CN1218088A - Hydrogenation catalyst and preparation thereof - Google Patents
Hydrogenation catalyst and preparation thereof Download PDFInfo
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- CN1218088A CN1218088A CN 97122135 CN97122135A CN1218088A CN 1218088 A CN1218088 A CN 1218088A CN 97122135 CN97122135 CN 97122135 CN 97122135 A CN97122135 A CN 97122135A CN 1218088 A CN1218088 A CN 1218088A
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Abstract
A catalyst for hydrogenating petroleum hydrocarbons (such as hydrocracking and hydrorefining, for example, removing sulfur, nitrogen and metals) is prepared from high-concentration and high-stability solution (containing at least one element in VIB family, such as Mo or W, one element in VIII family, such as Ni or Co,and one inorganic acid, such as HePO4) and pseudo-boehmite through mixing, kneading, extruding out to obtain bars, drying at 110-130 deg.C and three-stage constant-temp calcine. Said catalyst has high activity.
Description
The present invention relates to a kind of hydrocarbon hydrogenizing treamtent catalyst and preparation method thereof.
Contain sulphur, nitrogen, oxygen and metal impurities in crude oil and the heavy distillate that from crude oil, obtains.These impurity usually exist with heteroato mic organic compound form, and usually content is higher.The existence of these impurity not only influences the stability of its product, in use also gives off SO
x, NO
xDeng the obnoxious flavour contaminate environment.Face hydrogen in petroleum fractions and handle in (catalytic reforming, hydrogenation 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 hydrotreatment of excellent property (hydrofining) catalyzer requires to possess two conditions: (1) at first reactive metal such as molybdenum (tungsten), nickel (cobalt) etc. has higher chemical individual layer dispersion amount on catalyst surface; (2) reactive metal has high dispersity and good dispersion state on catalyst surface.In addition, from considering that economically the technology of Preparation of Catalyst (process) should be tried one's best simply.
About the preparation of hydrotreating catalyst, prior art mainly is to adopt two-step approach.Be the first step preparation carrier γ-Al earlier
2O
3(or SiO
2-Al
2O
3, zeolite-A l
2O
3Deng), then second step, with the solution impregnating carrier that contains Mo (w)-Ni (Co)-P, 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).Adopt two-step approach promptly earlier the preparation carrier then carrier through the advantage of dipping preparation catalyzer be: (1) prepares carrier separately 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 to compare the fixed ratio between the active ingredient (for example Mo, W, Ni, Co, P etc.), thereby active ingredient has higher dispersity and good dispersion state on catalyst surface.But, adopt two-step approach to prepare catalyzer, amount (loading) is subjected to certain restriction, for example MoO on the active ingredient
3Content only reaches 20w% usually, and it is then very difficult to surpass 25w%.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 metal loading of (1) catalyzer 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 7.0nm accounts for more than 80% of whole pore volume, even surpasses 90%.
The objective of the invention is: (1) adopts even kneading method of a step, directly prepares Mo-Ni (Co)-P/Al by pseudo-boehmite
2O
3Hydrotreating catalyst, thus the Catalyst Production process simplified, reduce production costs; (2) increase the catalyst activity component concentration with further raising 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.With pseudo-boehmite (pseudo-boehmite) is raw material, with solution with high metal concentration, through mixing, kneading, extruded moulding, thereby drying, roasting ＂ one step ground ＂ finish the method for preparation hydrotreatment (hydrocracking and hydrofining are as hydrodenitrification, hydrogenating desulfurization, hydrodemetallation (HDM) etc.) catalyzer then.
The present invention includes two aspects to achieve these goals: preparation high stability, Mo, the Ni (Co) of high density, P solution; With this solution with the pseudo-boehmite thorough mixing, be kneaded into plastic shape, be extruded into the trifolium strip, " the three sections constant temperature calcinings " program of employing, 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 said formulations prepared from solutions step of the present invention is as follows:
(1) phosphate aqueous solution is added in the molybdenum oxide, stir, slowly heat temperature raising is to little boiling, and heating
To the whole or most of dissolvings of molybdenum oxide.
(2) above-mentioned solution is cooled to 60 ℃～70 ℃ after, slowly add basic nickel carbonate or nickelous nitrate
(and/or Xiao Suangu) placed and is warming up to little boiling again after 10～30 minutes, and it is molten substantially to be heated to precipitation
Separate.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 have 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 more than 2 years.
Mo-Ni of the present invention (Co)-P/Al
2O
3The hydrotreating catalyst preparation process is as follows:
(1) with Mo-Ni (Co)-P solution and pseudo-boehmite (powder) 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 0.5～2 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.
Prepared Mo-Ni (Co)-P/Al according to the present invention
2O
3Hydrotreating catalyst has following character:
(1) metal content is MoO
324～40w%, NiO and/or CoO 2.5～10w%, P content are 1.5～4.0w%.
(2) specific surface area is 180～300m
2/ g; Pore volume is 0.25～0.38ml/g.
(3) active ingredient Mo, Ni (Co), P have 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/Al
2O
3Hydrotreating catalyst, simple, convenient, easy row.Therefore, production cost is lower than adopting usual way.
(2) catalyzer of the present invention is suitable for the hydrofining (as hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM) etc.) of heavy (as V O) and low-density oil cut, also is suitable for the hydrocracking of heavier petroleum fraction.The processing condition that catalyzer is suitable for are: temperature of reaction is 230 ℃～420 ℃; Reaction pressure 5.0～15.0MPa; LHSV0.5～3.0h
-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 2 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.
For further specifying all main points of the present invention, enumerate following examples and comparative example.
Embodiment 1
(1) preparation of Mo, Ni, P solution
With 18.3ml phosphoric acid H
3PO
4(85%) is dissolved in the 470ml water.Under agitation solution is joined 85g 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 60g nitric acid nickel (NO
3)
26H
2O, heating up is heated to throw out and dissolves substantially again.With the filtrate evaporation concentration to 200ml.
(2) Preparation of Catalyst
Mo-Ni-P solution thorough mixing, kneading twice with 300g pseudo-boehmite and top step (1) add 80ml 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 400 ℃ with 4 ℃ of minutes speed again, constant temperature 3 hours.Be warming up to 500 ℃ 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 18.3ml and 600ml.Molybdenum oxide MoO
3With nitric acid nickel (NO
3)
26H
2The O add-on is respectively 115g and 65g.The filtrate evaporation concentration is to 280ml.
(2) Preparation of Catalyst
300g is intended thin water aluminium and Mo-Ni-P solution thorough mixing, the kneading of top (1) to be made and is 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 110～130 ℃.
The dry sample of crossing places High Temperature Furnaces Heating Apparatus, is warming up to 300 ℃ with 4 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 410 ℃ with 4 ℃ of/minute speed again, constant temperature 4 hours.Be warming up to 530 ℃ with 4 ℃ of/minute speed at last, constant temperature calcining 2 hours.
Comparative example 1
(1) preparing carriers
Take by weighing pseudo-boehmite 200g, add 2.9ml acetate, 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 13.9ml phosphoric acid H
3PO
4(85%) is dissolved in the 420ml water.Under agitation solution is joined 73g 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 36g basic nickel carbonate, be warming up to again little boil and be heated to throw out dissolve substantially.Filtrate is concentrated into 150ml.
(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 105 ℃～115 ℃.
The dry catalyst sample of crossing is warming up to 190 ℃ with 3 ℃～5 ℃ of/minute speed, constant temperature calcining 0.5 hour.Be warming up to 368 ℃ with 3 ℃～5 ℃ 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.
Comparative example 2
(1) carrier γ-Al
2O
3Preparation process is identical with comparative example 1.
(2) Preparation of Catalyst
Catalyst soakage, drying step are identical with embodiment 1 corresponding section.
The dry catalyst sample of crossing is warming up to 180 ℃ with 4 ℃ of/minute speed, constant temperature calcining 0.5 hour.Be warming up to 350 ℃ with 4 ℃ of/minute speed again, constant temperature calcining 1 hour.Be warming up to 430 ℃ with 4 ℃ of/minute speed at last, constant temperature calcining 4 hours.
More than each routine prepared γ-Al
2O
3And Mo-Ni-P/Al
2O
3The physico-chemical property of catalyzer is listed in the 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 respectively under 260 ℃ and 370 ℃ 8 hours 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 90w%, i.e. it is 0.014w% 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.
By evaluation result (seeing Table 4) as can be seen: prepared catalyzer is under the close situation of metal content to adopt the present invention's (i.e. even kneading method of a step), and the hydrodenitrification reactive behavior is with close or slightly excellent with usual way (being two step method).If further increase metal component (Mo, Ni) content, prepared catalyzer will have higher hydrodenitrification reactive behavior (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 | |||
| ?γ-Al 2O 3 | Catalyzer | γ-Al 2O 2 | Catalyzer | |||
| Specific surface m 2/g | ?238 | ?196 | ?301 | ?145 | ?298 | ?139 |
| Pore volume ml/g | ?0.312 | ?0.278 | ?0.630 | ?0.292 | ?0.650 | ?0.300 |
| Chemical constitution, w% | ||||||
| ????MoO 3 | ?24.2 | ?33.6 | ?--- | ?23.6 | ?--- | ?23.9 |
| ????NiO | ?4.35 | ?5.90 | ?--- | ?4.26 | ?--- | ?4.38 |
| ????P | ?2.62 | ?2.63 | ?--- | ?2.48 | ?--- | ?2.56 |
| ????Al 2O 3 | Surplus | Surplus | Surplus | Surplus | ||
| Bulk density g/ml | ?0.89 | ?0.93 | ?0.60 | ?0.90 | ?0.60 | ?0.89 |
Table 2 stock oil character
| Stock oil | Triumph V O |
| Proportion d 4 20,g/ml | 0.900 |
| Sulphur, w% | 0.46 |
| Nitrogen, w% | 0.14 |
| 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 |
| H 2/ oil ratio, v/v | 1000 |
Each routine catalyst hydrogenation denitrification activity of table 4 relatively
| Catalyzer | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Temperature of reaction, ℃ | ?373 | ?366 | ?375 | ?375 |
Claims (4)
1. hydrotreating catalyst is by MoO
324～40w%, NiO and/or CoO 2.5～10w%, P1.5～4.0w%, and the aluminum oxide of surplus composition, its specific surface area is 180～300m
2/ g; Pore volume is 0.25～0.38ml/g, it is characterized in that catalyzer is by containing Mo, Ni (Co), P solution and pseudo-boehmite is mixed together, kneading, moulding, drying and roasting and make.
2. according to the catalyzer of claim 1, it is characterized in that the said Mo of containing, Ni or Co, the every 100ml of P solution contain 50～80gMoO
3, 10～20gNiO, 0～15gCoO, P/MoO
3Weight ratio is 0.08～0.20.
3. according to the catalyzer of claim 2, it is characterized in that the said Mo of containing, Ni or Co, P solution prepare 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 or most of 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 10～30 minutes, be heated to the basic dissolving of precipitation, reduce to the room temperature after-filtration to remove insoluble impurity;
(3) above-mentioned solution evaporation is concentrated into needed concentration.
4. according to the catalyzer of claim 1, it is characterized in that behind the shaping of catalyst dry sample being placed High Temperature Furnaces Heating Apparatus, 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, last speed with 3 ℃～5 ℃/minute is warming up to 471 ℃～560 ℃, constant temperature calcining 1～4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122135A CN1055955C (en) | 1997-11-24 | 1997-11-24 | Hydrogenation catalyst and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122135A CN1055955C (en) | 1997-11-24 | 1997-11-24 | Hydrogenation catalyst and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1218088A true CN1218088A (en) | 1999-06-02 |
| CN1055955C CN1055955C (en) | 2000-08-30 |
Family
ID=5176696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122135A Expired - Lifetime CN1055955C (en) | 1997-11-24 | 1997-11-24 | Hydrogenation catalyst and preparation thereof |
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| CN (1) | CN1055955C (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1169416A4 (en) * | 1999-01-15 | 2003-03-26 | Exxonmobil Res & Eng Co | Production of low sulfur/low nitrogen hydrocrackates |
| US6863803B1 (en) | 1997-07-15 | 2005-03-08 | Exxonmobil Research And Engineering Company | Production of low sulfur/low nitrogen hydrocrackates |
| US7229548B2 (en) | 1997-07-15 | 2007-06-12 | Exxonmobil Research And Engineering Company | Process for upgrading naphtha |
| US7232515B1 (en) | 1997-07-15 | 2007-06-19 | Exxonmobil Research And Engineering Company | Hydrofining process using bulk group VIII/Group VIB catalysts |
| US7288182B1 (en) | 1997-07-15 | 2007-10-30 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts |
| CN100435954C (en) * | 2002-12-18 | 2008-11-26 | 克斯莫石油株式会社 | Hydrotreating catalyst for gas oil, process for producing the same, and method of hydrotreating gas oil |
| US7513989B1 (en) | 1997-07-15 | 2009-04-07 | Exxonmobil Research And Engineering Company | Hydrocracking process using bulk group VIII/Group VIB catalysts |
| CN106622278A (en) * | 2017-01-20 | 2017-05-10 | 平潭自贸区金瑜环保材料有限公司 | Integral aluminum oxide loaded iron-manganese binary catalyst with high specific surface area |
| CN106693986A (en) * | 2017-01-20 | 2017-05-24 | 平潭自贸区金瑜环保材料有限公司 | High specific surface area enhanced integrated alumina supported iron-manganese binary catalyst |
| CN106732468A (en) * | 2017-01-20 | 2017-05-31 | 平潭自贸区金瑜环保材料有限公司 | A kind of high-specific surface area integral alumina carrier |
| CN106732595A (en) * | 2017-01-20 | 2017-05-31 | 平潭自贸区金瑜环保材料有限公司 | High-specific surface area integral alumina copper-loading catalyst |
| CN106799231A (en) * | 2017-01-20 | 2017-06-06 | 平潭自贸区金瑜环保材料有限公司 | A kind of high-specific surface area integral alumina supported nickel catalyst |
| CN106807374A (en) * | 2017-01-20 | 2017-06-09 | 平潭自贸区金瑜环保材料有限公司 | A kind of high-specific surface area integral alumina supported ferric catalyst |
| CN108620081A (en) * | 2017-03-24 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst maceration extract and preparation method thereof |
| CN110064405A (en) * | 2018-01-23 | 2019-07-30 | 中国石油天然气股份有限公司 | A kind of preparation method with desulphurizing activated hydrotreating catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4317746A (en) * | 1980-11-28 | 1982-03-02 | Union Oil Company Of California | Hydrotreating catalysts |
| US4568449A (en) * | 1982-08-16 | 1986-02-04 | Union Oil Company Of California | Hydrotreating catalyst and process |
| CN1041430C (en) * | 1995-05-06 | 1998-12-30 | 中国科学院山西煤炭化学研究所 | Hydro-treated catalyst and preparation method thereof |
-
1997
- 1997-11-24 CN CN97122135A patent/CN1055955C/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6863803B1 (en) | 1997-07-15 | 2005-03-08 | Exxonmobil Research And Engineering Company | Production of low sulfur/low nitrogen hydrocrackates |
| US7229548B2 (en) | 1997-07-15 | 2007-06-12 | Exxonmobil Research And Engineering Company | Process for upgrading naphtha |
| US7232515B1 (en) | 1997-07-15 | 2007-06-19 | Exxonmobil Research And Engineering Company | Hydrofining process using bulk group VIII/Group VIB catalysts |
| US7288182B1 (en) | 1997-07-15 | 2007-10-30 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts |
| US7513989B1 (en) | 1997-07-15 | 2009-04-07 | Exxonmobil Research And Engineering Company | Hydrocracking process using bulk group VIII/Group VIB catalysts |
| EP1169416A4 (en) * | 1999-01-15 | 2003-03-26 | Exxonmobil Res & Eng Co | Production of low sulfur/low nitrogen hydrocrackates |
| CN100435954C (en) * | 2002-12-18 | 2008-11-26 | 克斯莫石油株式会社 | Hydrotreating catalyst for gas oil, process for producing the same, and method of hydrotreating gas oil |
| CN106693986A (en) * | 2017-01-20 | 2017-05-24 | 平潭自贸区金瑜环保材料有限公司 | High specific surface area enhanced integrated alumina supported iron-manganese binary catalyst |
| CN106622278A (en) * | 2017-01-20 | 2017-05-10 | 平潭自贸区金瑜环保材料有限公司 | Integral aluminum oxide loaded iron-manganese binary catalyst with high specific surface area |
| CN106732468A (en) * | 2017-01-20 | 2017-05-31 | 平潭自贸区金瑜环保材料有限公司 | A kind of high-specific surface area integral alumina carrier |
| CN106732595A (en) * | 2017-01-20 | 2017-05-31 | 平潭自贸区金瑜环保材料有限公司 | High-specific surface area integral alumina copper-loading catalyst |
| CN106799231A (en) * | 2017-01-20 | 2017-06-06 | 平潭自贸区金瑜环保材料有限公司 | A kind of high-specific surface area integral alumina supported nickel catalyst |
| CN106807374A (en) * | 2017-01-20 | 2017-06-09 | 平潭自贸区金瑜环保材料有限公司 | A kind of high-specific surface area integral alumina supported ferric catalyst |
| CN108620081A (en) * | 2017-03-24 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst maceration extract and preparation method thereof |
| CN108620081B (en) * | 2017-03-24 | 2020-08-04 | 中国石油化工股份有限公司 | Hydrogenation catalyst impregnation liquid and preparation method thereof |
| CN110064405A (en) * | 2018-01-23 | 2019-07-30 | 中国石油天然气股份有限公司 | A kind of preparation method with desulphurizing activated hydrotreating catalyst |
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|---|---|
| CN1055955C (en) | 2000-08-30 |
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Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM & Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; FUSHUN PETROCHEMICAL INSTITUTE., CHINA PETROCHEMICAL CORP. |
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