CN102441411A - Hydrocracking catalyst with high activity and high-medium oil selectivity and preparation method of hydrocracking catalyst - Google Patents
Hydrocracking catalyst with high activity and high-medium oil selectivity and preparation method of hydrocracking catalyst Download PDFInfo
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Abstract
The invention relates to a hydrocracking catalyst with high activity and high-medium oil selectivity. According to the hydrocracking catalyst, amorphous silicon aluminum is used as a carrier, and a specially-modified Y-type molecular sieve is used as acid component, the molecular sieve has high degree of crystallization and low cell parameters, rich secondary holes, large surface area, less uniformly-distributed acid sites, no strong acid center, and most of medium-strength acid centers, and also has strong nitrogen-resisting performance and better damage capacity; and the hydrocracking catalyst using the molecular sieve has high hydrocracking activity and high middle oil selectivity, and stronger nitrogen resisting capacity. The catalyst provided by the invention is used in the process of producing an intermediate distillate product by adopting a heavy hydrocarbon single-section or one-section hydrocracking process, and has better activity and middle oil selectivity.
Description
Technical field
The present invention relates to the hydrocracking catalyst of a kind of high activity, high middle distillates oil selectivity, particularly contain the high activity of Modified Zeolite Y, the hydrocracking catalyst of high middle distillates oil selectivity.
Background technology
At present, worldwide petroleum resources are not enough, and crude oil becomes and heavily becomes bad; The intermediate oil demand increases, and petroleum chemicals upgrading and environmental regulation are more and more strict, have all promoted the heavy oil lighting greatly; And the very strong driving force of formation accelerated development hydrogen addition technology, hydrocracking is the effective means of raising the output intermediate oil, with normal vacuum distillate; Vacuum distillate, secondary operations light oil is raw material, after hydrocracking; Can produce fine-quality diesel oil and jet fuel, and product flexibility is big, good product quality.
The single hop technological process reduced investment of hydrocracking, simple to operate, and also air speed is big, and unconverted oil can rationally be utilized.But to the anti-nitrogen performance of catalyst, the hydrocracking performance all requires very high.The hydrocracking catalyst that the single-stage hydrocracking technical process is used is under the situation of not giving refining protection, to use.General under the situation of feed nitrogen content height to 1000～2000 μ g/g, directly the contact with hydrocracking catalyst reacted; This just requires hydrocracking catalyst to have the ability that anti-preferably nitride is poisoned; It is active promptly under reactant nitrogen content conditions of higher, to have good hydrocracking, also will have simultaneously to delay the performance that carbon deposit generates preferably.
Chinese patent ZL98114489.6 provides the heavy hydrocarbons hydrocraking catalyst of a kind of glue method altogether preparation; Used molecular sieve is the Modified Zeolite Y of ZL96119840.0 report; But this Y zeolite is the molecular sieve of strong-acid type; Therefore the hydrogenation cracking activity of this catalyst is higher, and middle distillates oil selectivity is relatively poor.This catalyst consists of: WO
322.0%, NiO 9.0%, ZrO
27.0%, SiO
233.0%, Al
2O
329.0%, wherein Y zeolite accounts for about 7.0%, and specific surface is 254m
2/ g, pore volume are 0.312ml/g, and reaction temperature is at 396 ℃ when handling heavy distillate, and middle distillates oil selectivity is lower.
Chinese patent ZL200410050778.X also provides the high-medium oil selective hydrocracking catalyst of a kind of glue method altogether preparation; Used molecular sieve is a kind of Modified Zeolite Y; Calculation is more in this Y zeolite weak acid; Therefore the hydrogenation cracking activity of this catalyst is lower, and middle distillates oil selectivity is higher.This catalyst consists of: WO
322.0%, NiO 9.0%, ZrO
27.0%, SiO
233.0%, Al
2O
329.0%, wherein Y zeolite accounts for about 20.0%, and specific surface is 240m
2/ g, pore volume are 0.34ml/g, and reaction temperature is about 397 ℃ when handling heavy distillate, and middle distillates oil selectivity is higher.
Summary of the invention
To the deficiency of prior art, the present invention provides hydrocracking catalyst of a kind of high activity, high middle distillates oil selectivity and preparation method thereof, and this catalyst had both had high hydrogenation cracking activity, has high middle distillates oil selectivity again.Catalyst of the present invention can be used for not having the single-stage hydrocracking technology of refining section, also can be used for having the one-stage serial hydrocracking technology of refining section.
The hydrocracking catalyst of high activity of the present invention, high middle distillates oil selectivity; Be to be carrier with the amorphous aluminum silicide; Y zeolite through special modification is acidic components, is the hydrogenation activity component with VI B family's metal and VIII family metal, is co-catalyst with IV B family metal; The content of Modified Zeolite Y is 15wt%～35wt%, better is 20wt%～30wt%.
The SiO of the employed Modified Zeolite Y of catalyst of the present invention
2/ Al
2O
3Mol ratio 90～110 is preferably 95～105, and cell parameter is 2.423～2.430nm, and being preferably cell parameter is 2.424～2.429nm, degree of crystallinity＞100%, specific area 750～950m
2/ g, the secondary pore of＞1.7nm (referring generally to the secondary pore that bore dia is 1.7～10nm) accounts for 60%～80% of total pore volume, is preferably 65%～75%.
The acid matter of the modified Y molecular sieve that catalyst of the present invention uses is following: infrared acidity 0.1～0.3mmol/g, and 150～250 ℃ of weak acid centers account for 8%～18%, and 250～450 ℃ of moderate strength acid sites account for 82%～92%, and＞450 ℃ strong acid center is 0.
In the catalyst of the present invention; VI B metal oxide content is 10wt%～40wt%; Be preferably 20wt%～25wt%, VIII family metal oxide content is 1wt%～20wt%, is preferably 7wt%～12wt%; Account for the 1wt%～10wt% of catalyst with IV B family metal oxide content, be preferably 6wt%～10wt%.Amorphous aluminum silicide content accounts for the 20wt%～50wt% of catalyst weight, is preferably 30wt%～40wt%.
In the catalyst of the present invention,
Catalyst of the present invention adopts conventional coprecipitation method preparation, and as preparing by the process that ZL98114489.6 introduced, detailed process is: with related amorphous aluminum silicide; The ratio that the salting liquid of auxiliary agent and reactive metal is formed in catalyst joins in the glue jar, adds precipitating reagent and processes gelatinous mixture, and precipitating reagent can be inorganic or organic alkalescent ammoniac compounds; The suspension that adds on demand through Modified Zeolite Y then mixes; Obtain containing the filter cake of certain moisture after the mixture of gained filters, this filter cake dewaters at a certain temperature, and the temperature range of cake dewatering is 40～110 ℃; Impurity is removed in washing behind the first extruded moulding in dehydration back; Wash temperature is 20～60 ℃, and the pH value is 7～12, and dry then, activation makes finished catalyst.Baking temperature is 50～120 ℃, and the time is 6～12 hours, and activation temperature is 450～550 ℃, and the time is 8～12 hours.
The molecular sieve that above-mentioned preparation process relates to is a raw material with the Modified Zeolite Y of ZL96119840.0 report; Carry out deep sealumination modified through hydrothermal treatment consists; Its essential condition is 760～800 ℃ of temperature, and normal pressure is to 0.3MPa, 20～30 hours time; Use little ammonia at water vapour during hydrothermal treatment consists, the ammonia dividing potential drop is 50～3000Pa (absolute pressure).Carry out acid treatment after the hydrothermal treatment consists again, use inorganic acid example hydrochloric acid, sulfuric acid or nitric acid etc., the concentration 1.0～10.0M of acid; 12～20 hours time; 50～80 ℃ of temperature, the ratio of sour consumption and molecular sieve weight is 1: 1～20: 1, obtains being applicable to molecular sieve of the present invention after the processing.
The Modified Zeolite Y character of ZL96119840.0 report is following: the aperture accounts for more than 45% greater than the pore volume of 1.7nm, surface area 750～900m
2/ g, cell parameter is at 2.423～2.545nm, degree of crystallinity 95～110%, SiO
2/ Al
2O
3Mol ratio 7～20.Concrete method of modifying is undertaken by the described method of this patent.
Catalyst of the present invention adopts Y zeolite through special modification as acidic components; This molecular sieve has high degree of crystallinity, high silica alumina ratio, low cell parameter; The secondary pore of molecular sieve is many; Help improving the diffusion velocity of raw material and product, reduce the second pyrolysis of product, improve the middle distillates oil selectivity of catalyst.The silica alumina ratio of this molecular sieve is high in addition, and acidity is low, and the acid site number is few, and the acid site degree that is evenly distributed is higher, and major part is the moderate strength acid site, makes this molecular sieve have very strong nitrogen resistance and breaks the ring ability preferably.Under the condition that molecular sieve content increases in catalyst, the hydrogenation cracking activity of catalyst is greatly improved, and the intermediate oil selectivity of catalyst also slightly improves or remains unchanged.Method for preparing catalyst metal dispersity of the present invention is high, and the catalyst serviceability is good.In order to reduce the metal loss of washing process, catalyst of the present invention adopts mode of washing after the first moulding, washs simultaneously under normal temperature and weak basic condition and carries out, and can adopt the pore structure of steam treatment process adjustment catalyst.The molecular sieve modified method of the present invention is through suitable atmosphere degree of depth hydrothermal treatment consists; In conjunction with degree of depth acid treatment; Make molecular sieve under the condition of advanced treating, obtain obtaining the modified product of required character, keep high degree of crystallinity simultaneously, prevent the framework of molecular sieve avalanche; The acid site of the modified molecular screen that obtains is most of approximately to be the acid site of moderate strength, helps improving the middle distillates oil selectivity of hydrocracking catalyst.Catalyst of the present invention is used for the single-stage hydrocracking technical process, has active height, and the intermediate oil selectivity is good, and liquid yield is high, characteristics such as good product quality.
The specific embodiment
Catalyst of the present invention is a carrier with the amorphous aluminum silicide, provides part acid, adds the Y zeolite adjustment of acidity through special modification; With the metal W of VI B family and/or Mo and metal Ni of VIII family and/or Co; Or its mixture is the hydrogenation activity component, and with IV B family metal Ti, Zr is a co-catalyst.The sial weight ratio of amorphous aluminum silicide is 0.1～10: 1, and preferred about 1: 1.
In general, hydrocracking catalyst can use following any method preparation, as: infusion process, kneading method, beating method, coprecipitation method can use ion-exchange for noble metal.Infusion process and kneading method all are to add metal again after earlier carrier and acidic components being processed, and coprecipitation method then is that acidic components and one on metal precipitate, and the metal loading is unrestricted, and metal dispersion is good.The preparation method that catalyst of the present invention relates to is a coprecipitation method, disperses more uniformly in the hope of obtaining metal component.
Catalyst of the present invention can be used for producing the hydrocracking process of intermediate oil, is specially adapted to produce the single-stage hydrocracking flow process of intermediate oil, and heavier hydrocarbon feeds is changed into than low-boiling point material.
The heavy charge scope that is applicable to this law is very wide; They comprise that vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, the various hydrocarbon ils of catalytic cracking circulation wet goods also can make up use; It is 250～550 ℃ hydro carbons that raw material contains boiling point usually, and nitrogen content can be at 50～2500 μ g/g.
Method of the present invention is preferably carried out under single hop single pass hydrocracking condition.Reaction temperature is 300～500 ℃, is more preferably 350～450 ℃; Pressure is 6～20MPa, is more preferably 13～17MPa; Liquid hourly space velocity (LHSV) is 0.5～3hr
-1, 0.8～1.5hr preferably
-1Hydrogen to oil volume ratio is 400～2000: 1, preferably 800～1500: 1.
The hydrocracking catalyst that uses in the single-stage hydrocracking technology requires higher middle distillates oil selectivity; The employing amorphous aluminum silicide is acidic components, is favourable to the middle distillates oil selectivity that improves catalyst, but uses lytic activity to show too low again separately; If adding an amount of acid moderate Y zeolite through special modification is acidic components; Then can obtain greater activity and have high middle distillates oil selectivity, take into account naphtha simultaneously, all comparatively ideal catalyst of jet fuel and diesel quality.
Following instance can further be understood the present invention.
Instance 1
Catalyst A is the catalyst of the inventive method preparation, and catalyst weight consists of: WO
322.5%, NiO 8.5%, ZrO
26.5%, SiO
235.5%, Al
2O
327.0%, wherein molecular sieve content is 25%, and specific surface is 260m
2/ g, pore volume are 0.35ml/g.
Concrete preparation process is following:
(1) preparation contains Al
2O
3Concentration is 600 milliliters of the liquor alumini chloridis of 90g/l, contains NiO and be 200 milliliters of the nickel chloride solutions of 140g/l, contains ZrO
2150 milliliters of 140g/l zirconyl chloride solutions, and be mixed in one 5 liters the container, add 2000 milliliters of water purification dilutions.
(2) prepare rare water glass solution, contain SiO
2550 milliliters of the water glass solutions of 75g/l add (2) in (1) under stirring state;
(3) mixture that ammoniacal liquor is added (1) and (2) under stirring state is until pH value 5.2;
(4) the preparation sodium tungstate solution is 1000 milliliters, contains WO
3Be 85g/l, and under stirring state, join (1)+mixture of (2)+(3) in;
(5) continuing to add ammoniacal liquor is 7.8 until pH value;
(6) whole one-tenth glue process should be carried out at 60 ℃;
(7) mixture left standstill in 70 ℃ of scopes aging 4 hours; Add the Y zeolite through the hydrothermal treatment consists modification before aging, molecular sieve is a raw material with the molecular sieve Y-A of ZL96119840.0 embodiment 1 preparation, carries out hydrothermal treatment consists, and the hydrothermal treatment consists condition is 760 ℃ of temperature; Pressure 0.1MPa, ammonia dividing potential drop 500Pa, 25 hours time; Carry out acid treatment then, 6500 milliliters of the hydrochloric acid of use 3.0M, hydrochloric acid and molecular sieve weight ratio are 1: 8; 60 ℃ of temperature, obtain modified molecular screen Y-A at 18 hours time
1, Y-A and Y-A
1Character is seen table 3, and modified molecular screen accounts for 25% of total catalyst weight;
(8) filter,, roll, with the orifice plate extruded moulding of 3 millimeters of diameters 60 ℃ of oven dryings 6 hours;
(9) ammonium acetate solution with pH=8.8 washs under the room temperature;
(10) 110 ℃ of oven dryings 8 hours, 500 ℃ of roastings got final product in 4 hours.
Instance 2
Be hydrocracking catalyst B of the present invention, the preparation method is identical with instance 1, except the Y zeolite that adds through the hydrothermal treatment consists modification before aging is 20%; Molecular sieve is a raw material with the molecular sieve Y-B of ZL96119840.0 embodiment 2 preparations, carries out hydrothermal treatment consists, and the hydrothermal treatment consists condition is 780 ℃ of temperature; Pressure 0.3MPa, ammonia dividing potential drop 1000Pa, 22 hours time; Carry out acid treatment then, 3000 milliliters in the sulfuric acid of use 2.0M, sulfuric acid and molecular sieve weight ratio are 1: 2; 50 ℃ of temperature, obtain modified molecular screen Y-B at 12 hours time
1, Y-B and Y-B
1Character is seen table 3.Catalyst weight consists of: WO
321.0%, NiO 7.5%, ZrO
26.5%, SiO
235.0%, Al
2O
330.0%, specific surface is 245m
2/ g, pore volume are 0.34ml/g.
Instance 3
Be hydrocracking catalyst C of the present invention, the preparation method is identical with instance 1, except the Y zeolite that adds through the hydrothermal treatment consists modification before aging is 30%; Molecular sieve is a raw material with the molecular sieve Y-C of ZL96119840.0 embodiment 3 preparations, carries out hydrothermal treatment consists, and the hydrothermal treatment consists condition is 800 ℃ of temperature; Pressure is 0.2MPa, ammonia dividing potential drop 2500Pa, 28 hours time; Carry out acid treatment then, 8500 milliliters of the hydrochloric acid of use 4.0M, hydrochloric acid and molecular sieve weight ratio are 1: 18; 70 ℃ of temperature, obtain modified molecular screen Y-C at 15 hours time
1, Y-C and Y-C
1Character is seen table 3.Catalyst weight consists of: WO
323.6%, NiO 7.4%, ZrO
27.0%, SiO
234.0%, Al
2O
328.0%, specific surface is 270m
2/ g, pore volume are 0.35ml/g.
Comparative example 1
Be reference catalyst E.Catalyst weight consists of: WO
322.0%, NiO 9.0%, ZrO
27.0%, SiO
233.0%, Al
2O
329.0%, specific surface is 254m
2/ g, pore volume are 0.312ml/g.
Press preparation method's preparation of the disclosed a kind of hydrocracking catalyst of Chinese patent ZL98114491.8, concrete preparation process is following:
(1) preparation contains Al
2O
3Concentration is 900 milliliters of the liquor alumini chloridis of 90g/l, contains NiO and be 200 milliliters of the nickel chloride solutions of 140g/l, contains ZrO
2150 milliliters of 140g/l zirconyl chloride solutions, and be mixed in one 5 liters the container, add 2000 milliliters of water purification dilutions.
(2) prepare rare water glass solution, contain SiO
2750 milliliters of the water glass solutions of 75g/l add (2) in (1) under stirring state;
(3) mixture that ammoniacal liquor is added (1) and (2) under stirring state is until pH value 5.2;
(4) the preparation sodium tungstate solution is 1000 milliliters, contains WO
3Be 85g/l, and under stirring state, join (1)+mixture of (2)+(3) in;
(5) continuing to add ammoniacal liquor is 7.8 until pH value;
(6) whole one-tenth glue process should be carried out at 60 ℃;
(7) mixture left standstill in 70 ℃ of scopes aging 4 hours; Add the Y-A molecular sieve of ZL96119840.0 embodiment 1 preparation before aging, account for 7% of total catalyst weight.
(8) filter,, roll, with the orifice plate extruded moulding of 3 millimeters of diameters 50 ℃ of oven dryings 6 hours;
(9) ammonium acetate solution with pH=8.8 washs under the room temperature;
(10) 110 ℃ of oven dryings 8 hours, 500 ℃ of roastings got final product in 4 hours.
Comparative example 2
Be reference catalyst F.Catalyst weight consists of: WO
323.6%, NiO7.4%, ZrO
27.0%, SiO
231.0%, Al
2O
331.0%, specific surface is 270m
2/ g, pore volume are 0.31ml/g.
The preparation method of Chinese patent ZL200410050778.X is identical with the preparation method of the disclosed a kind of hydrocracking catalyst of Chinese patent ZL98114489.6, and just the molecular sieve of (7) step adding is SiO
2/ Al
2O
3The Modified Zeolite Y of mol ratio 20～50, its addition are 20.0%.
Instance 5
With oil type hydrocracking catalyst A in of the present invention and reference catalyst E, F evaluation result on midget plant compares.Estimate and use Iranian VGO to be heavy distillate, its main character is following: density 0.9046g/cm
3, 342～520 ℃ of boiling ranges, sulphur 1.23wt%, nitrogen 0.12wt%, carbon residue 0.01wt%, 32 ℃ of condensation points, BMCI value 44.3.Table 1 has been listed comparing result.
Table 1 catalyst A, E, F comparing result
Can find out that from table 1 hydrogenation cracking activity of middle oil type hydrocracking catalyst of the present invention has surpassed reference catalyst E, F, middle distillates oil selectivity meets or exceeds reference catalyst F.
Instance 6
With hydrocracking catalyst B of the present invention, C estimates with process conditions of the present invention on midget plant, and table 2 has been listed evaluation result.
Table 2 catalyst B, the C evaluation result
Can find out that from table 2 catalyst of the present invention all can reach effect of the present invention under hydrocracking process condition of the present invention.
Modified molecular screen that table 3 the present invention relates to and use raw material properties
Explain: Y-A, Y-B, Y-C are the zeolite of ZL96119840.0 embodiment 1,2,3 preparations.
Claims (10)
1. the hydrocracking catalyst of a high activity, high middle distillates oil selectivity; Be to be carrier with the amorphous aluminum silicide; Y zeolite through special modification is acidic components, is the hydrogenation activity component with VI B family's metal and VIII family metal, is co-catalyst with IV B family metal; It is characterized in that: the content of Modified Zeolite Y is 15wt%～35wt%, the SiO of Modified Zeolite Y
2/ Al
2O
3Mol ratio 90～110, cell parameter are 2.423～2.430nm, degree of crystallinity＞100%, specific area 750～950m
2/ g, the secondary pore of＞1.7nm accounts for 60%～80% of total pore volume.
2. according to the described catalyst of claim 1, it is characterized in that: the content of Modified Zeolite Y is 20wt%～30wt%, the SiO of Modified Zeolite Y
2/ Al
2O
3Mol ratio is 95～105, and cell parameter is 2.424～2.429nm.
3. according to claim 1 or 2 described catalyst; It is characterized in that: the acid matter of modified Y molecular sieve is following: infrared acidity 0.1～0.3mmol/g; 150～250 ℃ of weak acid centers account for 8%～18%; 250～450 ℃ of moderate strength acid sites account for 82%～92%, and＞450 ℃ strong acid center is 0.
4. want 1 described catalyst according to right; It is characterized in that: VI B metal oxide content is 10wt%～40wt%; VIII family metal oxide content is 1wt%～20wt%; Account for the 1wt%～10wt% of catalyst with IV B family metal oxide content, amorphous aluminum silicide content accounts for the 20wt%～50wt% of catalyst weight.
5. according to the described catalyst of claim 1; It is characterized in that: VI B metal oxide content is 20wt%～25wt%; VIII family metal oxide content is 7wt%～12wt%; Account for catalyst 6wt%～10wt% with IV B family metal oxide content, amorphous aluminum silicide content accounts for the 30wt%～40wt% of catalyst weight.
6. according to the described catalyst of claim 1, it is characterized in that: with the metal W of VI B family and/or Mo and metal Ni of VIII family and/or Co, or its mixture is the hydrogenation activity component, and with IV B family metal Ti, Zr is a co-catalyst.
7. the said Preparation of catalysts method of claim 1 adopts the coprecipitation method preparation, and detailed process is: the ratio that the salting liquid of amorphous aluminum silicide, auxiliary agent and reactive metal is formed in catalyst joins in the glue jar; Add precipitating reagent and process gelatinous mixture, the suspension that adds on demand through Modified Zeolite Y then mixes, and obtains containing the filter cake of certain moisture after the mixture of gained filters; This filter cake dewaters at a certain temperature; The temperature range of cake dewatering is 40～110 ℃, and impurity is removed in washing behind the first extruded moulding in dehydration back, and wash temperature is 20～60 ℃; The pH value is 7～12, and dry then, activation makes finished catalyst.
8. according to the described method of claim 7, it is characterized in that: baking temperature wherein is 50～120 ℃, and the time is 6～12 hours, and activation temperature is 450～550 ℃, and the time is 8～12 hours.
9. according to the described method of claim 7, it is characterized in that: to be the aperture account for more than 45% surface area 750～900m greater than the pore volume of 1.7nm to the modified feedstock that Modified Zeolite Y adopts
2/ g, cell parameter is at 2.423～2.545nm, degree of crystallinity 95～110%, SiO
2/ Al
2O
3Mol ratio 7～20 obtains Modified Zeolite Y through hydrothermal treatment consists and acid treatment.
10. according to the described method of claim 9; The modifying process that it is characterized in that Modified Zeolite Y is: hydrothermal treatment consists is carried out deep sealumination modified; Its essential condition is 760～800 ℃ of temperature, and normal pressure is to 0.3MPa, 20～30 hours time; Use little ammonia at water vapour during hydrothermal treatment consists, the ammonia dividing potential drop is 50～3000Pa; Carry out acid treatment after the hydrothermal treatment consists again, use inorganic acid example hydrochloric acid, sulfuric acid or nitric acid etc., the concentration 1.0～10.0M of acid; 12～20 hours time; 50～80 ℃ of temperature, the ratio of sour consumption and molecular sieve weight is 1: 1～20: 1, obtains being applicable to Modified Zeolite Y of the present invention after the processing.
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| CN102786064A (en) * | 2012-08-21 | 2012-11-21 | 中国海洋石油总公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN104556120A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of metal modified Y type molecular sieve |
| CN104549431A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst containing acid modified molecular sieve |
| CN104588072A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method for hydrocracking catalyst |
| CN106031879A (en) * | 2015-03-20 | 2016-10-19 | 中国石油化工股份有限公司 | Multilevel-pore hydrocracking catalyst containing aluminum silicon and application of catalyst |
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| CN107029779A (en) * | 2015-07-28 | 2017-08-11 | 中国石油化工股份有限公司 | A kind of multi-stage porous hydrocracking catalyst and its application containing Y type molecular sieve |
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| RU2715713C2 (en) * | 2014-04-24 | 2020-03-03 | Шеврон Ю.Эс.Эй. Инк. | Catalyst for medium distillate hydrocracking, comprising base extrudate having high volume of nanopores |
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