CN1766051A - High activity medium oil type hydrocracking catalyst and its preparation method - Google Patents
High activity medium oil type hydrocracking catalyst and its preparation method Download PDFInfo
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Abstract
The invention relates to a hydrocracking catalyst with high activity and oil selectivity, which comprises: amorphous alumina silica as carrier; and special modified Y-shape molecular screen as acid constituent that has high crystallinity, low cell parameter, riched secondary pores, large superficial area, belongs to medium strength acid center, and has strong nitrogen-resistant and ring-splitting capacity. This invention has well activity and stability for middle distillate oil in heavy hydrocarbon single-section hydrocracking technique.
Description
Technical field
The present invention relates to hydrocracking catalyst of a kind of high reactivity, high middle distillates oil selectivity and preparation method thereof, particularly contain the high reactivity of Modified Zeolite Y, hydrocracking catalyst of high middle distillates oil selectivity and preparation method thereof.
Background technology
At present, worldwide petroleum resources deficiency, crude oil becomes and heavily becomes bad, the intermediate oil demand increases, petroleum chemicals upgrading and environmental regulation are more and more strict, 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 volume increase intermediate oil, with normal vacuum distillate, vacuum distillate, secondary processing light oil is raw material, after hydrocracking, can produce fine-quality diesel oil and rocket engine fuel, and product flexibility is big, good product quality.
The single hop technical 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 catalyzer, the hydrocracking performance all requires very high.The hydrocracking catalyst that the single-stage hydrocracking technological process is used is to use under the situation of not giving refining protection.General directly the contact with hydrocracking catalyst under the situation of feed nitrogen content height to 1000～2000 μ g/g reacted, this just requires hydrocracking catalyst to have the ability that anti-preferably nitride is poisoned, promptly under reactant nitrogen content conditions of higher, have good hydrocracking activity, 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 catalyzer is higher, and middle distillates oil selectivity is relatively poor.This catalyzer 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 temperature of reaction is at 396 ℃ when handling heavy distillate, and middle distillates oil selectivity is lower.
Chinese patent ZL00123131.6 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, the intensity in the acid site that this Y zeolite is is low, the molecular sieve that belongs to weak-type, therefore the hydrogenation cracking activity of this catalyzer is lower, and middle distillates oil selectivity is higher.This catalyzer consists of: WO
322.5%, NiO 8.5%, ZrO
26.5%, SiO
230.0%, Al
2O
332.5.0%, wherein Y zeolite accounts for about 10.0%, and specific surface is 223m
2/ g, pore volume are 0.307ml/g, and temperature of reaction is about 405 ℃ when handling heavy distillate, and its activity is lower.CN1253859A discloses a kind of medium oil type hydrocracking catalyst, catalyzer contains 4～40% Y zeolite and 10～50% components such as amorphous aluminum silicide, because the zeolite of this catalyzer is the super-hydrophobic Y zeolite of the lower not anti-nitrogen of degree of crystallinity, therefore the anti-nitrogen of this catalyzer is not strong, can only be used for the hydrocracking process with pre-refining.
Summary of the invention
At the deficiencies in the prior art, the invention provides hydrocracking catalyst of a kind of high reactivity, high middle distillates oil selectivity and preparation method thereof, this catalyzer had both had high hydrogenation cracking activity, had high middle distillates oil selectivity again.Catalyzer of the present invention has stronger anti-nitrogen performance, can be used for not having the single-stage hydrocracking technological process of refining section.
The hydrocracking catalyst of high reactivity 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, with group vib metal and VIII family metal is the hydrogenation activity component, with IVB family metal is promotor, wherein the vib metal oxide content is 10～40wt%, be preferably 20～25wt%, VIII family metal oxide content is 1～20wt%, be preferably 7～12wt%, account for 1～10wt% of catalyzer with IVB family metal oxide content, be preferably 6～10wt%.Amorphous aluminum silicide content accounts for 20～50wt% of catalyst weight, is preferably 30～40wt%.The content of Modified Zeolite Y is 10～30wt%, better is 15～25wt%.
The SiO of Modified Zeolite Y used in the present invention
2/ Al
2O
3Mol ratio 20～50, unit cell parameters are 2.380～2.423nm, degree of crystallinity＞100%, specific surface area 750～950m
2/ g, the hole of 1.7～10nm accounts for 50～70% of total pore volume, infrared acidity 0.1～0.3mmol/g, 150～250 ℃ of weak acid centers account for 20～30%, and 250～450 ℃ of medium tenacity acid sites account for 70～80%, and＞450 ℃ strong acid center is 0.
Catalyzer of the present invention adopts conventional coprecipitation method preparation, as preparing by the process that ZL98114489.6 introduced, detailed process is: with related amorphous aluminum silicide, the ratio that the salts solution of auxiliary agent and reactive metal is formed in catalyzer joins in the glue jar, add precipitation agent and make gelatinous mixture, precipitation agent can be inorganic or organic weakly alkaline ammoniac compounds, the suspension liquid that adds on demand through Modified Zeolite Y mixes then, after filtering, the mixture of gained obtains containing the filter cake of certain moisture, this filter cake dewaters at a certain temperature, the temperature range of cake dewatering is 40～110 ℃, the first extruded moulding after scouring in dehydration back is removed impurity, wash temperature is 20～60 ℃, and the pH value is 7～12, and is dry then, activation makes finished catalyst.Drying 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, the process hydrothermal treatment consists is carried out deep sealumination modified, and its underlying condition is temperature 700-800 ℃, pressure 0.3～0.5MPa, time 20-30 hour, obtain being applicable to molecular sieve of the present invention after the processing.
Catalyzer of the present invention adopts Y zeolite through special modification as acidic components, the existing high degree of crystallinity of this molecular sieve, low unit cell parameters is arranged again, the secondary pore of molecular sieve is many, help improving the velocity of diffusion of raw material and product, reduce the second pyrolysis of product, improve the middle distillates oil selectivity of catalyzer, the acidity of this molecular sieve is low in addition, the acid site number is few, be evenly distributed, and major part is the medium tenacity acid site, makes this molecular sieve have very strong nitrogen resistance and broken preferably ring ability, still can be used for the very high single-stage hydrocracking technological process of raw material nitrogen content under the relative condition with higher of molecular sieve content, the cracking activity of catalyzer and having good stability meets industrial application requirements.In addition, the existing abundant secondary pore of this molecular sieve has high surface area again, and the acid site number is less, is more suitable for improving the intermediate oil selectivity of hydrocracking catalyst.Method for preparing catalyst metal dispersity height of the present invention, loss of material is few, and the catalyzer use properties is good.In order to reduce the metal loss of washing process, catalyzer of the present invention adopts first moulding after scouring mode, washs simultaneously under normal temperature and weak basic condition and carries out, and can adopt steam treatment process to adjust the pore structure of catalyzer.Catalyzer of the present invention is used for the single-stage hydrocracking technological process, has the liquid yield height, advantages such as good product quality.
Embodiment
Catalyzer of the present invention is a carrier with the amorphous aluminum silicide, and part acidity is provided, and adds the Y zeolite adjustment of acidity through special modification, with group vib metal W and/or Mo and metal Ni of VIII family and/or Co, or its mixture is the hydrogenation activity component, and with IVB family metal Ti, Zr is a promotor.The silicon oxide silicon of amorphous aluminum silicide and alumina weight ratio are 0.1～10: 1, and preferred about 1: 1.
In general, hydrocracking catalyst can use following any method preparation, as: pickling process, kneading method, beating method, coprecipitation method may use ion exchange method for precious metal.Pickling process and kneading method all are to add metal again after earlier carrier and acidic components being made, and coprecipitated rule to be acidic components and one on metal precipitate, and the metal loading is unrestricted, metal dispersion is good.The preparation method that catalyzer of the present invention relates to is a coprecipitation method, in the hope of obtaining the more uniform dispersion of metal component.
Catalyzer 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 feed stock scope that is applicable to this law is very wide, they comprise that vacuum gas oil, coker gas oil, deasphalted oil, thermally splitting gas oil, catalytic gas oil, the various hydrocarbon ils of catalytic cracking circulation wet goods also can be used in combination, 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 preferably at single hop once by carrying out under the hydrocracking condition.Temperature of reaction is 300～500 ℃, is more preferably 350～450 ℃; Pressure is 6～20MPa, is more preferably 13～17MPa; Liquid hourly space velocity 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, middle distillates oil selectivity to the raising catalyzer is favourable, but use 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 petroleum naphtha simultaneously, all comparatively ideal catalyzer of rocket engine fuel and diesel quality.
Following example can further be understood the present invention.
Example 1
Catalyst A is the catalyzer of the inventive method preparation, and catalyst weight consists of: WO
322.0%, NiO 9.0%, ZrO
27% SiO
233%, Al
2O
329%, wherein molecular sieve content is 20%, and specific surface is 240m
2/ g, pore volume are 0.34ml/g.
Concrete preparation process is as follows:
(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) ammoniacal liquor is added the mixture of (1) and (2) until pH value 5.2 under stirring state;
(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, the hydrothermal treatment consists condition is 750 ℃ of temperature, pressure 0.4MPa, obtains modified molecular screen Y-A at 25 hours time
1, Y-A and Y-A
1Character sees Table 3, and modified molecular screen accounts for 20% 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) Spirit of Mindererus 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.
Example 2
Be hydrocracking catalyst B of the present invention, the preparation method is identical with example 1, except adding before aging is 25% through the Y zeolite of hydrothermal treatment consists modification, molecular sieve is a raw material with the molecular sieve Y-B of ZL96119840.0 embodiment 2 preparations, carry out hydrothermal treatment consists, the hydrothermal treatment consists condition is 800 ℃ of temperature, pressure 0.3MPa, 22 hours time, obtain modified molecular screen Y-B
1, Y-B and Y-B
1Character sees Table 3.Catalyst weight consists of: WO
321.0%, NiO 7.5%, ZrO
26.5%SiO
230%, Al
2O
335%, specific surface is 260m
2/ g, pore volume are 0.36ml/g.
Example 3
Be hydrocracking catalyst C of the present invention, the preparation method is identical with example 1, except adding before aging is 17% through the Y zeolite of hydrothermal treatment consists modification, molecular sieve is a raw material with the molecular sieve Y-C of ZL96119840.0 embodiment 3 preparations, carry out hydrothermal treatment consists, the hydrothermal treatment consists condition is 700 ℃ of temperature, and pressure is 0.5MPa, 28 hours time, obtain modified molecular screen Y-C
1, Y-C and Y-C
1Character sees Table 3.Catalyst weight consists of: WO
323.6%, NiO 7.4%, ZrO
27% SiO
231%, Al
2O
331%, specific surface is 270m
2/ g, pore volume are 0.31ml/g.
Example 4
Be hydrocracking catalyst D of the present invention, the preparation method is identical with example 1.Catalyst weight consists of: WO
320.3%, NiO 10.4%, ZrO
29.3%, SiO
235%, Al
2O
325%, modified molecular screen Y-A wherein
1Content is 30%, and specific surface is 250m
2/ g, pore volume are 0.38ml/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 as follows:
(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) ammoniacal liquor is added the mixture of (1) and (2) until pH value 5.2 under stirring state;
(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 catalyzer total 7%;
(8) filter,, roll, with the orifice plate extruded moulding of 3 millimeters of diameters 50 ℃ of oven dryings 6 hours;
(9) Spirit of Mindererus 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
322.5%, NiO 8.5%, ZrO
26.5%, SiO
230.0%, Al
2O
332.5%, specific surface is 223m
2/ g, pore volume are 0.307ml/g.
The preparation method of Chinese patent ZL00123131.6 is identical with the preparation method of the disclosed a kind of hydrocracking catalyst of Chinese patent ZL98114489.6, just the molecular sieve of (7) step adding is to be the weak-type Y-B molecular sieve of material modification with the Y-A molecular sieve, and its add-on is 10.0%.
Example 5
With oil type hydrocracking catalyst A in of the present invention and reference catalyst E, F evaluation result on packaged unit compares.Estimating with Iranian VGO is heavy distillate, and its main character is as follows: 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
| Catalyzer | A | E | F |
| Stock oil | Iran VGO | ||
| Temperature of reaction, ℃ | 397 | 396 | 404 |
| Product distributes, wt% C 5249 ℃～371 ℃ diesel oil＞371 ℃ tail oil C of 138 ℃～249 ℃ rocket engine fuels of 82～138 ℃ of heavy naphtha of～82 ℃ of light naphthars 5 +Liquid is received chemical hydrogen consumption | 5.9 11.6 26.6 24.7 30.0 98.8 2.42 | 7.0 12.7 29.4 20.0 29.9 98.0 2.38 | 5.9 11.5 26.7 25.7 28.6 98.4 2.40 |
| Middle distillates oil selectivity, wt% | 74.5 | 71.1 | 75.0 |
As can be seen from Table 1, the hydrogenation cracking activity that middle oil type hydrogenation of the present invention splits catalyzer is suitable with reference catalyst E, but middle distillates oil selectivity is better than reference catalyst E.
Example 6
With hydrocracking catalyst B of the present invention, C, D estimate with processing condition of the present invention on packaged unit, and table 2 has been listed evaluation result.
Table 2 catalyst B, C, D evaluation result
| The catalyzer numbering | B | C | D |
| Reaction pressure, MPa air speed, h -1Hydrogen-oil ratio, the V/V temperature of reaction, ℃ product distributes, wt% C 5249 ℃～371 ℃ diesel oil＞371 ℃ tail oil middle distillates oil selectivities of 138 ℃～249 ℃ rocket engine fuels of 82～138 ℃ of heavy naphtha of～82 ℃ of light naphthars, (to product) wt% | 15.7 0.92 1240 396 6.1 11.9 26.6 24.5 30.2 74.0 | 15.7 0.92 1240 398 5.7 11.4 27.0 24.6 30.4 75.1 | 15.7 0.92 1240 398 5.9 11.6 26.8 24.3 30.0 74.5 |
As can be seen from Table 2, catalyzer 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
| Zeolite character | Y-A | Y-A 1 | Y-B | Y-B 1 | Y-C | Y-C 1 |
| Degree of crystallinity, % α 0，nm SiO 2/Al 2O 3, mol/mol specific surface S BET，m 2/ g pore volume V AlwaysMl/g 1.7～10nm secondary pore accounts for total pore volume, the infrared total acid Ci of %, mmol/g Na 2O, 150～250 ℃ of acid sites of wt%, 250～450 ℃ of acid sites of %, ℃ acid site, %＞450, % | 96 2.443 8.43 828 0.443 46.0 1.17 0.078 | 102 2.423 25.27 782 0.408 57.0 0.27 0.079 26 74 0 | 96 2.442 10.96 805 0.457 47.0 1.10 0.097 | 104 2.395 26.38 755 0.416 62.0 0.19 0.046 22 78 0 | 95 2.439 12.05 839 0.506 48.0 0.999 0.093 | 103 2.417 28.56 782 0.457 59.0 0.14 0.054 20 80 0 |
Illustrate: 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 kind of high reactivity, high middle distillates oil selectivity, with the amorphous aluminum silicide is carrier, with the Modified Zeolite Y is acidic components, with group vib metal and VIII family metal is the hydrogenation activity component, with IVB family metal is promotor, the content that it is characterized in that described Modified Zeolite Y is 10～30wt%, and has following character: SiO
2/ Al
2O
3Mol ratio 20～50, unit cell parameters are 2.380～2.423nm, degree of crystallinity＞100%, specific surface area 750～950m
2/ g, the hole of 1.7～10nm accounts for 50～70% of total pore volume, infrared acidity 0.1～0.3mmol/g.
2, according to the described catalyzer of claim 1, it is characterized in that described vib metal oxide content is 10～40wt%, VIII family metal oxide content is 1～20wt%, account for 1～10wt% of catalyzer with IVB family metal oxide content, amorphous aluminum silicide content accounts for 20～50wt% of catalyst weight.
3,, it is characterized in that described modified molecular screen content is 15～25wt% according to the described catalyzer of claim 1.
4, according to claim 1 or 3 described catalyzer, it is characterized in that 150～250 ℃ of weak acid centers of described modified molecular screen account for 20～30%, 250～450 ℃ of medium tenacity acid sites account for about 70～80%, and＞450 ℃ of strong acid centers are 0.
5, according to claim 1 or 2 described catalyzer, it is characterized in that described group vib metal is W and/or Mo, in oxide compound content is 20～25wt%, VIII family metal is Ni and/or Co, in oxide compound content is 7～12wt%, IVB family metal is Ti or Zr, is 6～10wt% in oxide compound content.
6, the described Preparation of catalysts method of a kind of claim 1, it is characterized in that adopting the coprecipitation method preparation: with related amorphous aluminum silicide, the ratio that the salts solution of auxiliary agent and reactive metal is formed in catalyzer joins in the glue jar, add precipitation agent and make gelatinous mixture, precipitation agent is inorganic or organic weakly alkaline ammoniac compounds, the suspension liquid that adds Modified Zeolite Y then mixes, obtain containing the filter cake of certain moisture after the mixture of gained filters, filter cake makes finished catalyst through dehydration, moulding, washing, drying, activation.
7, in accordance with the method for claim 6, the temperature range that it is characterized in that described cake dewatering is 40～110 ℃, the temperature of extruded moulding after scouring is 20～60 ℃, the pH value is 7～12, drying temperature is 50～120 ℃, time is 6～12 hours, and activation temperature is 450～550 ℃, and the time is 8～12 hours.
8, in accordance with the method for claim 6, it is characterized in that described modified Y molecular sieve is a raw material with the Modified Zeolite Y of ZL96119840.0 report, carry out deep sealumination modified obtaining through hydrothermal treatment consists, the condition of hydrothermal treatment consists is temperature 700-800 ℃, pressure 0.3～0.5MPa, time 20-30 hour.
9, the application of the described catalyzer of a kind of claim 1 in the hydrocracking process of producing intermediate oil with heavy raw oil adopts single hop once by flow process, and temperature of reaction is 300～500 ℃, and pressure is 6～20MPa, and liquid hourly space velocity is 0.5～3hr
-1, hydrogen to oil volume ratio is 400～2000: 1.
10,, it is characterized in that described heavy feed stock comprises vacuum gas oil, coker gas oil, deasphalted oil, thermally splitting gas oil, catalytic gas oil, catalytic cracking turning oil, or mix and use according to the described application of claim 9.
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| CN101172259B (en) * | 2006-11-01 | 2010-05-12 | 中国石油化工股份有限公司 | Method for preparing carrier material |
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| CN1055063C (en) * | 1996-09-27 | 2000-08-02 | 中国石油化工总公司 | Modified zeolite and manufacture thereof |
| CN1073617C (en) * | 1998-11-18 | 2001-10-24 | 中国石油化工集团公司 | Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil |
| CN1123632C (en) * | 2000-10-26 | 2003-10-08 | 中国石油化工股份有限公司 | Medium-oilness hydrocracking catalyst and its preparing process and application |
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| CN102441411B (en) * | 2010-10-13 | 2014-04-02 | 中国石油化工股份有限公司 | Hydrocracking catalyst with high activity and high-medium oil selectivity and preparation method of hydrocracking catalyst |
| CN102441411A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Hydrocracking catalyst with high activity and high-medium oil selectivity and preparation method of hydrocracking catalyst |
| CN102441427A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Composite molecular sieve-containing hydrocracking catalyst and preparation method thereof |
| CN103100408A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN103100408B (en) * | 2011-11-11 | 2014-10-22 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN105709807A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN105709807B (en) * | 2014-12-04 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN106140316A (en) * | 2015-04-15 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and the application in hydrocarbon oil hydrogenation thereof |
| CN106140316B (en) * | 2015-04-15 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its application in hydrocarbon oil hydrogenation |
| CN106669801A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Catalyst for producing hydrocracking tail oil with low content of straight chain alkanes, and preparation method thereof |
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