阅读说明：本技术 一种负载型铂族金属催化剂的再生方法 (Regeneration method of supported platinum group metal catalyst ) 是由 赵佳 方先华 金春晓 岳玉学 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种在催化加氢反应过程中因含硫物质中毒而失活的负载型铂族金属催化剂的再生方法：在惰性气体氛围下,对失活的负载型铂族金属催化剂进行烘干处理,然后在X射线照射的条件下将烘干后的催化剂用再生试剂搅拌浸泡1～3h,之后过滤,用溶剂洗涤至洗涤液呈中性,回收洗涤滤液,将滤出的催化剂在40～110℃下真空干燥8～24h,即得再生后的负载型铂族金属催化剂；将回收的滤液用旋转蒸发仪旋蒸至液体的质量不再发生变化,旋蒸后的液体于150～200℃下加热处理2～8h,完成再生试剂的回收；本发明再生所得催化剂能恢复到原有的催化活性和选择性,回收的再生试剂能够循环使用。(The invention discloses a method for regenerating a supported platinum group metal catalyst inactivated due to poisoning of sulfur-containing substances in a catalytic hydrogenation reaction process, which comprises the following steps: drying the inactivated supported platinum group metal catalyst in an inert gas atmosphere, stirring and soaking the dried catalyst for 1-3 hours by using a regeneration reagent under the condition of X-ray irradiation, filtering, washing by using a solvent until a washing solution is neutral, recovering a washing filtrate, and drying the filtered catalyst for 8-24 hours in vacuum at 40-110 ℃ to obtain a regenerated supported platinum group metal catalyst; rotationally evaporating the recovered filtrate by using a rotary evaporator until the quality of the liquid does not change any more, and heating the rotationally evaporated liquid at 150-200 ℃ for 2-8 h to complete the recovery of the regenerated reagent; the catalyst obtained by regeneration of the invention can recover the original catalytic activity and selectivity, and the recovered regeneration reagent can be recycled.)

1. A method for regenerating a supported platinum group metal catalyst, wherein the supported platinum group metal catalyst is a supported platinum group metal catalyst deactivated by poisoning with sulfur-containing substances during a catalytic hydrogenation reaction, the method comprising:

(1) drying the inactivated supported platinum group metal catalyst in an inert gas atmosphere, stirring and soaking the dried catalyst for 1-3 hours by using a regeneration reagent under the condition of X-ray irradiation, filtering, washing by using a solvent until a washing solution is neutral, recovering a washing filtrate, and drying the filtered catalyst for 8-24 hours in vacuum at 40-110 ℃ to obtain a regenerated supported platinum group metal catalyst;

the regeneration reagent is selected from one or a mixture of any of the following: imidazole ionic liquid, quaternary phosphonium ionic liquid, quaternary ammonium ionic liquid, pyrrolidine ionic liquid, pyrrolidone ionic liquid, piperidine ionic liquid and pyridine ionic liquid;

(2) and (3) carrying out rotary evaporation on the filtrate recovered in the step (1) by using a rotary evaporator until the quality of the liquid does not change any more, and carrying out heat treatment on the rotary evaporated liquid at the temperature of 150-200 ℃ for 2-8 h to complete the recovery of the regenerated reagent.

2. The method for regenerating a supported platinum group metal catalyst as claimed in claim 1, wherein in the step (1):

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, acetate, trifluoroacetate, phosphate or dihydrogen phosphate;

the quaternary phosphonium ionic liquid is tributyl ethyl phosphonium bromide, tributyl ethyl phosphonium chloride, tributyl hexyl phosphonium bromide, tributyl hexyl phosphonium chloride, tributyl hexyl phosphonium bis (trifluoromethanesulfonyl) imide salt, tributyl ethyl phosphonium bis (trifluoromethanesulfonyl) imide salt, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, triphenyl ethyl phosphonium bromide, triphenyl ethyl phosphonium chloride, tetraphenyl phosphonium bromide or tetraphenyl phosphonium chloride;

the quaternary ammonium ionic liquid is trialkyl methyl ammonium (trifluoromethane sulfonyl) imide salt or trialkyl methyl ammonium chloride, wherein the alkyl is respectively and independently C1-C16 alkyl;

the pyrrolidine ionic liquid is N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt or N-butyl-N-methylpyrrolidine bromide salt;

the pyrrolidone ionic liquid is N-methylpyrrolidone hydrochloride, N-hydroxypyrrolidone bis (trifluoromethanesulfonyl) imide salt or N-butyl-N-methylpyrrolidone bromide salt;

the piperidine ionic liquid is N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt or N-butyl N-methylpiperidine bromide salt;

the pyridine ionic liquid is N-ethylpyridine bromide salt, N-butylpyridine bis (trifluoromethanesulfonyl) imide salt or N-butylhexafluorophosphate.

3. The method for regenerating a supported platinum group metal catalyst as claimed in claim 1, wherein in the step (1), the irradiation frequency of the X-ray is 30PHz to 30 EHz.

4. The method for regenerating a supported platinum group metal catalyst as claimed in claim 1, wherein the solvent used for washing in the step (1) is at least one of deionized water, ethanol, methanol, acetone, and tetrahydrofuran.

5. The method for regenerating a supported platinum group metal catalyst according to claim 1, wherein in the step (2), the rotary evaporation temperature is 60 to 100 ℃ and the rotary evaporation pressure is reduced to 400 to 600 mmHg.

6. The method of claim 1, further comprising the step of using the supported platinum group metal catalystThe preparation method is characterized in that the carrier of the supported platinum group metal catalyst is a porous solid material, and the porous solid material is selected from activated carbon, mesoporous carbon, carbon nano tube, graphene, silicon dioxide, aluminum oxide, titanium dioxide, molecular sieve, metal organic framework compound, covalent organic framework compound, non-metal heteroatom-doped carbon material and C₃N₄One or a mixture of any more of boron nitride, boron carbide, silicon nitride and silicon boride;

the active component of the supported platinum group metal catalyst is platinum group metal, the supporting rate of the platinum group metal is 0.01-10 wt%, and the platinum group metal is iridium, rhodium, palladium, platinum, osmium and ruthenium and is nano-particles with the particle size of 2-30 nm.

Technical Field

The invention relates to a regeneration method of a supported platinum group metal catalyst, in particular to a regeneration method of a supported platinum group metal catalyst which is inactivated due to poisoning of sulfur-containing substances in the catalytic hydrogenation reaction process.

Background

The supported platinum group metal catalyst is a typical hydrogenation catalyst and is widely applied to selective hydrogenation of phenol, nitrobenzene hydrogenation, benzoic acid hydrogenation, and hydrodechlorination of CFCS and FCFC. The inactivation of the supported platinum group metal catalyst in the hydrogenation reaction is a complex process, the performance of the catalyst can be affected by reaction raw materials, reaction temperature and the like in the reaction process, and the carrier and the supported active component of the catalyst can be subjected to physical or chemical changes in the reaction process. The deactivation modes of the supported platinum group metal catalyst mainly comprise four types of poisoning deactivation, carbon deposition deactivation, sintering deactivation and active component loss, wherein the poisoning deactivation is the most common chemical deactivation mode, and the main manifestation of the deactivation mode is that a stronger chemical bond is formed between the platinum group metal and sulfur element, and the chemical bond is difficult to break by using a conventional means.

Therefore, it is a problem to be studied to regenerate and reuse a catalyst that has been poisoned and deactivated, thereby improving its use value and reducing environmental pollution. The regeneration of the catalyst refers to an operation means and a method for recovering the activity and the selectivity of the catalyst by proper method treatment after the catalyst is used and the activity and the selectivity are reduced to a certain degree. For example, patent CN103191759A describes a regeneration method of a Pd/C catalyst and an application of the regenerated Pd/C catalyst, the regeneration method is to dry and oxidize an inactivated Pd/C catalyst at 50-140 ℃ in an air atmosphere to obtain a regenerated Pd/C catalyst, and the regenerated Pd/C catalyst is applied to a reaction of catalyzing hydrogenation synthesis of m-aminobenzenesulfonic acid from m-nitrobenzenesulfonic acid, the catalyst is recycled for more than 80 times, and the activity of the catalyst and the selectivity of a target product are basically unchanged.

The ionic liquid has the excellent performances of low volatility, low inflammability, high thermal stability, negligible vapor pressure, wide liquid temperature range, controllable good solubility to polar non-polar substances and the like, and simultaneously, the ionic liquid loaded on the porous solid carrier shows better sulfur resistance, so that the ionic liquid is very significant for applying to the platinum group metal catalyst inactivated by poisoning.

Disclosure of Invention

The invention aims to provide a regeneration method of a supported platinum group metal catalyst, wherein the supported platinum group metal catalyst is deactivated due to poisoning of sulfur-containing substances in the catalytic hydrogenation reaction process, and the regenerated catalyst can recover the original catalytic activity and selectivity.

The technical scheme of the invention is as follows:

a method for regenerating a supported platinum group metal catalyst, which is deactivated by poisoning with sulfur-containing substances during a catalytic hydrogenation reaction, comprising:

(1) drying the inactivated supported platinum group metal catalyst in an inert gas atmosphere, stirring the dried catalyst with a regeneration reagent under the condition of X-ray irradiation (at a speed of 100-1000 r/min), soaking for 1-3 h, filtering, washing with a solvent until a washing solution is neutral, recovering a washing filtrate, and vacuum-drying the filtered catalyst at 40-110 ℃ for 8-24 h to obtain the regenerated supported platinum group metal catalyst;

the inert gas is at least one of nitrogen, argon and helium;

the irradiation frequency of the X-ray is 30 PHz-30 EHz;

the dosage of the regeneration reagent is based on the fact that the catalyst is completely immersed;

the solvent for washing is at least one of deionized water, ethanol, methanol, acetone and tetrahydrofuran;

the drying temperature is 100-120 ℃, and the drying time is 4-8 h;

(2) rotationally evaporating the filtrate recovered in the step (1) by using a rotary evaporator until the quality of the liquid does not change, and heating the rotationally evaporated liquid at 150-200 ℃ for 2-8 h to complete the recovery (recycling) of the regeneration reagent;

the rotary evaporation temperature is 60-100 ℃, and the rotary evaporation pressure is reduced to 400-600 mmHg.

In the present invention, the reaction for deactivating the supported platinum group metal catalyst is, for example: a reaction in which nitrobenzene is hydrogenated to produce aminobenzene, a reaction in which m-nitrobenzenesulfonic acid is hydrogenated to produce m-aminobenzenesulfonic acid, an acetylene hydrogenation reaction, and the like, in these reactions, the catalyst is poisoned by a sulfur-containing substance and is deactivated.

The carrier of the supported platinum group metal catalyst is a porous solid material, and the porous solid material is selected from activated carbon, mesoporous carbon, carbon nano tubes, graphene, silicon dioxide, aluminum oxide, titanium dioxide, molecular sieves, metal organic framework compounds, covalent organic framework compounds, non-metal heteroatom-doped carbon materials, C₃N₄One or a mixture of any more of boron nitride, boron carbide, silicon nitride and silicon boride;

further, the activated carbon is columnar carbon or spherical activated carbon, and the particle size is 10-100 meshes; the carbon nano tube is columnar or spherical, and the particle size is 10-100 meshes; the graphene is columnar or spherical, and the particle size is 10-100 meshes; the aluminum oxide is gamma-Al₂O₃And processing the mixture into a columnar shape or a spherical shape with the particle size of 10-100 meshes; the silicon dioxide is columnar or spherical, and the particle size is 10-100 meshes; the titanium dioxide is columnar or spherical, and the particle size is 10-100 meshes; the molecular sieve is ZSM-5, beta molecular sieve, gamma molecular sieve, 5A molecular sieve, 10X molecular sieve or 13X molecular sieve; the metal organic framework compound is MOFs constructed by nitrogen-containing heterocyclic ligands and MOFs constructed by organic carboxylic acid ligands; the covalent organic framework compound is a boron-containing COFs material, an imine COFs material or a triazine COFs material; the heteroatom in the nonmetal heteroatom-doped carbon material is one or more of N, B, P and S.

The active component of the supported platinum group metal catalyst is platinum group metal, the loading rate (relative to the mass of a carrier) is 0.01-10 wt%, and the platinum group metal is iridium, rhodium, palladium, platinum, osmium and ruthenium and is nano-particles with the particle size of 2-30 nm.

The regeneration reagent is selected from one or a mixture of any of the following components:

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.

Compared with the prior art, the invention has the advantages that:

1. the invention adopts the ionic liquid as the regeneration reagent, so that the noble metal on the deactivated catalyst is reactivated and dispersed, the catalyst regeneration is realized, the activity and the selectivity of the catalyst are recovered to the level before deactivation, the catalyst can be reused, the production cost is saved, and the utilization rate of the noble metal is improved.

2. According to the invention, after the platinum group metal catalyst is regenerated by using the ionic liquid, the regeneration performance of the ionic liquid can be recovered by a heating treatment method, so that the regeneration reagent can be repeatedly used.

3. The invention adopts X-ray as assistance, which greatly increases the regeneration effect of the regeneration reagent on the platinum group metal catalyst.

Detailed Description

The present invention will be described with reference to specific examples. It should be noted that the examples are only intended to illustrate the invention further, but should not be construed as limiting the scope of the invention, which is in no way limited thereto. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.

Catalyst A: selecting 5g of supported platinum group metal catalyst, wherein the carrier of the catalyst is columnar alumina with the particle size of 10 meshes, the loading amount of the catalyst is 0.2 wt%, the particle size of active center palladium nano particles is 2nm, and the fresh catalyst is used in the catalytic reaction of nitrobenzene hydrogenation (the reaction gas contains 250ppm of H₂S) the catalytic activity is 99 percent, the selectivity is 99 percent, the catalyst is continuously used for carrying out nitrobenzene hydrogenation experiments, and when the activity of the catalyst is reduced to 15 percent, the catalyst is taken out for standby.

Catalyst B: selecting 5g of supported platinum group metal catalyst, wherein the carrier of the catalyst is spherical active carbon with the particle size of 20 meshes, the loading amount of the catalyst is 0.7 wt%, the particle size of active center ruthenium nano particles is 4nm, and the fresh catalyst is used in the hydrogenation reaction of m-nitrobenzenesulfonic acid (the reaction gas contains 250ppm of H₂S) the catalytic activity is 98.5 percent, the selectivity is 99.2 percent, the catalyst is continuously used for carrying out the m-nitrobenzenesulfonic acid hydrogenation experiment, and when the activity of the catalyst is reduced to 18.8 percent, the catalyst is taken out for standby.

Catalyst C: selecting 5g of supported platinum group metal catalyst, wherein the carrier of the catalyst is spherical titanium dioxide with the particle size of 50 meshes, the load capacity of the catalyst is 0.9 wt%, the particle size of active center rhodium nanoparticles is 6nm, and the fresh catalyst is used in the catalytic reaction of acetylene hydrogenation (the reaction gas contains 250ppm of H₂S) catalysisThe activity is 97.2%, the selectivity is 97.2%, and then the catalyst is continuously used for carrying out acetylene hydrogenation experiments, and when the activity of the catalyst is reduced to 14.3%, the catalyst is taken out for later use.

Catalyst D: selecting 5g of supported platinum group metal catalyst, wherein the carrier of the catalyst is a spherical carbon nano tube with the particle size of 60 meshes, the loading amount of the catalyst is 1 wt%, the particle size of the active center iridium nano particle is 10nm, and the fresh catalyst is used in the catalytic reaction of nitrobenzene hydrogenation (the reaction gas contains 250ppm of H₂S) the catalytic activity is 97.4 percent, the selectivity is 97.8 percent, the catalyst is continuously used for carrying out nitrobenzene hydrogenation experiments, and when the activity of the catalyst is reduced to 17.8 percent, the catalyst is taken out for standby.

Catalyst E: selecting 5g of supported platinum group metal catalyst, wherein the carrier of the catalyst is beta molecular sieve, the loading capacity of the catalyst is 1.2 wt%, the particle size of active center platinum nano particles is 12nm, and the fresh catalyst is used in the catalytic reaction of nitrobenzene hydrogenation (the reaction gas contains 250ppm of H₂S) the catalytic activity is 97.9 percent, the selectivity is 98.2 percent, the catalyst is continuously used for carrying out nitrobenzene hydrogenation experiments, and when the activity of the catalyst is reduced to 16.4 percent, the catalyst is taken out for standby.

Example 1

Weighing 5g of A deactivated catalyst, placing the A deactivated catalyst at 120 ℃, purging the A deactivated catalyst for 4 hours in a nitrogen atmosphere, and then cooling the A deactivated catalyst to room temperature. The obtained catalyst is irradiated under X-ray with the ray frequency of 30PHz, 20ml of monobutyl trimethyl imidazole perchlorate ionic liquid is added as a regeneration reagent, and the catalyst is soaked for 2 hours with the stirring speed of 100 r/min. And washing the catalyst with deionized water until the washing liquid is neutral, recovering the washed filtrate, and drying the washed catalyst for 24 hours in vacuum at 50 ℃. Thus obtaining the regenerated supported platinum group metal catalyst. And (3) carrying out rotary evaporation on the obtained filtrate at the temperature of 60 ℃ and under the pressure of 400mmHg by using a rotary evaporator until the quality of the liquid is not changed, and heating and treating the rotary-evaporated product at 150 ℃ for 2h to obtain the recycled regeneration reagent.

Example 2

Weighing 5g of B deactivated catalyst, placing the B deactivated catalyst at 115 ℃, purging the B deactivated catalyst for 4 hours in an argon atmosphere, and then cooling the B deactivated catalyst to room temperature. The obtained catalyst is irradiated under X-ray with the ray frequency of 100PHz, and then 20ml of tributyl ethyl phosphine bromide ionic liquid is added as a regeneration reagent to be soaked for 2h, and the stirring speed is 300 r/min. And washing the catalyst with a mixed solution of ethanol and methanol in equal proportion until the washing solution is neutral, recovering the washed filtrate, and drying the washed catalyst for 18 hours in vacuum at 80 ℃. Thus obtaining the regenerated supported platinum group metal catalyst. And (3) carrying out rotary evaporation on the obtained filtrate at the temperature of 70 ℃ and under the pressure of 450mmHg by using a rotary evaporator until the quality of the liquid is not changed, and heating and treating the rotary-evaporated product at 160 ℃ for 4 hours to obtain the recycled regeneration reagent.

Example 3

5g of the C-deactivated catalyst is weighed, placed at 110 ℃, purged for 4h in a helium atmosphere and then cooled to room temperature. The obtained catalyst is irradiated under X-ray with the ray frequency of 500PHz, and then 20ml of triethyl methyl ammonium bromide ionic liquid is added as a regeneration reagent to be soaked for 2h, and the stirring speed is 500 r/min. And washing the catalyst with acetone until the washing liquid is neutral, recovering the washed filtrate, and vacuum-drying the washed catalyst at 90 ℃ for 12 h. Thus obtaining the regenerated supported platinum group metal catalyst. And (3) carrying out rotary evaporation on the obtained filtrate at the temperature of 80 ℃ and under the pressure of 500mmHg by using a rotary evaporator until the quality of the liquid is not changed, and then carrying out heating treatment on the rotary evaporated product at 170 ℃ for 6h to obtain the recycled regeneration reagent.

Example 4

Weighing 5g of D deactivated catalyst, placing the D deactivated catalyst at 105 ℃, purging the D deactivated catalyst for 4 hours in an argon nitrogen equal-proportion mixed gas atmosphere, and then cooling the D deactivated catalyst to room temperature. The obtained catalyst is irradiated under X-ray with the ray frequency of 1EHz, 20ml of N-butyl-N-methylpyrrolidone bromide ionic liquid is added as a regeneration reagent, and the catalyst is soaked for 2 hours with the stirring speed of 600 r/min. And washing the catalyst with tetrahydrofuran until the washing liquid is neutral, recovering the washed filtrate, and drying the washed catalyst for 10h in vacuum at 100 ℃. Thus obtaining the regenerated supported platinum group metal catalyst. And (3) carrying out rotary evaporation on the obtained filtrate at the temperature of 90 ℃ and the pressure of 550mmHg by using a rotary evaporator until the quality of the liquid is not changed, and heating the rotary evaporated product at 180 ℃ for 8h to obtain the recycled regeneration reagent.

Example 5

5g of the E-deactivated catalyst was weighed, placed at 100 ℃ and purged under nitrogen for 4h and then cooled to room temperature. The obtained catalyst is irradiated under X-ray with the ray frequency of 10EHz, 20ml of N-butylpyridinium bis (trifluoromethanesulfonyl) imide salt ionic liquid is added as a regeneration reagent, and the catalyst is soaked for 2 hours with the stirring speed of 700 r/min. And washing the catalyst with deionized water until the washing liquid is neutral, recovering the washed filtrate, and drying the washed catalyst for 8 hours in vacuum at 110 ℃. And (3) carrying out rotary evaporation on the filtrate obtained by the regenerated supported platinum group metal catalyst at the temperature of 100 ℃ and under the pressure of 600mmHg by using a rotary evaporator until the quality of the liquid is not changed, and heating the rotary evaporated product at the temperature of 200 ℃ for 7 hours to obtain the regenerated reagent which can be recycled.

Comparative example 1

Comparative example 1 is a comparison with example 1, illustrating the non-replaceability of the regeneration agent in catalyst regeneration.

Weighing 5g of A deactivated catalyst, placing the A deactivated catalyst at 120 ℃, purging the A deactivated catalyst for 4 hours in a nitrogen atmosphere, and then cooling the A deactivated catalyst to room temperature. The obtained catalyst is irradiated under X-ray with the ray frequency of 30PHz, 20ml of deionized water is added as a regeneration reagent, and the catalyst is soaked for 2 hours with the stirring speed of 100 r/min. And washing the catalyst with deionized water until the washing liquid is neutral, recovering the washed filtrate, and drying the washed catalyst for 24 hours in vacuum at 50 ℃. Thus obtaining the regenerated supported platinum group metal catalyst. The activity of the catalytic hydrogenation reaction of the regenerated supported platinum group metal catalyst is 20 percent, and the selectivity is 26.3 percent.

Comparative example 2

Comparative example 2 is compared with example 2 to illustrate the irreplaceability of the heat treatment to allow recycling of the regeneration agent.

Weighing 5g of B deactivated catalyst, placing the B deactivated catalyst at 115 ℃, purging the B deactivated catalyst for 4 hours in an argon atmosphere, and then cooling the B deactivated catalyst to room temperature. The obtained catalyst is irradiated under X-ray with the ray frequency of 100PHz, and then 20ml of tributyl ethyl phosphine bromide ionic liquid which is not subjected to heating treatment is added as a regeneration reagent to be soaked for 2h, and the stirring speed is 300 r/min. And washing the catalyst with a mixed solution of ethanol and methanol in equal proportion until the washing solution is neutral, recovering the washed filtrate, and drying the washed catalyst for 18 hours in vacuum at 80 ℃. Thus obtaining the regenerated supported platinum group metal catalyst. The activity of the catalytic hydrogenation reaction of the regenerated supported platinum group metal catalyst is 35 percent, and the selectivity is 66.3 percent.

Comparative example 3

Comparative example 3 is compared with example 3 to illustrate the irreplaceability of X-ray irradiation for catalyst regeneration.

Weighing 5g of B deactivated catalyst, placing the B deactivated catalyst at 115 ℃, purging the B deactivated catalyst for 4 hours in an argon atmosphere, and then cooling the B deactivated catalyst to room temperature. Adding 20ml of tributyl ethyl phosphine bromide ionic liquid as a regeneration reagent, soaking for 2h, and stirring at the speed of 500 r/min. And washing the catalyst with a mixed solution of ethanol and methanol in equal proportion until the washing solution is neutral, recovering the washed filtrate, and drying the washed catalyst for 18 hours in vacuum at 80 ℃. Thus obtaining the regenerated supported platinum group metal catalyst. The activity of the catalytic hydrogenation reaction of the regenerated supported platinum group metal catalyst is 60 percent, and the selectivity is 67.8 percent.