CN111068795A - External presulfurization method of hydrogenation catalyst - Google Patents

External presulfurization method of hydrogenation catalyst Download PDF

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Publication number
CN111068795A
CN111068795A CN201811226404.7A CN201811226404A CN111068795A CN 111068795 A CN111068795 A CN 111068795A CN 201811226404 A CN201811226404 A CN 201811226404A CN 111068795 A CN111068795 A CN 111068795A
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catalyst
hydrogenation
hydrogenation catalyst
vulcanizing
oil
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高玉兰
方向晨
徐黎明
佟佳
杨涛
王继锋
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses an ex-situ presulfurization method of a hydrogenation catalyst, which comprises the following steps: (1) uniformly mixing a vulcanizing agent and an oxidation state hydrogenation catalyst, and then carrying out heat treatment; (2) further supplementing and pre-vulcanizing the intermediate material subjected to heat treatment in the step (1) by using a material containing hydrogen sulfide, wherein the conditions of supplementing and pre-vulcanizing the hydrogen sulfide are as follows: the temperature is 50-350 ℃, preferably 90-250 ℃, and the treatment time is 10-240 min, preferably 30-60 min; (3) and (3) loading excessive hydrocarbon oil on the intermediate material vulcanized by the hydrogen sulfide in the step (2) to obtain the deeply vulcanized presulfurized catalyst. The method can effectively solve the problem that ex-situ presulfurization of the hydrogenation catalyst is not matched with the start-up operation of the hydrogenation reactor.

Description

External presulfurization method of hydrogenation catalyst
Technical Field
The invention relates to an ex-situ presulfurization method of a hydrogenation catalyst, in particular to an ex-situ presulfurization technology which is coordinated with the start-up operation of a hydrogenation reactor.
Background
In recent years, the crude oil deterioration tendency is increasingly obvious, the requirement of each country for clean fuel is increasingly increased, the hydrogenation process is taken as one of the most effective means for producing the clean fuel, and the high-efficiency hydrogenation catalyst becomes the technical key of the hydrogenation process. The active metal of the conventional hydrogenation catalyst is in an oxidation state, and the material which really plays an active role in actual use is in a vulcanization state, so the material needs to be vulcanized in a reactor before use. The conventional catalyst is presulfurized in a reactor, but special equipment is needed, so that the production cost is increased, the vulcanization process is easy to cause pollution, and the required start-up time is longer. In response to this problem, in recent years, ex-situ prevulcanization techniques have been developed, such as EPRES developed by the institute of petrochemical engineering®And (3) an ex-situ presulfurization technology. The typical ex-situ presulfurization technology is to load sulfur-containing substances and auxiliaries onto oxidation state catalysts, and the initial reaction temperature of the sulfur-loaded ex-situ presulfurization catalysts during the start-up activation of a hydrogenation unit is low, and the catalysts need to be activated by raising the pressure to a certain pressure at a low temperature, otherwise, the activation effect is not ideal, and the contradiction is great to the operation of the hydrogenation reactor.
The hydrogenation reactor is the most main device of the hydrogenation device, the safety use of the hydrogenation reactor plays an important role, the common stainless steel material of the hot-wall hydrogenation reactor has the hydrogen brittleness characteristic (the toughness of the steel material dissolved with hydrogen at low temperature is greatly reduced, and the brittleness is greatly increased), and the tempering embrittlement of the material is inevitable after the reactor is put into use. Therefore, during the startup and shutdown of the hot wall hydrogenation reactor, when the temperature of the wall is low, the toughness of the wall material can be greatly reduced due to the combined action of hydrogen embrittlement and tempering embrittlement. In order to avoid accidents, the minimum pressure raising temperature of the reactor is usually set, and the minimum pressure raising temperature is usually set to be 125-145 ℃. During the use of the hot wall hydrogenation reactor, the material deterioration condition of the hot wall hydrogenation reactor is gradually increased along with the increase of the service time, so that the pressure limiting temperature rising measure which is deviated from the safety at the initial stage of the reactor operation is possibly dangerous when the temperature rises to the later stage of the reactor service. Therefore, it is very important to accurately infer the safe use state of the reactor according to the material degradation condition of the reactor and determine the reasonable minimum pressure rise temperature, so as to ensure the safety of the long-term use of the hot wall hydrogenation reactor.
Thus, there is a mismatch between the activation operation of the ex-situ presulfided catalyst and the start-up operation of the hydrogenation reactor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an ex-situ presulfurization treatment method for a hydrogenation catalyst, which can effectively solve the problem that ex-situ presulfurization of the hydrogenation catalyst is not matched with the start-up operation of a hydrogenation reactor.
The ex-situ presulfurization method of the hydrogenation catalyst comprises the following steps:
(1) uniformly mixing a vulcanizing agent and an oxidation state hydrogenation catalyst, and then carrying out heat treatment;
(2) further supplementing and pre-vulcanizing the intermediate material subjected to heat treatment in the step (1) by using a material containing hydrogen sulfide, wherein the conditions of supplementing and pre-vulcanizing the hydrogen sulfide are as follows: the temperature is 50-350 ℃, preferably 90-250 ℃, and the treatment time is 10-240 min, preferably 30-60 min;
(3) loading excessive hydrocarbon oil on the intermediate material vulcanized by the hydrogen sulfide in the step (2) to obtain a deeply vulcanized prevulcanized catalyst; the load of the hydrocarbon oil is 25-300% of the weight of the oxidation state hydrogenation catalyst, and preferably 25-75%.
In the method, the oxidation state hydrogenation catalyst in the step (1) is a plurality of catalysts such as gasoline, kerosene, diesel oil and wax oil hydrofining, hydrocracking pre-refining, paraffin hydrogenation, reforming pre-refining, residual oil hydrogenation and the like. The catalyst generally takes alumina as a carrier, takes one or more of W, Mo, Ni and Co as an active component, and can contain one or more of auxiliary agents such as Si, P, B, Ti, Zr and the like.
In the method of the present invention, the vulcanizing agent in step (1) may be a sulfur-containing substance conventional in the art, and may be elemental sulfur and/or a sulfur-containing compound. Can be a single substance or a mixture, and is preferably cheap elemental sulfur (namely sulfur). Such as carbon disulfide and dimethylOne or more of disulfide, tert-butyl polysulfide, tert-nonyl polysulfide, thiourea, n-butyl mercaptan, ethyl mercaptan, sulfur powder, SZ-54 (commercial product), polysulfide, ammonium sulfide, mercaptan, thiophenol, thioether, sulfolane, dimethyl sulfoxide and the like. The dosage of the vulcanizing agent is generally 50-110%, preferably 65-100%, and most preferably 80-95% of the theoretical sulfur demand of the catalyst. The theoretical sulfur demand of the catalyst is that the metal components contained in the catalyst are completely converted into sulfide (Co)9S8、MoS2、Ni3S2、WS2) The amount of sulfur is needed. In order to mix the sulfurizing agent and the oxidation state hydrogenation catalyst uniformly, other proper amount of sulfurization auxiliary agent can be added, such as organic solvent commonly used in the field. The vulcanizing assistant may be one or more of hydrocarbon oil and organic carboxylic ester, the hydrocarbon oil is one or more of various kerosene, diesel oil, lamp oil, white oil, lubricant base oil, straight-run and vacuum heavy fraction oil, etc., preferably hydrocarbon oil obtained by secondary processing, such as those obtained by catalytic cracking, thermal cracking, etc. The organic carboxylic acid ester can be organic carboxylic acid ester containing 6-60 carbon atoms, and fatty glyceride is preferred. The dosage of the vulcanization assistant is 0.1-30% of the weight of the catalyst, preferably 1-15%, more preferably 2-10%.
In the method, the heat treatment temperature in the step (1) is generally 70-300 ℃, preferably 90-230 ℃, and the heat treatment time is generally 10-480 min, preferably 15-240 min.
In the method, the material containing hydrogen sulfide in the step (2) can be a material containing hydrogen sulfide discharged from a hydrogenation device of a refinery enterprise, such as low-gas-separation of the hydrogenation device, and exhaust gas outside recycle hydrogen of the hydrogenation device. The amount of hydrogen sulfide introduced into the pre-vulcanizing device is generally 3% -30% of the theoretical sulfur demand of the catalyst, preferably 5% -20%, and most preferably 8% -15%. The total introduction amount of the vulcanizing agent and the hydrogen sulfide is generally not less than 90 percent of the theoretical sulfur demand of the catalyst.
In the method of the present invention, the hydrocarbon oil in step (3) is generally a hydrocarbon oil obtained in a petroleum processing process, and generally requires a preliminary boiling point of 150 ℃ or higher, preferably 180 ℃ or higher.
In the process of the present invention, a modifier such as an organic acid or an organic nitrogen may be introduced after the step (3) or simultaneously with the step (3) as necessary for adjusting the properties of the catalyst. The loading amount of the modifier is 0.5-20% of the weight of the catalyst, and preferably 2.0-10%. Suitable drying treatment may be employed after step (3).
In the method of the present invention, the selection of the excess hydrocarbon oil used in step (3) may be one or a mixture of several of gasoline, kerosene, diesel oil and wax oil, and is preferably the same hydrocarbon oil using the raw oil as the catalyst for hydrorefining, hydrocracking, etc.
The invention also provides a start-up method of the deep-vulcanized presulfurized catalyst, which comprises the following steps: when the catalyst hydrogenation device is started, the operation conditions are directly adjusted, and the raw oil is introduced for starting operation.
When the method is adopted to carry out ex-situ presulfurization on the hydrogenation catalyst, the following advantages are obtained: (1) compared with the conventional sulfur-carrying catalyst, the start-up time of the catalyst is further reduced; (2) the deeply-vulcanized ex-situ presulfurized catalyst can meet the initial reaction temperature of the hydrogenation device during start-up activation, thereby solving the requirement of the hydrogenation reactor during start-up operation and improving the safety of the hydrogenation reactor; (3) when the catalyst hydrogenation device is started, the operation conditions can be directly adjusted, raw oil is introduced for starting operation, the catalyst is not required to be activated, and heat release and raw water are avoided; (4) the catalyst is thoroughly vulcanized, and the step of passivating the presulfurized catalyst outside the reactor is not needed; (5) the deeply sulfurized catalyst has better activity after performance evaluation.
Detailed Description
The following is a selection of the prior art hydrogenation catalyst for the ex-situ presulfiding treatment to further illustrate the process and effect of the method of the present invention, but not to limit the scope of the invention, and the main material properties referred to in the examples are as follows.
TABLE 1 Diesel hydrogenation catalyst
Figure 209454DEST_PATH_IMAGE002
Table 2 main properties of industrial soybean oil
Figure 188911DEST_PATH_IMAGE004
TABLE 3 Main Properties of gasoline
Figure 968648DEST_PATH_IMAGE006
TABLE 4 essential properties of kerosene
Figure 363858DEST_PATH_IMAGE008
TABLE 5 Main Properties of Diesel
Figure DEST_PATH_IMAGE010
TABLE 6 Main Properties of the Mixed Diesel
Figure DEST_PATH_IMAGE012
Example 1
The FHUDS-5 catalyst in Table 1 was presulfided ex-situ.
(1) Uniformly mixing a vulcanizing agent (elemental sulfur, the dosage of which is 90 percent of the theoretical sulfur demand of FHUDS-5) and a vulcanizing additive (a mixture of industrial soybean oil and kerosene, the weight ratio of which is 1: 1, and the dosage of which is 5 percent of the weight of FHUDS-5) to obtain a pre-vulcanizing raw material; the pre-vulcanized raw material and FHUDS-5 are uniformly mixed, and the mixed material is subjected to heat treatment for 1 hour at the temperature of 140 ℃.
(2) And (2) treating the intermediate material in the step (1) by adopting low-pressure gas of a hydrogenation device (the volume content of hydrogen sulfide is 12%), wherein the introduced amount of the hydrogen sulfide is 15% of the theoretical sulfur demand of the diesel hydrogenation catalyst, the treatment pressure is 3.0MPa, and the intermediate material is treated for 1 hour at the temperature of 320 ℃.
(3) And (3) loading the intermediate material in the step (2) with straight-run diesel oil (properties are shown in Table 5), wherein the loading amount is 50% of the weight of FHUDS-5, obtaining the pre-vulcanized FHUDS-5 catalyst, and naming the catalyst I.
Comparative example 1
The same as example 1 except that the straight run diesel fuel (properties are shown in Table 5) in step (3) had a loading of 3% by weight of FHUDS-5, a presulfided FHUDS-5 catalyst was obtained, designated catalyst A.
Comparative example 2
The same procedure as in example 1, except that the heat treatment of step (1) was omitted, gave a presulfided FHUDS-5 catalyst, designated catalyst B.
Example 2
FHUDS-5 from Table 1 was presulfided ex-situ.
(1) Uniformly mixing a vulcanizing agent (elemental sulfur, the dosage of which is 65 percent of the theoretical sulfur demand of FHUDS-5) and a vulcanizing additive (a mixture of industrial soybean oil and gasoline in a weight ratio of 2: 1, and the dosage of which is 15 percent of the weight of FHUDS-5) to obtain a pre-vulcanized raw material; the prevulcanization raw material and FHUDS-5 are mixed evenly, and the mixture is heat treated for 0.5 hour under the condition of 150 ℃.
(2) And (2) treating the material obtained in the step (1) by using circulating hydrogen exhaust gas of a hydrogenation device (the volume content of hydrogen sulfide is 6%), wherein the introduced amount of the hydrogen sulfide is 40% of the theoretical sulfur demand of the diesel hydrogenation catalyst, the pressure is 0.6MPa, and the material is subjected to heat treatment for 1 hour at the temperature of 180 ℃.
(3) And (3) loading gasoline into the material obtained in the step (2), wherein the gasoline is 100% by weight of the catalyst, so as to obtain a pre-vulcanized catalyst, namely a catalyst II.
Comparative example 3
The same as example 2, except that the step (2) is cancelled, and the introduced amount of the elemental sulfur in the step (1) is 105 percent of the theoretical sulfur demand of the diesel hydrogenation catalyst, so as to obtain the presulfurized FHUDS-5 catalyst, named catalyst C.
Catalyst C needs to be activated: when the reaction pressure is 6.0MPa, the activated oil is introduced as diesel oil (Table 6), the reaction temperature is 350 ℃ at the heating rate of 15-25 ℃/h, and the temperature is kept for 2 h.
Example 3
FHUDS-5 from Table 1 was presulfided ex-situ.
(1) Uniformly mixing a vulcanizing agent (elemental sulfur, the using amount of which is 80% of the theoretical sulfur demand of FHUDS-5), a vulcanizing assistant (industrial soybean oil and mixed diesel oil (properties are shown in a table 6), a mixture with a weight ratio of 15: 1, and the using amount of which is 15% of the weight of FHUDS-5) to obtain a pre-vulcanizing raw material; uniformly mixing the pre-vulcanized raw material with FHUDS-5, and carrying out heat treatment on the mixed material at 300 ℃ for 5 hours;
(2) and (2) treating the material obtained in the step (1) by using circulating hydrogen exhaust gas of a hydrogenation device (the volume content of hydrogen sulfide is 6%), wherein the introduced amount of the hydrogen sulfide is 20% of the theoretical sulfur demand of the diesel hydrogenation catalyst, the pressure is 0.6MPa, and the material is subjected to heat treatment for 8 hours at the temperature of 150 ℃.
(3) And (3) loading citric acid and mixed diesel oil (properties are shown in a table 6) into the material obtained in the step (2), introducing the material containing 5% of citric acid and 150% of mixed diesel oil by weight of the catalyst to obtain a pre-vulcanized catalyst, namely the catalyst III.
Comparative example 4
In the same manner as in example 3, the step (3) was omitted, and the amount of elemental sulfur introduced in the step (1) was 120% of the theoretical sulfur demand of the diesel hydrogenation catalyst, to obtain a presulfurized FHUDS-5 catalyst, named catalyst D.
And (3) eliminating the steps (2) and (3), wherein the introduction amount of the elemental sulfur in the step (1) is 120 percent of the theoretical sulfur demand of the diesel hydrogenation catalyst, so as to obtain the presulfurized FHUDS-5 catalyst, namely the named catalyst E.
Example 4
Evaluation tests were conducted on the presulfided catalysts obtained in examples 1 to 3 and comparative examples 1 to 3. The initial activation temperature of different ex-situ presulfurization catalysts (the initial activation temperature is based on the obvious release of water in the presence of hydrogen and corresponds to the lowest pressure rise temperature of a hydrogenation reactor) and the relative activity after activation are mainly compared.
The initial activation temperature test method comprises the following steps: under the condition of 0.2MPa (gauge pressure) and hydrogen gas existence, the temperature is gradually raised, and the temperature of water obviously collected from the material at the outlet of the device is the initial activation temperature.
The activation process conditions are as follows: at 320 ℃ in the presence of 6.0MPa (gauge pressure) and hydrogen, for 15 hours.
The relative activity evaluation conditions were: diesel oil as raw oil (Table 6)The reaction pressure is 6.0MPa, the volume ratio of hydrogen to oil is 350:1, and the volume space velocity is 2.5h-1The reaction temperature was 350 ℃. Based on the activity of catalyst E (100).
TABLE 7 initial activation temperature (corresponding to the lowest pressure rise temperature of the hydrogenation reactor) comparison of catalysts
Figure DEST_PATH_IMAGE014
TABLE 8 comparison of hydrogenation activity of catalysts
Figure DEST_PATH_IMAGE016
From the above results, it can be seen that the ex-situ presulfided catalyst obtained by the method of the present invention has a higher initial activation temperature (which is advantageous to match the operating conditions of the hydrogenation reactor), and a higher catalytic performance.

Claims (10)

1. An ex-situ presulfurization method of a hydrogenation catalyst is characterized by comprising the following steps: (1) uniformly mixing a vulcanizing agent and an oxidation state hydrogenation catalyst, and then carrying out heat treatment; (2) further supplementing and pre-vulcanizing the intermediate material subjected to heat treatment in the step (1) by using a material containing hydrogen sulfide; (3) loading excessive hydrocarbon oil on the intermediate material vulcanized by the hydrogen sulfide in the step (2) to obtain a deeply vulcanized prevulcanized catalyst; the load of the hydrocarbon oil is 25-300% of the weight of the oxidation state hydrogenation catalyst.
2. The method of claim 1, wherein: the oxidation state hydrogenation catalyst in the step (1) is one or more of gasoline hydrofining, kerosene hydrofining, diesel hydrofining, wax oil hydrofining, hydrocracking catalysts, hydrocracking pre-refining catalysts, paraffin hydrogenation catalysts, reforming pre-refining catalysts or residual oil hydrogenation catalysts.
3. The method of claim 1, wherein: the vulcanizing agent in the step (1) is one or more of carbon disulfide, dimethyl disulfide, tert-butyl polysulfide, tert-nonyl polysulfide, thiourea, n-butyl mercaptan, ethyl mercaptan, sulfur powder, SZ-54, polysulfide, ammonia sulfide, mercaptan, thiophenol, thioether, sulfolane and dimethyl sulfoxide; the dosage of the vulcanizing agent is 50-110% of the theoretical sulfur demand of the catalyst.
4. The method of claim 1, wherein: after a vulcanizing agent and an oxidation state hydrogenation catalyst are uniformly mixed, a vulcanizing assistant is added; the vulcanizing assistant is one or more of hydrocarbon oil and organic carboxylic ester; the dosage of the vulcanization assistant is 0.1-30% of the weight of the catalyst.
5. The method of claim 1, wherein: the heat treatment temperature in the step (1) is 70-300 ℃, and the heat treatment time is 10-480 min.
6. The method of claim 1, wherein: the conditions of hydrogen sulfide supplement and pre-vulcanization are as follows: the temperature is 50-350 ℃, and the treatment time is 10-240 min.
7. The method of claim 1, wherein: the initial boiling point of the hydrocarbon oil in the step (3) is above 150 ℃.
8. The method of claim 1, wherein: the load of the hydrocarbon oil is 25-75% of the weight of the oxidation state hydrogenation catalyst.
9. The method of claim 1, wherein: after the step (3) or simultaneously with the step (3), introducing an organic acid or organic nitrogen modifier, wherein the loading amount of the modifier is 0.5-20% of the weight of the catalyst; and (4) drying after the step (3).
10. A method of operating a deep sulfided presulfided catalyst prepared by the method of claim 1, comprising: when the catalyst hydrogenation device is started, the operation conditions are adjusted, and the raw oil is introduced for starting operation.
CN201811226404.7A 2018-10-22 2018-10-22 External presulfurization method of hydrogenation catalyst Pending CN111068795A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4943547A (en) * 1988-09-13 1990-07-24 Seamans James D Method of presulfiding a hydrotreating catalyst
CN1351111A (en) * 2000-10-30 2002-05-29 中国石油化工股份有限公司 Process for presulfurizing hydrocatalyst
CN102443427A (en) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 Start-up vulcanizing method of hydrocracking process
CN103100444A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Preparation method of prevulcanization type catalyst
CN107456974A (en) * 2016-06-03 2017-12-12 中国石油化工股份有限公司 A kind of hydrogenation catalyst and its preprocess method methods and applications desulphurizing activated with hydrogenation catalyst is improved

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4943547A (en) * 1988-09-13 1990-07-24 Seamans James D Method of presulfiding a hydrotreating catalyst
CN1351111A (en) * 2000-10-30 2002-05-29 中国石油化工股份有限公司 Process for presulfurizing hydrocatalyst
CN102443427A (en) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 Start-up vulcanizing method of hydrocracking process
CN103100444A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Preparation method of prevulcanization type catalyst
CN107456974A (en) * 2016-06-03 2017-12-12 中国石油化工股份有限公司 A kind of hydrogenation catalyst and its preprocess method methods and applications desulphurizing activated with hydrogenation catalyst is improved

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Application publication date: 20200428