CN103157518A - Mesoporous magnesium oxide, hydrodesulfurization catalyst loading CoMo metal sulfide and application thereof - Google Patents
Mesoporous magnesium oxide, hydrodesulfurization catalyst loading CoMo metal sulfide and application thereof Download PDFInfo
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Abstract
The invention discloses a mesoporous magnesium oxide, a hydrodesulfurization catalyst loading CoMo metal sulfide and an application thereof. The mesoporous magnesium oxide is prepared through the following steps that (1) water is used as reaction medium, magnesium hydroxide fully reacts with carbon dioxide under room temperature in an airtight reaction still, then reaction liquid in the reaction still is filtered, and filtrate which contains Mg (HCO3)2 is obtained; (2) macromolecule surfactant N, N-Diethyl-N-Cetyl-N- (3-methoxy silane propane) ammonium iodide are added into the filtrate which contains the Mg (HCO3)2, mixture is heated to 80 DEG C-95 DEG C and maintained to 0.5h-2h under stirring, the mixture is calcinated for 3h-4h after the mixture is filtered and dried, and the mesoporous magnesium oxide is obtained. The hydrodesulfurization catalyst loading CoMo metal sulfide is prepared by that the mesoporous magnesium oxide is used as carriers, is suitable for hydrodesulfurization reactions of dibenzothiophene, and exerts high catalytic activity.
Description
(1) technical field
Hydrobon catalyst and the application thereof of the load C oMo sulfide that the present invention relates to a kind of mesoporous magnesia and make as carrier.
(2) background technology
In recent years, along with the raising of people's living standard and to the attention of ecological environment, more and more stricter environmental regulation was formulated out.The sulfurous gas that wherein derives from the release in the fuel oil combustion process has caused serious pollution to atmosphere, is the main cause that forms acid rain.In succession formulated more and more stricter fuel oil sulfur-bearing standard in countries in the world, as European Union's executed Europe V standard, sulfur content must not be higher than 10 μ g/g, the U.S. in 2010 have realized diesel oil sulfur content lower than 15 μ g/g.In China, in Beijing, the city such as Shanghai, Guangzhou takes the lead in having carried out state IV standards, wherein sulfur content must not higher than 50 μ g/g, in the near future, will be implemented state IV standards in China.As seen, produce low-sulfur and even become the active demand of environmental protection without the clean fuel oil of sulphur.
(NiW loads to γ-Al for CoMo, NiMo by traditional metal sulfide catalyst
2O
3) catalytic hydrogenation is the present industrial effective way that realizes the desulfurization of oil product cut fraction hydrogenation.But, traditional γ-Al
2O
3The metal sulfide catalyst of load is desulphurizing activated lower, needs the critical operation condition of high temperature, high pressure could satisfy the production clear gusoline.
CN 201210101713.8 discloses Hydrobon catalyst of a kind of porous zeolite load C oMo, NiMo, NiW metal sulfide and preparation method thereof, its catalyst to the hydrodesulfurization activity of dibenzothiophenes a little less than the catalyst in this patent.
Therefore, preparing highly active Hydrobon catalyst can realize deep desulfuration under lower temperature and pressure, be the key of low-cost production clear gusoline.
(3) summary of the invention
First purpose of the present invention is to provide a kind of mesoporous magnesia, and it has larger specific area, can make the Hydrobon catalyst of highly active load C oMo metal sulfide as carrier.
Second purpose of the present invention is to provide a kind of Hydrobon catalyst of the load C oMo metal sulfide take described mesoporous magnesia as carrier, and this catalyst has high activity.
The 3rd goal of the invention of the present invention is to provide the application of Hydrobon catalyst in the hydrodesulfurization reaction of dibenzothiophenes of described load C oMo metal sulfide.
For achieving the above object, the present invention adopts following technical scheme:
The invention provides a kind of mesoporous magnesia, it prepares as follows:
(1) in closed reactor, take water as reaction medium, magnesium hydroxide and carbon dioxide fully react, and then open reactor, with reacting liquid filtering, obtain containing Mg (HCO
3)
2Filtrate;
(2) containing Mg (HCO
3)
2Filtrate in add molecules surfactant N, N-diethyl-N-cetyl-N-(3-methoxy silane propane) ammonium iodide (being labeled as DM-3010), being heated to 80 ~ 95oC under stirring kept 0.5 ~ 2 hour, filtration, dry rear in 350 ~ 450 oC roasting 3 ~ 4 hours obtains mesoporous magnesia.
In described step (1), the reaction equation of the chemical reaction of generation is 2CO
2+ Mg (OH)
2=Mg (HCO
3)
2Owing to consuming a large amount of CO in course of reaction
2, therefore need constantly to fill CO in reactor
2, CO in the general control still in course of reaction
2Pressure is at 1.0 ~ 4.0MPa.Filter after still internal reaction certain hour, for improving Mg (OH)
2Utilization rate, filter residue can be reused repeatedly.
In described step (2), described molecules surfactant is N, N-diethyl-N-cetyl-N-(3-methoxy silane propane) ammonium iodide, every 500 mLMg (HCO
3)
2Filtrate in addition be 5～20mL.
The present invention also provides a kind of Hydrobon catalyst that utilizes the load C oMo metal sulfide of described mesoporous magnesia preparation, described Hydrobon catalyst is as carrier with described mesoporous magnesia, make by equi-volume impregnating, specifically comprise the steps:
The slaine that (a) will contain Co, Mo is dissolved in the solution that contains complexing agent, and the gained mixed solution dropwise is added in described mesoporous magnesia carrier, and room temperature is standing more than 12 hours, and drying obtains catalyst precursor; Control wherein that in the slaine contain Co, Mo, the atomic ratio of Co and Mo is 0.25 ~ 0.6:1, described mixed solution according to the Mo that wherein contains with MoO
3Form 4.0 ~ 20.0wt.% of being calculated as the mesoporous magnesia quality feed intake; Described complexing agent is ethylenediamine tetra-acetic acid or citric acid; When described complexing agent is ethylenediamine tetra-acetic acid, form the solution that contains complexing agent with the ammonia solvent complexing agent; When complexing agent was citric acid, water or ammonia solvent complexing agent formed the solution that contains complexing agent;
(b) catalyst precursor is at H
2S+H
2Mixed atmosphere in, in 350 ~ 450oC sulfuration 3 ~ 4 hours, namely get the Hydrobon catalyst of load C oMo metal sulfide.
In described step (a), described complexing agent and cobalt ions complexing are conducive to form highly active catalyst, and preferred complexing agent is ethylenediamine tetra-acetic acid; The molar ratio example of described ethylenediamine tetra-acetic acid and Co is 1:1.Because the application adopts equi-volume impregnating, therefore the rate of charge of described mixed solution and carrier is decided according to the character of carrier.
As preferably, the slaine that contains Co is Co (NO
3)
26H
2O, the slaine that contains Mo is (NH
4)
6Mo
7O
244H
2O。
In described step (b), described H
2S+H
2Mixed atmosphere in H
2The volume fraction of S is preferably 10 ~ 15%.
As preferably, catalyst precursor is at H
2S+H
2Mixed atmosphere in be warming up to 350 ~ 450oC with the speed of 2 ~ 5oC/min.
The Hydrobon catalyst of load C oMo metal sulfide of the present invention can be applicable to show high catalytic activity in the hydrodesulfurization reaction of dibenzothiophenes (DBT).
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention uses DM-3010 as template in the preparation of mesoporous magnesia, has improved the specific area of mesoporous magnesia, is conducive to improve it as the activity of the Hydrobon catalyst of carrier preparation.
(2) Hydrobon catalyst that makes of the present invention and traditional γ-Al
2O
3The catalyst of the catalyst of load, porous zeolite load is compared, and under identical reaction condition, (DBT) has hydrodesulfurization effect preferably to dibenzothiophenes.
(4) description of drawings
Fig. 1 is the XRD figure of the mesoporous magnesia (M-MgO) of embodiment 1 preparation.
Fig. 2 is the high resolution scanning electromicroscopic photograph of the CoMo/M-MgO of embodiment 2 preparations.
Fig. 3 is the pore distribution curve of the M-MgO of embodiment 1 preparation;
Fig. 4 is the isothermal adsorption desorption curve of the M-MgO of embodiment 1 preparation.
Fig. 5 is embodiment 2 to embodiment 6, changes load capacity to the impact of DBT hydrodesulfurization activity.
Fig. 6 is embodiment 5 and embodiment 7, take M-MgO as carrier, and the impact of the catalyst of different complexing agent preparations on the DBT hydrodesulfurization activity.
Fig. 7 is M-MgO and the industrial γ-Al of embodiment 5 preparations
2O
3The comparison of the metal sulfide catalyst of load to DBT hydrodesulfurization reaction activity.
Fig. 8 is that the metal sulfide catalyst of the M-MgO of embodiment 5 preparation and mesoporous mordenite (M-MOR) preparation is to the comparison of DBT hydrodesulfurization reaction activity.
(5) specific embodiment
The invention will be further described below in conjunction with experimental subjects, but protection scope of the present invention is not limited to this.
Embodiment 1:
The preparation of mesoporous magnesia is carried out in 300 mL autoclaves, at first takes 20g Mg (OH)
2Put into reactor, then pour the distilled water of 230mL in reactor.With the reactor sealing, with the CO of 1MPa
2Get rid of air in still, repeatedly operate three times, guarantee that the interior air of still is by emptying.
Fill CO in reactor
2, pressure is 4.0MPa, at room temperature stirs, and mixing speed is controlled at 350-500 rev/min, and chemical reaction occurs, and chemical equation is 2CO
2+ Mg (OH)
2=Mg (HCO
3)
2Owing to consuming a large amount of CO in course of reaction
2, therefore need constantly to fill CO in reactor
2Reacted 5 hours, and then slowly emitted remaining CO in still
2, still internal reaction liquid is filtered, for improving Mg (OH)
2Utilization rate, filter residue can be reused repeatedly.To contain Mg (HCO
3)
2Filtrate carry out pyrolysis.
Under room temperature, filtrate is poured in the beaker of 500mL, add the magneton rapid stirring, dropwise add the DM-3010 of 10mL in whipping process, slowly be warming up to 90oC simultaneously, kept 1 hour.Then with reacting liquid filtering, obtain the magnesium carbonate filter cake, dry 12 hours of 100oC after 4 hours, namely gets mesoporous magnesia in the 450oC roasting at last, is labeled as M-MgO.
Embodiment 2: the preparation of catalyst
2g M-MgO powder energy incipient impregnation 6g water is with 0.0982 (NH
4)
6Mo
7O
244H
2O, 0.0809g Co (NO
3)
26H
2O and 0.0812g ethylenediamine tetra-acetic acid (EDTA) are dissolved in 6.0g ammoniacal liquor (mass fraction is 28.0%), treat that it all is added drop-wise in 2g M-MgO powder after dissolving, after dipping is completed, put at room temperature standing 20 hours, drying is 20 hours in the 100oC baking oven, the catalyst precursors that makes at the certain pressure lower sheeting, is got the 40-60 order, at last at 10%H
2S+H
2Mixed atmosphere in, raising speed 2oC/min, under 400oC the sulfuration 3 hours, be labeled as the CoMo/M-MgO# 1 catalyst.Wherein, the load capacity of Mo is (with MoO
3Meter) being calculated in mass percent is that 4.0%, Co/Mo atomic ratio is that the atomic ratio of 0.5, EDTA/Co is 1.0.
Embodiment 3:
2g M-MgO powder can flood 6g water, with 0.1964 (NH
4)
6Mo
7O
244H
2O, 0.1618g Co (NO
3)
26H
2O and 0.1624g ethylenediamine tetra-acetic acid (EDTA) are dissolved in 6.0g ammoniacal liquor (mass fraction is 28.0%), treat that it all is added drop-wise in 2g M-MgO powder after dissolving, after dipping is completed, put at room temperature standing 20 hours, drying is 20 hours in the 100oC baking oven, the catalyst precursors that makes at the certain pressure lower sheeting, is got the 40-60 order, at last at 10%H
2S+H
2Mixed atmosphere in, raising speed 2oC/min, under 400oC the sulfuration 3 hours, be labeled as the CoMo/M-MgO# 2 catalyst.Wherein, the load capacity of Mo is (with MoO
3Meter) being calculated in mass percent is that 8.0%, Co/Mo atomic ratio is that the atomic ratio of 0.5, EDTA/Co is 1.0.
Embodiment 4:
2g M-MgO powder energy incipient impregnation 6g water is with 0.2946 (NH
4)
6Mo
7O
244H
2O, 0.2427g Co (NO
3)
26H
2O and 0.2436g ethylenediamine tetra-acetic acid (EDTA) are dissolved in 6.0g ammoniacal liquor (mass fraction is 28.0%), treat that it all is added drop-wise in 2g M-MgO powder after dissolving, after dipping is completed, put at room temperature standing 20 hours, drying is 20 hours in the 100oC baking oven, the catalyst precursors that makes at the certain pressure lower sheeting, is got the 40-60 order, at last at 10%H
2S+H
2Mixed atmosphere in, raising speed 2oC/min, under 400oC the sulfuration 3 hours, be labeled as the CoMo/M-MgO# 3 catalyst.Wherein, the load capacity of Mo is (with MoO
3Meter) being calculated in mass percent is that 12.0%, Co/Mo atomic ratio is that the atomic ratio of 0.5, EDTA/Co is 1.0.
Embodiment 5:
2g M-MgO powder energy incipient impregnation 6g water is with 0.3928g (NH
4)
6Mo
7O
244H
2O, 0.3236g Co (NO
3)
26H
2O and 0.3248g ethylenediamine tetra-acetic acid (EDTA) are dissolved in 6.0g ammoniacal liquor (mass fraction is 28.0%), treat that it all is added drop-wise in 2g M-MgO powder after dissolving, after dipping is completed, put at room temperature standing 20 hours, drying is 20 hours in the 100oC baking oven, the catalyst precursors that makes at the certain pressure lower sheeting, is got the 40-60 order, at last at 10%H
2S+H
2Mixed atmosphere in, raising speed 2oC/min, under 400oC the sulfuration 3 hours, be labeled as the CoMo/M-MgO# 4 catalyst.Wherein, the load capacity of Mo is (with MoO
3Meter) being calculated in mass percent is that 16.0%, Co/Mo atomic ratio is that the atomic ratio of 0.5, EDTA/Co is 1.0.
Embodiment: 6:
2g M-MgO powder energy incipient impregnation 6g water is with 0.4910 (NH
4)
6Mo
7O
244H
2O, 0.4045g Co (NO
3)
26H
2O and 0.4060g ethylenediamine tetra-acetic acid (EDTA) are dissolved in 6.0g ammoniacal liquor (mass fraction is 28.0%), treat that it all is added drop-wise in 2g M-MgO powder after dissolving, after dipping is completed, put at room temperature standing 20 hours, drying is 20 hours in the 100oC baking oven, the catalyst precursors that makes at the certain pressure lower sheeting, is got the 40-60 order, at last at 10%H
2S+H
2Mixed atmosphere in, raising speed 2oC/min, under 400oC the sulfuration 3 hours, be labeled as the CoMo/M-MgO#5 catalyst.Wherein, the load capacity of Mo is (with MoO
3Meter) being calculated in mass percent is that 20.0%, Co/Mo atomic ratio is that the atomic ratio of 0.5, EDTA/Co is 1.0.
Embodiment 7:
2g M-MgO powder energy incipient impregnation 6g water is with 0.3928g (NH
4)
6Mo
7O
244H
2O, 0.3236g Co (NO
3)
26H
2O and 0.3052g citric acid (CA) are dissolved in 6.0g water, treat that it all is added drop-wise in 2g M-MgO powder after dissolving, after dipping is completed, put at room temperature standing 20 hours, drying is 20 hours in the 100oC baking oven, the catalyst precursors that makes at the certain pressure lower sheeting, is got the 40-60 order, at last at 10%H
2S+H
2Mixed atmosphere in, raising speed 2oC/min, under 400oC the sulfuration 3 hours, be labeled as the CoMo/M-MgO# 6 catalyst.Wherein, the load capacity of Mo is (with MoO
3Meter) being calculated in mass percent is that 16.0%, Co/Mo atomic ratio is that the atomic ratio of 0.5, CA/Co is 1.4.
The comparative example 1: with industrial γ-Al
2O
3Prepare the CoMo catalyst as carrier
2g γ-Al
2O
3Powder energy incipient impregnation 3.0g water is with 0.3928g (NH
4)
6Mo
7O
244H
2O, 0.3236g Co (NO
3)
26H
2O and 0.3248g ethylenediamine tetra-acetic acid (EDTA) are dissolved in 3.0g ammoniacal liquor (mass fraction is 28.0%), treat that it all is added drop-wise to 2.5g γ-Al after dissolving
2O
3In powder, after dipping is completed, put at room temperature standing 20 hours, in the 100oC baking oven dry 20 hours, the catalyst precursors that makes at the certain pressure lower sheeting, is got the 40-60 order, at last at 10%H
2S+H
2Mixed atmosphere in, raising speed 2oC/min, under 400oC the sulfuration 3 hours, be labeled as CoMo/ γ-Al
2O
3Catalyst.Wherein, the load capacity of Mo is (with MoO
3Meter) being calculated in mass percent is that 16.0%, Co/Mo atomic ratio is that the atomic ratio of 0.5, EDTA/Co is 1.0.
The comparative example 2: prepare the CoMo catalyst with mesoporous mordenite as carrier
2g mesoporous mordenite powder (M-MOR) energy incipient impregnation 4.0g water is with 0.3928g (NH
4)
6Mo
7O
244H
2O, 0.3236g Co (NO
3)
2Be dissolved in 4.0g ammoniacal liquor (mass fraction is 28.0%) with 0.3248g ethylenediamine tetra-acetic acid (EDTA), treat that it all is added drop-wise in 2g M-MOR powder after dissolving, after dipping is completed, put at room temperature standing 20 hours, drying is 20 hours in the 100oC baking oven, the catalyst precursors that makes at the certain pressure lower sheeting, is got the 40-60 order, at last at 10%H
2S+H
2Mixed atmosphere in, raising speed 2oC/min, under 400oC the sulfuration 3 hours, be labeled as the CoMo/M-MOR catalyst.Wherein, the load capacity of Mo is (with MoO
3Meter) being calculated in mass percent is that 16.0%, Co/Mo atomic ratio is that the atomic ratio of 0.5, EDTA/Co is 1.0.
Application Example: on the high pressure fixed bed reactors, prepared catalyst is estimated
Reaction condition: loaded catalyst 0.2g, reactant liquor is for containing the decahydronaphthalene solution of dibenzothiophenes (DBT), the mass fraction of DBT is 0.6%, with measuring pump, reactant liquor is transported to reactor, flow is 5mL/h, reaction temperature is 260oC, is charged to reaction pressure 5MPa with hydrogen, and hydrogen flowing quantity is 110mL/min.
Fig. 6 is for respectively with M-MgO and γ-Al
2O
3For the CoMo catalyst of carrier preparation, to the comparison of DBT hydrodesulfurization activity.As shown in Figure 6, the catalytic performance of the catalyst take M-MgO as carrier is far above CoMo/ γ-Al
2O
3
Table 1 is M-MgO and the industrial γ-Al of embodiment 1 preparation
2O
3BET surface area, mesoporous pore volume, the comparison of Micropore volume.
Table 1
Claims (8)
1. mesoporous magnesia, it prepares as follows:
(1) in closed reactor, take water as reaction medium, under room temperature, magnesium hydroxide and carbon dioxide fully react, and then reactor internal reaction liquid are filtered, and obtain containing Mg (HCO
3)
2Filtrate;
(2) containing Mg (HCO
3)
2Filtrate in add molecules surfactant N, N-diethyl-N-cetyl-N-(3-methoxy silane propane) ammonium iodide, be heated to 80 ~ 95 ℃ under stirring and kept 0.5 ~ 2 hour, filtration, dry rear in 350 ~ 450 ℃ of roastings 3 ~ 4 hours obtains mesoporous magnesia.
2. mesoporous magnesia as claimed in claim 1, it is characterized in that: described molecules surfactant N, the addition of N-diethyl-N-cetyl-N-(3-methoxy silane propane) ammonium iodide is that every 500 mL contain Mg (HCO
3)
2Filtrate in add 5 ~ 20mL.
3. Hydrobon catalyst that utilizes the load C oMo metal sulfide of mesoporous magnesia as claimed in claim 1 preparation, it is characterized in that described Hydrobon catalyst is as carrier with described mesoporous magnesia, make by equi-volume impregnating, specifically comprise the steps:
The slaine that (a) will contain Co, Mo is dissolved in the aqueous solution that contains complexing agent, and the gained mixed solution dropwise is added in described mesoporous magnesia carrier, and room temperature is standing more than 12 hours, and drying obtains catalyst precursor; Control wherein that in the slaine contain Co, Mo, the atomic ratio of Co and Mo is 0.25 ~ 0.6:1, described mixed solution according to the Mo that wherein contains with MoO
3Form 8 ~ 20wt.% of being calculated as the mesoporous magnesia quality feed intake; Described complexing agent is ethylenediamine tetra-acetic acid or citric acid; When described complexing agent is ethylenediamine tetra-acetic acid, form the solution that contains complexing agent with the ammonia solvent complexing agent; When complexing agent was citric acid, water or ammonia solvent complexing agent formed the solution that contains complexing agent;
(b) catalyst precursor is at H
2S+H
2Mixed atmosphere in, in 350 ~ 450 ℃ of sulfurations 3 ~ 4 hours, namely get the Hydrobon catalyst of load C oMo metal sulfide.
4. the Hydrobon catalyst of load C oMo metal sulfide as claimed in claim 3, it is characterized in that: described complexing agent is ethylenediamine tetra-acetic acid.
5. the Hydrobon catalyst of load C oMo metal sulfide as claimed in claim 3, is characterized in that: described H
2S+H
2Mixed atmosphere in H
2The volume fraction of S is 10 ~ 15%.
6. the Hydrobon catalyst of load C oMo metal sulfide as described in claim 3 or 5, it is characterized in that: in described step (b), catalyst precursor is at H
2S+H
2Mixed atmosphere in be warming up to 350 ~ 450 ℃ with the speed of 2 ~ 5 ℃/min.
7. the Hydrobon catalyst of load C oMo metal sulfide as claimed in claim 3, it is characterized in that: the slaine that contains Co is Co (NO
3)
26H
2O, the slaine that contains Mo is (NH
4)
6Mo
7O
244H
2O。
8. the application of the Hydrobon catalyst of load C oMo metal sulfide as claimed in claim 3 in the hydrodesulfurization reaction of dibenzothiophenes.
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| US11168267B2 (en) | 2019-07-23 | 2021-11-09 | King Fahd University Of Petroleum And Minerals | Method of preparing silica supported CoMoS hydrodesulfurization catalysts |
| CN114570392A (en) * | 2020-12-02 | 2022-06-03 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
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| CN108636340A (en) * | 2018-06-12 | 2018-10-12 | 山东大学 | A kind of preparation method of mesoporous magnesia fiber and its application in purification of heavy metal waste water |
| CN109052437A (en) * | 2018-09-19 | 2018-12-21 | 常州大学 | A kind of preparation method of the mesoporous magnesia by the molecular floriform appearance of nanoparticle |
| CN109052437B (en) * | 2018-09-19 | 2020-07-07 | 常州大学 | Preparation method of flower-shaped mesoporous magnesium oxide composed of nanoparticles |
| US11168267B2 (en) | 2019-07-23 | 2021-11-09 | King Fahd University Of Petroleum And Minerals | Method of preparing silica supported CoMoS hydrodesulfurization catalysts |
| US11549071B2 (en) | 2019-07-23 | 2023-01-10 | King Fahd University Of Petroleum And Minerals | Catalyst preparation method using an acidified structural directing surfactant |
| US11549070B2 (en) | 2019-07-23 | 2023-01-10 | King Fahd University Of Petroleum And Minerals | CoMoS catalyst preparation method using a triblock copolymer |
| US11560522B2 (en) | 2019-07-23 | 2023-01-24 | King Fahd University Of Petroleum And Minerals | Method of making a hydrodesulfurization catalyst with a structural directing surfactant |
| US11584892B2 (en) | 2019-07-23 | 2023-02-21 | King Fahd University Of Petroleum And Minerals | Autoclave method for hydrothermal preparation of a hydrodesulfurization catalyst |
| US11613709B2 (en) | 2019-07-23 | 2023-03-28 | King Fahd University Of Petroleum And Minerals | Method for making hydrodesulfurization catalyst including calcination |
| CN114570392A (en) * | 2020-12-02 | 2022-06-03 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN114570392B (en) * | 2020-12-02 | 2023-10-10 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
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| CN103157518B (en) | 2015-05-20 |
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