阅读说明：本技术 一种n-p改性活性炭的乙炔氢氯化催化剂及其制备方法 (Acetylene hydrochlorination catalyst of N-P modified activated carbon and preparation method thereof ) 是由 朱瑞波 赵长森 解荣永 牛强 于 2021-07-26 设计创作，主要内容包括：本发明提供了一种N-P改性活性炭的乙炔氢氯化催化剂及其制备方法,涉及催化剂制备技术领域,主要通过制备木质活性炭的过程中添加N、P进行改性,活化成型后二次负载N元素和Cu的金属盐制备所得,从而提高催化剂的活性和稳定性。(The invention provides an acetylene hydrochlorination catalyst of N-P modified activated carbon and a preparation method thereof, relates to the technical field of catalyst preparation, and is mainly prepared by adding N, P in the process of preparing wood activated carbon for modification and secondarily loading N element and Cu metal salt after activation molding, thereby improving the activity and stability of the catalyst.)

1. A method for preparing a catalyst, which is characterized by comprising the following steps: the method comprises the following steps:

(1) pretreatment: crushing activated carbon, sieving, soaking in acid solution or alkali solution, and filtering;

(2) treating the phosphorus-containing solution: dipping the pretreated active carbon in a phosphorus-containing solution for soaking and then drying;

(3) treating the nitrogen-containing solution: dipping the activated carbon treated by the phosphorus-containing solution into a nitrogen-containing solution for soaking and then drying;

(4) and (3) clearing heat: carbonizing the activated carbon treated by the nitrogenous solution in a nitrogen atmosphere, and roasting in a mixed gas atmosphere of steam and carbon dioxide to obtain activated carbon A;

(5) acid washing, purifying and drying the activated carbon to obtain activated carbon B;

(6) dipping the activated carbon B in the solution A, drying and roasting to obtain activated carbon C;

(7) immersing activated carbon C in CuCl₂Drying the solution to obtain the catalyst.

2. The method of claim 1, wherein: the precursor of the activated carbon in the step (1) is wood chips or shells.

3. The method of claim 1, wherein: in the step (1), the acid solution is a sulfuric acid solution, and the alkali solution is hydrogen peroxide.

4. The method of claim 1, wherein: the soaking time in the step (2) and the step (3) is 5-10 h.

5. The method of claim 1, wherein: in the step (4), the carbonization temperature is 500-600 ℃, and the carbonization time is 2-6 h; the roasting temperature is 700-800 ℃, and the roasting time is 1-3 h.

6. The method of claim 1, wherein: in the step (6), the solution A is a mixed solution of urea and PVP, or a mixed solution of melamine and PVP.

7. The method of claim 1, wherein: the roasting temperature in the step (6) is 300-400 ℃, and the roasting time is 3-10 h.

8. The method of claim 1, wherein: the phosphorus-containing solution in the step (2) comprises one or more of phosphoric acid, ammonium phosphate and ammonium polyphosphate.

9. A catalyst prepared by the method according to any one of claims 1 to 8.

10. Use of the catalyst prepared by the process according to any one of claims 1 to 8 for the hydrochlorination of acetylene.

Technical Field

The invention relates to the technical field of catalyst preparation, in particular to an acetylene hydrochlorination catalyst of N-P modified activated carbon and a preparation method thereof.

Background

Vinyl chloride is a raw material for synthesizing polyvinyl chloride, and there are 3 kinds of methods for synthesizing vinyl chloride, namely an acetylene method, an ethylene method and an ethane method, and currently, the acetylene method using coal as a raw material and the ethylene method using petroleum as a raw material are mainly industrialized. At present, the acetylene method for producing polyvinyl chloride uses a mercury catalyst, mercury is volatile as a heavy metal, and the loss and volatilization of mercury in the use process of the mercury catalyst can cause serious pollution damage to the environment and people, so that the research and development of a mercury-free catalyst for replacing a mercury-containing catalyst are imperative.

The research and development of the metal mercury-free catalyst mainly comprise noble metals such as Au, Pd and Ru and non-noble metals such as Bi, Sn and Cu. For example, patent CN106362741B takes the form of Au⁺CeO₂The initial activity and selectivity of the catalyst can reach 99 percent as an active component, but the cost of large-scale industrialization of the noble metal catalyst is too high. In patent CN108187721A, silkworm cocoon shells are used as precursors, and a series of treatments such as carbonization and activation can be performed to obtain N-doped metal-free catalysts, but the disadvantages are also obvious, and the directly prepared N-doped activated carbon has low activity and unstable raw material source as an acetylene hydrochlorination catalyst, and is difficult to realize industrialization and meet the requirements of catalyst industrialization.

Based on the above problems, research and development of a carrier for high-quality acetylene hydrochlorination and improvement of the synergistic effect between the carrier and a non-noble metal are also one of important directions for solving the problem that active components of the catalyst are easy to run off.

Disclosure of Invention

The invention provides an acetylene hydrochlorination catalyst of N-P modified activated carbon and a preparation method thereof, aiming at the problems in the prior art, N, P is added for modification mainly in the process of preparing wood activated carbon, and the catalyst is prepared by carrying N element and Cu metal salt for the second time after activation molding, so that the activity and the stability of the catalyst are improved.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the invention provides a preparation method of a catalyst, which comprises the following steps:

(1) pretreatment: crushing activated carbon, sieving, soaking in acid solution or alkali solution, and filtering;

(2) treating the phosphorus-containing solution: dipping the pretreated active carbon in a phosphorus-containing solution for soaking and then drying;

(3) treating the nitrogen-containing solution: dipping the activated carbon treated by the phosphorus-containing solution into a nitrogen-containing solution for soaking and then drying;

(4) and (3) clearing heat: carbonizing the activated carbon treated by the nitrogenous solution in a nitrogen atmosphere, and roasting in a mixed gas atmosphere of steam and carbon dioxide to obtain activated carbon A;

(5) acid washing, purifying and drying the activated carbon to obtain activated carbon B;

(6) dipping the activated carbon B in the solution A, drying and roasting to obtain activated carbon C;

(7) immersing activated carbon C in CuCl₂Drying the solution to obtain the catalyst.

Further, the precursor of the activated carbon in the step (1) is wood chips or shells; after crushing, the mixture is sieved by a 20-mesh sieve.

Further, in the step (1), the acid solution is a sulfuric acid solution, and the alkali solution is hydrogen peroxide. The mass fraction of the sulfuric acid solution is 5-10%

Further, the soaking time in the step (1) is 16 h.

Further, the soaking time in the step (2) and the soaking time in the step (3) are both 5-10 h.

Further, the drying temperature in the steps (2) - (7) is 120 ℃.

Further, the phosphorus-containing solution in the step (3) comprises one or more of phosphoric acid, ammonium phosphate and ammonium polyphosphate, the concentration of a phosphorus source in the phosphorus-containing solution is 1-3mol/L, and the activated carbon is immersed in excess during soaking. And (4) the nitrogen-containing solution in the step (4) comprises one or more of urea, melamine and ethylenediamine, the concentration of a nitrogen source in the nitrogen-containing solution is 1-3.5mol/L, and the activated carbon is excessively immersed during soaking.

Further, in the step (4), the carbonization temperature is 500-; the roasting temperature is 700-800 ℃, and the roasting time is 1-3 h.

Further, the solution A in the step (6) is a mixed solution of urea and PVP, or a mixed solution of melamine and PVP. Preferably, the concentration of the urea is 0.5mol/L, the concentration of the PVP is 1mol/L and the concentration of the melamine is 0.5mol/L (this concentration is the concentration in the mixed solution).

Further, the roasting temperature in the step (6) is 300-400 ℃, and the time is 3-10 h.

Further, the impregnation in the step (7) adopts an isovolumetric impregnation method, CuCl₂The content of the catalyst accounts for 8 to 15 percent of the mass of the catalyst.

The invention also provides the catalyst prepared by the preparation method.

The invention also provides the catalyst prepared by the preparation method or the application of the catalyst in acetylene hydrochlorination.

The technical effects obtained by the invention are as follows:

the invention provides an N, P modified acetylene hydrochlorination metal-free catalyst, which is obtained by treating a pore-enlarging agent solution to obtain a catalyst with the specific surface area of 900-1500m²Activated carbon with the average pore diameter of 1.3-15nm, developed gaps, uniform and stable pores and high-quality carrier; the P-containing solution is modified to obtain the activated carbon with the P content of 2-5%, and the N-containing solution is modified to obtain the activated carbon with the N content of 2-5%, so that the stability of a metal or nonmetal load can be greatly improved.

Detailed Description

It should be noted that the raw materials used in the present invention are all common commercial products, and thus the sources thereof are not particularly limited.

Example 1:

firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in sulfuric acid with the mass concentration of 5% for 16 hours, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 3mol/L phosphoric acid solution for 5 hours, filtering and drying at 120 ℃ to obtain activated carbon treated by phosphorus-containing solution, immersing the activated carbon treated by phosphorus-containing solution in 1.2mol/L ethylenediamine solution for 7 hours, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, putting the activated carbon treated by nitrogen-containing solution into N₂Charring at 500 deg.C for 2 hr, activating at 800 deg.C for 3 hr in mixed gas atmosphere of water vapor and carbon dioxideObtaining active carbon A; washing and purifying the activated carbon A by using hydrochloric acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of a mixed solution of 0.5mol/L urea and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, drying at 120 ℃, and roasting at 300 ℃ for 3 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 2.03 percent, the content of the activated carbon P is detected to be 4.80 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume space velocity is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 94.1% and vinyl chloride selectivity greater than 98.5%.

Example 2

Firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in 7% sulfuric acid by mass concentration for 16 hours, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 2mol/L phosphoric acid solution for 10 hours, filtering and drying at 120 ℃ to obtain activated carbon treated by phosphorus-containing solution, immersing the activated carbon treated by phosphorus-containing solution in 1.2mol/L ethylenediamine solution for 5 hours, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, putting the activated carbon treated by nitrogen-containing solution into N₂Carbonizing at 500 ℃ for 2h in the atmosphere, and then activating at 800 ℃ for 3h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A by using hydrochloric acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of a mixed solution of 0.5mol/L urea and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, drying at 120 ℃, and roasting at 300 ℃ for 3 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 2.05 percent, the content of the activated carbon P is detected to be 3.7 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume airspeed is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 94.7% and vinyl chloride selectivity greater than 98.5%.

Example 3

Firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in 10% sulfuric acid by mass concentration for 16h, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 1mol/L phosphoric acid solution for 7h, filtering and drying at 120 ℃ to obtain activated carbon treated by phosphorus-containing solution, immersing the activated carbon treated by phosphorus-containing solution in 1.2mol/L ethylenediamine solution for 10h, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, putting the activated carbon treated by nitrogen-containing solution into N₂Carbonizing at 500 ℃ for 2h in the atmosphere, and then activating at 800 ℃ for 3h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A with sulfamic acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of a mixed solution of 0.5mol/L urea and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, drying at 120 ℃, and roasting at 300 ℃ for 3 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 2.05 percent, the content of the activated carbon P is detected to be 2.1 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume airspeed is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 93.5% and vinyl chloride selectivity of greater than 98.5%.

Example 4

Firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in sulfuric acid with the mass concentration of 5% for 16 hours, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in a 1mol/L phosphoric acid solution for 5 hours, filtering and drying at 120 ℃ to obtain activated carbon treated by a phosphorus-containing solution, immersing the activated carbon treated by the phosphorus-containing solution in a 2.5mol/L ethylenediamine solution for 10 hours, filtering and drying at 120 ℃ to obtain activated carbon treated by a nitrogen-containing solution, and mixing the activated carbon with water to obtain the activated carbonPutting activated carbon treated by nitrogenous solution into N₂Carbonizing at 550 ℃ for 4h in the atmosphere, and then activating at 700 ℃ for 2h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A by using hydrochloric acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of a mixed solution of 0.5mol/L urea and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, drying at 120 ℃, and roasting at 300 ℃ for 3 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 3.30 percent, the content of the activated carbon P is detected to be 2.18 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume airspeed is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 94.9% and vinyl chloride selectivity of greater than 98.5%.

Example 5

Firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in 5% hydrogen peroxide by mass concentration for 16h, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 1mol/L phosphoric acid solution for 5h, filtering and drying at 120 ℃ to obtain activated carbon treated by phosphorus-containing solution, immersing the activated carbon treated by phosphorus-containing solution in 3.2mol/L ethylenediamine solution for 10h, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, putting the activated carbon treated by nitrogen-containing solution into N₂Carbonizing at 600 ℃ for 2h in the atmosphere, and then activating at 800 ℃ for 1 h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A by using hydrochloric acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of a mixed solution of 0.5mol/L urea and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, drying at 120 ℃, and roasting at 300 ℃ for 10 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 4.79 percent, the content of the activated carbon P is detected to be 2.18 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume space velocity is 35h^-1The feed gas C₂H₂1:1, with an initial acetylene conversion of 95.1% and a vinyl chloride selectivity of greater than 98.5%.

Example 6

Firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in 7% hydrogen peroxide by mass concentration for 16h, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 1mol/L ammonium phosphate solution for 5h, filtering and drying at 120 ℃ to obtain activated carbon treated by phosphorus-containing solution, immersing the activated carbon treated by phosphorus-containing solution in 3.2mol/L ethylenediamine solution for 10h, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, putting the activated carbon treated by nitrogen-containing solution into N₂Carbonizing at 600 ℃ for 2h in the atmosphere, and then activating at 800 ℃ for 1 h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A by using hydrochloric acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of a mixed solution of 0.5mol/L urea and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, drying at 120 ℃, and roasting at 300 ℃ for 10 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 4.90 percent, the content of the activated carbon P is detected to be 2.05 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume airspeed is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 94.5% and vinyl chloride selectivity greater than 98.5%.

Example 7

Firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in hydrogen peroxide with the mass concentration of 10% for 16 hours, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 1.5mol/L ammonium polyphosphate solution for 5 hours, filtering and drying at 120 ℃ to obtain phosphorus-containing solutionImmersing the activated carbon treated by the phosphorus-containing solution in 2.5mol/L melamine solution for 10h, filtering and drying at 120 ℃ to obtain the activated carbon treated by the nitrogen-containing solution, and putting the activated carbon treated by the nitrogen-containing solution into N₂Carbonizing at 600 ℃ for 2h in the atmosphere, and then activating at 800 ℃ for 1 h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A by using hydrochloric acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of a mixed solution of 0.5mol/L urea and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, drying at 120 ℃, and roasting at 300 ℃ for 10 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 4.50 percent, the content of the activated carbon P is detected to be 2.68 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume space velocity is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 96.3% and vinyl chloride selectivity of greater than 98.5%.

Example 8

Firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in 7% hydrogen peroxide solution for 16h, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 2.5mol/L ammonium polyphosphate solution for 7h, filtering and drying at 120 ℃ to obtain activated carbon treated by phosphorus-containing solution, immersing the activated carbon treated by phosphorus-containing solution in 1mol/L urea solution for soaking for 10h, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, and putting the activated carbon treated by nitrogen-containing solution into N₂Carbonizing at 600 ℃ for 4h in the atmosphere, and then activating at 800 ℃ for 2h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A with benzenesulfonic acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of 0.5mol/L urea and 1mol/LPVP mixed solution, soaking the activated carbon B in the mixed solution for 6h, filtering, drying at 120 ℃, and roasting at 300 ℃ for 10h to obtain acetylene hydrochlorideActivated carbon C for non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 2.46 percent, the content of the activated carbon P is detected to be 3.97 percent, the catalyst is evaluated at the temperature of 180 ℃ and the volume space velocity of 35h^-1The feed gas C₂H₂1:1, with an initial acetylene conversion of 95.8% and a vinyl chloride selectivity of greater than 98.5%.

Example 9

Firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in 5% hydrogen peroxide by mass concentration for 16h, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 2mol/L ammonium phosphate solution for 5h, filtering and drying at 120 ℃ to obtain activated carbon treated by phosphorus-containing solution, immersing the activated carbon treated by the phosphorus-containing solution in 1.5mol/L urea solution for 10h, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, putting the activated carbon treated by the nitrogen-containing solution into N2 atmosphere for carbonization at 500 ℃ for 6h, and activating at 800 ℃ for 1 h in mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A with benzenesulfonic acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of a mixed solution of 0.5mol/L urea and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, filtering, drying at 120 ℃, and roasting at 400 ℃ for 3 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 2.88 percent, the content of the activated carbon P is detected to be 3.12 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume space velocity is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 93.8% and vinyl chloride selectivity of greater than 98.5%.

Example 10:

firstly, 130g of crushed and screened sawdust is weighed, and the mass concentration is 5%Soaking the active carbon in hydrogen peroxide for 16h, filtering, washing and drying to obtain pretreated active carbon, immersing the pretreated active carbon in 2mol/L ammonium phosphate solution for 5h, filtering and drying at 120 ℃ to obtain active carbon treated by phosphorus-containing solution, immersing the active carbon treated by phosphorus-containing solution in 1.5mol/L urea solution for soaking for 10h, filtering and drying at 120 ℃ to obtain active carbon treated by nitrogen-containing solution, and putting the active carbon treated by nitrogen-containing solution into N₂Carbonizing at 600 ℃ for 4h in the atmosphere, and then activating at 700 ℃ for 3h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A with benzenesulfonic acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of mixed solution of 0.5mol/L melamine and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, filtering, drying at 120 ℃, and roasting at 400 ℃ for 3 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 2.96 percent, the content of the activated carbon P is detected to be 3.18 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume airspeed is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 94.2% and vinyl chloride selectivity greater than 98.5%.

Example 11:

firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in 5% hydrogen peroxide by mass concentration for 16h, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 2mol/L ammonium phosphate solution for 5h, filtering and drying at 120 ℃ to obtain activated carbon treated by phosphorus-containing solution, immersing the activated carbon treated by phosphorus-containing solution in 1.5mol/L urea solution for 10h, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, putting the activated carbon treated by nitrogen-containing solution into N₂Carbonizing at 600 ℃ for 4h in the atmosphere, and then activating at 700 ℃ for 3h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; using 5 percent of benzene sulfonic acid as the active carbon A by mass fractionAcid washing, purifying and drying to obtain activated carbon B; preparing 200ml of mixed solution of 0.5mol/L melamine and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, filtering, drying at 120 ℃, and roasting at 400 ℃ for 5 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 2.7g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 2.82 percent, the content of the activated carbon P is detected to be 3.07 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume space velocity is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 96.8% and vinyl chloride selectivity of greater than 98.5%.

Example 12:

firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in 5% hydrogen peroxide by mass concentration for 16h, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 2mol/L ammonium phosphate solution for 5h, filtering and drying at 120 ℃ to obtain activated carbon treated by phosphorus-containing solution, immersing the activated carbon treated by phosphorus-containing solution in 1.5mol/L urea solution for 10h, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, putting the activated carbon treated by nitrogen-containing solution into N₂Carbonizing at 600 ℃ for 2h in the atmosphere, and then activating at 700 ℃ for 3h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A with benzenesulfonic acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of mixed solution of 0.5mol/L melamine and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, filtering, drying at 120 ℃, and roasting at 400 ℃ for 10 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 3.5g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 2.85 percent, the content of the activated carbon P is detected to be 3.15 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume airspeed is 35h^-1The feed gas C₂H₂:HCl＝1:1, initial acetylene conversion 98.2%, vinyl chloride selectivity greater than 98.5%.

Comparative example 1:

firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in sulfuric acid with the mass concentration of 5% for 16 hours, filtering, washing and drying, immersing pretreated activated carbon in 1.2mol/L ethylenediamine solution for 7 hours, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, putting the activated carbon treated by the nitrogen-containing solution into N₂Carbonizing at 500 ℃ for 2h in the atmosphere, and then activating at 800 ℃ for 3h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A by using hydrochloric acid with the mass fraction of 5%, and drying to obtain activated carbon B; preparing 200ml of a mixed solution of 0.5mol/L urea and 1mol/LPVP, soaking the activated carbon B in the mixed solution for 6 hours, drying at 120 ℃, and roasting at 300 ℃ for 3 hours to obtain activated carbon C for the acetylene hydrochlorination non-noble metal catalyst; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon C, putting into the copper chloride solution for soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 2.05 percent, the content of the activated carbon P is detected to be 0.05 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume airspeed is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 68.5% and vinyl chloride selectivity greater than 98.5%.

Comparative example 2:

firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in sulfuric acid with the mass concentration of 7% for 16 hours, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 2mol/L phosphoric acid solution for 10 hours, filtering the activated carbon at 120 ℃ and drying to obtain activated carbon treated by phosphorus-containing solution, and putting the activated carbon treated by the phosphorus-containing solution into N₂Carbonizing at 500 ℃ for 2h in the atmosphere, and then activating at 800 ℃ for 3h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A by using hydrochloric acid with the mass fraction of 5%, and drying to obtain activated carbon B; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of active carbon B, and putting into chlorinationDipping in copper solution, and drying at 120 ℃ to obtain the catalyst finished product.

The content of the activated carbon CN is detected to be 0.05 percent, the content of the activated carbon P is detected to be 3.65 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume airspeed is 35h^-1The feed gas C₂H₂HCl 1:1, with an initial acetylene conversion of 66.3% and vinyl chloride selectivity greater than 98.5%.

Comparative example 3:

firstly, weighing 130g of crushed and screened sawdust, soaking the sawdust in 10% sulfuric acid by mass concentration for 16h, filtering, washing and drying to obtain pretreated activated carbon, immersing the pretreated activated carbon in 1mol/L phosphoric acid solution for 7h, filtering and drying at 120 ℃ to obtain activated carbon treated by phosphorus-containing solution, immersing the activated carbon treated by phosphorus-containing solution in 1.2mol/L ethylenediamine solution for 10h, filtering and drying at 120 ℃ to obtain activated carbon treated by nitrogen-containing solution, putting the activated carbon treated by nitrogen-containing solution into N₂Carbonizing at 500 ℃ for 2h in the atmosphere, and then activating at 800 ℃ for 3h in the mixed gas atmosphere of water vapor and carbon dioxide to obtain activated carbon A; washing and purifying the activated carbon A with sulfamic acid with the mass fraction of 5%, and drying to obtain activated carbon B; weighing 1.8g of copper chloride, dissolving in 20g of deionized water, stirring and dissolving, taking 20g of activated carbon B, putting into the copper chloride solution, soaking, and drying at 120 ℃ to obtain a catalyst finished product.

The content of the activated carbon CN is detected to be 1.75 percent, the content of the activated carbon P is detected to be 2.2 percent, the evaluation of the catalyst is that the temperature is 180 ℃, the volume space velocity is 35h^-1The feed gas C₂H₂1:1, with an initial acetylene conversion of 81.6% and a vinyl chloride selectivity of greater than 98.5%.

Comparative example 4:

TABLE 1 comparison of catalyst Performance between examples 1-3 and comparative examples 1-3

Detecting items

Example 1

Example 2

Example 3

Comparative example 1

Comparative example 2

Comparative example 3

Vinyl chloride selectivity (%)

≥98.5

≥98.5

≥98.5

≥98.5

≥98.5

≥98.5

Acetylene conversion (%)

94.1

94.7

93.5

68.5

66.3

81.6

The following conclusions can be drawn by comparing examples 1 to 3 with comparative examples 1 to 3:

comparison of example 1 with comparative example 1 yields: the activity of the prepared catalyst for hydrochlorination of acetylene is obviously lower than that of a catalyst prepared from N, P modified activated carbon without P modification of the activated carbon;

example 2 and comparative example 2 comparison gave: the activity of the prepared catalyst for hydrochlorination of acetylene is obviously lower than that of the catalyst prepared from N, P modified activated carbon after the activated carbon is modified by N;

example 3 and comparative example 3 comparison gave: the activity of the prepared catalyst acetylene hydrochlorination reaction is improved by N, P modification compared with that of the catalyst in comparative examples 1 and 2, but the catalyst in comparative example 3 is obviously inferior to that of the catalyst in example 3 in the absence of activation doping reactivation of PVP and urea or PVP and melamine;

the technical scheme of the invention is not limited to the technical means disclosed by the technical means, and also comprises the technical scheme formed by any combination of the technical features. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.

Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.