CN102310006A - Method for regenerating and pre-vulcanizing hydrogenation catalyst - Google Patents
Method for regenerating and pre-vulcanizing hydrogenation catalyst Download PDFInfo
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- CN102310006A CN102310006A CN2010102220296A CN201010222029A CN102310006A CN 102310006 A CN102310006 A CN 102310006A CN 2010102220296 A CN2010102220296 A CN 2010102220296A CN 201010222029 A CN201010222029 A CN 201010222029A CN 102310006 A CN102310006 A CN 102310006A
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Abstract
The invention discloses a method for regenerating and pre-vulcanizing a hydrogenation catalyst, which comprises the following steps of: after carrying out charcoal burning on the inactivated hydrogenation catalyst, cooling to a certain temperature; and then directly carrying out suitable pre-vulcanizing treatment and passivating treatment outside a device. In the method disclosed by the invention, the regeneration and vulcanization of the inactivated hydrogenation catalyst are organically combined, so that the generated catalyst is directly subjected to pre-vulcanizing and passivating treatment without being cooled, active metal components can be in a certain active state, and at the time, if the pre-vulcanizing is directly carried out, the vulcanizing effect and the utilization rate of a vulcanizer can be improved. A test shows that in the process, the activity recovery effect of the regenerated catalyst can be improved and the service performance of the regenerated catalyst can be improved. Meanwhile, due to the adoption of the method disclosed by the invention, the energy consumption can be reduced, the production cost is reduced and the production period is shortened.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst regeneration and method for pre-sulphuration, the method that particularly presulfurization outside hydrogenation catalyst regeneration and the device is combined.
Technical background
Because crude output increasess slowly and heaviness day by day, and the world today constantly increases cleaning oil product demand, and product quality requires also more and more stricter.The petroleum distillate hydrogenation technique is the major technique of current production cleaning oil product, and wherein the technology of preparing of hydrogenation catalyst is the key of hydrogen addition technology.The active metal component of the hydrogenation catalyst of commonsense method preparation is an oxidation state, and oxidized catalyst is before industry is used, and its reactive metal need be converted into sulphided state and just have advantages of high catalytic activity.Along with catalyst turns round for a long time, hydrogenation catalyst exists deactivation phenomenom.The deactivation mechanism of hydrogenation catalyst divides three types of poisoning, coking and sintering.Coking is to form carbonaceous at catalyst surface, covers on the activated centre, and a large amount of cokings cause hole plug, stops reactant molecule to get into activated centre in the hole; Basic nitrogen, not only makes catalyst lose activity but also stops up aperture and inner duct on acid centre such as the pyridine compounds and their chemisorbed; Sintering then makes catalyst structure change and the loss of activity center, is meant that for hydrogenation catalyst accumulation of metal or crystal become big.The acid-base neutralization that coking and impurity chemisorbed cause all belongs to temporary poisoning, can burn through air and recover active, and this process is the regeneration of catalyst, and the catalyst of regeneration can continue to use, thereby has improved economic benefit.
The presulfurization of hydrogenation catalyst also has material impact to the performance of catalyst, is the important process step before the catalyst applications.The method for pre-sulphuration of catalyst can be divided into presulfurization and the outer presulfurization of device in the device by the mode of carrying sulphur.In the device presulfurization exist equipment investment high with shortcomings such as catalyst on-stream time is long, use inflammable and poisonous sulfide simultaneously, environment is prone to the generation pollution, have potential safety hazard.The hydrogenation catalyst of presulfurization also brings on-stream time long in the device in addition, and running cost is many, problems such as dangerous height.Thereby the outer method for pre-sulphuration of device arises at the historic moment.The advantage of the outer pre-curing technology of device is: the outer pre-curing technology of (1) device improves the utilization rate of activity of hydrocatalyst metal component, and catalyst vulcanization gets more abundant, and then reduces the generation probability of as-reduced metal compound; (2) the outer pre-curing technology of device can be saved on-stream time, make go into operation easier; (3) poisonous sulfide has been avoided using in the scene of going into operation of the outer pre-sulfide catalyst of device, nor needs to install special-purpose vulcanizing deice; When (4) being used for the commercial plant catalyst and casting aside, more can embody this technology characteristics easily that go into operation.But the outer method for pre-sulphuration of device exists deficiencies such as being afraid of strong collision, fearness high temperature, and storage and the transportation to catalyst simultaneously has higher requirement.Particularly when loading catalyst, need nitrogen protection.The research of presulfurization aspect outside eighties device abroad.Like the EasyActive technology of EURACAT company, the actiCAT technology of CRITERION company and the Xpress technology of TRICAT company etc.Domestic Fushun Petrochemical Research Institute has also successfully developed the outer pre-curing technology of hydrogenating catalyst, and has obtained wide range of industrial applications.
CN 1421510A adopts a kind of bed of material 70mm, carries out constant temperature regeneration in three sections different temperature, finally reaches the regeneration index request.
CN 1390645A is employed in three sections different temperature and carries out the constant temperature processing, finally reaches decaying catalyst and recovers original active requirement fully.
CN 1557556A directly adopts the inorganic sulphide agent solution to handle catalyst; Need not to add the organic compound that contains oxygen and unsaturated bond in the vulcanizing agent; Process in the introducing catalyst of vulcanizing agent is carried out under room temperature or lower temperature; Need not heat, the catalyst of sulfuration preparation need not with oxygen containing gas Passivation Treatment.
CN1611577 adopts a kind of component, organic polysulfide and auxiliary agent that contains alkene to mix, and the heating said mixture is 0.5～8.0 hour under 90～400 ℃ of conditions, obtains the mixture of Containing Sulfur alkene.The hydrogenation catalyst of the impregnation mixture oxidation state of the Containing Sulfur alkene that obtains; And under 100～300 ℃ of conditions, heated this solidliquid mixture 0.5～8.0 hour; Obtain product 20～120 ℃ with hydrocarbon ils dipping 1～12 hour after, the evaporate to dryness hydrocarbon ils makes the hydrogenation catalyst after the sulfuration.
US5169819 is at first at 0～50 ℃, no H
2Condition under with (NH
4)
2The S solution impregnating catalyst, then be lower than under 120 ℃ the oxygen-containing atmosphere dry, again with the (NH that contains additive
4)
2This catalyst of S aqueous solution dipping is being lower than dried under 130 ℃ of conditions at last.Additive is for containing sulphur compound, like thiophene, thio-acid, sulfo-amine, thiocyanate, thioesters, thiazole, thiocarbamide and mercaptan etc., preferably HOC
2H
4SSC
2H
4OH.
US5397756 adopts the impregnation mixture catalyst.Mixture is by vulcanizing agent, olefin component and solvent composition.Vulcanizing agent can be an elementary sulfur, also can be organic polysulfide.What this patent olefin component adopted is fatty acid triglyceride, and what solvent adopted is white oil.Need heat-treat (being higher than 100 ℃) behind the catalyst soakage, remove partial solvent on the one hand, make the two key reactions in elementary sulfur and the alkene component on the other hand.
In above-mentioned hydrogenation catalyst regeneration and the outer method for pre-sulphuration of device, be all catalyst to be carried out the outer perhaps presulfurization of regenerating of device handle.It is long to produce the production cycle like this, energy consumption high etc. problem.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of hydrogenation catalyst regeneration and method for pre-sulphuration.
Hydrogenation catalyst regeneration of the present invention and method for pre-sulphuration comprise following content:
(1) gets the inactivation hydrogenation catalyst, adopt the method for making charcoal to regenerate;
(2) behind the coke-burning regeneration, catalyst temperature is reduced to 125 ℃～220 ℃;
(3) vulcanizing agent is heated to 125 ℃～200 ℃, the vulcanizing agent consumption is theoretical 90%～120% of the sulfur content that needs of Hydrobon catalyst;
(4) be cooled to 125 ℃～220 ℃ hydrogenation catalyst after the regeneration of vulcanizing agent direct impregnation, and flood 1h～15h;
(5) when temperature is reduced to 70 ℃～110 ℃, in the regenerated catalyst of sulfuration, add organic compound and carry out passivation, constant temperature is handled 1h～8h.
In the inventive method, the preliminary treatment such as before coke-burning regeneration is handled, can sieve of inactivation hydrogenation catalyst; The coke-burning regeneration method of inactivation hydrogenation catalyst is well known to those skilled in the art; The general control charcoal temperature that adopts carries out stage regeneration; As at 250 ℃～350 ℃ constant temperature 2h～8h; At 400～550 ℃ of constant temperature 2～8h, can certainly take other suitable constant temperature coke-burning regeneration process then.The coke-burning regeneration process feeds the Control for Oxygen Content charcoal temperature in the gas when generally adopting control to make charcoal.
Hydrogenation catalyst is a carrier with the refractory porous oxide generally, like the composite oxides of aluminium oxide, silica, amorphous silicon aluminium, titanium oxide, molecular sieve and several kinds of elements or mixed oxide carrier etc.The hydrogenation activity component of Hydrobon catalyst is one or more among W, Mo, Ni and the Co, is generally 3wt%～50wt% in oxide hydrogenation activity constituent content.Concrete hydrogenation catalyst can be selected the commercial goods as required, also can prepare by this area general knowledge.
Hydrogenation catalyst is theoretical need sulfur content to be that contained hydrogenation metal component is converted into sulfide (Co on the catalyst
9S
8, MoS
2, Ni
3S
2, WS
2) time need the amount of sulphur.Vulcanizing agent can be elementary sulfur (being elemental sulfur) or sulfur-containing compound, and sulfur-containing compound comprises inorganic sulfocompound and sulfur-containing organic compound.
Vulcanizing agent can be one or more in elemental sulfur and the sulfur-containing compound, preferred elemental sulfur and (NH
4)
2S mixes use.Elemental sulfur and (NH
4)
2S mixes when using, and part by weight is 1: 0.2～1: 0.5.
Organic solvent is preferably the organic solvent that contains unsaturated bond, and like alkene, vegetable fat etc., alkene can be selected from the petroleum distillate that contains alkene, like catalytically cracked gasoline, catalytic cracking diesel oil, coker gasoline, coking kerosene, coker gas oil etc.Carbon number is generally 5～20 in the organic solvent, is preferably 7～16, and organic solvent can be a kind of, also can be that two or more mixes use.Consumption of organic solvent is 1%～50% of a catalyst weight, preferred 5%～30%.
In the step (4), the dipping vulcanizing agent is preferably 130 ℃～180 ℃ following impregnation process 2～8 hours.This processing can be carried out under conditions such as air atmosphere, oxygen denuded air atmosphere, inert gas atmosphere, water vapour atmosphere.
In the step (5), be impregnated with organic compounds preferably 80 ℃～100 ℃ following Passivation Treatment 2～5 hours.This processing can be carried out under conditions such as air atmosphere, oxygen denuded air atmosphere, inert gas atmosphere, water vapour atmosphere.
Hydrogenation catalyst regeneration of the present invention and method for pre-sulphuration have following advantage:
1, behind the hydrogenation catalyst inactivation provided by the invention regeneration and vulcanization process in; The inventor is surprised to find that; Regenerative process and sulfidation are organically combined, make regenerated catalyst directly carry out presulfurization, can make active metal component be in certain active state without cooling; Directly carry out presulfurization and can improve cure efficiency and vulcanizing agent utilization rate this moment; And then having improved the serviceability of catalyst, sulfuration has simultaneously solved the storing and transporting security problem of presulfurization type catalyst well after transpassivation is handled.Experiment shows that this process can also obviously improve the activation recovering effect of regenerated catalyst, improves the serviceability of regenerated catalyst.
2, because the present invention combines the regeneration of inactivation hydrogenation catalyst with the outer presulfurization of the device of catalyst, liberated heat when having made full use of decaying catalyst regeneration has reduced energy consumption, has reduced production cost, shortens the production cycle.
3, because the present invention makes suitable organic matter, to the processing and the (NH of oxidation state Hydrobon catalyst
4)
2The use of S; Not only can make catalyst have higher sulphur reservation degree, and be that pre-vulcanization process is more even, the even heat release when helping catalyst to go into operation; Simultaneously presulfurization back end hydrogenation catalyst for refining need not inert gas shielding, catalyst deposit, transport and filling need not nitrogen protection.
4, the inventive method technology is simple, adopt cheap industrial chemicals, and equipment is simple, and is workable, and particularly vulcanizing agent adopts inorganic sulfur, avoids contacting of people and organic sulfur, and minimizing is to the damage of human body.
The specific embodiment
Inactivation Hydrobon catalyst FH-DS behind the industrial operation one-period that is adopted in following examples of the present invention (Fushun Petrochemical Research Institute's development, Hua Hua group company in Wenzhou produces).This catalyst is a carrier with the aluminium oxide, is active component with W-Mo-Ni-Co, and its reactive metal counts 30% with oxide weight.The surface area of this catalyst is 180m
2/ g, pore volume are 0.34mL/g.The percentage that does not below indicate benchmark is weight percentage.
The feedstock oil character of catalyst system therefor evaluation usefulness is seen table 1, the evaluating catalyst condition in the embodiment of the invention simultaneously: 360 ℃ of reaction temperatures, reaction pressure 6MPa, hydrogen to oil volume ratio 500: 1, volume space velocity 4.0h during liquid
-1
Table 1 feedstock oil main character
Comparative Examples 1
Inactivation Hydrobon catalyst FH-DS is 100 grams, in air atmosphere, regenerates.280 ℃ of constant temperature calcinings 3 hours are warmed up to 480 ℃ of roastings 3 hours then, cool to room temperature.Oxidation state regeneration hydrogenation catalyst FH-DS carries out activity rating after the interior presulfurization sulfuration of device routinely, and catalyst activity the results are shown in Table 2.
Comparative Examples 2
Inactivation Hydrobon catalyst FH-DS is 100 grams, in air atmosphere, regenerates.280 ℃ of constant temperature calcinings 3 hours are warmed up to 480 ℃ of roastings 3 hours then, cool to room temperature.Oxidation state regeneration hydrogenation catalyst FH-DS carries out device and vulcanizes outward.Oxidation state regeneration hydrogenation catalyst FH-DS is immersed in 20g organic solvent (organic solvent is the coking kerosene cut), and the ratio of carbon number 9～12 is not less than 50% in the organic solvent, dip time 1 hour.(the NH of elementary sulfur 10g and 5g
4)
2S mixes.Catalyst behind the dipping is mixed with vulcanizing agent, and handled 3 hours down, cool to room temperature again at 180 ℃.Carry out activity rating, catalyst activity the results are shown in Table 2.
Embodiment 1
Inactivation Hydrobon catalyst FH-DS is 100 grams, in air atmosphere, regenerates.280 ℃ of constant temperature calcinings 3 hours are warmed up to 480 ℃ of roastings 3 hours then, lower the temperature 180 ℃.(NH with elemental sulfur 10g and 5g
4)
2S mixes, and 150 ℃ of heating mixing down.Handled 3 hours down again with the vulcanizing agent impregnated catalyst that mixes, and at 180 ℃.When cooling to 90 ℃ again, add 20g organic solvent (organic solvent is the coking kerosene cut), the ratio of carbon number 9～12 is not less than 50% in the organic solvent, and constant temperature 3 hours is reduced to room temperature again.Carry out activity rating, catalyst activity the results are shown in Table 2.
Embodiment 2
Inactivation Hydrobon catalyst FH-DS is 100 grams, in air atmosphere, regenerates.320 ℃ of constant temperature calcinings 4 hours are warmed up to 500 ℃ of roastings 4 hours then, lower the temperature 200 ℃.(NH with elemental sulfur 12g and 6g
4)
2S mixes, and under 150 ℃, heats mixing.Handled 6 hours down again with the vulcanizing agent impregnated catalyst that mixes, and at 200 ℃, when cooling to 80 ℃ again; Add 25g organic solvent (organic solvent is the coking kerosene cut); The ratio of carbon number 9～12 is not less than 50% in the organic solvent, and constant temperature 2 hours is reduced to room temperature again.Carry out activity rating, catalyst activity the results are shown in Table 2.
Embodiment 3
Inactivation Hydrobon catalyst FH-DS is 100 grams, in air atmosphere, regenerates.300 ℃ of constant temperature calcinings 3 hours are warmed up to 500 ℃ of roastings 3 hours then, lower the temperature 150 ℃.(NH with elemental sulfur 10g and 5g
4)
2S mixes, and under 135 ℃, heats mixing.To heat the vulcanizing agent impregnated catalyst that mixes again, and handle 6 hours down, when cooling to 85 ℃ again at 150 ℃; Add 25g organic solvent (organic solvent is the coking kerosene cut); The ratio of carbon number 9～12 is not less than 50% in the organic solvent, and constant temperature 3 hours is reduced to room temperature again.Carry out activity rating, catalyst activity the results are shown in Table 2.
Embodiment 4
Inactivation Hydrobon catalyst FH-DS is 100 grams, in air atmosphere, regenerates.320 ℃ of constant temperature calcinings 4 hours are warmed up to 550 ℃ of roastings 3 hours then, lower the temperature 200 ℃.(NH with elemental sulfur 10g and 5g
4)
2S mixes, and under 150 ℃, carries out heat and mixes.To heat the vulcanizing agent impregnated catalyst that mixes again, and handle 5 hours down, when cooling to 80 ℃ again at 200 ℃; Add 20g organic solvent (organic solvent is the coking kerosene cut); The ratio of carbon number 9～12 is not less than 50% in the organic solvent, and constant temperature 4 hours is reduced to room temperature again.Carry out activity rating, catalyst activity the results are shown in Table 2.
Embodiment 5
Inactivation Hydrobon catalyst FH-DS is 100 grams, in air atmosphere, regenerates.310 ℃ of constant temperature calcinings 3 hours are warmed up to 480 ℃ of roastings 3 hours then, lower the temperature 180 ℃.(NH with elemental sulfur 10g and 5g
4)
2S mixes, and under 150 ℃, heats mixing.To heat the vulcanizing agent impregnated catalyst that mixes again, and handle 3 hours down, when cooling to 85 ℃ again at 180 ℃; Add 30g organic solvent (organic solvent is the coking kerosene cut); The ratio of carbon number 9～12 is not less than 50% in the organic solvent, and constant temperature 4 hours is reduced to room temperature again.Carry out activity rating, catalyst activity the results are shown in Table 2.
Embodiment 6
Inactivation Hydrobon catalyst FH-DS is 100 grams, in air atmosphere, regenerates.320 ℃ of constant temperature calcinings 6 hours are warmed up to 450 ℃ of roastings 5 hours then, lower the temperature 160 ℃.(NH with elemental sulfur 10g and 5g
4)
2S mixes, and under 150 ℃, heats mixing.To heat mixed vulcanizing agent impregnated catalyst again, and handle 5 hours down, when cooling to 85 ℃ again at 160 ℃; Add 25g organic solvent (organic solvent is the coking kerosene cut); The ratio of carbon number 9～12 is not less than 50% in the organic solvent, and constant temperature 3 hours is reduced to room temperature again.Carry out activity rating, catalyst activity the results are shown in Table 2.
Embodiment 7
Inactivation Hydrobon catalyst FH-DS is 100 grams, in air atmosphere, regenerates.350 ℃ of constant temperature calcinings 6 hours are warmed up to 550 ℃ of roastings 3 hours then, lower the temperature 150 ℃.(NH with elemental sulfur 12g and 6g
4)
2S mixes, and under 150 ℃, carries out heat and mixes.To heat the vulcanizing agent impregnated catalyst that mixes again, and handle 5 hours down, when cooling to 100 ℃ again at 150 ℃; Add 25g organic solvent (organic solvent is the coking kerosene cut); The ratio of carbon number 9～12 is not less than 50% in the organic solvent, and constant temperature 2 hours is reduced to room temperature again.Carry out activity rating, catalyst activity the results are shown in Table 2.
Embodiment 8
Inactivation Hydrobon catalyst FH-DS is 100 grams, in air atmosphere, regenerates.280 ℃ of constant temperature calcinings 5 hours are warmed up to 480 ℃ of roastings 6 hours then, lower the temperature 180 ℃.(NH with elemental sulfur 10g and 5g
4)
2S mixes, and under 150 ℃, heats mixing.To heat the vulcanizing agent impregnated catalyst that mixes again, and handle 6 hours down, when cooling to 90 ℃ again at 180 ℃; Add 25g organic solvent (organic solvent is the coking kerosene cut); The ratio of carbon number 9～12 is not less than 50% in the organic solvent, and constant temperature 2 hours is reduced to room temperature again.Carry out activity rating, catalyst activity the results are shown in Table 2.
Table 2 embodiment and comparative example go into operation and the catalyst performance contrast
Result by table 2 can find out; Adopt hydrogenation catalyst regeneration provided by the invention and method for pre-sulphuration; With after the existing catalyst regeneration again the catalyst of sulfuration compare, not only flow process is simple, energy consumption is low, obtains the desulphurizing activated of catalyst and also is significantly improved and help.
Claims (10)
1. a hydrogenation catalyst is regenerated and method for pre-sulphuration, it is characterized in that comprising following content:
(1) gets the inactivation hydrogenation catalyst, adopt the method for making charcoal to regenerate;
(2) behind the coke-burning regeneration, catalyst temperature is reduced to 125 ℃～220 ℃;
(3) vulcanizing agent is heated to 125 ℃～200 ℃, the vulcanizing agent consumption is theoretical 90%～120% of the sulfur content that needs of Hydrobon catalyst;
(4) be cooled to 125 ℃～220 ℃ hydrogenation catalyst after the regeneration of vulcanizing agent direct impregnation, and flood 1h～15h;
(5) when temperature is reduced to 70 ℃～110 ℃, in the regenerated catalyst of sulfuration, add organic compound and carry out passivation, constant temperature is handled 1h～8h.
2. according to the described method of claim 1, it is characterized in that: the inactivation hydrogenation catalyst is handled the preliminary treatment of sieving before at coke-burning regeneration.
3. according to the described method of claim 1, it is characterized in that: the coke-burning regeneration method of inactivation hydrogenation catalyst adopts the control charcoal temperature to carry out stage regeneration, at 250 ℃～350 ℃ constant temperature 2h～8h, then at 400～550 ℃ of constant temperature 2～8h.
4. according to the described method of claim 1; It is characterized in that: hydrogenation catalyst is a carrier with the refractory porous oxide; The hydrogenation activity component of Hydrobon catalyst is one or more among W, Mo, Ni and the Co, is 3wt%～50wt% in oxide hydrogenation activity constituent content.
5. according to the described method of claim 1, it is characterized in that: vulcanizing agent is elemental sulfur or sulfur-containing compound, and sulfur-containing compound comprises inorganic sulfocompound and sulfur-containing organic compound.
6. according to claim 1 or 5 described methods, it is characterized in that: vulcanizing agent is elemental sulfur and (NH
4)
2S mixes use, elemental sulfur and (NH
4)
2The S part by weight is 1: 0.2～1: 0.5.
7. according to the described method of claim 1, it is characterized in that: organic solvent is alkene or vegetable fat, and alkene is selected from catalytically cracked gasoline, catalytic cracking diesel oil, coker gasoline, coking kerosene or coker gas oil.
8. according to claim 1 or 8 described methods, it is characterized in that: consumption of organic solvent is 1%～50% of a catalyst weight.
9. according to the described method of claim 1, it is characterized in that: the dipping vulcanizing agent was 130 ℃～180 ℃ following impregnation process 2～8 hours in the step (4).
10. according to the described method of claim 1, it is characterized in that: be impregnated with organic compounds in the step (5) 80 ℃～100 ℃ following Passivation Treatment 2～5 hours.
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| CN105939783A (en) * | 2013-10-31 | 2016-09-14 | 反应堆资源有限责任公司 | In-situ catalyst sulfiding, passivating and coking methods and systems |
| CN106694058A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Regeneration method of hydrogenation catalyst |
| CN107469798A (en) * | 2016-06-07 | 2017-12-15 | 中国石油化工股份有限公司 | A kind of renovation process of sulfur absorbent |
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| CN105939783A (en) * | 2013-10-31 | 2016-09-14 | 反应堆资源有限责任公司 | In-situ catalyst sulfiding, passivating and coking methods and systems |
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| US10960391B2 (en) * | 2018-11-28 | 2021-03-30 | Kunming University Of Science And Technology | Method and system of elemental sulfur recycling and catalyst regenerating for sulfur-deposited catalyst |
| CN111298811A (en) * | 2018-12-11 | 2020-06-19 | 中国石油天然气股份有限公司 | Environment-friendly pre-vulcanization reforming pre-hydrogenation catalyst and preparation method and application thereof |
| CN111298811B (en) * | 2018-12-11 | 2023-02-28 | 中国石油天然气股份有限公司 | Environment-friendly pre-vulcanization reforming pre-hydrogenation catalyst and preparation method and application thereof |
| CN112337501A (en) * | 2020-10-28 | 2021-02-09 | 中海油天津化工研究设计院有限公司 | Preparation method of vulcanization type regenerated hydrogenation catalyst |
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