CN1107702C - Hydrogenation catalyst and its producing process - Google Patents

Hydrogenation catalyst and its producing process Download PDF

Info

Publication number
CN1107702C
CN1107702C CN 00110707 CN00110707A CN1107702C CN 1107702 C CN1107702 C CN 1107702C CN 00110707 CN00110707 CN 00110707 CN 00110707 A CN00110707 A CN 00110707A CN 1107702 C CN1107702 C CN 1107702C
Authority
CN
China
Prior art keywords
preparation
solution
warming
catalyst
catalyzer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CN 00110707
Other languages
Chinese (zh)
Other versions
CN1335363A (en
Inventor
罗锡辉
何金海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN 00110707 priority Critical patent/CN1107702C/en
Publication of CN1335363A publication Critical patent/CN1335363A/en
Application granted granted Critical
Publication of CN1107702C publication Critical patent/CN1107702C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Abstract

The present invention discloses a petroleum hydrocarbon hydrotreatment (hydrorefining, such as hydrodenitrogenation, hydrodesulphurization, hydrodemetalization, hydroisomerization, hydrosaturation, etc.) catalyst and a preparation method thereof. The catalyst at least contains a group VIB element, such as molybdenum or tungsten, a group VIII element, such as nickel or cobalt, and an inorganic acid, such as H3PO4 as active constituents and contains pseudo thin alumina hydrate and a double-effect auxiliary agent substance as carrier raw materials. A high-stability solution containing the active constituents and the carrier raw materials are thoroughly mixed together, kneaded, extruded to form strips, dried at the temperature of 110DEG C to 130DEG C and calcined at a high temperature to obtain the high-activity hydrotreating catalyst.

Description

A kind of hydrotreating catalyst and preparation method thereof
The present invention relates to a kind of hydrocarbon hydrogenizing treamtent catalyst and preparation method thereof.
Petroleum fractions especially contains sulphur, nitrogen, oxygen and metal impurity such as (as nickel, vanadium) in the heavier petroleum fraction.These impurity often exist with many ring hetero atoms organic compound form, and usually content is higher.The existence of these impurity not only influences stability, in use also gives off SO x, NO xDeng the obnoxious flavour contaminate environment.Face hydrogen in petroleum fractions and handle in (catalytic reforming, hydrocracking, hydroisomerizing etc.) process, also may cause poisoning of catalyst.The main purpose that hydrocarbons hydrogenation is handled is the hazardous compound that removes in the raw material, for example organosulfur compound, organic nitrogen compound and organometallic compound etc.
The hydrotreating catalyst of excellent property requires to possess following condition: (1), at first reactive metal such as molybdenum (tungsten), nickel (cobalt) etc. have higher chemical individual layer dispersion amount on catalyst surface; (2), reactive metal has high dispersity and good dispersion state on catalyst surface.(3), " interaction between metal-carrier " intensity is wanted suitably will make its " just right " by modulation.(4) carrier surface will have certain acidity, is beneficial to the carrying out of hydrogenation process (for example hydrodenitrification reaction).In addition, from considering that economically Preparation of catalysts technology (process) should be tried one's best simply.
In the prior art, about the preparation of hydrotreating catalyst, mainly be to adopt two-step approach.Be the first step preparation carrier γ-Al earlier 2O 3(or SiO 2-Al 2O 3Deng).Then second step, with the solution impregnating carrier that contains active ingredient, catalyzer is made in drying, roasting.Existing a large amount of patent disclosure preparation γ-Al 2O 3Method (U.S. Pat P 4,513,097 and the clear 58-216740 of Japanese Patent JP), then with γ-Al 2O 3Be carrier, by the immersion process for preparing hydrotreating catalyst (U.S. Pat P 4,317,746; 4,446,248; 4,568,449; 4,738,767).The advantage that adopts two-step approach to prepare catalyzer is: (1), prepare carrier separately and can guarantee that carrier (thereby also being catalyzer) has enough big aperture and surface properties preferably; (2), adopt the immersion process for preparing catalyzer, can be evenly dispersed on the carrier surface with fixed ratio height relatively between the active ingredient, thereby active ingredient has higher dispersity and good dispersion state on catalyst surface.But, adopt two-step approach to prepare catalyzer, each active ingredient loading is subjected to certain restriction, for example MoO 3Content only reaches 20w% usually, and it is then relatively more difficult to surpass 24w%.Except two-step approach, also has gel method (United States Patent (USP) 4,832,827).This method directly begins with the preparation alumina gel from aluminium salt, contains Mo-Ni-P solution, vacuum-drying again, extrusion, oven dry through aging, washing, vacuum-drying, adding, after catalyzer is made in roasting.The advantage of this method is that preparation carrier and two steps of catalyzer are integrated, and specific surface area of catalyst is bigger.The shortcoming of this method is: the loading of (1), catalyst activity component (metal) still is restricted, even is lower than the catalyzer with the two-step approach preparation; (2), prepared catalyzer aperture is too little.Hole less than 7.0 nm accounts for more than 80% of whole pore volume, even surpasses 90%, is unfavorable for the diffusion and the reaction of macromolecule hydrocarbon compound (as heavy ends) molecule.
The objective of the invention is: even kneading method of one step of (1), employing, directly prepare hydrotreating catalyst by intending thin water aluminum oxide, thereby simplify the Catalyst Production process, reduce production costs; (2), increase the catalyst activity component concentration with further raising catalyst activity; (3), in catalyst preparation process, contain the economic benefits and social benefits material of silicon and fluorine element by interpolation, increase support acidity, improve the carrier surface character step of going forward side by side and become interaction between (weakening) metal-carrier, thereby further improve catalyst activity.
The present invention adopts even kneading method of a step, is about to prepare the preparation method of the hydrocarbon hydrogenizing treamtent catalyst that carrier and two steps of preparation catalyzer integrate.To intend thin water aluminum oxide (pseudo-boehmite) and to contain silicon and the compound of fluorine element is a raw material, with solution with high metal concentration, through mixing, kneading, extruded moulding, drying, roasting " thereby a step ground " are finished the method for preparation hydrotreatment (hydrofining,, hydrodemetallation (HDM) saturated as hydrodenitrification, hydrogenating desulfurization, hydrogenation etc.) catalyzer then.
To achieve these goals, the present invention includes two aspects: Mo-Ni (the Co)-P solution of preparation high stability, high density; With this solution with intending thin water aluminum oxide and containing silicon and the compound thorough mixing of fluorine element, be kneaded into plastic shape, be extruded into the trifolium strip, adopt " three sections constant temperature calcinings " program then, control suitable heat-up rate and each section maturing temperature to guarantee that active ingredient has higher dispersity and good dispersion state on catalyst surface, guarantee that simultaneously catalyzer has enough big specific surface area, suitable aperture and good pore structure.
The solution of the said high metal concentration of the present invention is Mo-Ni (Co)-P solution, and its preparation process is as follows:
(1), phosphate aqueous solution is added in the molybdenum oxide, stir, slowly heat temperature raising is to little boiling, and is heated to molybdenum oxide all dissolving or basic dissolving.
(2), above-mentioned solution is cooled to 60 ℃～70 ℃ after, slowly add basic nickel carbonate or nickelous nitrate (and/or Xiao Suangu), place and be warming up to little boiling again after 15 minutes, be heated to the basic dissolving of precipitation.Reduce to the room temperature after-filtration to remove insoluble impurity.
(3), with above-mentioned solution concentration to needed concentration.
Prepared Mo-Ni (Co)-P solution according to the present invention has following character:
(1), every 100ml solution can contain MoO 350～80g, NiO 10～20g, CoO 0～15g, P/MoO 3Weight ratio is 0.08～0.20.
(2), other composition can be added as required in solution, as silicon sol, Glacial acetic acid, tartrate, materials such as oxalic acid and citric acid.
(3), this solution at room temperature can be stablized and not produce muddiness or precipitation more than 3 years.
Mo-Ni of the present invention (Co)-P/F-SiO 2-Al 2O 3The hydrotreating catalyst preparation process is as follows:
(1), with thin water aluminum oxide (powder) of Mo-Ni (Co)-P solution and plan and ammonium hexafluorosilicate (NH 4) 2SiF 6And/or hexafluoro silicon hydracid thorough mixing, mediate to becoming plastic shape, be extruded into strip or trifolium (Herba Galii Bungei) strip then.Dry in the air, dry down at 110 ℃～130 ℃ then.
(2), dry sample is placed High Temperature Furnaces Heating Apparatus, the speed with 3 ℃～5 ℃/minute in air is warming up to 238 ℃～371 ℃, constant temperature calcining 0.5 hour～2 hours.Then, be warming up to 398 ℃～450 ℃, constant temperature calcining 2 hours～5 hours with 3 ℃～5 ℃/minute speed.Be warming up to 471 ℃～560 ℃, constant temperature calcining 1 hour～4 hours with 3 ℃～5 ℃/minute speed again.
Prepared Mo-Ni (Co)-P/F-SiO according to the present invention 2-Al 2O 3Hydrotreating catalyst has following character:
(1), this catalyzer consists of MoO 324w%～40w%, NiO and/or CoO 4.0w%～12w%, SiO 22.0～8.0w%, P 2.5w%～6.0w%, F 3.0w%～6.0w%, all the other are Al 2O 3
(2), specific surface area is 160～300m 2/ g; Pore volume is 0.25～0.38ml/g.
(3), active ingredient Mo-Ni (Co)-P has higher dispersity and preferable dispersion state on catalyst surface, and allow bigger dispersion amount, thereby the hydrotreatment activity is higher.
Advantage of the present invention is:
(1), adopt the present invention to prepare Mo-Ni (Co)-P/F-SiO 2-Al 2O 3Hydrotreating catalyst, simple to operate, easy row.Therefore, production cost is than adopting the low of usual way.
(2), catalyzer of the present invention is suitable for the hydrofining (as hydrogenating desulfurization, hydrodenitrification, hydrogenation is saturated and hydrodemetallation (HDM) etc.) of heavy (as VGO) and low-density oil cut.The processing condition that catalyzer is suitable for are: temperature of reaction is 230 ℃～420 ℃; Reaction pressure 5.0MPa～15.0MPa; LHSV 0.5h -1～3.0h -1Hydrogen/oil ratio is 300～1500 (V/V).
(3) Mo of the present invention, Ni (Co)-P solution, though under very high metal concentration also quite stable.At room temperature can stablize and not produce muddiness or precipitation more than 3 years.
(4) catalyzer of the present invention, the anti-nitrogen performance of its hydrogenation reaction activity and catalyzer all are better than the catalyzer that makes with usual way.
In order to further specify all main points of the present invention, enumerate following examples and comparative example.
Embodiment 1
(1), the preparation of Mo-Ni-P solution
With 20.0ml phosphoric acid H 3PO 4(85%) is dissolved in the 520ml water.Under agitation solution is joined 93g molybdenum oxide MoO 3In, be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 65 ℃, under agitation slowly add 67g nitric acid nickel (NO 3) 26H 2O, heating up is heated to throw out and dissolves substantially again.With the filtrate evaporation concentration to 220ml.
(2), Preparation of Catalyst
305g is intended thin water aluminum oxide, 25g (NH 4) 2SiF 6Mo-Ni-P solution thorough mixing, kneading twice with top step (1) preparation add 88ml HNO 3(3%) solution is mediated two times again, makes to be extruded into trifolium strip (φ=1.2mm) behind the plastic.After moist catalysis dried in air and spends the night, drying was 3 hours under 120 ℃.The sample that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 270 ℃ with 4 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 410 ℃ with 4 ℃ of/minute speed again, constant temperature 3 hours.Be warming up to 520 ℃ with 4 ℃ of/minute speed at last, constant temperature calcining 2 hours.
Embodiment 2
(1) step of Mo-Ni-P formulations prepared from solutions is identical with embodiment 1 (1).Phosphoric acid H 3PO 4(85%) and the add-on of water be respectively 20.0ml and 650ml.Molybdenum oxide MoO 3With nitric acid nickel (NO 3) 26H 2The O add-on is respectively 120g and 86g.The filtrate evaporation concentration is to 220ml.
(2) Preparation of Catalyst
305g is intended thin water aluminium and 25g (NH 4) 2SiF 6With the Mo-Ni-P solution thorough mixing of top (1), mediate to make and be extruded into trifolium strip (φ=1.2mm) behind the plastic.After moist catalysis dried in air and spends the night, drying was 3 hours under 120 ℃.
The dry sample of crossing places High Temperature Furnaces Heating Apparatus, is warming up to 270 ℃ with 4 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 410 ℃ with 4 ℃ of/minute speed again, constant temperature 3 hours.Be warming up to 520 ℃ with 4 ℃ of/minute speed at last, constant temperature calcining 2 hours.
Comparative example 1
(1) preparation of Mo-Ni-P solution
With 20.0ml phosphoric acid H 3PO 4(85%) is dissolved in the 520ml water.Under agitation solution is joined 93g molybdenum oxide MoO 3In, be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 65 ℃, under agitation slowly add 67g nitric acid nickel (NO 3) 26H 2O, heating up is heated to throw out and dissolves substantially again.With the filtrate evaporation concentration to 220ml.
(2) Preparation of Catalyst
Mo-Ni-P solution thorough mixing, kneading twice with thin water aluminum oxide of 330g plan and top step (1) preparation add 88ml HNO 3(3%) solution is mediated two times again, makes to be extruded into trifolium strip (φ=1.2mm) behind the plastic.After moist catalysis dried in air and spends the night, drying was 3 hours under 120 ℃.The sample that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 270 ℃ with 4 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 410 ℃ with 4 ℃ of/minute speed again, constant temperature 3 hours.Be warming up to 520 ℃ with 4 ℃ of/minute speed at last, constant temperature calcining 2 hours.
Comparative example 2
(1) preparing carriers
Take by weighing and intend thin water aluminum oxide 200g, add the 2.9ml Glacial acetic acid, 179ml HNO 3(concentration is 3%) and an amount of water.Through thorough mixing, be kneaded into plastic shape after, be extruded into trifolium strip (φ=1.2mm).After moist catalysis dried in air and spends the night, drying was 3 hours under 110 ℃.
The catalyzer that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 220 ℃ with 8 ℃ of/minute speed, constant temperature calcining 0.5 hour.Be warming up to 478 ℃ with 9 ℃ of/minute speed again, constant temperature 2.5 hours.Be warming up to 640 ℃ with 8 ℃ of/minute speed at last, constant temperature calcining 3 hours.
(2) preparation of Mo-Ni (Co)-P solution
With 18.5ml phosphoric acid H 3PO 4(85%) is dissolved in the 560ml water.Under agitation solution is joined 97g molybdenum oxide MoO 3In, be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 65 ℃, under agitation slowly add the 48g basic nickel carbonate, be warming up to again little boil and be heated to throw out dissolve substantially.Filtrate is concentrated into 200ml.
(3) Preparation of Catalyst
Take by weighing the γ-Al of step (1) preparation 2O 3Carrier 100g adds the Mo-Ni-P solution of 150ml according to step (2) preparation, at room temperature flood 4 hours after, leach redundant solution.After moist catalysis dries in air and spends the night, dried 3 hours down at 110 ℃.
The dry catalyst sample of crossing is warming up to 190 ℃ with 4 ℃ of/minute speed, constant temperature calcining 0.5 hour.Be warming up to 368 ℃ with 4 ℃ of/minute speed again, constant temperature calcining 0.5 hour.Be warming up to 470 ℃ with 4 ℃ of/minute speed at last, constant temperature calcining 3 hours.
More than each routine prepared γ-Al 2O 3And Mo-Ni-P/F-SiO 2-Al 2O 3The physico-chemical property of catalyzer sees Table 1.Raw materials used oil properties of evaluation of catalyst activity and reaction process condition see Table 2 and table 3.
Estimating catalyst system therefor vulcanized 8 hours down at 230 ℃ and 370 ℃ respectively with the grand celebration aviation kerosene cut that contains dithiocarbonic anhydride 1.5% (V).Sulfuration finishes, and swap-in stock oil is stablized under reaction conditions and begun to carry out the hydrodenitrification reaction test after 8 hours.When estimating each routine catalyzer, by the conditioned reaction temperature, making total denitrification percent is 95w%, i.e. it is 0.0065w% that control generates the nitrogen content in the oil.If catalyzer just can reach this denitrification percent than low reaction temperatures the time, show that this catalyzer has higher hydrodenitrification reactive behavior.Vice versa.
Evaluation result shows: adopt the prepared catalyzer of the present invention under the identical situation of metal content, the hydrodenitrification reactive behavior is with identical with the catalyzer of usual way (comparative example 1,2) preparation.If introduce siliceous and fluorine cpd, prepared catalyzer will have higher hydrodenitrification reactive behavior (embodiment 1).If when introducing fluorochemicals, increase active metallic content, the hydrodenitrification reactive behavior will be higher (embodiment 2).
This shows, adopt the present invention to prepare hydrotreating catalyst, not only simple to operate, thereby production cost is low, and also catalytic activity can be higher.
The physico-chemical property of each routine carrier of table 1 and catalyzer
Embodiment 1 Embodiment 2 Comparative example 1 Comparative example 2
Catalyzer Catalyzer Catalyzer γ-Al 2O 3 Catalyzer
Specific surface m 2/g 230 196 235 296 143
Pore volume ml/g 0.310 0.277 0.320 0.628 0.300
Chemical constitution, w%
MoO 3 24.2 32.9 24.3 --- 24.1
NiO 4.35 5.60 4.40 --- 4.36
P 2.62 2.63 2.63 --- 2.60
SiO 2 2.70 2.67 --- --- ---
F 4.85 4.80 --- --- ---
Al 2O 3 Surplus Surplus Surplus Surplus
Bulk density g/ml 0.90 0.93 0.89 0.62 0.90
Table 2 stock oil character
Stock oil Triumph VGO
Proportion d 4 20，g/ml 0.900
Sulphur, w% 0.47
Nitrogen, w% 0.13
Zero pour, ℃ 35
Carbon residue, w% 0.05
Boiling range, ℃
IBP/10％ 290/350
30％/50％ 375/392
70％/90％ 408/438
95％/EBP 448/466
Table 3 hydrodenitrification reaction process condition
Reaction pressure, MPa 6.36
LHSV，h -1 1.00
Hydrogen/oil ratio, v/v 1000∶1
Each routine catalyst hydrogenation denitrification activity of table 4 relatively
Catalyzer Embodiment 1 Embodiment 2 Comparative example 1 Comparative example 2
Temperature of reaction, ℃ 376 370 380 380

Claims (7)

1, a kind of preparation method of hydrotreatment catalyst, it is characterized in that to intend thin water aluminum oxide and to contain silicon and the compound of fluorine element is a raw material, with reactive metal solution, through mixing, kneading, extruded moulding, thereby drying, roasting " a step ground " are finished the preparation of hydrotreating catalyst then; Wherein said roasting process is: dry sample is placed High Temperature Furnaces Heating Apparatus, and the speed with 3 ℃～5 ℃/minute in air is warming up to 238 ℃～371 ℃, constant temperature calcining 0.5～2 hour; Then, be warming up to 398 ℃～450 ℃ with 3 ℃～5 ℃/minute speed, constant temperature calcining 2～5 hours; Be warming up to 471 ℃～560 ℃, constant temperature calcining 1～4 hour with 3 ℃～5 ℃/minute speed again.
2, preparation method according to claim 1 is characterized in that the said compound that contains silicon and fluorine element is ammonium hexafluorosilicate and/or hexafluoro silicon hydracid.
3, preparation method according to claim 1 is characterized in that said reactive metal solution is Mo, Ni and/or Co, P solution.
4, preparation method according to claim 3 is characterized in that consisting of of said Mo, Ni and/or Co, P solution: every 100ml solution contains MoO 350～80g, NiO 10～20g, CoO 0～15g, wherein P/MoO 3Weight ratio is 0.08～0.20.
5,, it is characterized in that the preparation process of said Mo, Ni and/or Co, P solution is as follows according to claim 3 or 4 described preparation methods:
(1), phosphate aqueous solution is added in the molybdenum oxide, stir, slowly heat temperature raising is to little boiling, and is heated to molybdenum oxide all dissolving or basic dissolving;
(2), above-mentioned solution is cooled to 60 ℃～70 ℃ after, slowly add basic nickel carbonate or nickelous nitrate and/or Xiao Suangu, place and be warming up to little boiling again after 15 minutes, be heated to the basic dissolving of precipitation, reduce to the room temperature after-filtration to remove insoluble impurity;
(3) with above-mentioned solution concentration to needed concentration.
6, the hydrotreating catalyst of the described method of a kind of claim 1 preparation is characterized in that the MoO that consists of of this catalyzer 324w%～40w%, NiO and/or CoO 4.0w%～12w%, SiO 22.0～8.0w%, P 2.5w%～6.0w%, F 3.0w%～6.0w%, all the other are Al 2O 3
7, hydrotreating catalyst according to claim 6, the specific surface area that it is characterized in that catalyzer is 160～300m 2/ g; Pore volume is 0.25～0.38ml/g.
CN 00110707 2000-07-24 2000-07-24 Hydrogenation catalyst and its producing process Expired - Lifetime CN1107702C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 00110707 CN1107702C (en) 2000-07-24 2000-07-24 Hydrogenation catalyst and its producing process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 00110707 CN1107702C (en) 2000-07-24 2000-07-24 Hydrogenation catalyst and its producing process

Publications (2)

Publication Number Publication Date
CN1335363A CN1335363A (en) 2002-02-13
CN1107702C true CN1107702C (en) 2003-05-07

Family

ID=4580686

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 00110707 Expired - Lifetime CN1107702C (en) 2000-07-24 2000-07-24 Hydrogenation catalyst and its producing process

Country Status (1)

Country Link
CN (1) CN1107702C (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8697598B2 (en) 2005-04-21 2014-04-15 China Petroleum & Chemical Corporation Hydrogenation catalyst and use thereof
US8679322B2 (en) * 2009-11-24 2014-03-25 Intevep, S.A. Hydroconversion process for heavy and extra heavy oils and residuals
US9168506B2 (en) 2010-01-21 2015-10-27 Intevep, S.A. Additive for hydroconversion process and method for making and using same

Also Published As

Publication number Publication date
CN1335363A (en) 2002-02-13

Similar Documents

Publication Publication Date Title
EP1402948B1 (en) Catalyst for hydrogenation treatment of gas oil and method for preparation thereof; and process for hydrogenation treatment of gas oil
CN1055955C (en) Hydrogenation catalyst and preparation thereof
CN108067243B (en) Hydrotreating catalyst and preparation method and application thereof
CN1243081C (en) Hydrotreating catalyst and preparing method thereof
CN1259393C (en) Hydroprocessing catalyst and its prepn process
CN1107702C (en) Hydrogenation catalyst and its producing process
CN1107703C (en) Petroleum hydrocarbon hydrogenating catalyst and its prepn
CN1075548C (en) Hydroprocessing catalyst and its preparing process
CN1211157C (en) Hydrocracking after-treatment catalyst and preparing method thereof
CN1132905C (en) Catalyst for hydrotreatment of petroleum hydrocarbon
CN1123624C (en) Hydrocarbon hydrogenizing treamtent catalyst and its preparing method
JP2000042413A (en) Catalyst for hydrogenation refining
CN1132906C (en) Catalyst for hydrotreatment of hydrocarbon and its prepn.
JP4954095B2 (en) Gas oil hydrotreating catalyst, method for producing the same, and gas oil hydrotreating method
CN1221313C (en) Petroleum fraction hydrofining catalyst and preparing method thereof
CN1219029C (en) Hydrotreating catalyst and preparing method thereof
CN112717965B (en) Hydrogenation pretreatment catalyst, and preparation method and application thereof
CN1252221C (en) Hydroprocessing catalyst for petroleum hydrocarbon and preparing method thereof
CN1283756C (en) Catalyst for deep hydrogenation of distillate and its preparing method
CN1102643C (en) Catalyst for hydrorefining pertroleum wax and its preparing process
CN109772400B (en) Hydrotreating catalyst and preparation method and application thereof
CN109718867B (en) Hydrofining catalyst system and application thereof, preparation method of hydrofining catalyst and hydrofining method of distillate oil
JP2986838B2 (en) Hydrotreatment of residual oil
CN1202220C (en) Catalyst for hydrorefining petroleum waxes and its prep.
CN112717949B (en) Hydrofining catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term

Granted publication date: 20030507

CX01 Expiry of patent term