CN111203281A - Regeneration method of acetylene hydrochlorination non-mercury catalyst - Google Patents

Regeneration method of acetylene hydrochlorination non-mercury catalyst Download PDF

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CN111203281A
CN111203281A CN202010126027.0A CN202010126027A CN111203281A CN 111203281 A CN111203281 A CN 111203281A CN 202010126027 A CN202010126027 A CN 202010126027A CN 111203281 A CN111203281 A CN 111203281A
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catalyst
treatment
mercury catalyst
mercury
regenerated
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赵佳
岳玉学
王柏林
李小年
张群峰
郭伶伶
王赛赛
朱文锐
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Zhejiang University of Technology ZJUT
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    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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Abstract

The invention discloses a regeneration method of a non-mercury catalyst for acetylene hydrochlorination, which comprises the following steps: 1) drying the inactivated non-mercury catalyst in air or inert gas atmosphere; 2) treating the non-mercury catalyst obtained in the step 1) by gamma ray irradiation or arc discharge or microwave or laser or plasma to decompose carbon deposition components in the catalyst into gas products; 3) carrying out oxidation treatment on the non-mercury catalyst obtained in the step 2) to oxidize the reduced active components in the catalyst into an oxidation state with catalytic activity; 4) washing and vacuum drying the non-mercury catalyst obtained in the step 3) to obtain a regenerated non-mercury catalyst. The catalyst regeneration method realizes the regeneration of the catalyst through simple operation steps, prolongs the service life of the catalyst, reduces the production cost and has good application prospect.

Description

Regeneration method of acetylene hydrochlorination non-mercury catalyst
(I) technical field
The invention relates to a regeneration method of a mercury-free catalyst for acetylene hydrochlorination.
(II) background of the invention
Polyvinyl chloride (PVC) is the third most common plastic, generally obtained by polymerization of its monomer vinyl chloride. Because of the characteristics of rich coal, poor oil and less gas in China, the preparation of vinyl chloride by a coal-based calcium carbide method (acetylene hydrochlorination method) is the mainstream process for producing polyvinyl chloride in China. The catalyst used for synthesizing chloroethylene in the prior art is mercuric chloride and mercury-free chloride taking metal chloride as an active component. Since mercury chloride causes serious pollution to the environment and the application of polyvinyl chloride is limited by the small amount of mercury in the polyvinyl chloride synthesized by the mercury chloride, research is gradually focused on mercury-free chlorides using metal chlorides as active components, wherein the noble metal chlorides show the best catalytic activity, such as gold (ACS catalysis.2018,8,8493-8505; Journal of catalysis.2018,365, 153-162; Journal of catalysis.2017,350,149-158), palladium (Petroleum Science and technology.2010,28, 1825) 1833), ruthenium (RSC Advances.2013,3,21062; Applied Catalysis B: environmental analysis.2016, 189, 56-64), copper (RSC Advances.2014,4,7766; Advances.RSC, 5,38159) and other metals as active components are reported to have higher catalytic activity than mercury. However, these non-mercury catalysts can cause problems such as reduction of active components and carbon deposition during the use process, which leads to the reduction and even deactivation of the catalyst activity and affects the catalyst life. Therefore, the regeneration treatment of the deactivated catalyst can recover the activity to a certain extent, prolong the service life of the catalyst, and is especially important for the industrial application of the non-mercury catalyst.
For the regeneration problem of non-mercury catalyst, many different improvements have appeared in the prior art, for example, chinese patent (CN 106582895 a) and chinese patent (CN 106732827 a) disclose a method for regenerating acetylene hydrochlorination noble metal non-mercury catalyst, which mainly utilizes the regeneration reagents of bromine water, sodium thiosulfate, potassium thiocyanate, thiourea, and mixed acid of hypochlorous acid, chloric acid, perchloric acid, hydrogen peroxide and hydrochloric acid, formic acid, acetic acid, tartaric acid, etc. to perform soaking treatment, so as to recover the catalyst performance. However, the above regeneration method can only reoxidize the reduced active component into an oxidation state having high activity, and the problem of carbon deposition of the catalyst cannot be solved well. Carbon deposition of the catalyst is one of the main reasons for catalyst deactivation, and in addition, carbon deposition covered on the surface of the active component can cause that an oxidation regeneration reagent cannot be in full contact with the active component, the treatment effect of the regeneration reagent is poor, and the deactivated catalyst cannot be well regenerated.
Disclosure of the invention
The invention aims to solve the problem of regeneration of a non-mercury catalyst in the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene, and provides a regeneration method of the non-mercury catalyst.
In order to achieve the above object, the present invention provides the following technical solutions:
a regeneration method of acetylene hydrochlorination non-mercury catalyst, wherein the acetylene hydrochlorination non-mercury catalyst comprises a metal precursor and a carrier, the metal precursor is one or more of gold, palladium, ruthenium and copper precursors, the carrier is a porous solid carrier, and the regeneration method comprises the following steps:
1) drying the inactivated non-mercury catalyst in air or inert gas atmosphere;
2) treating the non-mercury catalyst obtained in the step 1) by gamma ray irradiation or arc discharge or microwave or laser or plasma to decompose carbon deposition components in the catalyst into gas products, and blowing inert gas to remove the gas products when the gamma ray irradiation or microwave or laser treatment is adopted;
3) carrying out oxidation treatment on the non-mercury catalyst obtained in the step 2) to oxidize the reduced active components in the catalyst into an oxidation state with catalytic activity;
4) washing and vacuum drying the non-mercury catalyst obtained in the step 3) to obtain a regenerated non-mercury catalyst.
The invention decomposes organic matters and destroys molecular structure by gamma ray, thermal effect of arc discharge, thermal effect of high energy density, thermal effect of microwave, laser ray, plasma and physical and chemical action of carbon deposit, which decomposes carbon deposit component in inactivated non-mercury catalyst into small molecule gas product and removes it, which does not affect catalytic action of active site, then uses oxidant to reoxidize treated catalyst, which recovers catalytic performance of non-mercury catalyst obviously, realizes regeneration of catalyst, prolongs service life of catalyst obviously, and reduces unit consumption of catalyst.
The non-mercury catalyst comprises a metal precursor and a carrier; the metal precursor is selected from one or more of gold, palladium, ruthenium and copper precursors; the carrier is a porous solid carrier.
Preferably, the metal precursor is selected from one or more of halogen-containing metal salt, nitrogen-containing metal salt, sulfur-containing metal salt, phosphorus-containing metal salt, carboxylate and selenium-containing metal salt. Wherein, the halogen-containing metal salt can be one or more of metal chloride salt, bromine salt, iodine salt, chlorate, hypochlorite and perchlorate. The nitrogen-containing metal salt can be one or more of nitrate, ammonium salt, cyanide salt and thiocyanate. The sulfur-containing metal salt can be one or more of sulfate, metal sulfide salt, thiocyanate, thiosulfate and sulfite. The phosphorus-containing metal salt can be one or more of phosphate, monohydrogen phosphate, dihydrogen phosphate, hypophosphite and pyrophosphate. The carboxylate can be one or two of formate and acetate. The selenium-containing metal salt can be one or two of selenate and selenite.
Preferably, the porous solid carrier is selected from one or more of activated carbon, mesoporous carbon, carbon nanotubes, graphene, silicon dioxide, aluminum oxide, titanium dioxide, molecular sieves, metal organic framework compounds and covalent organic framework compounds. The activated carbon can be columnar carbon or spherical carbon activated carbon, and the particle size is 10-100 meshes. The carbon nano tube can be processed into a columnar shape or a spherical shape, and the particle size is 10-100 meshes. The graphene can be processed into a columnar shape or a spherical shape, and the particle size is 10-100 meshes. The alumina can be gamma-Al2O3The metal organic framework compound can be MOFs constructed by nitrogen-containing heterocyclic ligands and MOFs constructed by organic carboxylic acid ligands, and the covalent organic framework compound can be boron-containing COFs materials, imine COFs materials or triazine COFs materials.
Preferably, in the metal catalyst, the mass ratio of the active component to the carrier is 0.01-50: 1.
The non-mercury catalyst can further comprise an auxiliary agent, wherein the auxiliary agent is one or more of metal salt or ionic liquid.
Preferably, the metal salt is MX, wherein M represents a cation selected from one of Pt, Al, In, Bi, Fe, Mn, Ba and Ca; x represents an anion selected from SO4 2-、NO3 -、Cl-、I-、Br-、ClO4 -、PO4 3-、SO3 2-、NO2 -、ClO3 -One kind of (1).
Preferably, the ionic liquid is selected from at least one of the following ionic liquids:
a) the cation of the imidazole ionic liquid is dialkyl-substituted imidazole cation or trialkyl-substituted imidazole cation, the alkyl is respectively and independently selected from C1-C16 alkyl, and the anion of the imidazole ionic liquid is halogen ion, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogen sulfate, perchlorate, dinitrile amine radical, acetate, trifluoroacetate, phosphate radical or dihydrogen phosphate radical;
b) quaternary phosphonium ionic liquids, specifically tributylethylphosphonium bromide, tributylethylphosphonium chloride, tributylhexylphosphonium bromide, tributylhexylphosphonium chloride, tributylhexylphosphonium bis (trifluoromethanesulfonyl) imide salt, tributylethylphosphonium bis (trifluoromethanesulfonyl) imide salt, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium chloride, tetraphenylphosphonium bromide or tetraphenylphosphonium chloride;
c) the quaternary ammonium ionic liquid is trialkyl methyl ammonium (trifluoromethanesulfonyl) imide salt or trialkyl methyl ammonium chloride, wherein the alkyl is C1-C16 independently;
d) pyrrolidine ionic liquid, in particular N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt or N-butyl-N-methylpyrrolidine bromide salt;
e) pyrrolidone ionic liquid, specifically N-methyl pyrrolidone hydrochloride, N-hydroxy pyrrolidone bis (trifluoromethanesulfonyl) imide salt or N-butyl-N-methyl pyrrolidone bromide salt;
f) piperidine ionic liquid, in particular N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt or N-butyl-N-methylpiperidine bromide salt;
g) pyridine ionic liquid, in particular to N-ethylpyridine bromide salt, N-butylpyridine bis (trifluoromethanesulfonyl) imide salt or N-butylhexafluorophosphate.
Preferably, in the metal catalyst containing the auxiliary agent, the mass ratio of the active component, the auxiliary agent and the carrier is 0.01-50: 0.1-10: 1.
In steps 1) and 2) of the present invention, the inert gas is preferably one or a combination of nitrogen, argon and helium. In the step 1), the drying temperature is between room temperature and 200 ℃, and the treatment time is 0.5 to 2 hours.
In step 2) of the present invention, the γ -ray treatment conditions are preferably: the gamma ray irradiation source is60Co rays and137one of the Cs rays, the gamma ray irradiation intensity is 2.7-60 kGy/h, and the gamma ray irradiation time is 1-20 h.
In step 2) of the present invention, the arc discharge treatment conditions are preferably: the discharge field is an arc chamber, the discharge area is an arc column area, the buffer gas for arc discharge is hydrogen and helium, and the pressure ratio of the hydrogen to the helium is 1-10: 1; the discharge mode is direct current arc discharge; the discharge voltage is 40-70V; the discharge current is 60-120A; the discharge time is 10-30 min.
In step 2) of the present invention, the microwave treatment conditions are preferably: the microwave frequency is 915-2450 MHz; the microwave power is 0.5-1 kW; the microwave irradiation time is 1-30 min.
In step 2) of the present invention, the laser processing conditions are preferably: with CO2Carrying out laser irradiation treatment by a laser; the laser irradiation power is 50-400W; the laser irradiation speed is 10-30 mm/s; the laser irradiation time is 10-120 s.
In the step 2), the plasma is formed by forming an electric field between two plates and introducing working gas under a vacuum condition, the gas is thinner and thinner along with the increase of the vacuum degree, the molecular distance and the free movement distance of molecules or ions are longer and longer, the gas and the working gas collide with each other under the action of the electric field to form the plasma, the vacuum degree generated by the plasma is 50-1000Pa, the working gas of the plasma is one or a mixture of argon, nitrogen, oxygen, hydrogen and carbon tetrafluoride, the voltage between the plates is 200-5000V, and the distance between the plates is 6-10 mm. Preferably, in the step 2), the plasma treatment time is 10-120 min.
In step 3) of the present invention, the oxidizing agent may be selected according to an active component in the non-mercury catalyst, and the oxidizing conditions may also be set according to the selection of the oxidizing agent.
Preferably, the oxidant is one or more of hydrogen peroxide, hydrochloric acid, nitric acid, potassium thiocyanate, thiourea, hypochlorous acid, chloric acid, perchloric acid, chlorine gas and hydrogen chloride gas.
As a further preference, the specific operation of step 3) is: and the oxidant is chlorine or hydrogen chloride gas, and the chlorine or hydrogen chloride gas is passed through a reactor filled with a non-mercury catalyst, so that the treatment temperature of the chlorine or hydrogen chloride gas is between room temperature and 200 ℃, and the treatment time is 2-30 h.
As a further preference, the specific operation of step 3) is: and (3) placing the non-mercury catalyst in an oxidant aqueous solution, controlling the treatment temperature to be between room temperature and 200 ℃, treating for 2-30 h, and washing with water until the filtrate is neutral to obtain the oxidized non-mercury catalyst. The oxidant aqueous solution is at least one selected from hydrogen peroxide with the concentration of 20-50%, hydrochloric acid with the concentration of 31-38%, nitric acid with the concentration of 65-68%, potassium thiocyanate aqueous solution with the concentration of 10-50%, thiourea aqueous solution with the concentration of 0.2-0.3%, hypochlorous acid aqueous solution with the concentration of 45-48%, chloric acid with the concentration of 30-39% and perchloric acid with the concentration of 70-72%. In actual operation, the aqueous oxidant solution is used in an amount to immerse the catalyst.
In the oxidation treatment process in the step 3), if ultrasound is used for assistance, the treatment time can be shortened, and the oxidation treatment effect can be further improved. Preferably, the ultrasonic power is: 0.5-10 kW.
In the step 4), the washing solvent adopted for washing is preferably deionized water, and the washing treatment temperature is room temperature to 90 ℃. The vacuum drying conditions are preferably as follows: the vacuum degree is 100-100000 Pa, the processing temperature is 100-160 ℃, and the processing time is 10-24 h.
Furthermore, the inventors have unexpectedly found that, for the regeneration of the acetylene hydrochlorination non-mercury catalyst, if the pretreatment with a carbon elimination agent is carried out before the treatment in step 2), the regeneration effect of the catalyst can be further improved. Therefore, the regeneration method of the acetylene hydrochlorination non-mercury catalyst preferably further comprises the following steps a) and b):
a) adding a carbon removing agent into the non-mercury catalyst obtained in the step 1) for treatment, and carrying out subsequent step 2) treatment on the treated catalyst; the carbon eliminating agent is selected from at least one of the following simple substances, oxides, chlorides and hydroxides of metals: K. rb, Sr, Ba, Nd, Hf, Pr, or the carbon eliminating agent is selected from one or the combination of any of the following components: toluene, xylene, ethanol, carbon disulfide; when the carbon removing agent is a solid, the carbon removing agent is added in the form of solution, wherein the solvent is water, hydrochloric acid solution or aqua regia;
b) washing the catalyst obtained in the step 2), removing the carbon removing agent, drying, removing the washing solvent, and carrying out the subsequent step 3) treatment on the treated catalyst.
As a further preference, the specific operations of step a) are: placing the non-mercury catalyst obtained in the step 1) in a carbon removing agent or a carbon removing agent solution, and controlling the treatment temperature to be between room temperature and 150 ℃ and the time to be 0.5 to 24 hours (more preferably 1 to 10 hours). Preferably, the concentration of the carbon removing agent in the carbon removing agent solution is 1-20 wt%.
In the step b), the washing solvent is preferably one or a mixture of deionized water, methanol, ethanol, hydrochloric acid, nitric acid and sulfuric acid, and the washing treatment temperature is between room temperature and 90 ℃. After washing, the drying conditions of the catalyst are preferably: the vacuum degree is 100-100000 Pa; the treatment temperature is 60-160 ℃; the treatment time is 10-24 h.
The invention particularly preferably relates to a regeneration method of the acetylene hydrochlorination non-mercury catalyst, which comprises the following steps:
1) drying the inactivated non-mercury catalyst in air or inert gas atmosphere;
a) adding a carbon removing agent into the non-mercury catalyst obtained in the step 1) for treatment;
2) treating the non-mercury catalyst obtained in the step a) by gamma ray irradiation or arc discharge or microwave or laser or plasma to decompose carbon deposition components in the catalyst into gas products, and blowing inert gas to remove the gas products when the gamma ray irradiation or microwave or laser treatment is adopted;
b) washing the catalyst obtained in the step 2) to remove the carbon removing agent, and then drying to remove the washing solvent;
3) carrying out ultrasonic auxiliary oxidation treatment on the non-mercury catalyst obtained in the step b) to oxidize the reduced active components in the catalyst into an oxidation state with catalytic activity;
4) washing and vacuum drying the non-mercury catalyst obtained in the step 3) to obtain a regenerated non-mercury catalyst.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the inactivated non-mercury catalyst is subjected to gamma ray irradiation or arc discharge or microwave or laser or plasma treatment, so that carbon deposition is removed, the active site of the carbon deposition is exposed again, the effect of subsequent oxidation treatment is obviously improved, and the metal utilization rate is improved; the gamma-ray irradiation or arc discharge or microwave or laser or plasma treatment and oxidation treatment are synergistic, so that the catalytic performance of the non-mercury catalyst is obviously recovered, and the regeneration of the catalyst is realized;
2. the oxidation treatment is assisted by ultrasound, so that the regeneration treatment effect can be further improved;
3. according to the invention, the carbon removing agent is used for treatment before the treatment in the step 2), so that carbon deposition on the surface of the catalyst can be effectively dissolved and removed, and the regeneration treatment effect is improved.
In conclusion, the catalyst regeneration method realizes the regeneration of the catalyst through simple operation steps, prolongs the service life of the catalyst, reduces the production cost and has good application prospect.
(IV) detailed description of the preferred embodiments
The invention is illustrated by the following specific examples. It should be noted that the examples are only intended to illustrate the invention further, but should not be construed as limiting the scope of the invention, which is in no way limited thereto. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.
Preparation of catalyst A: 10g of 1-butyl-3-methylimidazolium chloride ionic liquid is dissolved in 50ml of 0.01g/ml palladium (palladium nitrate) standard solution, 50ml of concentrated hydrochloric acid is added, the mixture is stirred and mixed uniformly, 100g of 20-mesh activated carbon is added, vacuum degassing is firstly carried out at 160 ℃ for 12 hours, and then drying is carried out in the air at 110 ℃ for 12 hours. The catalyst is filled on a fixed bed reaction device, and the space velocity of acetylene is 1480h-1And carrying out an acetylene hydrochlorination experiment at the reaction temperature of 160 ℃, wherein the activity of the catalyst is reduced to 51% after the operation for 150 hours. Taking out the catalyst for later use.
Preparation of catalyst B: 10g of tributylmethylammonium chloride ionic liquid is dissolved in 20ml of 0.025g/ml gold (gold trichloride) standard solution, 80ml of concentrated hydrochloric acid is added to be stirred and mixed uniformly, 100g of 20-mesh activated carbon is added, vacuum degassing is firstly carried out at 160 ℃ for 12h, and then drying is carried out in 110 ℃ air for 12 h. The catalyst is filled on a fixed bed reaction device, and the space velocity of acetylene is 1480h-1And carrying out an acetylene hydrochlorination experiment at the reaction temperature of 180 ℃, and reducing the activity of the catalyst to 55% after running for 300 h. Taking out the catalyst for later use.
Preparation of catalyst C: 50ml of 0.01g/ml ruthenium (ruthenium trichloride) standard solution is taken, 50ml of deionized water is added, the mixture is stirred and mixed evenly, 100g of 20-mesh activated carbon is added, vacuum degassing is firstly carried out at 160 ℃ for 12h, and then drying is carried out in the air at 110 ℃ for 12 h. The catalyst is filled on a fixed bed reaction device, and the acetylene airspeed is 360h-1And carrying out an acetylene hydrochlorination experiment at the reaction temperature of 90 ℃, and reducing the activity of the catalyst to 10% after running for 10 hours. Taking out the catalyst for later use.
Preparation of catalyst D: taking 10ml of 0.01g/ml ruthenium (ruthenium tribromide) standard solution, adding 90ml of concentrated hydrochloric acid, stirring and mixing uniformly, and adding 100g g-C3N4The support was first degassed at 160 ℃ in vacuo for 12h and then dried in air at 110 ℃ for 12 h. The catalyst is filled on a fixed bed reaction device, and the acetylene airspeed is 90h-1And carrying out an acetylene hydrochlorination experiment at the reaction temperature of 150 ℃, and reducing the activity of the catalyst to 30% after running for 30 h. Taking out the catalyst for later use.
Preparation of catalyst E: 50ml of 1g/ml copper (copper hypochlorite) standard solution is taken, 50ml of deionized water is added and mixed evenly, 100g of HY molecular sieve with the particle size of 40 meshes is added, vacuum degassing is carried out at 160 ℃ for 12 hours, and then drying is carried out in the air at 110 ℃ for 12 hours. The catalyst is filled on a fixed bed reaction device, and the acetylene space velocity is 120h-1And the reaction temperature is 280 ℃, an acetylene hydrochlorination experiment is carried out, the highest running activity is 75%, and the activity is reduced to 22% after 10 hours. Taking out the catalyst for later use.
Preparation of catalyst F: 20g of N-methylpyrrolidone hydrochloride ionic liquid is dissolved in 16ml of 1g/ml copper (copper sulfate) standard solution, 84ml of deionized water is added, stirring and mixing are carried out uniformly, 100g of 20-mesh activated carbon is added, vacuum degassing is carried out at 160 ℃ for 12h, and drying is carried out in air at 110 ℃ for 12 h. The catalyst is filled on a fixed bed reaction device, and the space velocity of acetylene is 740h-1And carrying out an acetylene hydrochlorination experiment at the reaction temperature of 180 ℃, and reducing the activity of the catalyst to 13% after running for 160 h. Taking out the catalyst for later use.
Preparation of catalyst G: 10g of tetrabutyl phosphonium chloride ionic liquid is dissolved in 10ml of 0.05g/ml ruthenium (ruthenium trichloride) standard solution, 80ml of concentrated hydrochloric acid is added and stirred uniformly, 100g of 20-mesh activated carbon is added, vacuum degassing is firstly carried out at 160 ℃ for 12h, and then drying is carried out in 110 ℃ air for 12 h. The catalyst is filled on a fixed bed reaction device, and the space velocity of acetylene is 1480h-1And carrying out an acetylene hydrochlorination experiment at the reaction temperature of 100 ℃, and reducing the activity of the catalyst to 52% after running for 100 h. Taking out the catalyst for later use.
Preparation of catalyst H: 10g of N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt ionic liquid is dissolved in 24ml of 1g/ml copper (copper phosphate) standard solution, 76ml of deionized water is added, the mixture is stirred and mixed evenly, 100g of 4A molecular sieve with the particle size of 20 meshes is added, vacuum degassing is firstly carried out at 160 ℃ for 12h, and then drying is carried out in the air at 110 ℃ for 12 h. The catalyst is filled in a fixed bed for reactionOn the device, the space velocity of acetylene is 180h-1And carrying out an acetylene hydrochlorination experiment at the reaction temperature of 200 ℃, and reducing the activity of the catalyst to 15% after running for 72 hours. Taking out the catalyst for later use.
Preparation of catalyst I: taking 30ml of 1g/ml copper (cupric bromide) standard solution, adding 70ml of concentrated hydrochloric acid, stirring and mixing uniformly, adding 100g of ZrO2The oxide support, having a particle size of 16 mesh, was first degassed under vacuum at 160 ℃ for 12h and then dried in air at 110 ℃ for 12 h. The catalyst is filled on a fixed bed reaction device, and the acetylene airspeed is 60h-1And carrying out an acetylene hydrochlorination experiment at the reaction temperature of 200 ℃, and reducing the activity of the catalyst to 10% after running for 20 h. Taking out the catalyst for later use.
Preparation of catalyst J: 8ml of a 1g/ml copper (copper sulfite) standard solution was taken, 10g (about 5.3ml) of phosphoric acid was added to a concentration of 1.874g/ml, 86.7ml of deionized water was added and stirred at 90 ℃ for 1 hour, and finally 100g of 20 mesh activated carbon was added, first degassed under vacuum at 160 ℃ for 12 hours and then dried in air at 110 ℃ for 12 hours. The dried catalyst J was taken out and activated at 550 ℃ for 2 hours in a nitrogen atmosphere. The catalyst is filled on a fixed bed reaction device, and the space velocity of acetylene is 180h-1And carrying out an acetylene hydrochlorination experiment at the reaction temperature of 180 ℃, and reducing the activity of the catalyst to 51% after running for 25 h. Taking out the catalyst for later use.
Preparation of catalyst K: 8ml of a 1g/ml copper (pyrophosphate) standard solution was taken, 20ml of a 0.83g/ml Cs standard solution was added, followed by 72ml of hydrochloric acid and stirring at 60 ℃ for 1 hour, and finally 100g of 20 mesh activated carbon was added, first vacuum-degassed at 160 ℃ for 12 hours and then dried in air at 110 ℃ for 12 hours. The catalyst is filled on a fixed bed reaction device, and the space velocity of acetylene is 180h-1And carrying out an acetylene hydrochlorination experiment at the reaction temperature of 200 ℃, and reducing the activity of the catalyst to 10% after running for 200 h. Taking out the catalyst for later use.
In the present invention, the catalyst activity is expressed in acetylene conversion (%).
Example 1
1) Weighing 10g of A deactivated catalyst, placing at the temperature of 110 ℃, purging in a nitrogen atmosphere for 2h, and then cooling to room temperature;
2) then adding 50ml of 5% potassium hydroxide aqueous solution, soaking at 60 ℃ for 3h, and taking out the catalyst;
3) subsequently with an intensity of 60kGy/h60Co rays are used for carrying out irradiation treatment on the catalyst for 2 hours, and nitrogen purging is carried out simultaneously;
4) then washing the catalyst by using deionized water with the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12h in a 10000Pa vacuum environment;
5) adding 25ml of 27.5 wt% hydrogen peroxide into the treated catalyst, and soaking for 12h under the ultrasonic condition;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a 10000Pa vacuum environment to obtain the regenerated catalyst.
Examples 2 to 6 and comparative examples 1 to 2
Referring to example 1, the specific conditions are shown in table 1, wherein the operation conditions of step 1) are the same as example 1, and thus are not repeated in table 1, and the conditions not listed in the table are the same as example 1.
Figure BDA0002394403030000071
Wherein, aqua regia is mixed acid of 35% hydrochloric acid and 65% nitric acid (the volume ratio of hydrochloric acid to nitric acid is 3: 1).
And carrying out acetylene hydrochlorination evaluation on the regenerated catalyst A on a fixed bed reactor device, wherein the catalyst evaluation process comprises the steps of adopting a fixed bed micro reactor for evaluation, heating and controlling the temperature by an electric heating furnace, filling 2g of catalyst, activating hydrogen chloride for 0.5h before reaction, introducing acetylene for reaction after activation, adopting a gas chromatograph of an FID detector for analysis, and sampling frequency times/0.5 h. The results are shown in Table 2.
TABLE 2
Figure BDA0002394403030000081
Note: the activity data in table 2 are percentage data, and for convenience of presentation, the percentage numbers are omitted from the table, and the table below is presented in the same manner.
Example 7
1) Weighing 10g of the B deactivated catalyst, placing at the temperature of 110 ℃, purging in a nitrogen atmosphere for 2h, and then cooling to room temperature;
2) then adding 50ml of toluene, soaking for 3 hours at the temperature of 45 ℃, and taking out the catalyst;
3) subsequently with an intensity of 60kGy/h137The Cs rays are used for carrying out irradiation treatment on the catalyst for 2 hours, and nitrogen purging is carried out simultaneously;
4) then, washing the catalyst by using methanol with the temperature of 45 ℃ until the washing liquid is neutral, and drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 8000 Pa;
5) adding 100ml of perchloric acid solution with the concentration of 70% into the treated catalyst, and soaking for 12 hours under the ultrasonic condition;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 8000Pa to obtain the regenerated catalyst.
Examples 8 to 12 and comparative examples 3 to 4
Referring to example 7, the specific conditions are shown in table 3, wherein the operation conditions in step 1) are the same as those in example 7, and thus are not repeated in table 3, and the conditions not listed in the table are the same as those in example 7.
The regenerated catalyst B was subjected to acetylene hydrochlorination evaluation on a fixed bed reactor set up according to the evaluation method for regenerated catalyst A, and the results are shown in Table 4.
Figure BDA0002394403030000101
TABLE 4
Figure BDA0002394403030000111
Example 13
1) Weighing 10g of C deactivation catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and cooling to room temperature;
2) then adding 50ml of ethanol, and soaking for 3 hours at the temperature of 45 ℃;
3) subsequently, with an intensity of 60kGy/h137Carrying out irradiation treatment on the catalyst obtained in the previous step for 2h by using a Cs ray, and simultaneously blowing by using nitrogen;
4) then washing the catalyst by using deionized water with the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12h in a vacuum environment of 120 Pa;
5) adding 40ml of mixed solution of 25% potassium thiocyanate and 0.2% thiourea into the treated catalyst, and soaking for 12h under ultrasonic conditions;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 120Pa to obtain the regenerated catalyst.
Acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up.
Examples 14 to 18 and comparative examples 5 to 6
Referring to example 13, the specific conditions are shown in table 5, wherein the operating conditions in step 1) are the same as in example 13, and thus are not repeated in table 5, and the conditions not listed in the table are the same as in example 13.
The above regenerated C catalyst was subjected to acetylene hydrochlorination evaluation on a fixed bed reactor set up according to the evaluation method of regenerated catalyst A, and the results are shown in Table 6.
Figure BDA0002394403030000121
TABLE 6
Figure BDA0002394403030000131
Examples 19 to 24 and comparative examples 7 to 8
The deactivated catalyst was treated correspondingly under the conditions of the deactivated catalyst a shown in examples 1 to 6 and comparative examples 1 to 2 to obtain a corresponding regenerated catalyst D, and the regenerated catalyst D was evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in table 7.
TABLE 7
Figure BDA0002394403030000132
Figure BDA0002394403030000141
Examples 25 to 30 and comparative examples 9 to 10
The deactivated catalyst E was treated correspondingly under the conditions of the deactivated catalyst A shown in examples 1 to 6 and comparative examples 1 to 2 to obtain a corresponding regenerated catalyst E, and the regenerated catalyst E was evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in Table 8.
TABLE 8
Figure BDA0002394403030000142
Figure BDA0002394403030000151
Examples 31 to 36 and comparative examples 11 to 12
The deactivated catalyst was treated correspondingly under the conditions of the deactivated catalyst a shown in examples 1 to 6 and comparative examples 1 to 2 to obtain a corresponding regenerated catalyst F, and the regenerated catalyst F was evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in table 9.
TABLE 9
Figure BDA0002394403030000152
Examples 37 to 42 and comparative examples 13 to 14
The G deactivated catalyst was treated correspondingly under the conditions of the a deactivated catalyst shown in examples 1 to 6 and comparative examples 1 to 2 to obtain a corresponding regenerated G catalyst, and the regenerated G catalyst was evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in table 10.
Watch 10
Figure BDA0002394403030000161
Examples 43 to 48 and comparative examples 15 to 16
The deactivated H catalyst was treated correspondingly under the conditions of the deactivated a catalyst shown in examples 1 to 6 and comparative examples 1 to 2 to obtain a corresponding regenerated H catalyst, and the regenerated H catalyst was evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in table 11.
TABLE 11
Figure BDA0002394403030000162
Figure BDA0002394403030000171
Examples 49 to 54 and comparative examples 17 to 18
The deactivated catalysts were treated correspondingly under the conditions of the deactivated catalysts B shown in examples 7 to 12 and comparative examples 3 to 4 to obtain corresponding regenerated catalysts I, and the regenerated catalysts I were evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in Table 12.
TABLE 12
Figure BDA0002394403030000172
Figure BDA0002394403030000181
Examples 55 to 60 and comparative examples 19 to 20
The J deactivated catalyst was treated correspondingly under the conditions of the B deactivated catalysts shown in examples 7 to 12 and comparative examples 3 to 4 to obtain a corresponding regenerated J catalyst, and the regenerated J catalyst was evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in table 13.
Watch 13
Figure BDA0002394403030000182
Figure BDA0002394403030000191
Examples 61 to 66 and comparative examples 21 to 22
The K-deactivated catalysts were treated correspondingly under the conditions of the C-deactivated catalysts shown in examples 13 to 18 and comparative examples 5 to 6 to obtain corresponding regenerated K-catalysts, and the regenerated K-catalysts were evaluated for the acetylene hydrochlorination reaction in a fixed bed reactor unit, and the results are shown in table 14.
TABLE 14
Figure BDA0002394403030000192
Example 67
1) Weighing 10g of A deactivated catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and then cooling to room temperature;
2) then adding 50ml of 5 wt% potassium hydroxide aqueous solution, and soaking for 3h at 60 ℃;
3) then, placing the catalyst in a discharge chamber filled with argon and hydrogen with the total pressure of 30kPa (the pressure ratio is 1:1), wherein the discharge area is an arc column area, the used discharge mode is direct current arc discharge, the discharge voltage is 40-50V, the discharge current is 60-70A, and the discharge treatment is carried out for 30 min;
4) then taking out the catalyst from the discharge chamber, washing the catalyst by using deionized water at the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12 hours in a 10000Pa vacuum environment;
5) adding 25ml of 27.5% hydrogen peroxide into the treated catalyst, and soaking for 12h under an ultrasonic condition (ultrasonic power is 0.5 kW);
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a 10000Pa vacuum environment to obtain the regenerated catalyst.
And carrying out acetylene hydrochlorination evaluation on the regenerated catalyst A on a fixed bed reactor device, wherein the catalyst evaluation process comprises the steps of adopting a fixed bed micro reactor for evaluation, heating and controlling the temperature by an electric heating furnace, filling 2g of catalyst, activating hydrogen chloride for 0.5h before reaction, introducing acetylene for reaction after activation, adopting a gas chromatograph of an FID detector for analysis, and sampling frequency times/0.5 h. The results are shown in Table 16.
Examples 68 to 72 and comparative examples 23 to 24
Referring to example 67, the specific conditions are shown in table 15, wherein the operating conditions in step 1) are the same as in example 67, and are not repeated in table 15, and the conditions not listed in other tables are also the same as in example 67.
The regenerated catalyst was evaluated by the method of example 67 and the results are shown in Table 16.
Figure BDA0002394403030000211
TABLE 16
Figure BDA0002394403030000221
Example 73
1) Weighing 10g of the B deactivated catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and then cooling to room temperature;
2) then adding 50ml of toluene, and soaking for 3 hours at the temperature of 45 ℃;
3) then, placing the catalyst in a discharge chamber filled with argon and hydrogen with the total pressure of 30kPa (the pressure ratio is 1:1), wherein the used discharge mode is direct current arc discharge, the discharge voltage is 40-50V, the discharge current is 60-70A, and the discharge treatment is carried out for 30 min;
4) then taking out the catalyst from the discharge chamber, washing the catalyst by using methanol at the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12h under the vacuum environment of 8000 Pa;
5) adding 100ml of perchloric acid solution with the concentration of 70% into the treated catalyst, and soaking for 12 hours under the ultrasonic condition (the ultrasonic power is 0.5 kW);
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 8000Pa to obtain the regenerated catalyst.
Examples 74 to 78 and comparative examples 25 to 26
Referring to example 73, specific conditions are shown in table 17, where the operating conditions in step 1) are the same as in example 73, and thus are not repeated in table 17, and conditions not listed in other tables are also the same as in example 73.
The acetylene hydrochlorination evaluation of the regenerated B catalyst was carried out in a fixed bed reactor set-up according to the method of example 67 and the results are shown in Table 18.
Figure BDA0002394403030000241
Watch 18
Figure BDA0002394403030000251
Example 79
1) Weighing 10g of C deactivation catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and then cooling to room temperature;
2) then adding 50ml of ethanol, and soaking for 3 hours at the temperature of 45 ℃;
3) then placing the catalyst in a discharge chamber filled with argon and hydrogen with the total pressure of 30kPa, wherein the used discharge mode is direct current arc discharge, the discharge voltage is 60-70V, the discharge current is 110-120A, and the discharge treatment is carried out for 10 min;
4) then washing the catalyst by using deionized water with the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12h in a vacuum environment of 120 Pa;
5) adding 40ml of mixed solution of 25 percent potassium thiocyanate and 0.2 percent thiourea into the treated catalyst, and soaking for 12 hours under the ultrasonic condition (the ultrasonic power is 0.5 kW);
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 120Pa to obtain the regenerated catalyst.
Acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up.
Examples 80 to 84 and comparative examples 27 to 28
Referring to example 79, the specific conditions are shown in table 19, wherein the operation conditions in step 1) are the same as those in example 79, and therefore are not repeated in table 19.
The acetylene hydrochlorination evaluation of the regenerated C catalyst was carried out in the fixed bed reactor unit as in example 67 and the results are shown in Table 20.
Figure BDA0002394403030000261
Figure BDA0002394403030000271
Watch 20
Figure BDA0002394403030000281
Examples 85 to 90 and comparative examples 29 to 30
D deactivated catalysts were treated correspondingly under the conditions of the deactivated catalysts A shown in examples 67 to 72 and comparative examples 23 to 24 to give corresponding regenerated D catalysts, which were subjected to evaluation of the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in Table 21.
TABLE 21
Figure BDA0002394403030000282
Figure BDA0002394403030000291
Examples 91 to 96 and comparative examples 31 to 32
The deactivated catalyst E was treated correspondingly under the conditions of the deactivated catalyst A shown in examples 67 to 72 and comparative examples 23 to 24 to obtain a corresponding regenerated catalyst E, and the regenerated catalyst E was evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in Table 22.
TABLE 22
Figure BDA0002394403030000292
Examples 97 to 102 and comparative examples 33 to 34
The deactivated catalyst F was subjected to the corresponding treatment under the conditions of the deactivated catalyst A shown in examples 67 to 72 and comparative examples 23 to 24 to obtain a corresponding regenerated catalyst F, and the regenerated catalyst F was subjected to the evaluation of the hydrochlorination of acetylene in the fixed bed reactor apparatus, and the results are shown in Table 23.
TABLE 23
Figure BDA0002394403030000301
Example 103-108 and comparative examples 35-36
The deactivated catalyst G was treated correspondingly under the conditions of the deactivated catalyst A shown in examples 67 to 72 and comparative examples 23 to 24 to obtain a corresponding regenerated catalyst G, and the regenerated catalyst G was evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in Table 24.
Watch 24
Figure BDA0002394403030000302
Figure BDA0002394403030000311
Example 109-
The deactivated H catalysts were treated correspondingly under the conditions of the deactivated A catalysts shown in examples 67 to 72 and comparative examples 23 to 24 to obtain corresponding regenerated H catalysts, and the regenerated H catalysts were evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in Table 25.
TABLE 25
Figure BDA0002394403030000312
Example 115-120 and comparative examples 39-40
The deactivated catalysts were treated correspondingly under the conditions of the deactivated catalysts B shown in examples 73 to 78 and comparative examples 25 to 26 to obtain corresponding regenerated catalysts I, and the regenerated catalysts I were evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in Table 26.
Watch 26
Figure BDA0002394403030000321
Example 121-126 and comparative examples 41-42
The J deactivated catalysts were treated correspondingly under the conditions of the B deactivated catalysts shown in examples 73 to 78 and comparative examples 25 to 26 to obtain corresponding regenerated J catalysts, which were subjected to acetylene hydrochlorination evaluation on a fixed bed reactor set up, and the results are shown in table 27.
Watch 27
Figure BDA0002394403030000322
Figure BDA0002394403030000331
Example 127-132 and comparative examples 43-44
The deactivated K catalyst was treated correspondingly under the conditions of the deactivated C catalyst shown in examples 79 to 84 and comparative examples 27 to 28 to obtain a corresponding regenerated K catalyst, and the regenerated K catalyst was evaluated for the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in Table 28.
Watch 28
Figure BDA0002394403030000332
Example 133
1) Weighing 10g of A deactivated catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and cooling to room temperature;
2) then adding 50ml of 5% potassium hydroxide aqueous solution, and soaking for 3h at 60 ℃;
3) then, irradiating the catalyst for 30min by using microwaves of 0.5kW and 2450MHz, and simultaneously purging by using nitrogen;
4) then washing the catalyst by using deionized water with the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12h in a 10000Pa vacuum environment;
5) adding 25ml of 27.5% hydrogen peroxide into the treated catalyst, and soaking for 12 hours under the ultrasonic condition of 0.5 kW;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a 10000Pa vacuum environment to obtain the regenerated catalyst.
Example 134-138 and comparative examples 45-46
Referring to example 133, the specific conditions are shown in table 29, wherein the operating conditions in step 1) are the same as those in example 133, and thus are not repeated in table 29. The conditions not shown in the table were the same as in example 133.
And carrying out acetylene hydrochlorination evaluation on the regenerated catalyst A on a fixed bed reactor device, wherein the catalyst evaluation process comprises the steps of adopting a fixed bed micro reactor for evaluation, heating and controlling the temperature by an electric heating furnace, filling 2g of catalyst, activating hydrogen chloride for 0.5h before reaction, introducing acetylene for reaction after activation, adopting a gas chromatograph of an FID detector for analysis, and sampling frequency times/0.5 h. The results are shown in Table 30.
Figure BDA0002394403030000351
Watch 30
Figure BDA0002394403030000361
Example 139
1) Weighing 10g of the B deactivated catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and cooling to room temperature;
2) then adding 50ml of toluene, and soaking for 3 hours at the temperature of 45 ℃;
3) then, irradiating the glass substrate for 30min by using microwaves of 0.5kW and 2450MHz, and simultaneously purging by using nitrogen;
4) then, washing the catalyst by using methanol with the temperature of 45 ℃ until the washing liquid is neutral, and drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 8000 Pa;
5) adding 100ml of perchloric acid solution with the concentration of 70% into the treated catalyst, and soaking for 12 hours under the ultrasonic condition of 0.5 kW;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 8000Pa to obtain the regenerated catalyst.
Example 140 and comparative examples 47 to 48
Referring to example 139, the specific conditions are shown in table 31, wherein the operating conditions in step 1) are the same as those in example 139, and therefore are not repeated in table 31. The conditions not shown in the table were the same as in example 139.
The acetylene hydrochlorination evaluation of the regenerated B catalyst was carried out in the fixed bed reactor unit according to the method of example 133 and the results are shown in table 32.
Figure BDA0002394403030000371
Watch 32
Figure BDA0002394403030000381
Example 145
1) Weighing 10g of C deactivation catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and cooling to room temperature;
2) then adding 50ml of ethanol, and soaking for 3 hours at the temperature of 45 ℃;
3) then, irradiating the glass substrate for 15min by using microwaves of 0.7kW and 2450MHz, and simultaneously purging by using nitrogen;
4) then washing the catalyst by using deionized water with the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12h in a vacuum environment of 120 Pa;
5) adding 40ml of mixed solution of 25 percent potassium thiocyanate and 0.2 percent thiourea into the treated catalyst, and soaking for 12 hours under the ultrasonic condition of 0.5 kW;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 120Pa to obtain the regenerated catalyst.
Example 146-
Referring to example 145, the specific conditions are shown in table 33, wherein the operating conditions in step 1) are the same as in example 145, and thus are not repeated in table 33. The conditions not shown in the table were the same as in example 145.
The acetylene hydrochlorination evaluation of the regenerated C catalyst was carried out in the fixed bed reactor unit according to the method of example 133 and the results are shown in Table 34.
Figure BDA0002394403030000391
Watch 34
Figure BDA0002394403030000401
Example 151 reservoir 156 and comparative examples 51 to 52
The deactivated catalyst was treated under the conditions of the deactivated catalyst A shown in examples 133-138 and comparative examples 45-46 to obtain a regenerated catalyst D, and the regenerated catalyst D was subjected to the evaluation of the hydrochlorination of acetylene in a fixed bed reactor, and the results are shown in Table 35.
Watch 35
Figure BDA0002394403030000402
Figure BDA0002394403030000411
Example 157-
The deactivated catalyst E was treated under the conditions of the deactivated catalyst A shown in examples 133-138 and comparative examples 45-46 to obtain a regenerated catalyst E, and the regenerated catalyst E was subjected to the evaluation of the hydrochlorination of acetylene in a fixed bed reactor apparatus, and the results are shown in Table 36.
Watch 36
Figure BDA0002394403030000412
Example 163-
The F deactivated catalyst was treated correspondingly under the conditions of the A deactivated catalyst shown in examples 133-138 and comparative examples 45-46 to obtain a corresponding regenerated F catalyst, and the regenerated F catalyst was subjected to the evaluation of the acetylene hydrochlorination reaction in the fixed bed reactor apparatus, and the results are shown in Table 37.
Watch 37
Figure BDA0002394403030000421
Example 169 and comparative examples 57 to 58
The G deactivated catalyst was treated correspondingly under the conditions of the A deactivated catalysts shown in examples 133-138 and comparative examples 57-58 to obtain a corresponding regenerated G catalyst, and the regenerated G catalyst was subjected to the evaluation of the acetylene hydrochlorination reaction in the fixed bed reactor apparatus, and the results are shown in Table 38.
Watch 38
Figure BDA0002394403030000422
Figure BDA0002394403030000431
Example 175-
The H deactivated catalyst was treated correspondingly under the conditions of the A deactivated catalyst shown in example 133-138 and comparative examples 45-46 to obtain a corresponding regenerated H catalyst, and the result of the evaluation of the acetylene hydrochlorination reaction of the regenerated H catalyst in the fixed bed reactor apparatus is shown in Table 39.
Watch 39
Figure BDA0002394403030000432
Figure BDA0002394403030000441
Example 181-186 and comparative examples 61-62
The I deactivated catalyst was treated correspondingly under the conditions of B deactivated catalysts shown in examples 139-144 and comparative examples 47-48 to obtain corresponding regenerated I catalyst, which was subjected to the evaluation of the hydrochlorination of acetylene in a fixed bed reactor set up and the results are shown in Table 40.
Watch 40
Figure BDA0002394403030000442
Figure BDA0002394403030000451
Example 187-
The J deactivated catalyst was treated correspondingly under the conditions of the B deactivated catalysts shown in examples 139-144 and comparative examples 47-48 to obtain a corresponding regenerated J catalyst, and the regenerated J catalyst was subjected to acetylene hydrochlorination evaluation on a fixed bed reactor unit, the results of which are shown in Table 41.
Table 41
Figure BDA0002394403030000452
Example 193-
The K deactivated catalyst was treated correspondingly under the conditions of the C deactivated catalysts shown in example 145-150 and comparative examples 49-50 to obtain the corresponding regenerated K catalyst, and the acetylene hydrochlorination evaluation of the regenerated K catalyst was carried out on a fixed bed reactor apparatus, and the results are shown in Table 14.
Watch 42
Figure BDA0002394403030000453
Figure BDA0002394403030000461
Example 199
1) Weighing 10g of A deactivated catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and cooling to room temperature;
2) then adding 50ml of 5% potassium hydroxide aqueous solution, and soaking for 3h at 60 ℃;
3) subsequently, the CO is reused2A laser with an irradiation power of 50W and an irradiation speed of 30mm/s, wherein the irradiation treatment is carried out for 120s while purging with nitrogen;
4) then washing the catalyst by using deionized water with the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12h in a 10000Pa vacuum environment;
5) adding 25ml of 27.5% hydrogen peroxide into the treated catalyst, and soaking for 12 hours under the ultrasonic condition of 0.5 kW;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a 10000Pa vacuum environment to obtain the regenerated catalyst.
And carrying out acetylene hydrochlorination evaluation on the regenerated catalyst A on a fixed bed reactor device, wherein the catalyst evaluation process comprises the steps of adopting a fixed bed micro reactor for evaluation, heating and controlling the temperature by an electric heating furnace, filling 2g of catalyst, activating hydrogen chloride for 0.5h before reaction, introducing acetylene for reaction after activation, adopting a gas chromatograph of an FID detector for analysis, and sampling frequency times/0.5 h. The results are shown in Table 2.
Example 200 and comparative examples 67-68
Referring to embodiment 199, the specific conditions are shown in table 43, wherein the operation conditions in step 1) are the same as those in embodiment 199, and therefore are not repeated in table 43. The conditions not shown in the table were the same as in example 199.
The regenerated catalyst was evaluated in the same manner as in example 199, and the results are shown in Table 43.
Figure BDA0002394403030000471
Watch 44
Figure BDA0002394403030000481
Example 205
1) Weighing 10g of the B deactivated catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and cooling to room temperature;
2) then adding 50ml of toluene, and soaking for 3 hours at the temperature of 45 ℃;
3) subsequently, the CO is reused2A laser with an irradiation power of 50W and an irradiation speed of 30mm/s, wherein the irradiation treatment is carried out for 120s while purging with nitrogen;
4) then, washing the catalyst by using methanol with the temperature of 45 ℃ until the washing liquid is neutral, and drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 8000 Pa;
5) adding 100ml of perchloric acid solution with the concentration of 70% into the treated catalyst, and soaking for 12 hours under the ultrasonic condition of 0.5 kW;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 8000Pa to obtain the regenerated catalyst.
Acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up.
Example 206-210 and comparative examples 69-70
Referring to embodiment 205, specific conditions are shown in table 45, wherein the operating conditions in step 1) are the same as those in embodiment 205, and therefore are not repeated in table 45. The conditions not shown in the table were the same as in example 205.
The acetylene hydrochlorination evaluation of the regenerated B catalyst was carried out in the fixed bed reactor unit as in example 199 and the results are shown in table 46.
Figure BDA0002394403030000501
TABLE 46
Figure BDA0002394403030000511
Example 211
1) Weighing 10g of C deactivation catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and cooling to room temperature;
2) then adding 50ml of ethanol, and soaking for 3 hours at the temperature of 45 ℃;
3) subsequently, the CO is reused2A laser with the irradiation power of 150W and the irradiation speed of 10mm/s, wherein the irradiation treatment is carried out for 60s, and nitrogen purging is simultaneously used;
4) then washing the catalyst by using deionized water with the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12h in a vacuum environment of 120 Pa;
5) adding 40ml of mixed solution of 25 percent potassium thiocyanate and 0.2 percent thiourea into the treated catalyst, and soaking for 12 hours under the ultrasonic condition of 0.5 kW;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 120Pa to obtain the regenerated catalyst.
Example 212-216 and comparative examples 71-72
Referring to embodiment 211, the specific conditions are shown in table 47, wherein the operation conditions in step 1) are the same as those in embodiment 211, and thus are not repeated in table 47. The conditions not shown in the table were the same as in example 211.
The acetylene hydrochlorination evaluation of the regenerated C catalyst was carried out in the fixed bed reactor set-up as in example 199 and the results are shown in Table 48.
Figure BDA0002394403030000531
Watch 48
Figure BDA0002394403030000541
Example 217-222 and comparative examples 73-74
The deactivated catalyst was treated correspondingly under the conditions of the deactivated catalyst A shown in example 199-204 and comparative examples 67-68 to obtain a corresponding regenerated catalyst D, and the regenerated catalyst D was subjected to the evaluation of the hydrochlorination reaction of acetylene in the fixed bed reactor apparatus, and the results are shown in Table 49.
Watch 49
Figure BDA0002394403030000542
Figure BDA0002394403030000551
Example 223-
The deactivated catalyst E was treated correspondingly under the conditions of the deactivated catalyst A shown in example 199-204 and comparative examples 67-68 to obtain a corresponding regenerated catalyst E, and the regenerated catalyst E was subjected to the evaluation of the hydrochlorination reaction of acetylene in the fixed bed reactor apparatus, and the results are shown in Table 50.
Watch 50
Figure BDA0002394403030000552
Figure BDA0002394403030000561
Example 229-
The F deactivated catalyst was treated correspondingly under the conditions of the A deactivated catalyst shown in example 199-204 and comparative examples 67-68 to obtain a corresponding regenerated F catalyst, and the result of the evaluation of the acetylene hydrochlorination reaction of the regenerated F catalyst in the fixed bed reactor apparatus is shown in Table 51.
Watch 51
Figure BDA0002394403030000562
Figure BDA0002394403030000571
Example 235-240 and comparative examples 79-80
The G deactivated catalyst was treated correspondingly under the conditions of the A deactivated catalysts shown in examples 199-204 and comparative examples 67-68 to obtain a corresponding regenerated G catalyst, and the result of the evaluation of the acetylene hydrochlorination reaction of the regenerated G catalyst in the fixed bed reactor apparatus is shown in Table 52.
Table 52
Figure BDA0002394403030000572
Example 241-246 and comparative examples 81-82
The H deactivated catalyst was treated correspondingly under the conditions of the A deactivated catalysts shown in examples 199-204 and comparative examples 67-68 to obtain the corresponding regenerated H catalyst, and the result of the evaluation of the acetylene hydrochlorination reaction of the regenerated H catalyst in the fixed bed reactor apparatus is shown in Table 53.
Watch 53
Figure BDA0002394403030000581
Example 247-
The I deactivated catalyst was treated correspondingly under the conditions of B deactivated catalysts shown in example 205-210 and comparative examples 69-70 to obtain a corresponding regenerated I catalyst, and the regenerated I catalyst was subjected to acetylene hydrochlorination evaluation on a fixed bed reactor unit, the results of which are shown in Table 54.
Watch 54
Figure BDA0002394403030000582
Figure BDA0002394403030000591
Example 253-258 and comparative examples 85-86
The J deactivated catalyst was treated correspondingly under the conditions of B deactivated catalysts shown in example 205-210 and comparative examples 69-70 to obtain a corresponding regenerated J catalyst, and the regenerated J catalyst was subjected to acetylene hydrochlorination evaluation on a fixed bed reactor unit, the results of which are shown in Table 55.
Watch 55
Figure BDA0002394403030000592
Figure BDA0002394403030000601
Example 259 and comparative examples 87-88
The K deactivated catalyst was treated correspondingly under the conditions of the C deactivated catalysts shown in examples 211-216 and comparative examples 71-72 to obtain corresponding regenerated K catalysts, and the results of the acetylene hydrochlorination evaluation of the regenerated K catalysts in the fixed bed reactor apparatus are shown in Table 56.
Watch 56
Figure BDA0002394403030000602
Figure BDA0002394403030000611
Example 265
1) Weighing 10g of A deactivated catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and cooling to room temperature;
2) then adding 50ml of 5% potassium hydroxide aqueous solution, and soaking for 3h at 60 ℃;
3) then, using 200-210V voltage under 100Pa vacuum degree, using argon and hydrogen as working gas, discharging the working gas to generate plasma, and treating the catalyst for 120 min;
4) then washing the catalyst by using deionized water with the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12h in a 10000Pa vacuum environment;
5) adding 25ml of 27.5% hydrogen peroxide into the treated catalyst, and soaking for 12 hours under the ultrasonic condition of 0.5 kW;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a 10000Pa vacuum environment to obtain the regenerated catalyst.
Example 266-270 and comparative examples 89-90
Referring to example 265, the specific conditions are shown in table 57, wherein the operating conditions in step 1) are the same as those in example 265, and thus are not repeated in table 57. The conditions not shown in the table were the same as in example 265.
And carrying out acetylene hydrochlorination evaluation on the regenerated catalyst A on a fixed bed reactor device, wherein the catalyst evaluation process comprises the steps of adopting a fixed bed micro reactor for evaluation, heating and controlling the temperature by an electric heating furnace, filling 2g of catalyst, activating hydrogen chloride for 0.5h before reaction, introducing acetylene for reaction after activation, adopting a gas chromatograph of an FID detector for analysis, and sampling frequency times/0.5 h. The results are shown in Table 58.
Figure BDA0002394403030000621
Watch 58
Figure BDA0002394403030000631
Example 271
1) Weighing 10g of the B deactivated catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and cooling to room temperature;
2) then adding 50ml of toluene, and soaking for 3 hours at the temperature of 45 ℃;
3) then, 4990-5000V voltage is used under the vacuum degree of 1000Pa, the working gas is argon and hydrogen, and the catalyst is treated for 10min after the working gas is discharged to generate plasma;
4) then, washing the catalyst by using methanol with the temperature of 45 ℃ until the washing liquid is neutral, and drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 8000 Pa;
5) adding 100ml of perchloric acid solution with the concentration of 70% into the treated catalyst, and soaking for 12 hours under the ultrasonic condition of 0.5 kW;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 8000Pa to obtain the regenerated catalyst.
Example 272 and 276 and comparative examples 91 to 92
Referring to embodiment 271, the specific conditions are shown in table 59, wherein the operating conditions in step 1) are the same as those in embodiment 271, and therefore are not repeated in table 59. The conditions not shown in the table were the same as in example 271.
The acetylene hydrochlorination evaluation of the regenerated B catalyst was carried out in the fixed bed reactor unit as in example 265 and the results are shown in table 60.
Figure BDA0002394403030000651
Watch 60
Figure BDA0002394403030000661
Example 277
1) Weighing 10g of C deactivation catalyst, placing at the temperature of 110 ℃, purging for 2h in a nitrogen atmosphere, and cooling to room temperature;
2) then adding 50ml of ethanol, and soaking for 3 hours at the temperature of 45 ℃;
3) then, the 800-810V voltage is used under the vacuum degree of 1000Pa, the working gas is argon and hydrogen, and the catalyst is treated for 30min after the working gas is discharged to generate plasma;
4) then washing the catalyst by using deionized water with the temperature of 45 ℃ until the washing liquid is neutral, and drying at the temperature of 110 ℃ for 12h in a vacuum environment of 120 Pa;
5) adding 40ml of mixed solution of 25 percent potassium thiocyanate and 0.2 percent thiourea into the treated catalyst, and soaking for 12 hours under the ultrasonic condition of 0.5 kW;
6) and washing the oxidized catalyst to be neutral by using deionized water again, and finally drying the catalyst for 12 hours at the temperature of 110 ℃ in a vacuum environment of 120Pa to obtain the regenerated catalyst.
Example 278-
Referring to example 277, the specific conditions are shown in table 61, wherein the operating conditions in step 1) are the same as in example 277, and thus are not repeated in table 61. The conditions not shown in the table were the same as in example 277.
The acetylene hydrochlorination evaluation of the regenerated C catalyst was carried out in the fixed bed reactor set-up as in example 265 and the results are shown in Table 62.
Figure BDA0002394403030000681
Watch 62
Figure BDA0002394403030000691
Example 283-
The deactivated catalyst was treated correspondingly under the conditions of the deactivated catalyst A shown in example 265-270 and comparative examples 89-90 to obtain a corresponding regenerated catalyst D, and the regenerated catalyst D was subjected to the evaluation of the hydrochlorination of acetylene in a fixed bed reactor unit, and the results are shown in Table 63.
Table 63
Figure BDA0002394403030000692
Figure BDA0002394403030000701
Example 289-
The deactivated catalyst E was treated correspondingly under the conditions of the deactivated catalyst A shown in example 265-270 and comparative examples 89-90 to obtain a corresponding regenerated catalyst E, and the regenerated catalyst E was subjected to the evaluation of the hydrochlorination of acetylene in a fixed bed reactor unit, and the results are shown in Table 64.
Table 64
Figure BDA0002394403030000702
Figure BDA0002394403030000711
Example 295-300 and comparative examples 99-100
The F deactivated catalyst was treated correspondingly under the conditions of the A deactivated catalyst shown in examples 265-270 and comparative examples 89-90 to obtain a corresponding regenerated F catalyst, and the regenerated F catalyst was subjected to acetylene hydrochlorination evaluation on a fixed bed reactor unit, the results of which are shown in Table 65.
Table 65
Figure BDA0002394403030000712
Figure BDA0002394403030000721
Example 301-
The G deactivated catalyst was treated correspondingly under the conditions of the A deactivated catalyst shown in example 265-270 and comparative examples 89-90 to obtain a corresponding regenerated G catalyst, and the regenerated G catalyst was subjected to the evaluation of the acetylene hydrochlorination reaction in the fixed bed reactor apparatus, and the results are shown in Table 66.
TABLE 66
Figure BDA0002394403030000722
Example 307-
The H deactivated catalyst was treated correspondingly under the conditions of the A deactivated catalysts shown in examples 265-266 and comparative examples 89-90 to obtain the corresponding regenerated H catalyst, and the result of the acetylene hydrochlorination evaluation of the regenerated H catalyst in the fixed bed reactor apparatus is shown in Table 67.
Watch 67
Figure BDA0002394403030000731
Example 313 and comparative examples 105 and 106
The I deactivated catalyst was treated correspondingly under the conditions of the B deactivated catalysts shown in examples 271-276 and comparative examples 91-92 to obtain the corresponding regenerated I catalyst, and the regenerated I catalyst was subjected to the evaluation of the acetylene hydrochlorination reaction in the fixed bed reactor unit, and the results are shown in Table 68.
Table 68
Figure BDA0002394403030000732
Figure BDA0002394403030000741
Examples 319, 324 and comparative examples 107, 108
The J deactivated catalyst was treated correspondingly under the conditions of the B deactivated catalysts shown in examples 271-276 and comparative examples 91-92 to obtain a corresponding regenerated J catalyst, and the regenerated J catalyst was subjected to acetylene hydrochlorination evaluation on a fixed bed reactor unit, and the results are shown in Table 69.
Watch 69
Figure BDA0002394403030000742
Figure BDA0002394403030000751
Examples 325 and 330 and comparative examples 109 and 110
The K deactivated catalyst was treated correspondingly under the conditions of the C deactivated catalysts shown in example 277-282 and comparative examples 93-94 to obtain the corresponding regenerated K catalyst, and the acetylene hydrochlorination evaluation of the regenerated K catalyst was carried out on the fixed bed reactor apparatus, and the results are shown in Table 70.
Watch 70
Figure BDA0002394403030000752
Figure BDA0002394403030000761

Claims (10)

1. A regeneration method of acetylene hydrochlorination non-mercury catalyst, wherein the acetylene hydrochlorination non-mercury catalyst comprises a metal precursor and a carrier, the metal precursor is selected from one or more of gold, palladium, ruthenium and copper precursors, and the carrier is a porous solid carrier, and is characterized in that: the regeneration method comprises the following steps:
1) drying the inactivated non-mercury catalyst in air or inert gas atmosphere;
2) treating the non-mercury catalyst obtained in the step 1) by gamma ray irradiation or arc discharge or microwave or laser or plasma to decompose carbon deposition components in the catalyst into gas products, and blowing inert gas to remove the gas products when the gamma ray irradiation or microwave or laser treatment is adopted;
3) carrying out oxidation treatment on the non-mercury catalyst obtained in the step 2) to oxidize the reduced active components in the catalyst into an oxidation state with catalytic activity;
4) washing and vacuum drying the non-mercury catalyst obtained in the step 3) to obtain a regenerated non-mercury catalyst.
2. The regeneration method of claim 1, wherein: the regeneration method of the acetylene hydrochlorination non-mercury catalyst further comprises the following steps a) and b):
a) adding a carbon removing agent into the non-mercury catalyst obtained in the step 1) for treatment, and carrying out subsequent step 2) treatment on the treated catalyst; the carbon eliminating agent is selected from at least one of the following simple substances, oxides, chlorides and hydroxides of metals: K. rb, Sr, Ba, Nd, Hf, Pr, or the carbon eliminating agent is selected from one or the combination of any of the following components: toluene, xylene, ethanol, carbon disulfide; when the carbon removing agent is a solid, the carbon removing agent is added in the form of solution, wherein the solvent is water, hydrochloric acid solution or aqua regia;
b) washing the catalyst obtained in the step 2), removing the carbon removing agent, drying, removing the washing solvent, and carrying out the subsequent step 3) treatment on the treated catalyst.
3. The regeneration method according to claim 1 or 2, characterized in that: the oxidation treatment process in the step 3) is assisted by using ultrasound.
4. The regeneration method according to claim 2, wherein: the regeneration method of the acetylene hydrochlorination non-mercury catalyst comprises the following steps:
1) drying the inactivated non-mercury catalyst in air or inert gas atmosphere;
a) adding a carbon removing agent into the non-mercury catalyst obtained in the step 1) for treatment;
2) treating the non-mercury catalyst obtained in the step a) by gamma ray irradiation or arc discharge or microwave or laser or plasma to decompose carbon deposition components in the catalyst into gas products, and blowing inert gas to remove the gas products when the gamma ray irradiation or microwave or laser treatment is adopted;
b) washing the catalyst obtained in the step 2) to remove the carbon removing agent, and then drying to remove the washing solvent;
3) carrying out ultrasonic auxiliary oxidation treatment on the non-mercury catalyst obtained in the step b) to oxidize the reduced active components in the catalyst into an oxidation state with catalytic activity;
4) washing and vacuum drying the non-mercury catalyst obtained in the step 3) to obtain a regenerated non-mercury catalyst.
5. Regeneration method according to one of claims 1 to 4, characterized in that: the non-mercury catalyst further comprises an auxiliary agent, wherein the auxiliary agent is one or more of metal salt or ionic liquid.
6. Regeneration method according to one of claims 1 to 4, characterized in that: in the step 2), the gamma-ray irradiation treatment conditions are as follows: the gamma ray irradiation source is60Co rays and137one of the Cs rays, wherein the gamma ray irradiation intensity is 2.7-60 kGy/h, and the gamma ray irradiation time is 1-20 h;
the arc discharge treatment conditions were: the discharge field is an arc chamber, the discharge area is an arc column area, the buffer gas for arc discharge is hydrogen and helium, and the pressure ratio of the hydrogen to the helium is 1-10: 1; the discharge mode is direct current arc discharge; the discharge voltage is 40-70V; the discharge current is 60-120A; the discharge time is 10-30 min;
the microwave treatment conditions were: the microwave frequency is 915 and 2450 MHz; the microwave power is 0.5-1 kW; the microwave irradiation time is 1-30 min;
the laser processing conditions were: with CO2Carrying out laser irradiation treatment by a laser; the laser irradiation power is 50-400W; the laser irradiation speed is 10-30 mm/s; the laser irradiation time is 10-120 s;
the plasma treatment time is 10-120 min.
7. Regeneration method according to one of claims 1 to 4, characterized in that: in the step 3), the oxidant is one or more of hydrogen peroxide, hydrochloric acid, nitric acid, potassium thiocyanate, thiourea, hypochlorous acid, chloric acid, perchloric acid, chlorine gas and hydrogen chloride gas.
8. Regeneration method according to one of claims 1 to 4, characterized in that: the specific operation of the step 3) is as follows: and the oxidant is chlorine or hydrogen chloride gas, and the chlorine or hydrogen chloride gas is passed through a reactor filled with a non-mercury catalyst, so that the treatment temperature of the chlorine or hydrogen chloride gas is between room temperature and 200 ℃, and the treatment time is 2-30 h.
9. Regeneration method according to one of claims 1 to 4, characterized in that: the specific operation of the step 3) is as follows: placing the non-mercury catalyst in an oxidant aqueous solution, controlling the treatment temperature to be between room temperature and 200 ℃, washing with water after the treatment time is 2-30 hours until filtrate is neutral, and obtaining the non-mercury catalyst after oxidation treatment; the oxidant aqueous solution is at least one selected from hydrogen peroxide with the concentration of 20-50%, hydrochloric acid with the concentration of 31-38%, nitric acid with the concentration of 65-68%, potassium thiocyanate aqueous solution with the concentration of 10-50%, thiourea aqueous solution with the concentration of 0.2-0.3%, hypochlorous acid aqueous solution with the concentration of 45-48%, chloric acid with the concentration of 30-39% and perchloric acid with the concentration of 70-72%.
10. Regeneration method according to one of claims 2 to 4, characterized in that: the specific operation of the step a) is as follows: placing the non-mercury catalyst obtained in the step 1) in a carbon removing agent or a carbon removing agent solution, and controlling the treatment temperature to be between room temperature and 150 ℃ and the time to be 0.5 to 24 hours.
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