CN103801334A - Preparation method of sulfuration-type hydrogenation catalyst - Google Patents
Preparation method of sulfuration-type hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a sulfuration-type hydrogenation catalyst. The preparation method is as follows: using a carrier precursor and elemental sulphur and an auxiliary agent for kneading, molding and drying, loading a hydrogenation active metal component, and then performing heat treatment to obtain the sulfuration-type hydrogenation catalyst. The method is simple in preparation process and low in cost. The prepared sulfuration-type hydrogenation catalyst is good in sulfuration effect and high in hydrogenation activity.
Description
Technical field
The present invention relates to a kind of preparation method of sulfurized hydrogenation catalyst.
Background technology
Conventional hydrogenation catalyst is oxidation state, and the material that really plays active function when actual use is sulphided state, so need vulcanize in reactor before use.This has not only increased production cost, and sulfidation easily pollutes human and environment, and therefore the scientific research personnel of countries in the world actively seeks redress.Current research is mainly concentrated both ways: being the outer presulfurization of device on the one hand, is directly to prepare sulfide type catalyst on the other hand.The outer presulfurization of device refers to and adopts the method for distillation, melting or dipping vulcanizing agent to be introduced in the hole of oxidized catalyst, then under the existence of inert gas, make catalyst member presulfurization through hyperthermic treatment, finally catalyst is packed in reactor, under hydrogen exists, complete the final presulfurization of catalyst.The research of the outer presulfurization of device is comparatively deep, and relevant report is also more, as the outer method for pre-sulphuration of the EPRES hydrogenating catalyst of Fushun Petrochemical Research Institute etc.The outer pre-curing technology of device is compared with sulfuration in device, there is catalyst activity high, save on-stream time, simplify Star-up, human and environment is polluted to the advantages such as little, but the outer presulfurization of device is the same with presulfurization in device, in pre-vulcanization process, under hydrogen effect, may there is hydrogenolysis in oxidized catalyst, and active component and carrier adhesion often too strong, make the hydrogenation catalyst can not be by complete cure, cause the activity of catalyst further not improve.Catalyst, through oxidation state presulfurization use again, increases the production stage of catalyst, and production cost strengthens, and directly affects the economy of technique.Therefore various countries very pay attention to the research of directly preparing sulfide type catalyst.
US4,528,089 have introduced the preparation method of a kind of hydrodesulfurization and hydrodenitrogenation catalyst, with ammonium thiomolybdate or alkyl ammonium thiomolybdate be raw material, in airtight autoclave hydrogen exist under reaction obtain powder catalyst.US4,650,563 first by the inorganic salts of nickel or cobalt and ammonium thiomolybdate and ethylenediamine mixing, and reaction under certain condition generates compound, and then in the hydrogen that contains hydrogen sulfide, reaction obtains required catalyst.US7,132,386 have reported a kind of method of preparing cobalt molybdenum sulfide type catalyst, first ammonium thiomolybdate, cobalt chloride and alkyl ammonia bromide are mixed and generate intermediate product, then moved in reactor, at 300 ℃, under 500psi hydrogen pressure, reaction generates MoS
2and Co
9s
8.US6,451,729 are dissolved in ammonium thiomolybdate in organic solvent, produce the non-loading type MoS of high-ratio surface under high-temperature hydrogen exists
2catalyst, the hydrogenation cracking activity of this catalyst is high.CN1569331A discloses a kind of modified cobalt molybdenum base sulfide catalyst and preparation method thereof, by preparation ammonium thiomolybdate solution, and co-precipitation molybdenum, cobalt and the third transition metal constituent element, roasting under nitrogen protection, makes black powder shape catalyst.Prepared by above-mentioned technology is sulphided state catalyst, and unsupported catalyst is not suitable for using in large-scale hydrogenation reactor.
CN1557917A discloses a kind of sulfurized hydrogenation catalyst and preparation method thereof; the preparation method of this catalyst is mainly by adopting solubility Thiomolybdate and thiqtung state solution the presoma of group vib metal M o and W to be incorporated in the hole of catalyst carrier for hydrgenating to the carrier of conventional catalyst; 350 ℃ of roastings 4 hours under nitrogen protection; again with containing Ni; the solution impregnation of Co; 350 ℃ of roastings 4 hours under nitrogen protection, thereby the support type sulfide catalyst of preparation Mo, W, Co, Ni.This patent adopts two-step method Kaolinite Preparation of Catalyst, first form molybdenum bisuphide phase, after carried metal nickel, post-cure is difficult for forming highly active Co-Mo-S or Ni-Mo-S phase, and the generation of part metals nickel is without the nickel sulfide phase of hydrogenation activity, has caused the waste of metallic nickel.Two one-step baking preparation technologies are loaded down with trivial details, less economical, are unfavorable for large-scale industrial production.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of the sulfurized hydrogenation catalyst that a kind of preparation process is simple, cost is low.The cure efficiency of the sulfurized hydrogenation catalyst of gained is good, and hydrogenation activity is high.
The preparation method of sulfurized hydrogenation catalyst of the present invention, comprise: adopt carrier predecessor and elementary sulfur, adjuvant kneading, moulding, dry, load hydrogenation active metals component, then heat treatment under inert gas exists, obtain sulfurized hydrogenation catalyst, the addition of wherein said elementary sulfur is 100wt% ~ 250wt% that catalyst theory needs sulfur content, be preferably 100wt% ~ 150wt%, adjuvant is unsaturated hydro carbons or the mixture that contains unsaturated hydro carbons, the boiling point of adjuvant is 150～370 ℃, the addition of adjuvant is counted 3%～50% of carrier predecessor butt weight with unsaturated hydro carbons, described heat treated condition is as follows: at inert gas, under at least one gas in hydrogen exists, treatment temperature is 200～600 ℃, processing time is 2～15 hours.
In the preparation method of sulfurized hydrogenation catalyst of the present invention, carrier comprises the carrier component that is conventionally used as hydrogenation catalyst, comprises one or more of aluminium oxide, silica, titanium dioxide, zirconia etc.Carrier predecessor refers to the compound before carrier component dehydration, is generally hydroxide corresponding to carrier component.In the inventive method, can also add other ratio of component as one or more in molecular sieve, bentonite, kaolin, sepiolite etc.In order to obtain the special nature of required carrier, can add auxiliary agent as contained one or more in P, B, Si, F, Mg, Zn etc., auxiliary agent adds with conventional method, such as the form of its oxide or salt, can in the time preparing carrier predecessor, add, also can in the time of kneading, add.
Described adjuvant is unsaturated hydro carbons, comprise one or more in alkene, alkadienes, alkynes, also can select to be rich in the mixture of unsaturated hydro carbons, such as in coker gasoline, coker gas oil, catalytically cracked gasoline, catalytic cracking diesel oil etc. one or more, wherein the concentration of unsaturated hydro carbons is 30 v% ~ 60v%.
In the inventive method, in the time of moulding, can optionally add shaping assistant, such as one or more in adhesive, extrusion aid.Described binding agent refers to various acids, comprise the organic acids such as inorganic acid and acetic acid, citric acid such as nitric acid, hydrochloric acid, sulfuric acid one or more.Extrusion aid refers to one or more in the materials such as sesbania powder, starch, talcum powder.
In the inventive method, need to be dried after moulding, dry can carrying out in air also can carry out under inert gas, for guaranteeing the simplicity of process, is preferably in air drying.Drying condition is as follows: 50～200 ℃ and baking temperature be lower than the boiling point of adjuvant, dry 1～10 hour, is preferably 120～180 ℃ and the baking temperature boiling point lower than adjuvant, dry 2～5 hours.
In sulfurized hydrogenation catalyst of the present invention, consumption and the ratio of hydrogenation active metals are well known to those skilled in the art, and those skilled in the art can specifically determine according to the needs of produced catalyst.Usually. take the weight of catalyst as benchmark, the content of hydrogenation active metals is 5wt% ~ 50wt%.In the inventive method, described hydrogenation active metals is one or more of group VIB, group VIII metal.Group VIB metal is preferably Mo and/or W, and group VIII metal is preferably Ni and/or Co, and preferably the content of group VIB metal is 15%～30%, and the content of group VIII metal is 1%～6%.
In the inventive method, the method of described load hydrogenation active metals component can adopt conventional method, be generally kneading method or infusion process, wherein infusion process is the maceration extract of first preparing containing hydrogenation active metals, then flood above-mentioned maceration extract with the dry support after moulding, after dipping, need to be dried, general drying condition is as follows: 50～200 ℃ and baking temperature were lower than the boiling point of adjuvant, dry 1～10 hour.Kneading method is to carry out kneading by adding with the form of solid or the aqueous solution containing the compound of hydrogenation active metals component in the mixture of carrier predecessor, elementary sulfur and adjuvant, then through moulding and dry.Infusion process and kneading method can adopt this area conventional method to carry out.Described infusion process can be passed through repeatedly the content of active metal on dipping, saturated dipping, excessive impregnating dipping technique adjusting catalyst.
In the preparation method of sulfide type catalyst of the present invention, described heat treatment is to carry out under at least one gas in inert gas, hydrogen exists, preferably adopt Fractional Heat-treatment, specific as follows: to process 0～5 hour at 200～280 ℃ of constant temperature, then at 290～350 ℃, constant temperature is processed 1～5 hour, finally processes 1～5 hour at 360～600 ℃ of constant temperature.
Compared with prior art, tool has the following advantages the preparation method of sulfurized hydrogenation catalyst for refining of the present invention:
(1) catalyst is without oxidation state, and production technology is simple, and catalyst preparation cost is low;
(2) addition element sulphur and adjuvant in kneading process, then be dried under certain conditions, be conducive to like this elementary sulfur and be combined with adjuvant, be easier to form high activity phase with hydrogenation active metals, and sulphur more evenly, is more stably present in carrier component.In heat treatment process; especially adopt Fractional Heat-treatment; be conducive to adjuvant and water and generate the oxy radicals such as aldehyde, carboxylic acid, alcohol or ketone; promote hydrogenation active metals and sulphur to form the active phase of highly active II class; and vulcanize more completely, more abundant; and be converted in the process of sulphided state metal in hydrogenation active metals; simultaneously can generating portion gas; be conducive to improve the distribution of hydrogenation active metals and the pore structure of catalyst on catalyst; be conducive to the diffusion of raw material, and then effectively improved the hydrogenation activity of catalyst;
(3) catalyst is complete cure type catalyst, directly under hydrogen exists, heats up and goes into operation, and empty calory and hydrogen sulfide gas are emitted, and effectively the outer pre-sulfide catalyst bed of preventer is easy to the problems such as temperature runaway and intensification initial stage device be airtight.
Accompanying drawing explanation
Fig. 1 is the TEM figure of sulfide type catalyst A;
Fig. 2 is the TEM figure of sulfide type catalyst B;
Fig. 3 is the TEM figure of sulfide type catalyst C;
Fig. 4 is the TEM figure of sulfide type catalyst D;
Fig. 5 is the TEM figure of sulfuration rear catalyst E;
Fig. 6 is the TEM figure of sulfuration rear catalyst F.
The specific embodiment
Concrete preparation method is as follows for sulfide type catalyst of the present invention:
Mode 1:
1, the preparation of catalyst carrier: adopt conventional method Kaolinite Preparation of Catalyst carrier predecessor, carrier predecessor is mixed with elementary sulfur, adjuvant, shaping assistant, extrusion on banded extruder, drying is made catalyst carrier.Dry can carrying out in air also can carry out under inert gas.Drying condition is: 50～200 ℃ of dry 2～10h;
2, the preparation of sulfide type catalyst
Active metal is made into the maceration extract impregnated carrier of desired concn and composition, then dry, drying condition is: 50～200 ℃ of dry 2～10h, and also can natural air drying.Described heat treatment is to carry out under at least one gas in inert gas, hydrogen exists, treatment temperature is 200～600 ℃, processing time is 2～15 hours, heat treatment preferably adopts segment processing, specific as follows: to process 0～5 hour at 200～280 ℃ of constant temperature, then at 290～350 ℃, constant temperature is processed 1～5 hour, finally processes 1～5 hour at 360～600 ℃ of constant temperature.
Mode 2:
Active metal is introduced in the time preparing carrier, can in the time of kneading, add hydrogenation active metals salting liquid, also hydrogenation active metals salt can be mixed with carrier predecessor, elementary sulfur, adjuvant, shaping assistant, dry after moulding, drying condition is: 50～200 ℃ of dry 2～10h, then heat-treat.Described heat treatment is to carry out under at least one gas in inert gas, hydrogen exists, treatment temperature is 200～600 ℃, processing time is 2～15 hours, heat treatment preferably adopts segment processing, specific as follows: to process 0～5 hour at 200～280 ℃ of constant temperature, then at 290～350 ℃, constant temperature is processed 1～5 hour, finally processes 1～5 hour at 360～600 ℃ of constant temperature.
The technical characterstic that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention.Wt% is mass fraction.
The preparation of embodiment 1 sulfide type catalyst A
(Shandong alumina producer is produced to take boehmite, butt is 73wt%) 900g, sesbania powder 19g, elementary sulfur powder 80g, citric acid 32g, hexene 54ml, nitric acid (weight concentration 30%) 48ml, silica gel (by weight containing silica 30%) 159ml, deionized water 250ml mixes, on banded extruder, be extruded into 1.2mm clover bar, in air dry oven in 150 ℃ dry 3 hours, obtain required catalyst carrier A.
Get containing ammonium molybdate and nickel nitrate solution and (contain molybdenum oxide 30g/100ml; containing nickel oxide 5g/100ml) after impregnated carrier A in 150 ℃ dry 3 hours; under nitrogen protection, heat-treat afterwards; first be warming up to 240 ℃; constant temperature 2 hours; be warming up to afterwards 320 ℃, constant temperature 1 hour, is finally warming up to 450 ℃ of constant temperature 3 hours again.The TEM of catalyst the results are shown in Figure 1.
The preparation of embodiment 2 sulfide type catalyst B
Identical with embodiment 1, be the catalytic gasoline (presence of unsaturates is 49.8v%) that adjuvant is changed into 100ml.The TEM of catalyst the results are shown in Figure 2.
The preparation of embodiment 3 sulfide type catalyst C
(Shandong alumina producer is produced to take boehmite; butt is 73wt%) 900g; sesbania powder 19g; sulphur powder 100g; citric acid 32g; laurylene 30ml, ammonium molybdate 245g, nickel nitrate 127g; nitric acid (weight concentration 30%) 48ml; silica gel (by weight containing silica 30%) 159ml, deionized water 250ml mixes, and is extruded into 1.2mm clover bar on banded extruder; in air dry oven, be dried 5 hours in 120 ℃; heat treatment under hydrogen shield afterwards, first 290 ℃ of constant temperature 2 hours, then obtain catalyst C for 3 hours at 400 ℃ of constant temperature.TEM the results are shown in Figure 3.
The preparation of embodiment 4 sulfide type catalyst D
Identical with embodiment 3, just adopt one section of heat treatment, within 6 hours, obtain catalyst D at 400 ℃ of constant temperature.TEM the results are shown in Figure 4.
The preparation of comparative example 1 oxidized catalyst E
(Shandong alumina producer is produced to take boehmite, butt is 73% by weight) 900g, sesbania powder 19g, citric acid 32g, nitric acid (weight concentration 30%) 48ml, silica gel (by weight containing silica 30%) 159ml, deionized water 250ml mixes, on banded extruder, be extruded into 1.2mm clover bar, in air dry oven in 150 ℃ dry 3 hours, 600 ℃ of roastings obtain required catalyst carrier B for 3 hours.
Get containing after ammonium molybdate and nickel nitrate solution (containing molybdenum oxide 30g/100ml, containing nickel oxide 5g/100ml) impregnated carrier B in 150 ℃ dry 3 hours, in Muffle furnace, within 3 hours, obtain catalyst E in 500 ℃ of roastings afterwards.Catalyst TEM after sulfuration the results are shown in Figure 5.
The preparation of the outer pre-sulfide catalyst F of comparative example 2 devices
The elementary sulfur that dissolves is introduced to oxidized catalyst E, and the introduction volume of sulphur is theoretical amount 105%, and then with diesel oil distillate dipping, its consumption is catalyst weight 40%.Under normal pressure, process 3 hours for 180 ℃, obtain the outer pre-sulfide catalyst F of device.Catalyst TEM after sulfuration the results are shown in Figure 6.
The activity of embodiment 4 sulfide type catalysts is investigated
Experiment completes on micro-reactor, and carrier gas is hydrogen.Feedstock oil is atmosphere 3rd side cut oil, sulfur content 6524.1 μ g/g, and nitrogen content is 50.6 μ g/g.Embodiment catalyst is carried out to temperature programming, 3 ℃/min, enter feedstock oil at 150 ℃.Continue to be warming up to 350 ℃ stablize after 6 hours, start constant.Process conditions are: pressure 3.4MPa, air speed 2.0,350 ℃ of temperature, hydrogen to oil volume ratio 500.Evaluation result is in table 2.
The activity of embodiment 5 oxidized catalyst is investigated
Comparative example 1 catalyst is packed in hydrogenation reactor, after importing hydrogen, the reactor that catalyst is housed is directly warming up to 150 ℃, enter sulfurized oil (for the mixture of boat coal and carbon disulfide), rising to subsequently 350 ℃ carries out presulfurization, and constant temperature was adjusted to reaction condition after 6 hours.Feedstock oil and process conditions are with embodiment 4.Evaluation result is in table 2.
The activity of the outer pre-sulfide catalyst of embodiment 6 devices is investigated
Experiment completes on micro-reactor, and carrier gas is hydrogen.Comparative example 2 catalyst are carried out to temperature programming, 3 ℃/min, enter feedstock oil at 90 ℃.Continue to be warming up to 350 ℃ stablize after 6 hours, start constant.Feedstock oil and process conditions are with embodiment 4.Evaluation result is in table 2.
The physico-chemical property of table 1 catalyst
| Catalyst numbering | Total metal contents in soil, wt % | Specific area, m 2/g | Pore volume, mL/g | Average pore diameter, nm |
| Catalyst A | 28 | 240 | 0.45 | 7.5 |
| Catalyst B | 28 | 236 | 0.44 | 7.5 |
| Catalyst C | 28 | 220 | 0.44 | 8.0 |
| Catalyst D | 28 | 221 | 0.43 | 7.8 |
| Catalyst E | 28 | 173 | 0.32 | 7.4 |
| Catalyst F | 28 | 173 | 0.32 | 7.4 |
Note: the pore structure of catalyst is for changing into oxidation state post analysis gained.
The evaluation result of table 2 catalyst
| Catalyst numbering | S，μg/g | N，μg/g |
| Catalyst A | 33.1 | <1.0 |
| Catalyst B | 21.7 | <1.0 |
| Catalyst C | 36.7 | <1.0 |
| Catalyst D | 45.9 | <1.0 |
| Catalyst E | 78.6 | 1.5 |
| Catalyst F | 72.4 | 1.5 |
Can be found out by Fig. 1～6 and table 1, table 2, active phase prepared by the inventive method is the active phase of highly active II class.In the situation that catalyst composition is identical with process conditions, the hydrogenation activity of the hydrogenation activity of sulfide type catalyst pre-sulfide catalyst outside oxidized catalyst and device.The preparation technology of catalyst is simple, good economy performance.Catalyst is the sulfide type catalyst of complete meaning, and start-up process is simple, has avoided the generation of the phenomenons such as the outer pre-sulfide catalyst initial temperature of device is low, and heat release is concentrated.
Claims (16)
1. the preparation method of a sulfurized hydrogenation catalyst, comprise: adopt carrier predecessor and elementary sulfur, adjuvant kneading, moulding, dry, load hydrogenation active metals component, then heat-treat, obtain sulfurized hydrogenation catalyst, the addition of wherein said elementary sulfur is 100wt% ~ 250wt% that catalyst theory needs sulfur content, adjuvant is unsaturated hydro carbons or the mixture that contains unsaturated hydro carbons, the boiling point of adjuvant is 150～370 ℃, the addition of adjuvant is counted 3%～50% of carrier predecessor butt weight with unsaturated hydro carbons, described heat treated condition is as follows: at inert gas, under at least one gas in hydrogen exists, treatment temperature is 200～600 ℃, processing time is 2～15 hours.
2. in accordance with the method for claim 1, it is characterized in that described drying condition is as follows: 50～200 ℃ and baking temperature were lower than the boiling point of adjuvant, dry 1～10 hour.
3. in accordance with the method for claim 1, it is characterized in that described drying condition is as follows: 120～180 ℃ and baking temperature were lower than the boiling point of adjuvant, dry 2～5 hours.
4. in accordance with the method for claim 1, it is characterized in that described carrier be aluminium oxide, silica, titanium dioxide, zirconic one or more, carrier predecessor is the compound before carrier dehydration.
5. in accordance with the method for claim 1, it is characterized in that adding in described kneading raw material one or more in molecular sieve, bentonite, kaolin, sepiolite.
6. it is characterized in that in accordance with the method for claim 1: in the time preparing carrier predecessor or in the time of kneading, introduce one or more in auxiliary agent P, B, Si, F, Mg, Zn.
7. in accordance with the method for claim 1, it is characterized in that described adjuvant is unsaturated hydro carbons, comprise one or more in alkene, alkadienes, alkynes.
8. in accordance with the method for claim 1, the mixture that adjuvant described in it is characterized in that contains unsaturated hydro carbons is one or more in coker gasoline, coker gas oil, catalytically cracked gasoline, catalytic cracking diesel oil, and the concentration of unsaturated hydro carbons is 30 v%～60v%.
9. in accordance with the method for claim 1, it is characterized in that: in the time of moulding, add one or more in adhesive, extrusion aid, described adhesive is one or more in nitric acid, hydrochloric acid, sulfuric acid, acetic acid, citric acid, and extrusion aid is one or more in sesbania powder, starch, talcum powder.
10. in accordance with the method for claim 1, it is characterized in that: take the weight of catalyst as benchmark, the content of hydrogenation active metals is 5wt% ~ 50wt%.
11. according to the method described in claim 1 or 10, it is characterized in that: described hydrogenation active metals is one or more in group VIB, group VIII metal, and group VIB metal is Mo and/or W, and group VIII metal is Ni and/or Co.
12. in accordance with the method for claim 11, it is characterized in that: take the weight of catalyst as benchmark, the content of group VIB metal is 15%～30%, and the content of group VIII metal is 1%～6%.
13. in accordance with the method for claim 1, it is characterized in that: the method for described load hydrogenation active metals component adopts kneading method or infusion process.
14. in accordance with the method for claim 13, it is characterized in that described infusion process is the maceration extract of first preparing containing hydrogenation active metals, then use the dry support after above-mentioned maceration extract dip forming, after dipping, need to be dried, drying condition is as follows: 50～200 ℃ and baking temperature be lower than the boiling point of adjuvant, dry 1～10 hour.
15. in accordance with the method for claim 13, it is characterized in that described kneading method is to carry out kneading by adding with the form of solid or the aqueous solution containing the compound of hydrogenation active metals component in the mixture of carrier predecessor, elementary sulfur and adjuvant, then through moulding and dry.
16. in accordance with the method for claim 1, it is characterized in that described heat treatment is to carry out under at least one gas existence in inert gas, hydrogen, adopt Fractional Heat-treatment, specific as follows: to process 0～5 hour at 200～280 ℃ of constant temperature, then process 1～5 hour at 290～350 ℃ of constant temperature, finally process 1～5 hour at 360～600 ℃ of constant temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106732666A (en) * | 2015-11-20 | 2017-05-31 | 中国石油化工股份有限公司 | The preparation method of one-time formed macropore sulfurized hydrogenation catalyst |
| CN106946807A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | Hydrotreating catalyst intermediate, hydrotreating catalyst and preparation method thereof |
| CN106944125A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN108067256A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of preparation method of sulfurized hydrogenation catalyst |
| CN111468142A (en) * | 2020-04-08 | 2020-07-31 | 中国石油天然气股份有限公司 | Co-Mo-S catalyst and preparation method thereof |
| CN115505425A (en) * | 2022-09-19 | 2022-12-23 | 连云港鹏辰特种新材料有限公司 | Preparation method of high-boiling-point high-purity solvent oil for hydrogen peroxide production |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106732666A (en) * | 2015-11-20 | 2017-05-31 | 中国石油化工股份有限公司 | The preparation method of one-time formed macropore sulfurized hydrogenation catalyst |
| CN106946807A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | Hydrotreating catalyst intermediate, hydrotreating catalyst and preparation method thereof |
| CN106944125A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN106946807B (en) * | 2016-01-07 | 2020-05-19 | 中国石油化工股份有限公司 | Hydrotreating catalyst intermediate, hydrotreating catalyst and preparation method thereof |
| CN108067256A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of preparation method of sulfurized hydrogenation catalyst |
| CN111468142A (en) * | 2020-04-08 | 2020-07-31 | 中国石油天然气股份有限公司 | Co-Mo-S catalyst and preparation method thereof |
| CN115505425A (en) * | 2022-09-19 | 2022-12-23 | 连云港鹏辰特种新材料有限公司 | Preparation method of high-boiling-point high-purity solvent oil for hydrogen peroxide production |
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