阅读说明：本技术 一种非贵金属催化剂及其采用该催化剂生产氯乙烯的工艺 (Non-noble metal catalyst and process for producing vinyl chloride by adopting same ) 是由 李通 于 2020-12-30 设计创作，主要内容包括：本发明提供一种非贵金属催化剂,所述催化剂的制备方法,包括活性炭预处理、载体颗粒的制备、吸附液的配置、吸附、负载、平衡、干燥。本发明还提供一种采用所述催化剂生产氯乙烯的工艺,包括：催化剂装填、活化、合成氯乙烯。本发明的非贵金属催化剂,其催化剂活化温度仅需80-90℃,催化剂活化时间仅需7-8h；培养期仅需7-9天,所述培养温度仅需90-100℃,有效降低生产资源成本、时间成本的消耗。所述非贵金属催化剂,在反应温度为105℃,乙炔空速130～(-1)条件下,其乙炔初始转化率超过99.0%,氯乙烯选择性超过99.1%。(The invention provides a non-noble metal catalyst, and a preparation method of the catalyst comprises the steps of activated carbon pretreatment, carrier particle preparation, adsorption liquid preparation, adsorption, loading, balancing and drying. The invention also provides a process for producing vinyl chloride by using the catalyst, which comprises the following steps: catalyst filling, activating and synthesizing chloroethylene. The activation temperature of the non-noble metal catalyst is only 80-90 ℃, and the activation time of the catalyst is only 7-8 h; the culture period only needs 7-9 days, the culture temperature only needs 90-100 ℃, the production resource cost is effectively reduced,Consumption of time cost. The non-noble metal catalyst has an acetylene space velocity of 130 ℃ at a reaction temperature of 105 DEG C ‑1 Under the condition, the initial conversion rate of acetylene is over 99.0 percent, and the selectivity of chloroethylene is over 99.1 percent.)

1. The non-noble metal catalyst is characterized in that in the process of preparing chloroethylene by catalyzing the reaction of acetylene and chloroethylene, the reaction temperature is 105 ℃, and the acetylene airspeed is 130^-1Under the condition, the initial conversion rate of acetylene is over 99.0 percent, and the selectivity of chloroethylene is over 99.1 percent;

the preparation method of the catalyst comprises the steps of active carbon pretreatment, carrier particle preparation, adsorption liquid preparation, adsorption, loading, balancing and drying;

preparing the carrier particles by mixing raw materials, reacting and shaping to obtain carrier particles, activating by microwave, modifying by mixed modification liquid, and controlling the nitrogen content of the carrier particles to be 2-5% to obtain the carrier particles;

the mixed modification liquid is prepared by mixing the following raw materials: absolute ethyl alcohol, N-methyl pyrrolidone, N-methyl-4-bromo-2-hydroxypyridine and dimethyldichlorosilane.

2. A non-noble metal catalyst according to claim 1, wherein the activated carbon is pretreated;

the active carbon pretreatment comprises active carbon selection and impurity removal;

selecting the activated carbon, namely selecting the activated carbon with the specific surface area of 800-1000 square meters per gram, the carbon tetrachloride adsorption rate of 70-80 percent, the bulk density of 320-370g/L, the average pore diameter of 80-120nm and the nitrogen content of 1-3 percent;

removing impurities, namely putting the activated carbon into 0.5mol/L phosphoric acid, raising the temperature to 50 ℃ at a heating rate of 1.5-2.0 ℃/min, stirring, and keeping the temperature for 1 hour; filtering out the activated carbon, and leaching the activated carbon by using 5% hydroxylamine hydrochloride solution at 35 ℃, wherein the leaching time is 1-1.5 h; and after leaching, washing the activated carbon by using sufficient deionized water until the pH value of the activated carbon is 5-6.

3. A non-noble metal catalyst according to claim 1, wherein the support particles are prepared by mixing, reacting, shaping, activating, modifying;

in the mixing step, the lutetium chloride and the lanthanum chloride in preset parts are put into deionized water to prepare mixed rare earth liquid 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-pentanol and hexadecyl trimethyl ammonium bromide, heating to 60 ℃, and stirring at 50-100RPM for 1-2h to prepare a mixed liquid; then, simultaneously dripping 0.2-0.3mol/L uridylic acid disodium aqueous solution and 0.1mol/L ammonium fluoride aqueous solution into the mixed solution in predetermined parts, wherein the dripping speed is 5ml/min, keeping the temperature at 60 ℃, and stirring for 1-2h at 100-130 RPM; then adding a predetermined part of disodium glutarate aqueous solution, preserving the heat at 50 ℃, and stirring at 200-300RPM for 1-2 h.

4. A non-noble metal catalyst as recited in claim 3, wherein the lutetium chloride: the molar ratio of lanthanum chloride is 20-30: 1;

the mixed rare earth liquid: n-heptane: n-pentanol: the weight ratio of the hexadecyl trimethyl ammonium bromide to the hexadecyl trimethyl ammonium bromide is 1:15:5: 1;

the mixed rare earth liquid: uridylate disodium aqueous solution: aqueous ammonium fluoride solution: the volume part ratio of the disodium glutarate aqueous solution is 1:1.2:1.5: 1.

5. The non-noble metal catalyst according to claim 3, wherein in the reaction, the mixed solution obtained in the mixing step is put into a temperature of between 18 and 22MPa and 160 ℃ for reaction forming for 7 to 8 hours;

the shaping step, adding a predetermined part of acetone into the material after the shaping step, separating at 7000-8000RPM for 2-3min, and taking out the solid; then, sequentially washing the solid by using 3-5 times of acetone, absolute ethyl alcohol and deionized water; drying for 1-2h at the temperature of 60-70 ℃ under the conditions of-0.07 to-0.08 MPa to prepare the carrier particles;

and the activation is carried out by adopting intermittent microwave radiation under the nitrogen environment of 5-10MPa, controlling the temperature of the carrier to be kept within the range of 80-90 ℃ and treating for 5-10 min.

6. The non-noble metal catalyst according to claim 1, wherein in the adsorption, the carrier particles are put into an adsorption solution with 5-6 times of volume, the temperature is raised to 55 ℃ at the temperature raising rate of 2 ℃/min, and the adsorption is carried out for 1-2h under the condition of heat preservation; then heating to 70 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation and adsorption for 1-2 h;

the adsorption solution is a mixed solution of copper chloride and 6% ammonium chloride solution;

and the loading step, the activated carbon prepared in the activated carbon pretreatment step is put into a mixed solution of carrier particles and an adsorption solution, naturally cooled to 45-50 ℃, kept at a temperature, pressurized to 3-5MPa, and stirred at 30-60RPM for 3-5h to prepare the activated carbon loaded with the carrier particles.

7. A non-noble metal catalyst according to claim 1, wherein in the balancing step, the activated carbon loaded with carrier particles is placed in a nitrogen atmosphere, pressurized to 1-2MPa and kept standing at 30-40 ℃ for 5-8 h;

and drying, namely placing the activated carbon loaded with carrier particles in a vacuum environment, and drying for 6-8h at 90 ℃ to obtain the non-noble metal catalyst.

8. A non-noble metal catalyst as recited in claim 1 in which the weight ratio of the absolute ethanol, N-methylpyrrolidone, N-methyl-4-bromo-2-hydroxypyridine, and dimethyldichlorosilane is 30-50:2-3:5-7: 0.5-1.

9. A process for the production of vinyl chloride using a non-noble metal catalyst as claimed in any one of claims 1 to 8, comprising: filling and activating a catalyst, and synthesizing chloroethylene;

filling the catalyst, namely filling the non-noble metal catalyst into a reactor with a clean and dry inner wall at the temperature of 30-35 ℃ for 20 min;

after the catalyst is filled, introducing hydrogen chloride gas dried at the temperature of 80-90 ℃ into the reactor for activation treatment, wherein the activation time is 7-8 h;

and introducing the hydrogen chloride gas at the flow velocity of 5-6 m/h.

10. The process for producing vinyl chloride according to claim 9, wherein the synthesis of vinyl chloride comprises introducing acetylene and hydrogen chloride gas preheated to 35-40 ℃ into a reactor, controlling the temperature within the range of 90-100 ℃ and the culture period for 7-9 days; after the culture period is finished, the reaction period is started, the reaction temperature is 105 ℃, and the acetylene space velocity is 130^-1Vinyl chloride is synthesized by reaction under the condition that the reaction pressure is 0.02 MPa;

the culture period, the acetylene: the molar ratio of hydrogen chloride is 1: 0.9;

the reaction period, the acetylene: the molar ratio of hydrogen chloride was 1: 1.05.

Technical Field

The invention relates to the field of chloroethylene production, in particular to a non-noble metal catalyst and a process for producing chloroethylene by adopting the catalyst.

Background

Vinyl chloride, a monomer for the synthesis of 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 step in the polyvinyl chloride industry.

The synthesis of vinyl chloride falls into two broad categories, namely ethylene oxychlorination and acetyleneHydrochlorination method, wherein acetylene hydrochlorination method is the main method. Acetylene and hydrogen chloride gas with certain purity are used as raw materials, mixed according to a certain proportion, added into a converter containing a catalyst, and heated to react to generate chloroethylene. The chemical reaction equation is as follows: c₂H₂ + HCl → C₂H₃Cl

At present, the research on the catalyst for preparing vinyl chloride by the acetylene hydrochlorination method 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 stability, profound research is carried out on Au (gold) catalysis acetylene hydrogen chloride solid-phase reaction by professor Graham.J. Hutchings, British cadov university, the catalytic mechanism and inactivation mechanism of the Au catalyst are provided, industrial tests are carried out, the test result is better than that of a harmful heavy metal catalyst, but the catalyst is expensive, the production cost of polyvinyl chloride is greatly increased, and the economic feasibility is not available.

The non-metal catalyst has lower catalytic activity than the metal catalyst, higher energy consumption for preparation, and complicated steps, and cannot meet the requirement of large-scale industrial application.

The non-noble metal catalyst is mainly researched in the direction of tin, copper, barium, zinc, molybdenum, bismuth and the like, and compared with a noble metal catalyst, the non-noble metal catalyst is low in cost, small in environmental hazard, high in catalytic activity and capable 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 needs to be carried out on the non-noble metal catalyst in order to ensure better catalytic performance and more ideal catalytic life, but in the activation treatment process, the time for activating the non-noble metal catalyst is long, the temperature is high, and 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 the converter for a long time, the optimal culture temperature is often over 110 ℃, and the time cost and the resource cost are high. Meanwhile, the applicant also finds that incomplete activation or insufficient culture period can adversely affect the performance of the catalyst during the activation or culture period 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 using mercury-free catalyst, which adopts catalyst with specific components and ratio to catalyze the production of vinyl chloride by a specific process method. However, in the process of catalyzing the catalyst, the activation time required by the catalyst activation is long, and the activation temperature is high; meanwhile, in the early stage of vinyl chloride synthesis, the culture period of the acetylene and hydrogen chloride mixed gas in the converter is as long as 10-30 days, and the optimal culture temperature reaches 120 ℃.

Chinese patent CN106215977A discloses a mercury-free catalyst with high catalytic activity for synthesizing vinyl chloride and a preparation method thereof, wherein the mercury-free catalyst is prepared by adopting specific raw material components and proportions and a specific preparation method and is used for catalyzing the production of vinyl chloride. However, in the process of catalyzing by the mercury-free catalyst, the time required by preheating and activating the mercury-free catalyst is long, and the activation temperature is high; meanwhile, in the early stage of vinyl chloride synthesis, the culture period of the mixed gas of acetylene and hydrogen chloride in the converter is as long as 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 purposes:

(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 acetylene and hydrogen chloride mixed gas in the converter is shortened and the required culture temperature is reduced in the early stage of vinyl chloride synthesis.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the non-noble metal catalyst is used in the catalytic preparation of vinyl chloride through the reaction of acetylene and vinyl chloride at reaction temperature of 105 deg.c and acetylene space velocity of 130%^-1Under the condition ofThe initial conversion rate of alkyne is over 99.0 percent, and the selectivity of chloroethylene is over 99.1 percent;

the preparation method of the catalyst comprises the steps of active carbon pretreatment, carrier particle preparation, adsorption liquid preparation, adsorption, loading, balancing and drying;

the preparation of the carrier particles comprises the steps of firstly mixing raw materials, reacting and shaping to obtain carrier particles, and then carrying out microwave activation, modifying by using a mixed modification solution, and controlling the nitrogen content of the carrier particles to be 2-5% to obtain the carrier particles;

the mixed modification liquid is prepared by mixing the following raw materials: absolute ethyl alcohol, N-methyl pyrrolidone, N-methyl-4-bromo-2-hydroxypyridine and dimethyldichlorosilane.

Further, pretreating the activated carbon;

the active carbon pretreatment comprises active carbon selection and impurity removal;

selecting the activated carbon, namely selecting the activated carbon with the specific surface area of 800-1000 square meters per gram, the carbon tetrachloride adsorption rate of 70-80 percent, the bulk density of 320-370g/L, the average pore diameter of 80-120nm and the nitrogen content of 1-3 percent;

removing impurities, namely putting the activated carbon into 0.5mol/L phosphoric acid, raising the temperature to 50 ℃ at a heating rate of 1.5-2.0 ℃/min, stirring, and keeping the temperature for 1 hour; filtering out the activated carbon, and leaching the activated carbon by using 5% hydroxylamine hydrochloride solution at 35 ℃, wherein the leaching time is 1-1.5 h; and after leaching, washing the activated carbon by using sufficient deionized water until the pH value of the activated carbon is 5-6.

Further, the preparation of the carrier particles comprises mixing, reacting, shaping, activating and modifying;

in the mixing step, the lutetium chloride and the lanthanum chloride in preset parts are put into deionized water to prepare mixed rare earth liquid 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-pentanol and hexadecyl trimethyl ammonium bromide, heating to 60 ℃, and stirring at 50-100RPM for 1-2h to prepare a mixed liquid; then, simultaneously dripping 0.2-0.3mol/L uridylic acid disodium aqueous solution and 0.1mol/L ammonium fluoride aqueous solution into the mixed solution in predetermined parts, wherein the dripping speed is 5ml/min, keeping the temperature at 60 ℃, and stirring for 1-2h at 100-130 RPM; then adding a predetermined part of disodium glutarate aqueous solution, preserving the heat at 50 ℃, and stirring at 200-300RPM for 1-2 h.

Further, the lutetium chloride: the molar ratio of lanthanum chloride is 20-30: 1.

The mixed rare earth liquid: n-heptane: n-pentanol: the weight ratio of the hexadecyl trimethyl ammonium bromide is 1:15:5: 1.

The mixed rare earth liquid: uridylate disodium aqueous solution: aqueous ammonium fluoride solution: the volume part ratio of the disodium glutarate aqueous solution is 1:1.2:1.5: 1.

Further, the reaction is carried out, namely the mixed solution prepared in the mixing step is put into a temperature of between 18 and 22MPa and is subjected to reaction forming for 7 to 8 hours at the temperature of 160 ℃;

the shaping step, adding a predetermined part of acetone into the material after the shaping step, separating at 7000-8000RPM for 2-3min, and taking out the solid; then, sequentially washing the solid by using 3-5 times of acetone, absolute ethyl alcohol and deionized water; drying for 1-2h at the temperature of 60-70 ℃ under the conditions of-0.07 to-0.08 MPa to prepare the carrier particles;

and the activation is carried out by adopting intermittent microwave radiation under the nitrogen environment of 5-10MPa, controlling the temperature of the carrier to be kept within the range of 80-90 ℃ and treating for 5-10 min.

Further, in the adsorption, the modified carrier particles are put into adsorption liquid with the volume 5-6 times that of the carrier particles, the temperature is raised to 55 ℃ at the temperature rise rate of 2 ℃/min, and the carrier particles are subjected to heat preservation and adsorption for 1-2 h; then heating to 70 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation and adsorption for 1-2 h;

the adsorption solution is a mixed solution of copper chloride and 6% ammonium chloride solution;

and the loading step, the activated carbon prepared in the activated carbon pretreatment step is put into a mixed solution of carrier particles and an adsorption solution, naturally cooled to 45-50 ℃, kept at a temperature, pressurized to 3-5MPa, and stirred at 30-60RPM for 3-5h to prepare the activated carbon loaded with the carrier particles.

Further, balancing, namely placing the activated carbon loaded with carrier particles in a nitrogen atmosphere, pressurizing to 1-2MPa, standing at the temperature of 30-40 ℃ for 5-8 h;

and drying, namely placing the activated carbon loaded with carrier particles in a vacuum environment, and drying for 6-8h at 90 ℃ to obtain the non-noble metal catalyst.

Furthermore, the weight ratio of the absolute ethyl alcohol, the N-methyl pyrrolidone, the N-methyl-4-bromo-2-hydroxypyridine and the dimethyl dichlorosilane is 30-50:2-3:5-7: 0.5-1.

A process for producing vinyl chloride by adopting the non-noble metal catalyst prepared by the preparation method comprises the following steps: filling and activating a catalyst, and synthesizing chloroethylene;

filling the catalyst, namely filling the non-noble metal catalyst into a reactor with a clean and dry inner wall at the temperature of 30-35 ℃ for 20 min;

after the catalyst is filled, introducing hydrogen chloride gas dried at the temperature of 80-90 ℃ into the reactor for activation treatment, wherein the activation time is 7-8 h;

and introducing the hydrogen chloride gas at the flow velocity of 5-6 m/h.

The synthesis of chloroethylene comprises introducing acetylene and hydrogen chloride gas with the preheating temperature of 35-40 ℃ into a reactor, controlling the temperature within the range of 90-100 ℃ and the culture period for 7-9 days; after the culture period is finished, the reaction period is started, the reaction temperature is 105 ℃, and the acetylene space velocity is 130^-1Vinyl chloride is synthesized by reaction under the condition that the reaction pressure is 0.02 MPa;

the culture period, the acetylene: the molar ratio of hydrogen chloride is 1: 0.9;

the reaction period, the acetylene: the molar ratio of hydrogen chloride was 1: 1.05.

Compared with the prior art, the invention has the beneficial effects that:

(1) on the premise of ensuring excellent catalytic performance and catalytic life, the non-noble metal catalyst has high activity, the activation temperature of the catalyst is only 80-90 ℃, the activation time of the catalyst is only 7-8h, and the optimal catalytic activity can be achieved, compared with the prior art, the activation temperature is reduced by about 20-25%, and the catalytic time is shortened by about 30-40%.

(2) On the premise of ensuring excellent catalytic performance and catalytic life, the non-noble metal catalyst has the advantages that in the early stage of vinyl chloride synthesis, the culture period of the acetylene and hydrogen chloride mixed gas in the converter is only 7-9 days, the culture temperature is only 90-100 ℃, and the consumption of production resource cost and time cost is effectively reduced.

(3) The non-noble metal catalyst can achieve the best catalytic performance at the reaction temperature of 105 ℃, meanwhile, the reaction is carried out at the temperature, no by-product is generated, and the adverse phenomenon that the by-product influences the performance of the catalyst due to more side reactions when the reaction temperature is too high can be effectively avoided.

(4) The non-noble metal catalyst of the invention has a reaction temperature of 105 ℃ and an acetylene space velocity of 130^-1Under the condition, the initial conversion rate of acetylene is over 99.0 percent, and the selectivity of chloroethylene is over 99.1 percent.

(5) The non-noble metal catalyst has lasting and stable catalytic activity and good long-term stability; tests prove that the total service life of the catalyst exceeds 11000h, and the requirement of large-scale industrial production can be met.

Detailed Description

In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.

Example 1

A non-noble metal catalyst comprises the steps of activated carbon pretreatment, carrier particle preparation, adsorption liquid preparation, adsorption, loading, balancing and drying.

The active carbon pretreatment comprises active carbon selection and impurity removal.

The activated carbon is selected, and the activated carbon with the specific surface area of 800 square meters per gram, the carbon tetrachloride adsorption rate of 70 percent, the bulk density of 330g/L, the average pore diameter of 80nm and the nitrogen content of 1.5 percent is selected.

The impurity removal is carried out, the active carbon is put into 0.5mol/L phosphoric acid with the volume of 1.5 times, the temperature is raised to 50 ℃ at the heating rate of 1.5 ℃/min, the stirring is carried out at 50RPM, and the heat preservation is carried out for 1 hour; filtering out the activated carbon, and leaching the activated carbon by using 5% hydroxylamine hydrochloride solution at 35 ℃, wherein the leaching time is 1 h; and after leaching, washing the activated carbon by using sufficient deionized water until the PH value 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 mixing, reacting, shaping, activating and modifying.

In the mixing step, the lutetium chloride and the lanthanum chloride in preset parts are put into deionized water to prepare mixed rare earth liquid 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 at 50RPM for 1h to prepare a mixed liquid; then, simultaneously dripping 0.2mol/L uridylic acid disodium water solution and 0.1mol/L ammonium fluoride water solution into the mixed solution at a dripping speed of 5ml/min, preserving heat at 60 ℃, and stirring for 1h at 100 RPM; then adding a predetermined part of disodium glutarate aqueous solution, preserving the temperature at 50 ℃, and stirring at 200RPM for 1 h.

The lutetium chloride: the molar ratio of lanthanum chloride is 20: 1.

The mixed rare earth liquid: n-heptane: n-pentanol: the weight ratio of the hexadecyl trimethyl ammonium bromide is 1:15:5: 1.

The mixed rare earth liquid: uridylate disodium aqueous solution: aqueous ammonium fluoride solution: the volume part ratio of the disodium glutarate aqueous solution is 1:1.2:1.5: 1.

And (3) reacting, namely putting the mixed solution prepared in the mixing step into a reactor under the conditions of 18MPa and 160 ℃, and reacting and forming for 7 hours.

The shaping is carried out, acetone with a preset part is added into the material after the shaping step, 7000RPM is adopted for separation for 2min, and solid is taken; then, sequentially washing the solid by using acetone, absolute ethyl alcohol and deionized water with the volume of 3 times of that of the solid; drying for 1h at the temperature of 60 ℃ below zero under the pressure of-0.07 MPa to obtain the carrier particles.

The mixed rare earth liquid: the volume part ratio of the acetone is 1: 2.

The carrier particles have a particle size of 30nm and a specific surface area of 85m²/g。

And in the activation, intermittent microwave radiation is adopted in a nitrogen environment of 5MPa, the temperature of the carrier is controlled to be kept within 80 ℃, the treatment time is 5min, and the activation of the carrier particles is completed.

The microwave radiation has the microwave energy of 21w/g and the microwave radiation power of 0.7 KW.

And in the modification, the activated carrier particles are put into a mixed modification solution, the temperature is raised to 50 ℃, the carrier particles are modified in a heat preservation way under the stirring condition of 50RPM, the nitrogen content of the carrier particles is controlled to be 2.5%, and the carrier particles are separated for later use.

The mixed modification liquid comprises absolute ethyl alcohol, N-methyl pyrrolidone, N-methyl-4-bromo-2-hydroxypyridine and dimethyldichlorosilane. The weight ratio of the absolute ethyl alcohol to the N-methyl pyrrolidone to the N-methyl-4-bromo-2-hydroxypyridine to the dimethyldichlorosilane is 30:2:7: 0.5.

The preparation of the adsorption liquid comprises the steps of mixing copper chloride in a preset part and 6% ammonium chloride solution, stirring, heating to 70 ℃, and fully and uniformly mixing to prepare the metal ammonium salt complex adsorption liquid without crystals or macroscopic mechanical impurities.

Wherein the molar ratio of the copper chloride to the ammonium chloride is 1: 5.

The adsorption step comprises the steps of putting the modified carrier particles into a preset part of adsorption solution, heating to 55 ℃ at a heating rate of 2 ℃/min, and carrying out heat preservation adsorption for 1 h; then heating to 70 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for adsorption for 1 h.

The carrier particles are: the volume ratio of the adsorption solution is 1: 5.

and the loading step, the pretreated activated carbon is put into a mixed solution of carrier particles and an adsorption solution, the mixed solution is naturally cooled to 45 ℃ and is kept warm, the mixed solution is pressurized to 3MPa, the mixed solution is stirred for 3 hours at 30RPM, so that the carrier particles are fully loaded on the activated carbon, and finally the activated carbon loaded with the carrier particles is separated.

The activated carbon is as follows: the volume ratio of the adsorption liquid is 1: 1.3.

And balancing, namely placing the activated carbon loaded with carrier particles in a nitrogen atmosphere, pressurizing to 1MPa, standing for 5 hours at the temperature of 30 ℃, and finishing the balancing step.

And drying, namely placing the activated carbon loaded with carrier particles in a vacuum environment, and drying for 6 hours at 90 ℃ to obtain the non-noble metal catalyst.

The process for producing vinyl chloride by adopting the non-noble metal catalyst comprises the following steps: catalyst filling, activating and synthesizing chloroethylene.

And filling the catalyst, namely filling the non-noble metal catalyst into a reactor with a clean and dry inner wall at the temperature of 35 ℃, wherein the filling time is 20 min.

And in the activation step, after the catalyst is filled, introducing 90 ℃ dry hydrogen chloride gas into the reactor for activation treatment, wherein the activation time is 8 h.

The flow rate of the hydrogen chloride gas is 6 m/h.

And in the activation process, acid is put at the bottom of the reactor every 3 hours.

The synthesis of chloroethylene comprises introducing acetylene and hydrogen chloride gas with the preheating temperature of 40 ℃ into a reactor, controlling the temperature within the range of 95-100 ℃ and culturing for 9 days; after the culture period is finished, the reaction period is started, the reaction temperature is 105 ℃, and the acetylene space velocity is 130^-1And the reaction pressure is 0.02MPa, and vinyl chloride is synthesized by reaction.

The culture period, the acetylene: the molar ratio of hydrogen chloride was 1: 0.9.

The reaction period, the acetylene: the molar ratio of hydrogen chloride was 1: 1.05.

Through detection, on the premise of ensuring excellent catalytic performance and catalytic life, the non-noble metal catalyst of the embodiment has high activity, the catalyst activation temperature is only 90 ℃, and the catalyst activation time is only 8 hours, so that the optimal catalytic activity can be achieved; meanwhile, in the early stage of vinyl chloride synthesis, the culture period of the acetylene and hydrogen chloride mixed gas in the converter is only 9 days, and the culture temperature is only 95-100 ℃;

meanwhile, the non-noble metal catalyst of the embodiment can achieve the best catalytic performance at a reaction temperature of 105 ℃.

Further, the space velocity of acetylene is 130 ℃ at the reaction temperature of 105 DEG C^-1Under the condition, the initial conversion rate of acetylene is 99.1 percent, and the selectivity of chloroethylene is 99.3 percent. Meanwhile, the service life of the catalyst is more than 11000 h.

Example 2

A non-noble metal catalyst comprises the steps of activated carbon pretreatment, carrier particle preparation, adsorption liquid preparation, adsorption, loading, balancing and drying.

The active carbon pretreatment comprises active carbon selection and impurity removal.

The activated carbon is selected, and the activated carbon with the specific surface area of 900 square meters per gram, the carbon tetrachloride adsorption rate of 80 percent, the bulk density of 350g/L, the average pore diameter of 110nm and the nitrogen content of 2 percent is selected.

The impurity removal is carried out, the active carbon is put into 0.5mol/L phosphoric acid with 2 times volume, the temperature is raised to 50 ℃ at the heating rate of 2.0 ℃/min, the stirring is carried out at 80RPM, and the heat preservation is carried out for 1 hour; filtering out the activated carbon, and leaching the activated carbon by using 5% hydroxylamine hydrochloride solution at 35 ℃, wherein the leaching time is 1.5 h; and after leaching, washing the activated carbon by using sufficient deionized water until the PH value 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 mixing, reacting, shaping, activating and modifying.

In the mixing step, the lutetium chloride and the lanthanum chloride in preset parts are put into deionized water to prepare mixed rare earth liquid 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 for 2 hours at 100RPM to prepare a mixed liquid; then, simultaneously dripping 0.3mol/L uridylic acid disodium water solution and 0.1mol/L ammonium fluoride water solution into the mixed solution at a dripping speed of 5ml/min, preserving heat at 60 ℃, and stirring for 1h at 120 RPM; then adding a predetermined part of disodium glutarate aqueous solution, preserving the temperature at 50 ℃, and stirring at 250RPM for 1.5 h.

The lutetium chloride: the molar ratio of lanthanum chloride is 26: 1.

The mixed rare earth liquid: n-heptane: n-pentanol: the weight ratio of the hexadecyl trimethyl ammonium bromide is 1:15:5: 1.

The mixed rare earth liquid: uridylate disodium aqueous solution: aqueous ammonium fluoride solution: the volume part ratio of the disodium glutarate aqueous solution is 1:1.2:1.5: 1.

And (3) reacting, namely putting the mixed solution prepared in the mixing step into a reactor under the conditions of 22MPa and 160 ℃, and reacting and forming for 8 hours.

The shaping is carried out, acetone with a preset part is added into the material after the shaping step, separation is carried out for 3min at 8000RPM, and solid is taken out; then, sequentially washing the solid by using acetone, absolute ethyl alcohol and deionized water with the volume of 5 times of that of the solid; drying for 2h at the temperature of 65 ℃ below zero under the condition of-0.08 MPa to obtain the carrier particles.

The mixed rare earth liquid: the volume part ratio of the acetone is 1: 3.

The carrier particles have a particle size of 23nm and a specific surface area of 100m²/g。

And in the activation, intermittent microwave radiation is adopted in a 6MPa nitrogen environment, the temperature of the carrier is controlled to be kept within a range of 90 ℃, the treatment time is 10min, and the activation of the carrier particles is completed.

The microwave radiation has the microwave energy of 21w/g and the microwave radiation power of 0.7 KW.

And in the modification, the activated carrier particles are put into a mixed modification solution, the temperature is raised to 55 ℃, the carrier particles are modified in a heat preservation way under the stirring condition of 70RPM, the nitrogen content of the carrier particles is controlled to be 3.5%, and the carrier particles are separated for later use.

The mixed modification liquid comprises absolute ethyl alcohol, N-methyl pyrrolidone, N-methyl-4-bromo-2-hydroxypyridine and dimethyldichlorosilane. The weight ratio of the absolute ethyl alcohol to the N-methyl pyrrolidone to the N-methyl-4-bromo-2-hydroxypyridine to the dimethyldichlorosilane is 40:3:5: 1.

The preparation of the adsorption liquid comprises the steps of mixing copper chloride in a preset part and 6% ammonium chloride solution, stirring, heating to 70 ℃, and fully and uniformly mixing to prepare the metal ammonium salt complex adsorption liquid without crystals or macroscopic mechanical impurities.

Wherein the molar ratio of the copper chloride to the ammonium chloride is 1: 6.

The adsorption step comprises the steps of putting the modified carrier particles into a preset part of adsorption solution, heating to 55 ℃ at a heating rate of 2 ℃/min, and carrying out heat preservation adsorption for 2 hours; then heating to 70 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for adsorption for 2 h.

The carrier particles are: the volume ratio of the adsorption solution is 1: 6.

and the loading step, the pretreated activated carbon is put into a mixed solution of carrier particles and an adsorption solution, the mixed solution is naturally cooled to 50 ℃, the temperature is kept, the pressure is increased to 4MPa, the mixed solution is stirred at 50RPM for 4 hours, the carrier particles are fully loaded on the activated carbon, and finally the activated carbon loaded with the carrier particles is separated.

The activated carbon is as follows: the volume ratio of the adsorption liquid is 1: 1.5.

And balancing, namely placing the activated carbon loaded with carrier particles in a nitrogen atmosphere, pressurizing to 2MPa, standing for 8 hours at the temperature of 35 ℃, and finishing the balancing step.

And drying, namely placing the activated carbon loaded with carrier particles in a vacuum environment, and drying for 8 hours at 90 ℃ to obtain the non-noble metal catalyst.

The process for producing vinyl chloride by adopting the non-noble metal catalyst comprises the following steps: catalyst filling, activating and synthesizing chloroethylene.

And filling the catalyst, namely filling the non-noble metal catalyst into a reactor with a clean and dry inner wall at the temperature of 30 ℃, wherein the filling time is 20 min.

And in the activation step, after the catalyst is filled, introducing hydrogen chloride gas dried at 80 ℃ into the reactor, and performing activation treatment for 7 hours.

The flow rate of the hydrogen chloride gas is 5 m/h.

And in the activation process, acid is put at the bottom of the reactor every 3 hours.

The synthesis of chloroethylene comprises the steps of introducing acetylene and hydrogen chloride gas with the 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, the reaction is carried outAt a reaction temperature of 105 ℃ and a space velocity of acetylene of 130^-1And the reaction pressure is 0.02MPa, and vinyl chloride is synthesized by reaction.

The culture period, the acetylene: the molar ratio of hydrogen chloride was 1: 0.9.

The reaction period, the acetylene: the molar ratio of hydrogen chloride was 1: 1.05.

Through detection, on the premise of ensuring excellent catalytic performance and catalytic life, the non-noble metal catalyst of the embodiment has high activity, the catalyst activation temperature is only 80 ℃, and the catalyst activation time is only 7 hours, so that the optimal catalytic activity can be achieved; meanwhile, in the early stage of vinyl chloride synthesis, the culture period of the acetylene and hydrogen chloride mixed gas in the converter is only 7 days, and the culture temperature is only 90-95 ℃;

meanwhile, the non-noble metal catalyst of the embodiment can achieve the best catalytic performance at a reaction temperature of 105 ℃.

Further, the space velocity of acetylene is 130 ℃ at the reaction temperature of 105 DEG C^-1Under the condition, the initial conversion rate of acetylene is 99.5 percent, and the selectivity of chloroethylene is 99.3 percent. Meanwhile, the service life of the catalyst is more than 11000 h.

Comparative example 1

The technical scheme of the embodiment 2 is adopted, and the difference is that: the steps of 'preparation of carrier particles' and 'loading' are deleted, the active carbon prepared after the 'pretreatment of the active carbon' is put into the 'mixed modification liquid' in the embodiment 2, the heat preservation and the modification are carried out at 55 ℃ under the condition of stirring at 70RPM, the nitrogen content of the active carbon is controlled to be 3.5%, and the active carbon is separated for standby. Then, the activated carbon is used as catalyst carrier particles, and the subsequent steps of adsorption, balance and drying are continuously carried out.

Through detection, the activation temperature of the non-noble metal catalyst in the comparative example is 100 ℃, and the activation time of the catalyst needs 10 hours; meanwhile, in the early stage of vinyl chloride synthesis, the culture period of the acetylene and hydrogen chloride mixed gas in the converter needs 10 days, and the culture temperature is 95-105 ℃;

at a reaction temperature of 105 ℃ and an acetylene space velocity of 130^-1Under the condition that acetylene is initially presentThe conversion rate is 98.7 percent, and the selectivity of the chloroethylene is 99.0 percent. Meanwhile, the service life of the catalyst is about 8000 h.

All percentages used in the present invention are mass percentages unless otherwise indicated.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.