has the advantages that the activation temperature is reduced by about 20-25%, and the catalytic time is shortened by about 30-40%.
(2) The non-noble metal catalyst provided by the invention has the advantages that under the premise of ensuring excellent catalytic performance and catalytic life, the culture period of the mixed gas of acetylene and hydrogen chloride in the converter is only 7-9 days in the earlier stage of vinyl chloride synthesis, and meanwhile, the culture temperature is only 90-100 ℃, so that the consumption of production resource cost and time cost is effectively reduced.
(3) The non-noble metal catalyst can achieve optimal catalytic performance at the reaction temperature of 105 ℃, and meanwhile, the non-noble metal catalyst can react at the reaction temperature without generating byproducts, so that adverse phenomena that the side reactions are more and the byproducts influence the performance of the catalyst when the reaction temperature is too high can be effectively avoided.
(4) The non-noble metal catalyst of the invention has the reaction temperature of 105 ℃ and the acetylene airspeed of 130 -1 Under the condition, the initial conversion rate of acetylene is more than 99.0%, and the selectivity of chloroethylene is more than 99.1%.
(5) The non-noble metal catalyst has durable and stable catalytic activity and good long-term stability; through experiments, the overall service life of the catalyst exceeds 11000h, and the requirement of large-scale industrial production can be met.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A non-noble metal catalyst comprises the steps of active carbon pretreatment, carrier particle preparation, adsorption liquid configuration, adsorption, load balancing and drying.
The activated carbon pretreatment comprises activated carbon selection and impurity removal.
The activated carbon is selected, the specific surface area is 800 square meters per gram, the carbon tetrachloride adsorption rate is 70%, the bulk density is 330g/L, the average pore diameter is 80nm, and the nitrogen content is 1.5%.
The impurity removal is carried out, the activated carbon is put into 0.5mol/L phosphoric acid with the volume being 1.5 times, the temperature is increased to 50 ℃ at the heating rate of 1.5 ℃/min, and the mixture is stirred at 50RPM and kept for 1 hour; filtering out the activated carbon, and leaching the activated carbon by adopting a 5% hydroxylamine hydrochloride solution at 35 ℃ for 1h; and after leaching, washing the activated carbon by using enough deionized water until the PH of the activated carbon is 5-6, and finishing the impurity removal step for later use.
The hydroxylamine hydrochloride solution: the volume ratio of the activated carbon is 8:1.
The preparation of the carrier particles comprises the steps of mixing, reacting, shaping, activating and modifying.
The mixing, namely adding predetermined parts of lutetium chloride and lanthanum chloride into deionized water to prepare mixed rare earth solution with the concentration of 0.2 mol/L; then mixing the mixed rare earth liquid with a predetermined part of n-heptane, n-amyl alcohol and hexadecyl trimethyl ammonium bromide, heating to 60 ℃, and stirring for 1h at 50RPM to obtain a mixed liquid; then, simultaneously dripping 0.2mol/L of disodium uridylate aqueous solution and 0.1mol/L of ammonium fluoride aqueous solution into the mixed solution, wherein the dripping speed is 5ml/min, preserving heat at 60 ℃, and stirring for 1h at 100 RPM; then, a predetermined portion of disodium glutarate aqueous solution is added, the temperature is kept at 50 ℃ and the stirring is carried out at 200RPM for 1h.
The lutetium chloride: the molar ratio of lanthanum chloride is 20:1.
The mixed rare earth liquid comprises the following components: n-heptane: n-amyl alcohol: the weight ratio of the cetyl trimethyl ammonium bromide to the mixture is 1:15:5:1.
The mixed rare earth liquid comprises the following components: disodium uridylate aqueous solution: aqueous ammonium fluoride solution: the volume ratio of the disodium glutarate aqueous solution is 1:1.2:1.5:1.
And (3) the reaction is carried out, and the mixed solution prepared in the mixing step is put into 18MPa and 160 ℃ for reaction molding for 7 hours.
The shaping is carried out, a predetermined part of acetone is added into the material after the shaping step, 7000RPM is used for separating for 2 minutes, and solid matters are taken; then, sequentially washing the solid by adopting acetone, absolute ethyl alcohol and deionized water with the volume of 3 times; drying at-0.07 MPa at 60deg.C for 1 hr to obtain the carrier particles.
The mixed rare earth liquid comprises the following components: the volume ratio of the acetone is 1:2.
The carrier particles have a particle diameter of 30nm and a specific surface area of 85m 2 /g。
And activating, namely, under the nitrogen environment of 5MPa, adopting intermittent microwave radiation, controlling the temperature of the carrier to be within the range of 80 ℃ and the treatment time to be 5min, so as to complete the activation of the carrier particles.
The microwave energy of the microwave radiation is 21w/g, and the microwave radiation power is 0.7KW.
And (3) the modification, namely adding the activated carrier particles into a mixed modification liquid, heating to 50 ℃, and under the condition of 50RPM stirring, carrying out heat preservation modification, controlling the nitrogen content of the carrier particles to be 2.5%, and separating out the carrier particles for standby.
The mixed modification liquid comprises absolute ethyl alcohol, N-methyl pyrrolidone, N-methyl-4-bromo-2-hydroxypyridine and dimethyl dichlorosilane. The weight ratio of the absolute ethyl alcohol to the N-methylpyrrolidone to the N-methyl-4-bromo-2-hydroxypyridine to the dimethyl dichlorosilane is 30:2:7:0.5.
And (3) preparing the adsorption liquid, namely mixing a predetermined part of copper chloride and a 6% ammonium chloride solution, stirring, heating to 70 ℃, and fully and uniformly mixing to prepare the adsorption liquid of the metal ammonium salt complex without crystallization or macroscopic mechanical impurities.
Wherein the molar ratio of the copper chloride to the ammonium chloride is 1:5.
The adsorption, namely, the modified carrier particles are put into a preset part of adsorption liquid, the temperature is increased to 55 ℃ at the heating rate of 2 ℃/min, and the heat is preserved and adsorbed for 1h; then heating to 70 ℃ at a heating rate of 3 ℃/min, and preserving heat and adsorbing for 1h.
The carrier particles: the volume ratio of the adsorption liquid is 1:5.
and (3) loading, namely putting the pretreated activated carbon into a mixed solution of carrier particles and adsorption liquid, naturally cooling to 45 ℃, preserving heat, pressurizing to 3MPa, stirring for 3 hours at 30RPM, fully loading the carrier particles on the activated carbon, and finally separating the activated carbon loaded with the carrier particles.
The activated carbon comprises the following components: the volume ratio of the adsorption liquid is 1:1.3.
And (3) balancing, namely placing the activated carbon loaded with the carrier particles in a nitrogen atmosphere, pressurizing to 1MPa, and standing for 5 hours at the temperature of 30 ℃ to complete the balancing step.
And (3) drying, namely placing the activated carbon loaded with the carrier particles in a vacuum environment, and drying at 90 ℃ for 6 hours to obtain the non-noble metal catalyst.
The process for producing vinyl chloride by using the non-noble metal catalyst comprises the following steps: and (3) filling, activating and synthesizing the vinyl chloride by using the catalyst.
And filling the catalyst, namely filling the non-noble metal catalyst into a reactor with clean and dry inner walls at the temperature of 35 ℃ for 20min.
And after the catalyst is filled, introducing hydrogen chloride gas dried at 90 ℃ into the reactor for activation treatment for 8 hours.
The flow rate of the hydrogen chloride gas is 6m/h.
And in the activation process, acid is discharged at the bottom of the reactor every 3 hours.
The method comprises the steps of synthesizing chloroethylene, introducing acetylene and hydrogen chloride gas with preheating temperature of 40 ℃ into a reactor, and controlling the temperatureThe temperature is within the range of 95-100 ℃ and the culture period is 9 days; after the culture period is finished, the reaction period is started, and the reaction temperature is 105 ℃ and the acetylene airspeed is 130 -1 And reacting to synthesize chloroethylene under the condition of the reaction pressure of 0.02 MPa.
The incubation period, the acetylene: the molar ratio of the hydrogen chloride is 1:0.9.
The reaction period, the acetylene: the molar ratio of the hydrogen chloride is 1:1.05.
According to detection, the non-noble metal catalyst of the embodiment has high activity under the premise of ensuring excellent catalytic performance and catalytic life, the catalyst activation temperature is only 90 ℃, and the catalyst activation time is only 8 hours to achieve the optimal catalytic activity; meanwhile, in the early stage of vinyl chloride synthesis, the culture period of the mixed gas of acetylene and hydrogen chloride in a converter only needs 9 days, and the culture temperature only needs 95-100 ℃;
meanwhile, the non-noble metal catalyst of the embodiment can achieve the optimal catalytic performance when the reaction temperature is 105 ℃.
Further, at a reaction temperature of 105 ℃, the space velocity of acetylene is 130 -1 Under the condition, the initial conversion rate of acetylene is 99.1 percent, and the selectivity of chloroethylene is 99.3 percent. Meanwhile, the overall service life of the catalyst exceeds 11000h.
Example 2
A non-noble metal catalyst comprises the steps of active carbon pretreatment, carrier particle preparation, adsorption liquid configuration, adsorption, load balancing and drying.
The activated carbon pretreatment comprises activated carbon selection and impurity removal.
The activated carbon is selected, wherein the specific surface area is 900 square meters per gram, the carbon tetrachloride adsorption rate is 80%, the bulk density is 350g/L, the average pore diameter is 110nm, and the nitrogen content is 2%.
The impurity removal is carried out, the activated carbon is put into 0.5mol/L phosphoric acid with the volume being 2 times, the temperature is increased to 50 ℃ at the heating rate of 2.0 ℃/min, and the mixture is stirred at 80RPM and kept for 1 hour; filtering out the activated carbon, and leaching the activated carbon by adopting a 5% hydroxylamine hydrochloride solution at 35 ℃ for 1.5h; and after leaching, washing the activated carbon by using enough deionized water until the PH of the activated carbon is 5-6, and finishing the impurity removal step for later use.
The hydroxylamine hydrochloride solution: the volume ratio of the activated carbon is 9:1.
The preparation of the carrier particles comprises the steps of mixing, reacting, shaping, activating and modifying.
The mixing, namely adding predetermined parts of lutetium chloride and lanthanum chloride into deionized water to prepare mixed rare earth solution with the concentration of 0.25 mol/L; then mixing the mixed rare earth liquid with a predetermined part of n-heptane, n-amyl alcohol and hexadecyl trimethyl ammonium bromide, heating to 60 ℃, and stirring at 100RPM for 2 hours to prepare a mixed liquid; then, simultaneously dripping 0.3mol/L of disodium uridylate aqueous solution and 0.1mol/L of ammonium fluoride aqueous solution into the mixed solution, wherein the dripping speed is 5ml/min, preserving heat at 60 ℃, and stirring at 120RPM for 1h; then, a predetermined portion of disodium glutarate aqueous solution is added, the temperature is kept at 50 ℃ and the mixture is stirred at 250RPM for 1.5 hours.
The lutetium chloride: the molar ratio of lanthanum chloride is 26:1.
The mixed rare earth liquid comprises the following components: n-heptane: n-amyl alcohol: the weight ratio of the cetyl trimethyl ammonium bromide to the mixture is 1:15:5:1.
The mixed rare earth liquid comprises the following components: disodium uridylate aqueous solution: aqueous ammonium fluoride solution: the volume ratio of the disodium glutarate aqueous solution is 1:1.2:1.5:1.
And (3) the reaction is carried out, and the mixed solution prepared in the mixing step is put into a condition of 22MPa and 160 ℃ for reaction molding for 8 hours.
The shaping is carried out, a predetermined part of acetone is added into the material after the shaping step, 8000RPM is used for separation for 3min, and solid matters are taken; then sequentially washing the solid by adopting acetone, absolute ethyl alcohol and deionized water with the volume of 5 times; drying at 65 ℃ for 2 hours under the condition of minus 0.08MPa to obtain the carrier particles.
The mixed rare earth liquid comprises the following components: the volume ratio of the acetone is 1:3.
The carrier particles have a particle diameter of 23nm and a specific surface area of 100m 2 /g。
And activating, namely, under the nitrogen environment of 6MPa, adopting intermittent microwave radiation, controlling the temperature of the carrier to be kept within the range of 90 ℃ and processing for 10min to finish the activation of the carrier particles.
The microwave energy of the microwave radiation is 21w/g, and the microwave radiation power is 0.7KW.
And (3) modifying, namely adding the activated carrier particles into a mixed modifying liquid, heating to 55 ℃, and under the condition of 70RPM stirring, carrying out heat preservation modification, controlling the nitrogen content of the carrier particles to be 3.5%, and separating out the carrier particles for standby.
The mixed modification liquid comprises absolute ethyl alcohol, N-methyl pyrrolidone, N-methyl-4-bromo-2-hydroxypyridine and dimethyl dichlorosilane. The weight ratio of the absolute ethyl alcohol to the N-methyl pyrrolidone to the N-methyl-4-bromo-2-hydroxypyridine to the dimethyl dichlorosilane is 40:3:5:1.
And (3) preparing the adsorption liquid, namely mixing a predetermined part of copper chloride and a 6% ammonium chloride solution, stirring, heating to 70 ℃, and fully and uniformly mixing to prepare the adsorption liquid of the metal ammonium salt complex without crystallization or macroscopic mechanical impurities.
Wherein the molar ratio of the copper chloride to the ammonium chloride is 1:6.
The adsorption, namely, the modified carrier particles are put into a preset part of adsorption liquid, the temperature is increased to 55 ℃ at the heating rate of 2 ℃/min, and the heat is preserved and adsorbed for 2 hours; then heating to 70 ℃ at a heating rate of 3 ℃/min, and preserving heat and adsorbing for 2 hours.
The carrier particles: the volume ratio of the adsorption liquid is 1:6.
and (3) loading, namely putting the pretreated activated carbon into a mixed solution of carrier particles and adsorption liquid, naturally cooling to 50 ℃, preserving heat, pressurizing to 4MPa, stirring for 4 hours at 50RPM, fully loading the carrier particles on the activated carbon, and finally separating the activated carbon loaded with the carrier particles.
The activated carbon comprises the following components: the volume ratio of the adsorption liquid is 1:1.5.
And (3) balancing, namely placing the activated carbon loaded with the carrier particles in a nitrogen atmosphere, pressurizing to 2MPa, and standing for 8 hours at 35 ℃ to complete the balancing step.
And (3) drying, namely placing the activated carbon loaded with the carrier particles in a vacuum environment, and drying at 90 ℃ for 8 hours to obtain the non-noble metal catalyst.
The process for producing vinyl chloride by using the non-noble metal catalyst comprises the following steps: and (3) filling, activating and synthesizing the vinyl chloride by using the catalyst.
And filling the catalyst, namely filling the non-noble metal catalyst into a reactor with clean and dry inner walls at the temperature of 30 ℃ for 20min.
And after the catalyst is filled, introducing hydrogen chloride gas dried at 80 ℃ into the reactor for activation treatment for 7 hours.
The flow rate of the hydrogen chloride gas is 5m/h.
And in the activation process, acid is discharged at the bottom of the reactor every 3 hours.
The method comprises the steps of synthesizing chloroethylene, introducing acetylene and hydrogen chloride gas with preheating temperature of 35 ℃ into a reactor, controlling the temperature within the range of 90-95 ℃ and culturing for 7 days; after the culture period is finished, the reaction period is started, and the reaction temperature is 105 ℃ and the acetylene airspeed is 130 -1 And reacting to synthesize chloroethylene under the condition of the reaction pressure of 0.02 MPa.
The incubation period, the acetylene: the molar ratio of the hydrogen chloride is 1:0.9.
The reaction period, the acetylene: the molar ratio of the hydrogen chloride is 1:1.05.
According to detection, the non-noble metal catalyst of the embodiment has high activity under the premise of ensuring excellent catalytic performance and catalytic life, the catalyst activation temperature is only 80 ℃, and the catalyst activation time is only 7 hours to achieve the optimal catalytic activity; meanwhile, in the early stage of vinyl chloride synthesis, the culture period of the mixed gas of acetylene and hydrogen chloride in a converter only needs 7 days, and the culture temperature only needs 90-95 ℃;
meanwhile, the non-noble metal catalyst of the embodiment can achieve the optimal catalytic performance when the reaction temperature is 105 ℃.
Further, at a reaction temperature of 105Acetylene space velocity 130 -1 Under the condition, the initial conversion rate of acetylene is 99.5 percent, and the selectivity of chloroethylene is 99.3 percent. Meanwhile, the overall service life of the catalyst exceeds 11000h.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is that: deleting the steps of carrier particle preparation and loading, putting the activated carbon obtained after the activated carbon pretreatment into the mixed modification liquid in the embodiment 2, carrying out heat preservation modification at 55 ℃ under the stirring condition of 70RPM, controlling the nitrogen content of the activated carbon to 3.5%, and separating the activated carbon for later use. And then adopting the activated carbon as catalyst carrier particles, and continuing the subsequent steps of adsorption, balancing and drying.
According to detection, the catalyst activation temperature of the non-noble metal catalyst of the comparative example is 100 ℃, and the catalyst activation time is 10 hours; meanwhile, in the early stage of vinyl chloride synthesis, the culture period of the mixed gas of acetylene and hydrogen chloride in a converter takes 10 days, and the culture temperature is 95-105 ℃;
at a reaction temperature of 105 ℃, the space velocity of acetylene is 130 -1 Under the condition, the initial conversion rate of acetylene is 98.7 percent, and the selectivity of chloroethylene is 99.0 percent. Meanwhile, the overall service life of the catalyst is about 8000h.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A non-noble metal catalyst is characterized in that in the process of preparing vinyl chloride by catalyzing the reaction of acetylene and vinyl chloride,at a reaction temperature of 105 ℃, the space velocity of acetylene is 130 -1 Under the condition that the initial conversion rate of acetylene exceeds 99.0%, and the selectivity of chloroethylene exceeds 99.1%;
the preparation method of the catalyst comprises the steps of active carbon pretreatment, carrier particle preparation, adsorption liquid configuration, adsorption, load, balancing and drying;
the preparation of the carrier particles comprises mixing, reaction, shaping, activation and modification; firstly, preparing carrier particles by mixing, reacting and shaping raw materials, and then, modifying by mixing a modifying liquid after microwave activation, wherein the nitrogen content of the carrier particles is controlled to be 2-5% by mass fraction, so as to prepare the carrier particles;
the mixing, namely adding predetermined parts of lutetium chloride and lanthanum chloride into deionized water to prepare mixed rare earth solution with the concentration of 0.2-0.3 mol/L; then mixing the mixed rare earth liquid with a predetermined part of n-heptane, n-amyl alcohol and hexadecyl trimethyl ammonium bromide, heating to 60 ℃, and stirring for 1-2 hours at 50-100RPM to prepare a mixed liquid; then, simultaneously dripping 0.2-0.3mol/L of disodium uridylate aqueous solution and 0.1mol/L of ammonium fluoride aqueous solution into the mixed solution, wherein the dripping speed is 5ml/min, preserving heat at 60 ℃, and stirring at 100-130RPM for 1-2 hours; then adding a predetermined part of disodium glutarate aqueous solution, preserving heat at 50 ℃ and stirring for 1-2h at 200-300 RPM;
the reaction is carried out, the mixed solution prepared in the mixing step is put into 18-22MPa and 160 ℃ for reaction molding for 7-8h;
the shaping is carried out, a predetermined part of acetone is added into the materials after the reaction step, 7000-8000RPM is used for separation for 2-3min, and solid matters are taken; then, sequentially washing the solid by adopting acetone, absolute ethyl alcohol and deionized water with the volume of 3-5 times; drying at 60-70 ℃ for 1-2h under the condition of minus 0.07-minus 0.08MPa to prepare the carrier particles;
the activation, under the nitrogen environment of 5-10MPa, adopts intermittent microwave radiation, controls the temperature of the carrier to be kept in the range of 80-90 ℃ and the treatment time to be 5-10min;
the modification is carried out by mixing the following raw materials: absolute ethanol, N-methylpyrrolidone, N-methyl-4-bromo-2-hydroxypyridine, and dimethyldichlorosilane;
the adsorption, namely, the carrier particles are put into adsorption liquid with the volume of 5-6 times, the temperature is raised to 55 ℃ at the heating rate of 2 ℃/min, and the heat is preserved for adsorption for 1-2 hours; then heating to 70 ℃ at a heating rate of 3 ℃/min, and preserving heat and adsorbing for 1-2h;
the adsorption liquid is a mixed liquid of copper chloride and 6% ammonium chloride solution by mass fraction;
and (3) loading, namely putting the activated carbon prepared in the activated carbon pretreatment step into a mixed solution of carrier particles and adsorption liquid, naturally cooling to 45-50 ℃, preserving heat, pressurizing to 3-5MPa, and stirring at 30-60RPM for 3-5h to prepare the activated carbon loaded with the carrier particles.
2. A non-noble metal catalyst according to claim 1, wherein the activated carbon is pretreated;
the activated carbon pretreatment comprises activated carbon selection and impurity removal;
the activated carbon is selected, the specific surface area is 800-1000 square meters per gram, the carbon tetrachloride adsorption rate is 70-80%, the bulk density is 320-370g/L, the average pore diameter is 80-120nm, and the nitrogen content is 1-3% of the mass fraction;
the impurity is removed, the activated carbon is put into 0.5mol/L phosphoric acid, the temperature is increased to 50 ℃ at the heating rate of 1.5-2.0 ℃/min, and the mixture is stirred and kept for 1 hour; filtering out the activated carbon, and leaching the activated carbon by using hydroxylamine hydrochloride solution with the mass fraction of 5% at 35 ℃ for 1-1.5h; and after leaching, washing the activated carbon by using enough deionized water until the PH of the activated carbon is 5-6.
3. A non-noble metal catalyst in accordance with claim 1, wherein said lutetium chloride: the molar ratio of lanthanum chloride is 20-30:1;
the mixed rare earth liquid comprises the following components: n-heptane: n-amyl alcohol: the weight ratio of the cetyl trimethyl ammonium bromide to the water is 1:15:5:1;
the mixed rare earth liquid comprises the following components: disodium uridylate aqueous solution: aqueous ammonium fluoride solution: the volume ratio of the disodium glutarate aqueous solution is 1:1.2:1.5:1.
4. The non-noble metal catalyst according to claim 1, wherein the balance is that the active carbon loaded with carrier particles is placed under nitrogen atmosphere, pressurized to 1-2mpa, and kept stand for 5-8h in the environment of 30-40 ℃;
and (3) drying, namely placing the activated carbon loaded with the carrier particles in a vacuum environment, and drying at 90 ℃ for 6-8 hours to obtain the non-noble metal catalyst.
5. The non-noble metal catalyst according to claim 1, wherein the ratio of parts by weight of the absolute ethyl alcohol, the N-methyl pyrrolidone, the N-methyl-4-bromo-2-hydroxypyridine and the dimethyldichlorosilane is 30-50:2-3:5-7:0.5-1.
6. A process for producing vinyl chloride using the non-noble metal catalyst according to any one of claims 1 to 5, comprising: catalyst filling, activating and synthesizing chloroethylene;
the catalyst is filled, the non-noble metal catalyst is filled into a reactor with clean inner wall and dried at the temperature of 30-35 ℃ for 20min;
after the catalyst is filled, introducing 80-90 ℃ dry hydrogen chloride gas into the reactor for activation treatment for 7-8 hours;
the flow rate of the hydrogen chloride gas is 5-6m/h.
7. The process for producing vinyl chloride according to claim 6, wherein the vinyl chloride is synthesized by introducing acetylene and hydrogen chloride gas having a preheating temperature of 35 to 40 ℃ into the reactor, controlling the temperature within a range of 90 to 100 ℃ and a cultivation period of 7 to 9 days; after the culture period is finished, the reaction period is started, and the reaction temperature is 105 ℃ and the acetylene airspeed is 130 -1 Reacting to synthesize chloroethylene under the condition that the reaction pressure is 0.02 MPa;
the incubation period, the acetylene: the molar ratio of the hydrogen chloride is 1:0.9;
the reaction period, the acetylene: the molar ratio of the hydrogen chloride is 1:1.05.
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