CN102051205A - In-situ presulfurization method of hydrogenation catalyst - Google Patents
In-situ presulfurization method of hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses an in-situ presulfurization method of a hydrogenation catalyst. The method comprises the following steps: in the wetting stage of the catalyst, introducing sulfurized oil and hydrogen gas from the bottom of a reactor; when the reactor is full of the sulfurized oil, introducing the sulfurized oil and the hydrogen gas from the top of the reactor for closed cycle; and filling a vulcanizing agent into the sulfurized oil gradually to complete sulfurization. In the method provided by the invention, the mode of introducing the sulfurized oil from the bottom of the reactor into the reactor is adopted for the wetting process of the catalyst, thus the wetting of the catalyst is more sufficient and complete, and the dry area in a catalyst bed can be effectively prevented; and meanwhile, as the catalyst is fully wetted, the condition that the catalyst in the oxidation state is reduced by hydrogen gas thus the sulfurization is difficult to perform can be effectively avoided. The sulfurization method provided by the invention is simple in process and is convenient to operate, and the sulfurization effect is better than that of the conventional method, thereby being favorable for improving the activity of the catalyst.
Description
Technical field
The present invention relates to a kind of interior sulfuration of device start-up method of hydrogenation catalyst, relate to a kind of interior prevulcanized start-up method of device of oxidation state hydrogenation catalyst specifically.
Technical background
Because crude production rate increasess slowly and heaviness day by day, and the world today constantly increases cleaning oil product demand, and quality product requires also more and more stricter.The petroleum fractions 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 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.Therefore, the sulfuration of catalyzer has material impact to the performance of catalyzer, is the important process step before catalyzer is used.
Up to now, both at home and abroad most refinery still adopts prevulcanized mode in the device, and promptly fresh or regenerated catalyst loads into to be introduced vulcanizing agent behind the reactor and vulcanize.According to the state difference of vulcanizing agent, the prevulcanized mode can be divided into wet method sulfuration and dry method sulfuration again in the device.The wet method sulfuration also claims the liquid phase sulfuration.Be in the presence of hydrogen, elder generation is dissolved in the liquid curing agent and forms vulcanized oil in the benzoline, and interior the contact with hydrogenation catalyst of input reactor carried out vulcanization reaction then.Its sulfidation is roughly, and is warmed up to certain temperature earlier, introduces vulcanized oil again to the wetting sulfuration of catalyzer, wetting stability number hour, the last persistently overheating vulcanization reaction that carries out.In this process, the uniform wet processes of hydrogenation catalyst has very important effect to its follow-up sulfuration and final activity of such catalysts.It act as:
1, make granules of catalyst all be in wetting regime, prevent the existence in " dried district " in the beds, the existence of " doing the district " will reduce the gross activity of catalyzer;
2, make that sulfide is adsorbed on the catalyzer in the sulfur-bearing oil, prevent that active metal oxide from by hydrogen reducing, causing difficulty to sulfuration,, help improving activity of such catalysts because the vulcanization rate of metal oxide is more faster than the vulcanization rate of metal;
3, avoid the influence of the water molecules that generates in the sulfidation to catalyzer.
And the heat and mass environment of liquid is better than gas phase, so the liquid phase sulfidation is easy to control with respect to the gas phase sulfidation.So both at home and abroad most refinery is in adopting device during the prevulcanized mode, great majority adopts the wet methods sulfuration.
USP4725571 discloses a kind of wet method sulfuration of catalyzer, and this kind method is to adopt to add two kinds of vulcanizing agents in vulcanized oil.The vulcanization process of a Chinese patent CN1362493A catalyst for hydroprocessing of heavy oil, at first solid-state inorganic sulphide and Hydrodemetalation catalyst are mixed, then by adopting the means that dry method sulfuration under the low temperature is combined with wet method vulcanization process under the high temperature, reduced the consumption of vulcanized oil, reduced the sulfuration cost, and the vulcanizing agent sulfurization rate is good, has given full play to the performance of catalyzer.One kind of CN99123716.1 filling is two/reformer of multimetallic catalyst start-up method again, comprise and use the nitrogen purging reaction unit, at 350～420 ℃ of following dry catalysts, feed stock oil afterwards in reforming reactor then, the control water chloride balance is until the operational condition that reaches ordinary production.CN101003749A provides a kind of and is adopting under the existing hydrocracking catalyst condition, need not to carry out the start-up method of oxidation state hydrocracking catalyst of the prevulcanized of catalyzer.With the oxidation state hydrocracking catalyst reactor of packing into; Reach the air in the reactor line in the logical nitrogen replacement reactor, the reactive system adherence pressure is to the required pressure of hydrocracking reaction; Switch hydrogen behind the steady air current, the temperature that promotes beds after hydrogen flowing quantity is stable again is to required catalyst reduction temperature, constant temperature, and it is temperature required that bed temperature is adjusted to hydrocracking reaction, and hydrogen is transferred to the required flow of hydrocracking reaction; Incision reacted hydrocarbon raw material.Need not to add again vulcanizing agent the catalyzer of oxidation state is carried out prevulcanized, avoid the problem brought by prevulcanized, and the catalyzer of partial reduction has higher hydrogenation cracking activity.
In the above-mentioned hydrogenation catalyst vulcanization process, be that all oxidation state hydrogenation catalysts are seated in the reactor, vulcanizing agent is one or both, but its all to be liquid phase enter reactor from reactor head.Its main deficiency is in the hydrogenating catalyst that sulfuration is wetting may be not exclusively, vulcanize insufficiently, or for guaranteeing that sulfuration fully adds two kinds of vulcanizing agents, makes the processing cost increase, complicated operation.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of interior sulfuration of device start-up method of hydrogenation catalyst.
Hydrogenation catalyst sulfuration start-up method of the present invention may further comprise the steps:
(1) gets the oxidation state hydrogenation catalyst;
(2) the oxidation state hydrogenation catalyst is loaded into reactor at normal temperatures and pressures, feed the air in the nitrogen replacement reactive system, and carry out the catalyzer drying;
(3) behind dry the end, reduce reactor batch temperature, use hydrogen exchange nitrogen, it is close to carry out hydrogen;
(4) continue to adjust reactor batch temperature, and introduce vulcanized oil, carry out wetting catalyzer from reactor bottom;
(5) after reactive system is filled with vulcanized oil, vulcanized oil and hydrogen are changed into by the reactor head introducing, vulcanizing agent is progressively injected in the reactive system closed cycle in vulcanized oil, continue to heat up and finish sulfuration;
(6) after sulfuration finishes, introduce stock oil from reactor head.
Oxidation state hydrogenation catalyst described in the step (1) is a carrier with the refractory porous oxide generally, as the composite oxides of aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, molecular sieve and several 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 compound hydrogenation activity component concentration.Concrete hydrogenation catalyst can be selected the commercial goods as required, can also can be that decaying catalyst is through the regenerated catalyst after regenerating by the preparation of this area general knowledge also.
Drying conditions described in the step (2) is: under nitrogen pressure 1.0～3.0MPa, recycle compressor full dose circulation rises to 150～300 ℃ of constant temperature with the heat-up rate of 10～30 ℃/h with reactor batch temperature.Treat the double open fire＜1L/h of putting of high score, constant temperature finishes.
After the drying described in the step (3), reactor batch temperature is reduced to 95～180 ℃, carry out hydrogen exchange, and it is airtight to carry out hydrogen.
Adjusting reactor batch temperature in the step (4) is 95～180 ℃, and vulcanized oil and hydrogen are introduced the reactor at the bottom of reactor.
Vulcanized oil described in the step (4) is straight-run spirit, virgin kerosene, straight-run diesel oil, refined diesel oil, kerosene raffinate etc.The vulcanized oil air speed is 0.5～2h
-1, hydrogen to oil volume ratio is 100～1000.
After reactor is filled with vulcanized oil described in the step (5), vulcanized oil and hydrogen changed into by reactor head enter reactor, reactive system carries out closed cycle.In vulcanized oil, progressively inject vulcanizing agent, carry out bed with 10 ℃/h～30 ℃/h and heat up, when bed temperature rises to 200 ℃～250 ℃, constant temperature sulfuration 2h～10h.After constant temperature finishes, carry out bed and heat up with 10 ℃/h～30 ℃/h again, when bed temperature rises to 280～320 ℃, constant temperature sulfuration 2～10h, sulfuration finishes.
Vulcanizing agent described in the step (5) is selected from dithiocarbonic anhydride (CS2), dimethyl disulphide (DMDS), ethanol sulphur (EM), n-butyl mercaptan (NBM), two uncles and appoints Quito sulfide (TNPS), dimethylsulphide (DMS) etc.
After sulfuration finishes described in the step (6), adjust bed, switch stock oil to temperature of reaction.
Oxidation state hydrogenation catalyst vulcanization process of the present invention has following advantage:
1, the vulcanization process of oxidation state Hydrobon catalyst provided by the invention can guarantee higher sulfuration rate and greater catalytic agent activity.
2, since in the inventive method vulcanized oil enter reactor from reactor bottom and carry out wettingly, make the oxidation state hydrogenation catalyst wetting more fully thoroughly, can effectively prevent the existence of " doing the district " in the beds; Hydrogenation catalyst fully wetting prevents active metal oxide effectively by hydrogen reducing simultaneously, thereby causes difficulty to sulfuration, because the vulcanization rate of metal oxide is more faster than the vulcanization rate of as-reduced metal.Thereby the inventive method helps improving activity of such catalysts, and reduces the stable step in the wetting back of oxidation state hydrogenation catalyst.
3, owing to adopt reactor bottom introducing vulcanized oil when vulcanizing, the vulcanizing agent that is contained in the vulcanized oil is behind injecting reactor progressively like this, make that sulfide can fully be adsorbed on the catalyzer in the vulcanized oil of Containing Sulfur agent, make that the hydrogenation catalyst vulcanization reaction is more complete, and the vulcanization reaction process is an exothermic process, such flow pattern can better prevent localized heat release in the reaction process and the district is done in the part that causes, and the hydrogenation catalyst that makes is a moistening state sulfuration all the time.
4, adopt the vulcanization process of oxidation state Hydrobon catalyst provided by the invention, its technology is simple, simple operation, and hydrogenation catalyst can have advantages of high catalytic activity.
Embodiment
The oxidation state Hydrobon catalyst that is adopted among the embodiment among the present invention is FH-UDS (Fushun Petrochemical Research Institute's development, Hua Hua group company in Wenzhou produces).This catalyzer is a carrier with the aluminum oxide, is active ingredient with W-Mo-Ni-Co, and its reactive metal counts 30% with oxide weight.The surface-area of this catalyzer is 180m
2/ g, pore volume are 0.34mL/g.The per-cent that does not wherein indicate benchmark is weight percentage.
Used stock oil character sees Table 1 in the embodiment of the invention simultaneously.
Table 1 stock oil main character
| The oil product title | Stock oil (straight bavin, urge the bavin Medium diesel oil) |
| Density (20 ℃)/gcm -3 | 0.8571 |
| The boiling range scope/℃ | 176～371 |
| Sulphur/μ gg -1 | 16053 |
| Nitrogen/μ gg -1 | 170 |
| Existent gum/mg (100mL) -1 | 92 |
| Condensed-nuclei aromatics/v% | 13.6 |
| Cetane value | 47.5 |
Comparative Examples 1
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.This simultaneous test is selected small-sized reaction unit for use, so do not need this process.Catalyzer 100g packs in the mini-reactor, airtight qualified, the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h intensification, rising to 140 ℃ is to begin to add vulcanized oil from reactor head, carry out wettingly, closed cycle is installed after being full of vulcanized oil by system, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1, constant temperature is 3 hours simultaneously.Treat that constant temperature finishes to continue to be warming up to 210 ℃ with 20 ℃/h, constant temperature 6 hours treats that constant temperature finishes to continue to be warming up to 280 ℃ with 20 ℃/h, and constant temperature 8 hours finishes constant temperature and continues to be warming up to 320 ℃ with 20 ℃/h, constant temperature 3 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product oil sample and analyze, catalyst activity the results are shown in Table 2.
Embodiment 1
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.Small-sized reaction unit is selected in this test for use, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, changes into from reactor head and enter vulcanized oil, the luggage of going forward side by side is put closed cycle, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 220 ℃ with 20 ℃/h, and constant temperature 8 hours finishes constant temperature and continues to be warming up to 320 ℃ with 20 ℃/h, constant temperature 3 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Embodiment 2
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.Small-sized reaction unit is selected in this test for use, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, changes into from reactor head and enter vulcanized oil, the luggage of going forward side by side is put closed cycle, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 220 ℃ with 20 ℃/h, and constant temperature 8 hours finishes constant temperature and continues to be warming up to 320 ℃ with 20 ℃/h, constant temperature 3 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Embodiment 3
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.Small-sized reaction unit is selected in this test for use, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, changes into from reactor head and enter vulcanized oil, the luggage of going forward side by side is put closed cycle, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 230 ℃ with 20 ℃/h, and constant temperature 6 hours finishes constant temperature and continues to be warming up to 320 ℃ with 20 ℃/h, constant temperature 5 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Embodiment 4
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.This selects small-sized reaction unit for use to testing, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, changes into from reactor head and enter vulcanized oil, the luggage of going forward side by side is put closed cycle, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 230 ℃ with 20 ℃/h, and constant temperature 6 hours finishes constant temperature and continues to be warming up to 320 ℃ with 20 ℃/h, constant temperature 5 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Embodiment 5
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.Small-sized reaction unit is selected in this test for use, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, changes into from reactor head and enter vulcanized oil, the luggage of going forward side by side is put closed cycle, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 210 ℃ with 20 ℃/h, and constant temperature 6 hours continues to be warming up to 300 ℃ with 20 ℃/h, constant temperature 5 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Embodiment 6
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.Small-sized reaction unit is selected in this test for use, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, carry out the device closed cycle, vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 210 ℃ with 20 ℃/h, and constant temperature 6 hours finishes constant temperature and continues to be warming up to 300 ℃ with 20 ℃/h, constant temperature 5 hours, and constant temperature finishes, and switches stock oil by operation.Change into from the incoming stock oil of reactor head this moment.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Table 2 embodiment and comparative example go into operation and the catalyst performance contrast
| The embodiment numbering | The product sulphur content, μ g/g | Product nitrogen content, μ g/g |
| Comparative Examples 1 | ?361 | ?37 |
| Embodiment 1 | ?329 | ?29 |
| Embodiment 2 | ?331 | ?28 |
| Embodiment 3 | ?335 | ?30 |
| Embodiment 4 | ?322 | ?28 |
| Embodiment 5 | ?328 | ?29 |
| Embodiment 6 | ?321 | ?28 |
By the result of table 2 as can be seen, adopt sulfuration start-up method provided by the invention to compare conventional hydrogenation catalyst sulfuration start-up method and save steady time after wetting, its catalyst activity also is better than conventional hydrogenation catalyst sulfuration start-up method.But, just can reach good activity of hydrocatalyst because the inventive method only needs existing installation is transformed.
Claims (9)
1. vulcanize start-up method in the device of a hydrogenation catalyst, may further comprise the steps:
(1) gets the oxidation state hydrogenation catalyst;
(2) the oxidation state hydrogenation catalyst is loaded into reactor at normal temperatures and pressures, feed the air in the nitrogen replacement reactive system, and carry out the catalyzer drying;
(3) behind dry the end, reduce reactor batch temperature, use hydrogen exchange nitrogen, it is close to carry out hydrogen;
(4) continue to adjust reactor batch temperature, and introduce vulcanized oil, carry out wetting catalyzer from reactor bottom;
(5) after reactive system is filled with vulcanized oil, vulcanized oil and hydrogen are changed into by the reactor head introducing, vulcanizing agent is progressively injected in the reactive system closed cycle in vulcanized oil, continue to heat up and finish sulfuration;
(6) after sulfuration finishes, introduce stock oil from reactor head.
2. according to the described start-up method of claim 1, it is characterized in that, oxidation state hydrogenation catalyst described in the step (1) is a carrier with the composite oxides or the mixed oxide of aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, molecular sieve and several elements, active ingredient is one or more among W, Mo, Ni and the Co, is 3wt%～50wt% in oxide compound hydrogenation activity component concentration.
3. according to the described start-up method of claim 1, it is characterized in that, described drying conditions is: under nitrogen pressure 1.0～3.0MPa, the circulation of recycle compressor full dose, heat-up rate with 10～30 ℃/h rises to 150～300 ℃ of constant temperature with reactor batch temperature, treat the double open fire＜1L/h of putting of high score, constant temperature finishes.
4. according to the described start-up method of claim 1, it is characterized in that, behind dry the end, reactor batch temperature is reduced to 95～180 ℃ in the step (3), carry out hydrogen exchange, and it is airtight to carry out hydrogen.
5. according to the described start-up method of claim 1, it is characterized in that adjusting reactor batch temperature in the step (4) is 95～180 ℃, vulcanized oil and hydrogen are introduced the reactor from reactor bottom.
6. according to the described start-up method of claim 1, it is characterized in that the vulcanized oil described in the step (4) is straight-run spirit, virgin kerosene, straight-run diesel oil, refined diesel oil, kerosene raffinate etc.The vulcanized oil air speed is 0.5～2h
-1, hydrogen to oil volume ratio is 100～1000.
7. according to the described start-up method of claim 1, it is characterized in that step (5) is progressively injected vulcanizing agent in vulcanized oil, carry out bed with 10 ℃/h～30 ℃/h and heat up, when bed temperature rises to 200 ℃～250 ℃, constant temperature sulfuration 2h～10h; Continuation is carried out bed with 10 ℃/h～30 ℃/h and is heated up, when bed temperature rises to 280～320 ℃, and constant temperature sulfuration 2～10h.
8. according to the described start-up method of claim 1, it is characterized in that the vulcanizing agent described in the step (5) comprises that dithiocarbonic anhydride, dimethyl disulphide, ethanol sulphur, n-butyl mercaptan, two uncles appoint one or more in Quito sulfide and the dimethylsulphide.
9. according to the described start-up method of claim 1, it is characterized in that described hydrogenation catalyst is the regenerated catalyst after live catalyst or the regeneration of decaying catalyst process.
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| CN105709859A (en) * | 2014-12-20 | 2016-06-29 | 中国石油化工股份有限公司 | Fixed-bed hydrogenation catalyst sulfurization method |
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| CN110653007B (en) * | 2018-06-29 | 2022-08-09 | 中国石油化工股份有限公司 | Hydrogenation catalyst start-up vulcanization method |
| CN111822058A (en) * | 2019-04-19 | 2020-10-27 | 中国石油化工股份有限公司 | Pre-sulfurizing process of hydrogenation catalyst |
| CN117299233A (en) * | 2023-11-29 | 2023-12-29 | 淄博市临淄恒兴化工厂有限公司 | Sulfided hydrogenation catalyst and preparation method thereof |
| CN117299233B (en) * | 2023-11-29 | 2024-02-23 | 淄博市临淄恒兴化工厂有限公司 | Sulfided hydrogenation catalyst and preparation method thereof |
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