CN100431703C - Microporous and mesoporous composite hydrogenation catalyst carrier materials and process for preparing same - Google Patents
Microporous and mesoporous composite hydrogenation catalyst carrier materials and process for preparing same Download PDFInfo
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- CN100431703C CN100431703C CNB2005100772489A CN200510077248A CN100431703C CN 100431703 C CN100431703 C CN 100431703C CN B2005100772489 A CNB2005100772489 A CN B2005100772489A CN 200510077248 A CN200510077248 A CN 200510077248A CN 100431703 C CN100431703 C CN 100431703C
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 239000012876 carrier material Substances 0.000 title claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000002808 molecular sieve Substances 0.000 claims abstract description 49
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 3
- 238000000352 supercritical drying Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 8
- 239000003208 petroleum Substances 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000320 mechanical mixture Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 239000011218 binary composite Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PHTHEUNUXVDUOD-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[O-2].[Al+3] PHTHEUNUXVDUOD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a carrier material of microporous/mesoporous composite type hydrogenation catalysts. The present invention provides a path and method of a preparing technology for preparing a molecular sieve-oxide type composite material by sol-gel combination with supercritical drying. In the preparing method of the composite material provided by the present invention, a sol-gel method is adopted to prepare oxide or composite oxide, molecular sieves are added in different stages of solation and gelatinization, and therefore, the oxide can grow centered by the particles of the molecular sieves to obtain the composite material composed of microporous molecular sieves and mesoporous oxide. The material with gradient pore distribution and acidity distribution is an excellent carrier for preparing hydrogenation catalysts of different petroleum fractions, particularly the carrier for preparing hydrogenation catalysts of heavy petroleum fractions.
Description
Technical field:
The invention provides a class novel composite catalyst carrier material and a preparation method.Specifically, the present invention proposes a kind of the have molecular sieve/oxide material of micropore/mesoporous distribution and the new method of growth in situ preparation thereof, more particularly with titanium dioxide, silica, oxides such as aluminium oxide reach the wherein mesoporous composite oxides and the Y of the two formation, β, micro porous molecular sieves such as ZSM-5 complex group respectively are fitted together, constitute a class micropore/mesoporous composite material, gradient pore size distribution that this type of material has and the acid characteristics that distribute, the needs that are suitable for catalytic hydrogenation conversion reaction of heavy crude fraction and diffusion are the good heavy crude fraction processing catalyst carrier materials of a class.
Background technology:
Aggravation and improving constantly along with crude oil heaviness and inferiorization trend to the vehicle fuel quality requirement, the heavy charge of poor quality need be converted into the vehicle fuel of cleaning, in order to adapt to the needs of big molecular diffusion of heavy oil and reaction, catalyst need have certain gradient pore size distribution and acid the distribution.The molecular sieve that is usually used in PETROLEUM PROCESSING as Y, β, ZSM-5 etc., is poromerics, has stronger acidity; And oxides such as aluminium oxide, titanium dioxide, silica are mesoporous host material, have more weak acidity.Thereby, with oxide and molecular sieve is compound can make the catalyst carrier material that satisfies the processing of heavy oil needs.
But domestic and international employed catalyst carrier for hydrgenating heavy oil major part is to adopt simple mechanical mixture method to make with aluminium oxide and molecular sieve at present, the hole link of these materials mesopore orbit, specific area poor, that lack the big molecular diffusion of adaptation heavy oil is less, thereby both at home and abroad carrying out a few thing aspect the employing of carrier material and the preparation, as:
CN 1393522A provides the complex carrier preparation method of a kind of aluminium oxide and molecular sieve, and the preparation process of this material adopts the method for mechanical mixture that aluminium oxide and molecular sieve are mixed, and extruded moulding gets catalyst carrier.The characteristics of this complex method are simple, are the common used in industry preparation method; But also there are deficiencies such as mixing uniformity is poor, hole link is bad, mesoporous ratio is little.
CN1171982A and CN1172295A have proposed a kind of method that adopts sol-gel process to prepare the sial composite oxides, the composite oxides of preparing have bigger specific surface and pore volume, but the mesoporous ratio of this based composite oxide is less, be not suitable for the needs of the big molecular diffusion of heavy oil, and the acidity of composite oxides is weak, the acid amount is lower, the saturated and cracking scarce capacity to the macromolecular partial hydrogenation of heavy oil.
U.S4459367 discloses the method that a kind of aluminium oxide and zeolite prepare complex carrier, this method is to use the salt acid treatment again behind aluminium oxide and the molecular sieve mixed-forming, with the macropore that generates some and mesoporous, but also there is certain dealuminization in the method for this sour corrosion reaming to molecular sieve, the acidity of complex carrier is weakened, molecular sieve crystallinity descends, and is unfavorable for the preparation of high performance catalyst.
CN1107105C discloses a kind of preparation method who prepares molecular sieve and sial composite carrier, this method employing mixes and pinches, the mechanical mixture forming method of extrusion, molecular sieve and sial are combined with each other, prepared carrier has bigger specific area, but pore volume, aperture are less relatively, acid strength a little less than, thereby the hydrogenation performance of the catalyst towards heavy matter distillate that makes with this carrier is also not satisfactory.
Summary of the invention:
The objective of the invention is, a kind of novel molecular sieve and composite of oxide formation and preparation method thereof are provided; Wherein oxide can be aluminium oxide, titanium dioxide, silica, mainly be the binary composite oxides that aluminium oxide-titanium dioxide, titania-silica constitute, the advantage of binary composite oxides is to obtain the host material of mesoporous class by changing Ti/Al, Ti/Si pore structure, acidity and the surface nature than the regulation and control composite oxides; Molecular sieve of the present invention is Y zeolite, beta-molecular sieve and a ZSM-5 molecular sieve commonly used during petroleum refining industry produces; Preparation method provided by the invention adopts sol-gel process to make the colloidal sol of oxide or composite oxides, in changing the process of gel into, colloidal sol preparation and colloidal sol adds a certain amount of molecular sieve, make oxide in-situ be grown in the surface of molecular sieve, colloidal sol changes gel under field conditions (factors), and gel is through CO
2Supercritical fluid drying obtains the composite powder that the present invention proposes, and composite 500 ℃ of roastings in air atmosphere just obtain the composite carrier material of micro porous molecular sieve and mesopore oxide formation.
Characteristics of the present invention are: prepare mesopore oxide by sol-gel, or/and mesoporous composite oxides; By regulating the surface characteristic and the pore property of the atomic ratio change composite oxides in the composite oxides; Different phase in the colloidal sol preparation adds molecular sieve, can change the growth conditions of oxide on the molecular sieve surface; Dissimilar molecular sieves are compound with oxide in varing proportions, can regulate and control specific area, pore size distribution and acid distribution of carrier, is suitable for the catalyst carrier that the different petroleum cuts of weight, different hydrogenation require thereby can make.
The molecular sieve and the composite oxides of the present invention's preparation constitute in the carrier, and the ratio of molecular sieve is 0～40%; Composite oxides are TiO
2-SiO
2The time, TiO
2Content is 20%～100%, SiO
2Content is 0%～80%; Composite oxides are TiO
2-Al
2O
3The time, TiO
2Content is 0%～100%, Al
2O
3Content is 0%～100%.
The preparation process of composite carrier material provided by the present invention is as follows:
The preparation process of composite carrier material provided by the present invention is as follows:
(1) adopt known ion-exchange to change hydrogen type molecular sieve into Y zeolite or beta-molecular sieve or ZSM-5 molecular sieve, 300～900 ℃ of roastings are 2～8 hours in air atmosphere, obtain preparing the complex carrier molecular sieve.
(2) butyl titanate of metering and ethyl orthosilicate or aluminum nitrate are dissolved in respectively evenly mix again behind the ethanol solution A; With a certain amount of water, acetic acid and absolute ethyl alcohol mix solution B, the mol ratio of compounding substances is: (Ti+Si): H
2O: ROH: HAc=1: 1～4: 10～15: 1～3, (Ti+Al): H
2O: ROH: HAc=1: 1～3: 8～13: 1～2
(3) under strong agitation, solution B dropwise splashed among the A react; Obtain colloidal sol behind reaction 10～60min, the aging under field conditions (factors) 3～72h of colloidal sol just obtains TiO
2-SiO
2Or TiO
2-Al
2O
3Gel.
(4) molecular sieve of step (1) gained is joined in the reaction system in step (3) preparation colloidal sol or colloidal sol change the process of gel into, hydrolysate just is that core is assembled growth with the sieve particle, obtains the plural gel of composite oxides coating molecular sieve.The addition of molecular sieve is 0～40% in the hope of the content in carrier.
(5) with obtain in step (3) and/or the step (4) gel carry out CO
2Fluid supercritical drying, drying condition are 40～60 ℃ of temperature, pressure 8.0～12.0MPa, 1～4 hour time, obtain composite oxide powder.
(6) step (5) is obtained composite oxide powder in Muffle furnace in 400～800 ℃ of roastings 2～5 hours, obtain needed catalyst carrier.
The specific embodiment
Further set forth characteristics of the present invention below by embodiment:
Embodiment one:
The ratio that takes by weighing the ethyl orthosilicate of 34.0g butyl titanate and 20.8g be dissolved in respectively evenly mix again behind the ethanol solution A; With water, 41.2ml acetic acid and the 40ml absolute ethyl alcohol of 19ml mix solution B.Under strong agitation, solution B dropwise splashed among the A react; Obtain colloidal sol behind the reaction 30min, the aging under field conditions (factors) gel that just obtains of colloidal sol; It is dry to adopt supercritical carbon dioxide fluid that this gel is implemented, and drying condition is 40～60 ℃ of temperature, pressure 8.0～12.0Mpa, and the time is approximately 1～2 hour (detect less than aqueous vapor or organic matter smell substantially this moment) in tail gas, obtain white powder; With white powder in Muffle furnace in 500 ~ 600 ℃ of roastings 3 hours, obtain TiO
2-SiO
2Composite oxides; A certain amount of Y zeolite and Ti-Si composite oxide are ground in mortar jointly, make mixed-powder, powder process compression molding, drying, roasting with obtaining obtain needed composite oxide material, and note is a.
Embodiment two
With being dissolved in respectively of the ethyl orthosilicate of 34.0g butyl titanate and 20.8g evenly mix again behind the ethanol solution A; In A solution, add 3gY type molecular sieve under the intense stirring condition; With water, 41.2ml acetic acid and the 40ml absolute ethyl alcohol of 19ml mix solution B.Under stirring condition, solution B dropwise splashed among the A react; Obtain colloidal sol behind the reaction certain hour, the aging under field conditions (factors) certain hour of colloidal sol just obtains gel; Adopt the step identical that gel is carried out drying and roasting, obtain needed composite oxide material note and be b with embodiment.
Embodiment three
With the ratio of the ethyl orthosilicate of 34.0g butyl titanate and 20.8g be dissolved in respectively evenly mix again behind the ethanol solution A; With water, 41.2ml acetic acid and the 40ml absolute ethyl alcohol of 19ml mix solution B.Under strong magnetic stirs, solution B dropwise splashed among the A react; After reaction is finished, under intense stirring condition, in reaction product, add the 3g Y zeolite; Continue to obtain colloidal sol behind the reaction certain hour, the aging under field conditions (factors) certain hour of colloidal sol just obtains gel; Adopt the step identical that gel is carried out drying and roasting, obtain needed composite oxide material note and be c with embodiment.
Embodiment four
Change the ethyl orthosilicate among the embodiment one, two, three into aluminum nitrate, wherein the amount of butyl titanate is the amount 30g of 40.8g aluminum nitrate, and molecular sieve is changed to the ZSM-5 molecular sieve, and other conditions are identical with step, the composite oxide material that obtains, note is d, e, f respectively.
Embodiment five
According to the method among the embodiment one, two, three, change the amount of butyl titanate and ethyl orthosilicate wherein into 54.4g and 8.3g respectively, molecular sieve is changed to beta-molecular sieve, and other conditions and step are constant, obtain three carriers, and note is g, h, i respectively.
Embodiment six
The method of employing BET is measured the specific area and the pore volume of laboratory sample in the foregoing description, and the gained experimental data is shown in following table one.Data can be seen from table, the prepared composite of each embodiment has higher specific surface area, pore volume and bigger average pore size among the present invention, and 10～20nm mesoporous occupies very big ratio, so this class advanced composite material (ACM) not only is suitable as the catalyst carrier in the light petroleum cut fraction hydrogenation processing procedure; Especially adapt to the catalyst carrier in the heavy distillate hydrotreatment process.Because this class carrier material both provided the duct combination of micropore-mesopore, was beneficial to the big molecular diffusion of heavy oil, provide in molecular sieve highly acid and the composite oxides again, weakly acidic combination, be adapted to the needs of dissimilar hydrogenation reactions.Therefore composite provided by the present invention is the carrier material of good catalyst for hydro-processing heavy distillate, and suitable application prospects is arranged.
The fundamental property of table one, complex carrier
Claims (2)
1, a kind of novel microporous/the mesoporous composite hydrogenation catalyst carrier material, it is characterized in that: the molecular sieve of preparation and composite oxides constitute in the carrier, the ratio of molecular sieve for greater than 0 to being less than or equal to 40%; Composite oxides are TiO
2-SiO
2The time, TiO
2Content is more than or equal to 20% to less than 100%, SiO
2Content is to being less than or equal to 80% greater than 0; Composite oxides are TiO
2-Al
2O
3The time, TiO
2Content is greater than 0 to less than 100%, Al
2O
3Content is to less than 100% greater than 0.
2, a kind of novel microporous/preparation method of mesoporous composite hydrogenation catalyst carrier material, it is characterized in that: the preparation process of above-mentioned composite carrier material is as follows:
1. adopt known ion-exchange to change oxygen type molecular sieve into Y zeolite or beta-molecular sieve or ZSM-5 molecular sieve, 300～900 ℃ of roastings are 2～8 hours in air atmosphere, obtain preparing the complex carrier molecular sieve:
2. the butyl titanate of metering and ethyl orthosilicate or aluminum nitrate are dissolved in respectively evenly mix again behind the ethanol solution A; With water, acetic acid and absolute ethyl alcohol mix solution B, the mol ratio of compounding substances is: (Ti+Si): H
2O: ROH: HAc=1: 1～4: 10～15: 1～3, (Ti+Al): H
2O: ROH: HAc=1: 1～3: 8～13: 1～2;
3. under strong agitation, solution B dropwise splashed among the A react; Obtain colloidal sol behind reaction 10～60min, the aging under field conditions (factors) 3～72h of colloidal sol just obtains TiO
2-SiO
2Or TiO
2-Al
2O
3Gel:
4. with step 1. the molecular sieve of gained 8. prepare in the process that colloidal sol or colloidal sol changes gel in step and join in the reaction system, hydrolysate just is that core is assembled growth with the sieve particle, obtains the plural gel that composite oxides coat molecular sieve; The addition of molecular sieve is to being less than or equal to 40% greater than 0 in the hope of the content in carrier;
5. with step 3. or step obtain in 4. gel carry out CO
2Fluid supercritical drying, drying condition are temperature 40-60 ℃, pressure 8.0～12.0MPa, 1～4 hour time, obtain the combined oxidation object;
6. 5. step is obtained composite oxide powder in Muffle furnace in 400～800 ℃ of roastings 2～5 hours, obtain needed catalyst carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100772489A CN100431703C (en) | 2005-06-20 | 2005-06-20 | Microporous and mesoporous composite hydrogenation catalyst carrier materials and process for preparing same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100772489A CN100431703C (en) | 2005-06-20 | 2005-06-20 | Microporous and mesoporous composite hydrogenation catalyst carrier materials and process for preparing same |
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|---|---|
| CN1883802A CN1883802A (en) | 2006-12-27 |
| CN100431703C true CN100431703C (en) | 2008-11-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102327772B (en) * | 2010-11-01 | 2013-04-03 | 华东理工大学 | Preparation method of composite metal mesoporous oxide and application thereof |
| CN103372464A (en) * | 2012-04-13 | 2013-10-30 | 中国石油天然气股份有限公司 | Dual-pore composite alumina material |
| CN102773112B (en) * | 2012-08-10 | 2014-06-04 | 西安交通大学 | Method for preparing ternary complex carrier supported nickel phosphide catalyst |
| CN111085244A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Preparation method of hierarchical pore composite material |
| CN111086999A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Preparation method of composite material containing Y-type molecular sieve |
| CN114669287A (en) * | 2022-04-26 | 2022-06-28 | 西安科技大学 | Ordered mesoporous titanium-aluminum composite oxide coated TS-1 molecular sieve material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171982A (en) * | 1996-07-31 | 1998-02-04 | 三星电子株式会社 | Method for fabricating porous composite oxide |
| CN1393522A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Hydrocracking catalyst for inceasing output of jet fuel and diesel oil |
| CN1107105C (en) * | 2000-10-26 | 2003-04-30 | 中国石油化工股份有限公司 | High-or medium-oilness hydrocracking catalyst |
-
2005
- 2005-06-20 CN CNB2005100772489A patent/CN100431703C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171982A (en) * | 1996-07-31 | 1998-02-04 | 三星电子株式会社 | Method for fabricating porous composite oxide |
| CN1107105C (en) * | 2000-10-26 | 2003-04-30 | 中国石油化工股份有限公司 | High-or medium-oilness hydrocracking catalyst |
| CN1393522A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Hydrocracking catalyst for inceasing output of jet fuel and diesel oil |
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|---|---|
| CN1883802A (en) | 2006-12-27 |
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