CN103252256A - Composite molecular sieve hydrocracking catalyst carrier - Google Patents
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Abstract
The invention relates to a composite molecular sieve hydrocracking catalyst carrier; the catalyst carrier comprises 30-75 wt% of amorphous silicon-aluminum, 10-30 wt% of macroporous alumina, 10-30 wt% of binder, 5-45 wt% of composite molecular sieve and 1.5 wt% of extrusion aid5 percent of the raw materials are mixed; the composite molecular sieve is an AlSBA-15/Y meso-microporous composite molecular sieve and a beta microporous molecular sieve, and the weight ratio is 4: 1-15: 1; the weight ratio of the Y molecular sieve to the AlSBA-15 mesoporous molecular sieve is 1: 9-9: 1, and the SiO of the AlSBA-15 mesoporous molecular sieve2/Al2O3Framework SiO of Y molecular sieve with molar ratio of 10-402/Al2O3The molar ratio is 5-30; beta microporous molecular sieve SiO2/Al2O3The molar ratio is 40-100; the hydrocracking catalyst prepared by the carrier is used for hydrocracking heavy hydrocarbon oil, and has high catalytic activity and middle distillate oil selectivity.
Description
Technical field
The present invention relates to a kind of mesoporous-microporous composite molecular screen carrier of hydrocracking catalyst.
Background technology
Hydrocracking technology is one of important process means of heavy oil deep processing, can directly produce clean fuel for vehicle and high-quality industrial chemicals in the raw material lighting, is the most effective technology of utilizing crude resources.Hydrocracking technology has plurality of advantages such as adaptability to raw material is strong, processing scheme is flexible, liquid product yield is high, good product quality, therefore, along with the crude quality increasingly stringent of variation and environmental regulation year by year, hydrocracking technology has become a kind of requisite processing of heavy oil means, worldwide obtains increasingly extensive application.Simultaneously, the demand to middle distillate in the world wide constantly increases, and the pressure of oil plant production high-quality midbarrel oil product is increasing.Therefore, middle oil type hydrocracking technology that can production high-quality clean fuel obtains application more and more widely.As the core of hydrocracking technology, middle oil type hydrocracking catalyst development is the key of producing clean fuel.
Carrier is the important component part of catalyst, not only disperses the place for metal active center component provides, and carrier itself also participates in reaction simultaneously, works in coordination with other active component and finishes whole catalytic reaction.Hydrocracking catalyst is a kind of bifunctional catalyst with hydrogenating function and cracking function, its carrier is generally amorphous aluminum silicide and/or the zeolite molecular sieve that the cracking function can be provided, middle oil type hydrocracking catalyst major part all contains zeolite molecular sieve, and the molecular sieve that uses is mainly modified Y molecular sieve, part is used beta-molecular sieve or Y and β composite molecular screen, because Y and beta-molecular sieve are micro porous molecular sieve, the aperture is less, the molecule that diameter is bigger in the reaction raw materials is difficult to be diffused into the inside, duct of molecular sieve, and less pore passage structure also influence reacted product molecule rapid diffusion and overflow, thereby cause being in the cut secondary cracking in the purpose product scope, reduced the yield of intermediate oil, therefore, micro porous molecular sieve has certain limitation in big molecule hydrocracking process, realize macromolecular hydrocracking, exploitation has homogeneous, the molecular sieve of larger aperture is very necessary.So countries in the world scientific research institution all is devoted to develop wide-aperture novel molecular sieve catalysis material.
Since Mobile company in 1992 synthesized M41S series mesopore molecular sieve, Study of Mesoporous Molecular Sieve was one of heat subject of catalysis material research always.People wish to utilize mesopore molecular sieve to become the catalysis material of realizing that bulky molecular catalysis transforms, but, because the hole wall of mesoporous molecule is in amorphous state, therefore, the hydrothermal stability of mesopore molecular sieve and acidity are compared low with micro porous molecular sieve, this has limited mesopore molecular sieve greatly as the carrier of catalytic active component or as the application of catalysis material at petroleum chemical industry.Therefore, the mesopore molecular sieve with appropriate acid and high hydrothermal stability is one of focus of mesopore molecular sieve research always.
Advantage in view of micro porous molecular sieve and mesopore molecular sieve, the composite molecular screen that exploitation has the double-hole structure, make the two mutual supplement with each other's advantages, make micro porous molecular sieve and mesopore molecular sieve form composite, the existence of existing micropore has mesoporous existence again in composite, and this type of composite molecular screen has broad application prospects for the heavy-oil hydrogenation Cracking catalyst.
US Patent No. 5183557 discloses a kind of hydrocracking catalyst, and this catalyst is used a kind of MCM-41 mesopore molecular sieve, a kind of Y type or ZSM-5 micro porous molecular sieve, and a kind of aluminium oxide and amorphous silicon aluminum are carrier component, form the acid site more than three.Wherein the part by weight of mesoporous material and micro porous molecular sieve was generally 10: 1～1: 10, was preferably in 1: 1.By the metal Ni of metal W, the 14.8wt% of this composite carrier load 4.4wt%, at hydrogen dividing potential drop 8.3MPa, hydrogen to oil volume ratio 1400: 1, volume space velocity 0.5h
-1, 389 ℃ of reaction temperatures, in the raw material＞condition of 343 ℃ of cut conversion ratio 45wt% under, the yield of 166～227 ℃ of cuts is 10.5wt%, the yield of 227～343 ℃ of cuts is 22wt%, and the yield of 343～399 ℃ of cuts is 18wt%, and the intermediate oil yield is lower.
2004 154 volumes have announced that a kind of ITQ-21 of application mesopore molecular sieve is the hydrocracking catalyst of acidic components preparation in " Studies in Surface Science and Catalysis ", and this catalyst at first loads on Al with metal Ni, Mo component
2O
3On, then with ITQ-21 molecular sieve mechanical mixture.Because the topological structure that the ITQ-21 molecular sieve is special makes this catalyst handle 103～490 ℃ of boiling ranges, total sulfur 2.5wt%, during the vacuum distillate of total nitrogen 1000 μ g/g, control＞380 ℃, distillate conversion ratio 60wt%, reaction pressure 5.0MPa, air speed 2.8h
-1, under 1000: 1 the condition of hydrogen-oil ratio, 400 ℃ of reaction temperatures, 150～250 ℃ of yields are 27.4wt%, and 250～380 ℃ of yields are 39.0wt%, and the intermediate oil yield of this catalyst is higher, but activity is on the low side relatively.
Oil type hydrocracking catalyst was carrier with the composite molecular screen of amorphous aluminum silicide, Y and β during CN1393521A was disclosed, catalyst is being handled 244～545 ℃ of boiling ranges, total sulfur 1.67%, during the Iranian VGO of total nitrogen 1944 μ g/g, at reaction pressure 15.7MPa, at 379 ℃ of reaction temperatures, hydrogen to oil volume ratio 1150, volume space velocity 1.42h
-1Condition under, intermediate oil yield 49.45wt%, middle distillates oil selectivity is 68.49wt%, middle distillates oil selectivity is relatively low.
Summary of the invention
The invention provides a kind of preparation method who contains the carrier of hydrocracking catalyst of mesoporous-microporous composite molecular screen, this catalyst carrier is compound with the mesoporous-microporous composite molecular screen of AlSBA-15/Y and β micro porous molecular sieve, well collaborative and complementary effect takes place, and the prepared hydrocracking catalyst of carrier of the present invention is applicable to the charging for the treatment of of heavy hydrocarbon class.
The preparation method of catalyst carrier of the present invention mixes amorphous aluminum silicide, macroporous aluminium oxide, adhesive, composite molecular screen, extrusion aid.Percentage by weight with catalyst carrier calculates: amorphous silicon aluminium 30～75wt% is preferably 40～60wt%; Macroporous aluminium oxide 10～30wt% is preferably 10～20wt%; Adhesive 10～30wt% is preferably 10～20wt%; Composite molecular screen 5～45wt% is preferably 5～35wt%; Extrusion aid is 1.5～5wt%, is preferably 2～4wt%.
Used amorphous aluminum silicide can be by coprecipitation or grafting copolymerization process preparation in the catalyst carrier of the present invention, press in the document conventional method and prepares and get final product.SiO in the amorphous aluminum silicide that makes
2Weight content be 20～75wt%, be preferably 30～50wt%, pore volume is 0.5～1.2ml/g, is preferably 0.8～1.1ml/g; Specific area is 150～500m
2/ g is preferably 300～500m
2/ g.
The macroporous aluminium oxide that the present invention is used, pore volume is 0.5～1.2ml/g, is preferably 0.7～1.0ml/g; Specific area is 200～600m
2/ g is preferably 300～450m
2/ g.
Adhesive therefor of the present invention is to be made by a kind of little porous aluminum oxide and a kind of inorganic acid and/or organic acid.Used little porous aluminum oxide is 0.25～0.6ml/g than pore volume; Specific area is 150～450m
2/ g.Used inorganic acid can be one or more in hydrochloric acid, nitric acid, phosphoric acid and the sulfuric acid.
The composite molecular screen that the present invention is used, composite molecular screen for the mesoporous-microporous composite molecular screen of AlSBA-15/Y and β micro porous molecular sieve, wherein: the weight ratio of the mesoporous-microporous composite molecular screen of AlSBA-15/Y and β micro porous molecular sieve is 4: 1～15: 1, is preferably 4: 1～10: 1;
The specific area of the mesoporous-microporous composite molecular screen of above-mentioned AlSBA-15/Y is 500～900m
2/ g, pore volume are 0.5～1.0ml/g, meleic acid amount 0.1～0.5mmol/g.Wherein, the weight ratio of Y molecular sieve and AlSBA-15 mesopore molecular sieve is 1: 9～9: 1, the SiO of AlSBA-15 mesopore molecular sieve
2/ Al
2O
3Mol ratio 10～40, the skeleton SiO of Y molecular sieve
2/ Al
2O
3Mol ratio 5～30.
The concrete synthesis step of this composite molecular screen is as follows: template agent P123 is dissolved in HCl solution, add 35～45 ℃ of hydrolysis 12～20h of ethyl orthosilicate then, 90～120 ℃ of hydrothermal crystallizing 40～48h obtain the SBA-15 mesopore molecular sieve after filtration, drying, the roasting.Under the room temperature condition, use SBA-15 molecular sieve and the HY molecular sieve of the mixed aqueous solution processing gained of aluminium salt and inorganic acid, obtain the mesoporous-microporous composite molecular screen of AlSBA-15/Y.Used HY molecular sieve specific area 500～900m
2/ g, total pore volume 0.4～0.7ml/g, infrared acidity is 0.1～0.5mmol/g, skeleton SiO
2/ Al
2O
3Mol ratio 5～30.
Above-mentioned β micro porous molecular sieve SiO
2/ Al
2O
3Mol ratio is 40～100, is generally 40～80, and specific area is 400～700m
2/ g, pore volume are 0.35～0.5ml/g, relative crystallinity＞80%.This β micro porous molecular sieve preparation method: be the silicon source with the silochrom, being the aluminium source with the sodium metaaluminate, is the template agent with the tetraethyl ammonium hydroxide, carries out Separation of Solid and Liquid behind 140～170 ℃ of crystallization 48～72h, 100～140 ℃ of dryings, 600～650 ℃ of roasting 18～32h obtain final products.
Extrusion aid of the present invention is the sesbania powder.
Carrier of hydrocracking catalyst of the present invention mainly adopts the preparation of extrusion method, detailed process: with the mesoporous-microporous composite molecular screen of AlSBA-15/Y, the β micro porous molecular sieve, amorphous aluminum silicide, macroporous aluminium oxide and extrusion aid powder mix, with required little porous aluminum oxide, the adhesive of dilute nitric acid solution preparation adds to mix pinches into paste, be made generally in cylindrical vector after the wet mixing, also can be made into special-shaped bar such as clover or bunge bedstraw herb shape, carrier dry 4～12h under 80～150 ℃ temperature with above-mentioned moulding, calcination activation 3～8h in 500～600 ℃ of air atmospheres makes catalyst carrier.
The specific area of carrier of hydrocracking catalyst of the present invention is 300～500m
2/ g, pore volume are 0.60～0.90ml/g, and infrared acidity is 0.2～0.5mmol/g.
Catalyst carrier of the present invention is during for the preparation of hydrocracking catalyst, can adopt carrying method conventional in the prior art, preferred infusion process, can be saturatedly soak, excessive soak or complexing is soaked, namely with the solution impregnated catalyst carrier that contains required active component, after soaked carrier drying, the roasting, make final hydrocracking catalyst.
The present invention's AlSBA-15 mesopore molecular sieve that large aperture, thick hole wall, high pore volume and structure height is orderly with have highly acid micropore Y and beta-molecular sieve and carry out compoundly, formed effective gradient pore size distribution and acid strength and distributed.Macroporous structure and proper acidic coupling, can improve the big diffusion of molecule hydrocarbon in catalyst in the course of reaction, aromatic hydrocarbons in the raw material behind macromolecular cycloalkane or the hydrogenation can enter in the duct of catalyst, carry out cracking at the acid catalysis center, thereby make and contain more cyclic hydrocarbon and aromatic hydrocarbons in the heavy naphtha, kept more alkane in the tail oil, therefore, it is acidic components that carrier of the present invention adopts the mesoporous-microporous composite molecular screen of this AlSBA-15/Y and β micro porous molecular sieve, be conducive to improve the heavy-oil hydrogenation Cracking catalyst to macromolecular cracking open-loop performance, improve intermediate oil yield and oil quality.
The specific embodiment
The technical characterstic that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention.
Embodiment 1
Get in the hydrochloric acid solution that 2274g P123 joins 100L 1.7M, be warmed up to 40 ℃ after constant temperature stir 6h, after masterplate agent P123 dissolves fully, add the 4798g ethyl orthosilicate, constant temperature hydrolysis 16h is warming up to 98 ℃ of hydrothermal crystallizing 36h.Then, filter, washing, at 120 ℃ of dry 12h, 550 ℃ of roasting 4h, production code member are SBA-1, gained SBA-1 molecular sieve is through N
2Adsorption-desorption records, specific area 834m
2/ g, pore volume 1.12ml/g, average pore size 8.82nm.
Under 30 ℃, the 576g aluminium isopropoxide is dissolved in the hydrochloric acid solution of 100L 0.03M, in solution, add 1272g SBA-1 then, stir 12h, add the HY zeolite 434g of silica alumina ratio 40 then, continue to stir 2h, filter 120 ℃ of dry 12h, 550 ℃ of roasting 4h, production code member ASBAY-1, character sees Table 1.
Embodiment 2
Get in the hydrochloric acid solution that 2527g P123 joins 100L 2.OM, be warmed up to 40 ℃ after constant temperature stir 6h, after masterplate agent P123 dissolves fully, add the 4495g ethyl orthosilicate, constant temperature hydrolysis 12h is warming up to 100 ℃ of hydrothermal crystallizing 48h, then, filter, washing, at 120 ℃ of dry 12h, 550 ℃ of roasting 4h, production code member is SBA-2, and gained SBA-2 molecular sieve is through N
2Adsorption-desorption records, specific area 822m
2/ g, pore volume 1.12ml/g, average pore size 8.69nm.
Under 40 ℃, the 198g aluminium isopropoxide is dissolved in the hydrochloric acid solution of 100L 0.015M, in solution, add 1165g SBA-2 then, stir 16h, add the HY zeolite 3538g of silica alumina ratio 20 then, continue to stir 4h, filter 120 ℃ of dry 12h, 550 ℃ of roasting 4h, numbering ASBAY-2, character sees Table 1.
Embodiment 3
Get in the hydrochloric acid solution that 2342g P123 joins 100L 1.5M, be warmed up to 35 ℃ after constant temperature stir 6h, after masterplate agent P123 dissolves fully, add the 5645g ethyl orthosilicate, constant temperature hydrolysis 24h is warming up to 100 ℃ of hydrothermal crystallizing 48h, then, filter, washing, at 120 ℃ of dry 12h, 550 ℃ of roasting 4h, production code member is SBA-3, and gained SBA-3 molecular sieve is through N
2Adsorption-desorption records, specific area 804m
2/ g, pore volume 1.10ml/g, average pore size 8.68nm.
Under 40 ℃, the 598g aluminium isopropoxide is dissolved in the hydrochloric acid solution of 100L 0.04M, in solution, add 1465g SBA-3 then, stir 16h, add the HY zeolite 1502g of silica alumina ratio 6.5 then, continue to stir 4h, filter 120 ℃ of dry 12h, 550 ℃ of roasting 4h, numbering ASBAY-3, character sees Table 1.
Embodiment 4
Get the 25.49g tetraethyl ammonium hydroxide, add 12.27gH
2O dilution adds the 0.46g sodium metaaluminate again, adds the 12.14g silochrom after being dissolved to clear solution, is stirred to even back at 150 ℃ of crystallization 48h, with the product washing that obtains, filter, dry, roasting takes off amine, obtains the beta-molecular sieve product, this molecular sieve SiO
2/ Al
2O
3Mol ratio 50, specific area are 608m
2/ g, pore volume are 0.38ml/g, relative crystallinity 87%.
Embodiment 5
With the mesoporous-microporous composite molecular screen of 80.2g ASBAY-1,18.0g β micro porous molecular sieve, the amorphous aluminum silicide (SiO of 85.9g
2Content 38wt%, pore volume 0.85ml/g, specific area 380m
2/ g), 24.6g macroporous aluminium oxide (pore volume 0.80ml/g, specific area 350m
2/ g), 6.0g sesbania powder, 127g adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 1.0) put into the roller mixed grind, adds water, be rolled into paste, be extruded into the cylindrical bar of 1.5mm, 120 ℃ of dry 4h, roasting 4h gets carrier I in 550 ℃ of air atmospheres, and character sees Table 2.
Embodiment 6
With the mesoporous-microporous composite molecular screen of 30.7g ASBAY-2,6.1g β micro porous molecular sieve, the amorphous aluminum silicide (SiO of 110.5g
2Content 38wt%, pore volume 0.85ml/g, specific area 380m
2/ g), 61.4g macroporous aluminium oxide (pore volume 0.80ml/g, specific area 350m
2/ g), 6.0g sesbania powder, 127g adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 1.0) put into the roller mixed grind, adds water, be rolled into paste, be extruded into the cylindrical bar of 1.5mm, 120 ℃ of dry 4h, roasting 4h gets carrier II in 550 ℃ of air atmospheres, and character sees Table 2.
Embodiment 7
With the mesoporous-microporous composite molecular screen of 41.0g ASBAY-3,8.1g β micro porous molecular sieve, the amorphous aluminum silicide (SiO of 123.4g
2Content 38wt%, pore volume 0.85ml/g, specific area 380m
2/ g), 36.8g macroporous aluminium oxide (pore volume 0.80ml/g, specific area 350m
2/ g), 6.0g sesbania powder, 127g adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 1.0) put into the roller mixed grind, adds water, be rolled into paste, be extruded into the cylindrical bar of 1.5mm, 120 ℃ of dry 4h, roasting 4h gets carrier III in 550 ℃ of air atmospheres, and character sees Table 2.
Carrier floods 2h with the maceration extract room temperature of tungstenic nickel phosphorus, 120 ℃ of dry 4h, and roasting 4h in 500 ℃ of air atmospheres gets catalyst I II, and carrier and corresponding catalyst character see Table 2.
Comparative example
A kind of middle oil type hydrocracking catalyst IV of commercial Application, molecular sieve is a kind of Y molecular sieve of modification, its main physico-chemical property: WO
3Content is 24.3wt%, and NiO content is 5.9wt%, specific area 230m
2/ g, pore volume 0.32ml/g.
Embodiment 8
Present embodiment has been introduced the activity of such catalysts evaluation result that is prepared by carrier of the present invention.Get catalyst I II and catalyst I V among the embodiment, estimate appreciation condition at 200ml small stationary bed hydroprocessing evaluating apparatus: reaction stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1500: 1, air speed 1.5h
-1, use vacuum distillate (VGO) to be feedstock oil, feedstock property is listed in table 3.Evaluation result is listed in table 4.
The physico-chemical property of table 1 embodiment gained composite molecular screen
| Sample number into spectrum | ASBAY-1 | ASBAY-2 | ASBAY-3 |
| AlSBA-15 and HY weight ratio | 3∶1 | 1∶3 | 1∶1 |
| The SiO of AlSBA-15 2/Al 2O 3Mol ratio | 15 | 40 | 20 |
| The SiO of HY 2/Al 2O 3Mol ratio | 28.4 | 19.2 | 6.7 |
| Infrared acidity, mmol/g | 0.204 | 0.415 | 0.294 |
| Specific area, m 2/g | 679 | 598 | 622 |
| Pore volume, ml/g | 0.92 | 0.54 | 0.70 |
The physico-chemical property of table 2 catalyst carrier and catalyst
| Carrier is formed and character | |||
| Numbering | I | II | III |
| Composite molecular screen, wt% | 40 | 15 | 20 |
| Amorphous aluminum silicide, wt% | 35 | 45 | 50 |
| Macroporous aluminium oxide, wt% | 10 | 25 | 15 |
| Adhesive, wt% | 15 | 15 | 15 |
| Specific area, m 2/g | 350 | 322 | 338 |
| Pore volume, ml/g | 0.71 | 0.61 | 0.69 |
| Catalyst is formed and character | |||
| Numbering | II | ||
| WO 3，wt％ | 25.3 | ||
| NiO，wt％ | 4.9 | ||
| Specific area, m 2/g | 221 | ||
| Pore volume, ml/g | 0.43 |
Table 3 feedstock oil character
| Feedstock oil | VGO |
| Boiling range, ℃ | |
| Initial boiling point | 281 |
| 10％ | 359 |
| 50％ | 432 |
| 90％ | 487 |
| The end point of distillation | 542 |
| Density, g/cm 3(20℃) | 0.8618 |
| The BMCI value | 23.1 |
| Condensation point, ℃ | 41.2 |
| Total sulfur, μ g/g | 958 |
| Total nitrogen, μ g/g | 1051 |
| Carbon residue, wt% | 0.06 |
| Form wt% | |
| Alkane | 39.9 |
| Cycloalkane | 39.4 |
| Aromatic hydrocarbons | 20.7 |
Table 4 evaluating catalyst result
| The catalyst numbering | III | IV |
| Reaction pressure, MPa | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1500∶1 | 1500∶1 |
| Volume space velocity, h -1 | 1.5 | 1.5 |
| Average reaction temperature, ℃ | 382 | 404 |
| C 5 +Liquid yield, wt% | 98.2 | 98.0 |
| Product distributes and oil property | ||
| HK～65 ℃ light naphthar, wt% | 3.95 | 4.42 |
| 65～138 ℃ of heavy naphtha, wt% | 10.56 | 10.88 |
| Virtue is dived, wt% | 43.6 | 41.0 |
| 138～370 ℃ of diesel oil, wt% | 61.45 | 60.37 |
| Condensation point, ℃ | -12 | -10 |
| Cetane number | 59 | 60 |
| ＞370 ℃ of tail oils, wt% | 24.04 | 24.33 |
| The BMCI value | 5.6 | 10.4 |
| ＜370 ℃ of distillate middle distillates oil selectivities, % | 80.9 | 79.8 |
Claims (1)
1. composite molecular screen carrier of hydrocracking catalyst is characterized in that:
Catalyst carrier is by weight percentage by amorphous silicon aluminium 30～75wt%, macroporous aluminium oxide 10～30wt%, and adhesive 10～30wt%, composite molecular screen 5～45wt% and extrusion aid 1.5～5wt% mix;
Composite molecular screen is the composite molecular screen of the mesoporous-microporous composite molecular screen of AlSBA-15/Y and β micro porous molecular sieve, and the weight ratio of the mesoporous-microporous composite molecular screen of AlSBA-15/Y and β micro porous molecular sieve is 4: 1～15: 1;
The specific area of the mesoporous-microporous composite molecular screen of AlSBA-15/Y is 500～900m
2/ g, pore volume are 0.5～1.0ml/g, meleic acid amount 0.1～0.5mmol/g; Wherein, the weight ratio of Y molecular sieve and AlSBA-15 mesopore molecular sieve is 1: 9～9: 1, the SiO of AlSBA-15 mesopore molecular sieve
2/ Al
2O
3Mol ratio 10～40, the skeleton SiO of Y molecular sieve
2/ Al
2O
3Mol ratio 5～30; Template agent P123 is dissolved in HCl solution, adds 35～45 ℃ of hydrolysis 12～20h of ethyl orthosilicate then, 90～120 ℃ of hydrothermal crystallizing 40～48h obtain the SBA-15 mesopore molecular sieve after filtration, drying, the roasting; Under the room temperature condition, use SBA-15 molecular sieve and the HY molecular sieve of the mixed aqueous solution processing gained of aluminium salt and inorganic acid, obtain the mesoporous-microporous composite molecular screen of AlSBA-15/Y; Used HY molecular sieve specific area 500～900m
2/ g, total pore volume 0.4～0.7ml/g, infrared acidity is 0.1～0.5mmol/g, skeleton SiO
2/ Al
2O
3Mol ratio 5～30;
β micro porous molecular sieve SiO
2/ Al
2O
3Mol ratio is 40～100, and specific area is 400～700m
2/ g, pore volume are 0.35～0.5ml/g, meleic acid amount 0.15～0.40mmol/g, relative crystallinity＞80%; Being the silicon source with the silochrom, is the aluminium source with the sodium metaaluminate, is the template agent with the tetraethyl ammonium hydroxide, carries out Separation of Solid and Liquid behind 140～170 ℃ of crystallization 48～72h, 100～140 ℃ of dryings, and 600～650 ℃ of roasting 18～32h obtain.
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| CN107715908A (en) * | 2016-08-12 | 2018-02-23 | 中国石油天然气股份有限公司 | Hierarchical pore hydrocracking catalyst and preparation method thereof |
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| CN113023748A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Y/Al-SBA-15 composite molecular sieve and preparation method and application thereof |
| WO2021129760A1 (en) * | 2019-12-25 | 2021-07-01 | 中国石油化工股份有限公司 | Dlm-1 molecular sieve, manufacturing method therefor, and use thereof |
| CN113023748B (en) * | 2019-12-25 | 2022-08-12 | 中国石油化工股份有限公司 | Y/Al-SBA-15 composite molecular sieve and preparation method and application thereof |
| US12145137B2 (en) | 2019-12-25 | 2024-11-19 | China Petroleum & Chemical Corporation | DLM-1 molecular sieve, process for preparing the same, and use thereof |
| CN114453010A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method and application thereof |
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