CN107344120A - Carrier of hydrocracking catalyst and its preparation method - Google Patents
Carrier of hydrocracking catalyst and its preparation method Download PDFInfo
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- CN107344120A CN107344120A CN201610289560.2A CN201610289560A CN107344120A CN 107344120 A CN107344120 A CN 107344120A CN 201610289560 A CN201610289560 A CN 201610289560A CN 107344120 A CN107344120 A CN 107344120A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 142
- 239000011148 porous material Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 40
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 13
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 13
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 13
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 120
- 238000001035 drying Methods 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 26
- 230000008025 crystallization Effects 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- 238000009415 formwork Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 239000003921 oil Substances 0.000 description 43
- 239000000047 product Substances 0.000 description 17
- 238000001354 calcination Methods 0.000 description 15
- 238000005336 cracking Methods 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000002803 maceration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005216 hydrothermal crystallization Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- -1 decentralized sial Chemical compound 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of carrier of hydrocracking catalyst and its preparation method.The carrier includes Modified Zeolite Y, beta-molecular sieve and aluminum oxide, wherein described Modified Zeolite Y, its property is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 55 ~ 100, and cell parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume.The characteristics of hydrocracking catalyst prepared by the catalyst carrier is used in the hydrocracking process of the good midbarrel oil product of high-output qulified low temperature flow, and active high and selectivity is good, while high-quality hydrogenation tail oil and can be produced.
Description
Technical field
The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, is particularly suitable for high-output qulified low solidifying
Carrier of hydrocracking catalyst of intermediate oil and preparation method thereof.
Background technology
In recent years, countries in the world refined products market constantly increases always to the demand of high-quality middle cut oil product, with
Developing rapidly for economy, this imbalance between supply and demand seems more prominent.Hydrocracking technology turns into weight with its exclusive advantage
The best means of the oily high-quality cleaning intermediate oil of deep processing production.At present, oil type hydrocracking catalyst in countries in the world
Activity be not very high, the condensation point of gained diesel oil is also higher, it is difficult to meet refinery existing apparatus is transformed or increase processing
Amount further increases production the purpose of intermediate oil to reach.
The key for being hydrocracked the low solidifying intermediate oil that raises productivity and improves the quality is to develop and using suitable catalyst.Containing single
Although the hydrocracking catalyst of molecular sieve component is with very high activity, its middle distillates oil selectivity is poor, containing composite molecular screen
Catalyst but show to improve the synergy that active and can improves selectivity.
Can there are Y types, β types and ZSM type molecules as the molecular sieve of cracking active component in hydrocracking heavy oil field
Sieve etc., wherein Y type molecular sieve application is the most universal.The method of industrial production Y type molecular sieve is essentially all using beautiful at present
The directing agent method that GRACE companies of state propose in USP 3639099 and USP 4166099, the Y type molecular sieve original powder duct of synthesis
Orifice diameter be 0.74nm × 0.74nm, its micropore pore volume accounts for more than the 95% of total pore volume.Wax oil hydrogenation cracked stock
In polycyclic heavy constituent molecular diameter generally in more than 1nm, the cracking reaction for heavy constituent macromolecular, be adapted to its reaction and production
The preferable duct pore diameter range of thing diffusion is 2nm ~ 10nm macropore range, can be by outside more accessible acid centre
Dew, while the also desorption and diffusion of the absorption beneficial to raw material macromolecular and reaction and purpose product, improve molecular sieve cracking choosing
Selecting property.To improve the low situation for being unfavorable for wax oil macromolecular reaction of the mesoporous pore volume content of Y type molecular sieve, generally to Y type molecules
Sieve former powder and be modified processing, can obtain the Modified Zeolite Y of different pore passage structures and acid distribution.
CN201310240740.8 discloses a kind of ultra-steady Y molecular sieve（USY）Method of modifying.The characteristics of this method be
Organic acid and inorganic salts dealuminzation reagent are added in modifying process simultaneously, the combination for carrying out organic acid-inorganic salts is modified.Use this
The mesopore volume of USY molecular sieve of the total volume less than 50% made from method reality, its crystallinity is below 85%.
CN201510147788.3 discloses Y molecular sieve that a kind of silica alumina ratio is high and second hole is abundant and preparation method thereof.
This method includes：Y type molecular sieve is handled into 1 ~ 5h at 300 DEG C ~ 600 DEG C, dry Y type molecular sieve is obtained, is cooled to 200 ~ 600
℃；In dried over anhydrous environment, it is passed through into dry Y type molecular sieve by the dry gas of dealumination complement silicon agent saturation, reaction
0.5h ~ 7.0h, or in dried over anhydrous environment, while temperature to be at the uniform velocity warming up to 500 ~ 700 DEG C into dry y-type zeolite
It is passed through by the dry gas of dealumination complement silicon agent saturation, reacts 0.5h ~ 7.0h, obtain crude product；By crude product at 30 ~ 100 DEG C
Alkali process 10min ~ 5h, the solid-liquid mass ratio of alkali process is 1 ~ 50：1, obtain the Y molecular sieve that silica alumina ratio is high and second hole is abundant.
US 4,820,402 discloses a kind of hydrocracking catalyst of high selectivity to middle distillates, is characterized in using a kind of high
The molecular sieve of silica alumina ratio such as ZSM-20, Y and β, molecular sieve silica alumina ratio are at least 50:1, preferably 200:More than 1.This method will not
When being used for hydrocracking catalyst with high silica alumina ratio molecular sieve, middle distillates oil selectivity most preferably ZSM-20, next to that β.The catalysis
The activity and middle distillates oil selectivity of agent are up for further improving.
US 4,419,271 discloses a kind of hydrocarbon conversion catalyst.Cracking Component is modified HY molecular sieves（LZ-10）With
Decentralized sial, active metal component are tungsten, nickel.The wherein content of LZ-10 molecular sieves is 10wt% ~ 70wt%, decentralized sial
Content be 30wt% ~ 90wt%, WO3Content be 10wt% ~ 30wt%, NiO content is 3wt% ~ 10wt%.The catalyst can use
Production intermediate oil is hydrocracked in heavy gas oil（Such as turbine fuel and diesel oil）.The catalyst middle distillates oil selectivity is low.
A kind of method using beta-molecular sieve selective hydrogenation cracking is described in CN101578353A.Beta-molecular sieve without
The mol ratio of hydro-thermal process or at relatively low temperatures hydro-thermal process, silica and aluminum oxide is less than 30：1 and at least
28wt% SF6Adsorbance, by modified obtained this beta-molecular sieve as cracking component and the catalyst prepared, midbarrel
The selectivity of oil is not high.
US 5,350,501, US 5,447,623, US 5,279,726, US 5,536,687 describe one kind and contain beta molecule
The catalyst of sieve and Y type molecular sieve.During for producing intermediate oil, consisting of：Y type molecular sieve（1wt%~15wt%）, β points
Son sieve（1wt%~15wt%）, decentralized sial, aluminum oxide, metal W and Ni.Y type molecular sieve wherein used is that NaY hands over by ammonium
Change, hydro-thermal process, ammonium exchange, prepared by the method for hydro-thermal process, the crystallinity of modified molecular screen is not high, and product selectivity is poor.Should
Catalyst reaction activity and middle distillates oil selectivity be not high, it is difficult to meets manufacturer's aggrandizement apparatus disposal ability, further volume increase
The needs of intermediate oil.
From the molecular sieve with cracking function from the point of view of the application during Industrial Catalysis, its performance depends primarily on following
Two aspects：Selective absorption and reaction.When reactant molecule size is less than molecular sieve aperture and overcomes molecular sieve crystal surface
It energy barrier, can just diffuse into molecular sieve pore passage, specific catalytic reaction occurs, at this moment be adsorbed molecule and pass through molecular sieve crystal
Hole and cage diffusion serve it is conclusive.Molecular sieve total pore volume and mesoporous pore volume prepared by conventional method of modifying
It is less than normal, it is unfavorable for the conversion of raw material macromolecular, therefore the modification point that pore structure is open, mesoporous content is high and acid site exposure is more
Son sieve can handle the raw material that molecule is bigger, oil product is heavier, improve macromolecular conversion probability etc. show it is more superior
Performance, so as to lift the level of hydrocracking catalyst.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of carrier of hydrocracking catalyst and its system
Preparation Method.The carrier uses Modified Zeolite Y with beta-molecular sieve collectively as cracking center, wherein Y type molecular sieve used is
A kind of Y type molecular sieve concentrated rich in meso-hole structure, effective pore sife distribution, hydrocracking catalyst prepared therefrom are used for fecund
In the hydrocracking process of high-quality midbarrel oil product, it is active it is high and selectivity it is good the characteristics of, while can and production it is high-quality
Hydrogenation tail oil.
Carrier of hydrocracking catalyst of the present invention, comprising Modified Zeolite Y, beta-molecular sieve and aluminum oxide, wherein modified Y
The property of type molecular sieve is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 55 ~ 100, and cell parameter is
2.425 ~ 2.435nm, total pore volume are 0.55 ~ 1.0mL/g, preferably 0.6 ~ 1.0mL/g, and mesoporous pore volume accounts for total pore volume
More than 70%, preferably 80% ~ 95%.
The grain size of described Modified Zeolite Y is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
In described Modified Zeolite Y, mesoporous bore dia is 2 ~ 10nm.
The specific surface area of described Modified Zeolite Y is 650 ~ 1000m2/ g, preferably 750 ~ 1000m2/g。
The infrared total acid content of described Modified Zeolite Y is 0.1 ~ 0.5mmol/g.
In described Modified Zeolite Y, Na2O weight content is below 0.15wt%.
The property of described beta-molecular sieve is as follows：Average grain diameter is 200 ~ 400nm, and specific surface area is 600 ~ 800m2/
G, pore volume are 0.35 ~ 0.50mL/g, and relative crystallinity 100% ~ 140%, infrared total acid content is 0.1 ~ 0.5mmoL/g, SiO2/
Al2O3Mol ratio is 40 ~ 80.The beta-molecular sieve can use hydrothermal crystallization method to synthesize, and typically using organic amine as template, then pass through
Conventional ammonium exchanges, the method for acid treatment and hydro-thermal process is modified and obtains.
In described hydrocracking catalyst, the carrier, on the basis of the weight of carrier, Modified Zeolite Y contains
Measure as 10% ~ 40%, the content of beta-molecular sieve is 5% ~ 20%, and the content of aluminum oxide is 40% ~ 85%.
Carrier of hydrocracking catalyst property of the present invention is as follows：Specific surface area is 300 ~ 500m2/ g, pore volume be 0.5 ~
1.0mL/g。
The preparation method of carrier of hydrocracking catalyst of the present invention, including：By Modified Zeolite Y, beta-molecular sieve, oxidation
Aluminium mixes, and shaping, then dries and is calcined, and the preparation method of catalyst carrier, wherein Modified Zeolite Y is made, including such as
Lower step：
（1）NaY types molecular sieve with（NH4）2SiF6Aqueous solution contact is reacted, through filtering and drying after reaction；
（2）To step（1）Gained Y type molecular sieve carries out hydro-thermal process；Hydrothermal conditions：Gauge pressure is 0.20 ~ 0.40MPa, temperature
Spend for 600 ~ 800 DEG C, processing time is 0.5 ~ 5.0 hour；
（3）By step（2）Gained Y type molecular sieve carries out hydrothermal crystallizing processing, Ran Houjing under the conditions of existing for organic formwork agent
Filter and dry；
（4）By step（3）The Y type molecular sieve of gained is calcined under low temperature oxygen-enriched atmosphere, and the Y type molecular sieve of the present invention is made.
The inventive method step（1）In, the property of NaY type molecular sieves is as follows：
SiO2/Al2O3Mol ratio be 3 ~ 6, preferably 4.5 ~ 5.5, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm, relatively
Crystallinity is 80% ~ 110%, cell parameter 2.465 ~ 2.470nm, Na2O weight content is 6.0wt% ~ 8.0wt%, specific surface area
For 600 ~ 900m2/ g, the mL/g of total pore volume 0.3 ~ 0.4, micropore pore volume account for more than the 75% of total pore volume.
The inventive method step（1）In,（NH4）2SiF6Addition for NaY type molecular sieve butt weight 5wt% ~
20wt%。
The inventive method step（1）In,（NH4）2SiF6The mass concentration of the aqueous solution is 50 ~ 100g/L.NaY type molecular sieves
With（NH4）2SiF6The reaction condition that aqueous solution contact is reacted：Temperature is 80 ~ 150 DEG C, preferably 90 ~ 120 DEG C, during reaction
Between be 0.1 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
The inventive method step（1）In, NaY types molecular sieve with（NH4）2SiF6After aqueous solution contact is reacted, separation point
Son sieve and accessory substance, can wash, refilter, dry, preferably dry after gained Y type molecular sieve butt for 60wt% ~
80wt%.Dry condition is usually to be dried 0.5 ~ 5.0 hour at 50 ~ 95 DEG C.
The inventive method step（2）In, hydro-thermal process is to use saturated steam processing step（1）In obtained molecular sieve,
Treatment conditions：0.20 ~ 0.40MPa of gauge pressure, preferably 0.25 ~ 0.40MPa, preferably 600 ~ 800 DEG C of temperature, 610 ~ 750 DEG C, place
Manage 0.5 ~ 5.0 hour time, preferably 1.0 ~ 3.0 hours.
The inventive method step（3）In, organic formwork agent is tetraethyl ammonium hydroxide, TMAH, tetrapropyl
One or more in ammonium hydroxide.Wherein, by step（2）In after obtained Y type molecular sieve uniformly mixes with organic formwork agent,
Hydrothermal crystallizing is carried out, process is as follows：By step（2）In obtained Y type molecular sieve be beaten in the organic formwork agent aqueous solution, liquid is solid
Weight ratio is 3：1~8：1, temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and the mass concentration of the organic formwork agent aqueous solution is
3% ~ 10%, mixed material is then placed in crystallization in crystallizing kettle, crystallization temperature is 80 ~ 120 DEG C, and crystallization time is 4 ~ 10h, gauge pressure
For 0.1 ~ 0.2MPa.After crystallization, filtered and drying can use conventional method to carry out, and typically dry condition is as follows：50 ~
1 ~ 10h is dried at 110 DEG C.
In the inventive method, step（4）It is by step（3）Obtained Y type molecular sieve be calcined under low temperature oxygen-enriched atmosphere,
Wherein oxygen-enriched atmosphere refers to that oxygen content is more than 50v%, and sintering temperature is 300 ~ 450 DEG C, and roasting time is 5 ~ 10h.Roasting is general
Using the method being calcined under temperature programming again constant temperature, heating rate is preferably 1 ~ 2 DEG C/min.
Y type molecular sieve in carrier of hydrocracking catalyst of the present invention is to use（NH4）2SiF6NaY molecular sieve is changed
Property processing, while modulation molecular sieve silica alumina ratio is realized, the sodium ion in NaY molecular sieve can be deviate from together, then have
Hydrothermal crystallizing is carried out to the molecular sieve after hydro-thermal process in the presence of machine template, so can have part silicon atom and aluminium atom
The effect of machine template is lower to enter framework of molecular sieve structure, in the same of skeleton structure that is further stable and improving modified molecular screen
When, caused non-skeleton structure in zeolite-water heat treatment process, unimpeded pore passage structure are eliminated, part organic formwork agent also can
Enter in the duct of molecular sieve, coordinate follow-up oxygen-enriched low-temperature treatment, can be controllable in order by the organic formwork agent in molecular sieve
Removing, so as to produce a large amount of ordered mesopore structures, and pore size distribution is more concentrated.
Y type molecular sieve in carrier of hydrocracking catalyst of the present invention, acidity is suitable, crystallinity is high, mesoporous proportion
High, pore-size distribution is more concentrated, suitably as Cracking Component.Because the Y type molecular sieve has bigger pore volume and mesoporous body
Product, more acid centres are exposed, are advantageous to raw material heavy oil macromolecular and are cracked, but also with more preferably aperture point
Cloth scope, can efficiently control the cracking degree of reactant, and is advantageous to product and is diffused in duct, so in cracking
In reaction, can relative increase activated centre, and can make heavy oil macromolecular carry out suitable degree cracking reaction, both improve heavy oil
Cracking capability, while reduce coke yield, catalyst can show good cracking activity and product selectivity.
Carrier of hydrocracking catalyst of the present invention using Modified Zeolite Y and beta-molecular sieve collectively as cracking center, both
Its respective performance characteristics is given full play to, and can enough acts on concerted catalysis caused by two kinds of molecular sieves, i.e. beta molecular sieve pair
Long side chain on alkane or aromatic hydrocarbons has good isomerization, can effectively reduce the condensation point of product, while Y type molecular sieve pair
Aromatic hydrocarbons has very high selectivity of ring-opening, improves the product property of purpose product.The active height of hydrocracking catalyst of the present invention, can
High-output qulified midbarrel oil product（Jet fuel+diesel oil）, while high-quality hydrogenation tail oil and can be produced.
When the hydrocracking catalyst prepared by carrier of the present invention is used for heavy oil hydrocracking, particularly in condition of high voltage
（12~20MPa）Lower processing wax slop（VGO, CGO and DAO）, poor ignition quality fuel can also be added（Coker gas oil and catalytic diesel oil
Deng）, there is very high catalytic activity and intermediate oil selectivity, and the condensation point reduction amplitude of diesel oil distillate is big, and centre evaporates
The product property of point oil is improved, and can meet refinery's increase operating flexibility, increase device disposal ability, further in volume increase
Between distillate needs.
Brief description of the drawings
Fig. 1 is the SEM electromicroscopic photographs of the gained Modified Zeolite Y of embodiment 1；
Fig. 2 is the SEM electromicroscopic photographs of the gained Modified Zeolite Y of comparative example 1；
Fig. 3 is the XRD diffraction patterns of the gained Modified Zeolite Y of embodiment 1.
Embodiment
Aluminum oxide can use oxygen used in conventional hydrocracking catalyst in carrier of hydrocracking catalyst of the present invention
Change aluminium, such as macroporous aluminium oxide and ∕ or small porous aluminum oxide.0.6 ~ 1.3mL/g of pore volume of macroporous aluminium oxide used, specific surface area
300~450m2/g.The pore volume of small porous aluminum oxide used is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
Conventional shaping assistant such as peptization acid, extrusion aid can also be added in catalyst carrier preparation process of the present invention
Deng.
Detailed process prepared by carrier of hydrocracking catalyst of the present invention is as follows：By Modified Zeolite Y, beta-molecular sieve, oxygen
Change aluminium mixing, extruded moulding, then dry and be calcined, be prepared into carrier；Drying can dry 3 at a temperature of 80 DEG C to 150 DEG C ~
6 hours, roasting was calcined 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
The following examples are used to technical scheme be described in more detail, but the scope of the present invention is not limited solely to this
The scope of a little embodiments.In the present invention, wt% is mass fraction.
Analysis method of the present invention：Specific surface area, pore volume, mesoporous pore volume use low temperature liquid nitrogen determination of adsorption method, relatively
Crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio uses XRF methods（X ray fluorescence spectrometry）Measure, molecular sieve
Grain size use SEM（SEM）Mode determine.Meleic acid amount uses Pyridine adsorption IR spectra method, sodium
Content uses plasma emission spectrometry.
Embodiment 1
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6
The aqueous solution, it is 72g/L's that 307mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature stirs after completion of dropwise addition
2 hours, constant temperature was filtered and dried after terminating, and the butt of molecular sieve is 65.3wt% after drying；By above-mentioned dried molecule
Sieve is added in hydrothermal treatment device, in gauge pressure 0.25MPa, 610 DEG C of temperature, under the conditions of 1.0 hours processing times molecular sieve is entered
Water-filling is heat-treated；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl ammonium hydroxide that 520mL mass concentrations are 5.3%
In the aqueous solution, constant temperature is stirred 4 hours under the conditions of 80 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing,
90 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 10 hours, crystallization is filtered after terminating and drying process；Hydro-thermal is brilliant
To change obtained drying sample to be calcined under oxygen-enriched state, oxygen content is 70v% in calcination atmosphere, and heating rate is 1 DEG C/min,
Constant temperature calcining temperature is 420 DEG C, and the constant temperature calcining time is 6 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-1, molecular sieve
Property is listed in table 1.
Embodiment 2
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 55g/L's that 182mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature after completion of dropwise addition
Stirring 2 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 68.0wt% after drying；Will be above-mentioned dried
Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.30MPa, 670 DEG C of temperature, under the conditions of 2.0 hours processing times to point
Son sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetrapropyl hydrogen that 910mL mass concentrations are 7.5%
Aoxidize in aqueous ammonium, constant temperature is stirred 4 hours under the conditions of 90 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal
Crystallization, 110 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 10 hours, crystallization is filtered after terminating and drying process；Will
The drying sample that hydrothermal crystallizing obtains is calcined under oxygen-enriched state, and oxygen content is 65v% in calcination atmosphere, heating rate 1
DEG C/min, constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 10 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-
2, molecular sieve property is listed in table 1.
Embodiment 3
Take NaY original powder 278g to be put into 1000mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 85g/L's that 417mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature after completion of dropwise addition
Stirring 3 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 67.2wt% after drying；Will be above-mentioned dried
Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.35MPa, 700 DEG C of temperature, under the conditions of 3.0 hours processing times to molecule
Sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl hydrogen-oxygen that 1040mL mass concentrations are 3.5%
Change in aqueous ammonium, constant temperature is stirred 3 hours under the conditions of 85 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal crystalline substance
Change, 80 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 5 hours, crystallization is filtered after terminating and drying process；By hydro-thermal
The drying sample that crystallization obtains is calcined under oxygen-enriched state, and oxygen content is 75v% in calcination atmosphere, and heating rate is 1 DEG C/
Min, constant temperature calcining temperature are 320 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-3, point
Son sieve property is listed in table 1.
Embodiment 4
Take NaY original powder 278g to be put into 1400mL water purification, be warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 60g/L's that 200mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature after completion of dropwise addition
Stirring 2 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 68.1wt% after drying；Will be above-mentioned dried
Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.30MPa, 750 DEG C of temperature, under the conditions of 2.0 hours processing times to point
Son sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetrapropyl hydrogen that 520mL mass concentrations are 6.8%
Aoxidize in aqueous ammonium, constant temperature is stirred 3 hours under the conditions of 90 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal
Crystallization, 95 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 8 hours, crystallization is filtered after terminating and drying process；By water
The drying sample that thermal crystallisation obtains is calcined under oxygen-enriched state, and oxygen content is 70v% in calcination atmosphere, and heating rate is 1 DEG C/
Min, constant temperature calcining temperature are 380 DEG C, and the constant temperature calcining time is 10 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-4,
Molecular sieve property is listed in table 1.
Comparative example 1
Take NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concns are 1.5mol/L, be warming up to 95 DEG C, constant temperature stirring
2 hours, constant temperature was filtered, washed and dried after terminating, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming will divide
Son sieve is calcined 3 hours at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；After taking second of ammonium of 100g to exchange
Molecular sieve be put into 650mL mass concentrations be 7.5% the tetraethyl ammonium hydroxide aqueous solution in, constant temperature stirs under the conditions of 80 DEG C
Mix 2 hours, then mixed material is transferred in crystallizing kettle and carries out crystallization, 100 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization
8 hours time, crystallization is filtered after terminating and drying process；The drying sample that crystallization obtains is calcined under oxygen-enriched state,
Oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is
8 hours, obtain molecular sieve.Sample number into spectrum LDAY-1, molecular sieve property are listed in table 1.
Comparative example 2
Take NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concns are 1.5mol/L, be warming up to 95 DEG C, constant temperature stirring
2 hours, constant temperature divides after terminating to be filtered, washed and dried, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming will
Molecular sieve is calcined 3 hours at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；Second of ammonium of 100g is taken to exchange
Molecular sieve afterwards is put into the dust technology that 800mL concentration is 0.3mol/L, and constant temperature stirs 2 hours under the conditions of 80 DEG C, constant temperature
Filtered after end and drying process；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, in gauge pressure
0.30MPa, 670 DEG C of temperature, molecular sieve is obtained to molecular sieve progress hydro-thermal process under the conditions of 2.0 hours processing times；Sample is compiled
Number LDAY-2, molecular sieve property are listed in table 1.
Comparative example 3
Molecular sieve, sample number into spectrum LDAY-3, molecular sieve property row are prepared using the method for embodiment in CN201510147788.3 1
In table 1.
The property of the Y type molecular sieve of table 1
| Production code member | LAY-1 | LAY-2 | LAY-3 | LAY-4 |
| Specific surface area, m2/g | 912 | 887 | 941 | 923 |
| Pore volume, cm3/g | 0.74 | 0.69 | 0.88 | 0.72 |
| Lattice constant, nm | 2.433 | 2.431 | 2.428 | 2.426 |
| Relative crystallinity, % | 131 | 119 | 140 | 132 |
| Average crystallite size, μm | 1.7 | 1.7 | 1.7 | 1.7 |
| SiO2/Al2O3Mol ratio | 73.6.3 | 62.3 | 81.9 | 65.8 |
| Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account for total pore volume ratio, % | 86 | 83 | 91 | 87 |
| Infrared total acid content, mmol/g | 0.45 | 0.33 | 0.30 | 0.21 |
| Na2O, wt% | 0.05 | 0.06 | 0.03 | 0.07 |
Continued 1
| Production code member | LDAY-1 | LDAY-2 | LDAY-3 |
| Specific surface area, m2/g | 633 | 703 | 603 |
| Pore volume, cm3/g | 0.44 | 0.37 | 0.38 |
| Lattice constant, nm | 2.439 | 2.433 | 2.449 |
| Relative crystallinity, % | 98 | 103 | 86 |
| Average crystallite size, μm | 1.7 | 1.7 | 1.7 |
| SiO2/Al2O3Mol ratio | 7.5 | 33.5 | 8.6 |
| Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account for total pore volume ratio, % | 47 | 31 | 37 |
| Infrared total acid content, mmol/g | 0.77 | 0.35 | 0.71 |
| Na2O, wt% | 0.21 | 0.19 | 0.45 |
Embodiment 5
By 44.44 grams of LAY-1 molecular sieves（Butt 90wt%）, 22.22 grams of beta-molecular sieves（Crystal grain=250nm, SiO2/Al2O3=50, hole
Volume 0.45mL/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g, butt 90wt%）, 142.7 grams of macroporous aluminium oxides
（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid and aperture
The mol ratio of aluminum oxide is 0.4）Mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion bar dries 4 at 110 DEG C
Hour, then it is calcined 4 hours at 550 DEG C, obtains carrier ZS-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst Z C-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 6
By 44.44 grams of LAY-2 molecular sieves（Butt 90wt%）, 33.3 grams of beta-molecular sieves（Crystal grain=250nm, SiO2/Al2O3=50, hole
Volume 0.45mL/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g, butt 90wt%）, 128.6 grams of macroporous aluminium oxides
（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid and aperture
The mol ratio of aluminum oxide is 0.4）Mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion bar dries 4 at 110 DEG C
Hour, then it is calcined 4 hours at 550 DEG C, obtains carrier ZS-2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst Z C-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 7
By 66.66 grams of LAY-3 molecular sieves（Butt 90wt%）, 11.11 grams of beta-molecular sieves（Crystal grain=250nm, SiO2/Al2O3=50, hole
Volume 0.45mL/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g, butt 90wt%）, 142.7 grams of macroporous aluminium oxides
（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid and aperture
The mol ratio of aluminum oxide is 0.4）Mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion bar dries 4 at 110 DEG C
Hour, then it is calcined 4 hours at 550 DEG C, obtains carrier ZS-3.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst Z C-3 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 8
By 55.55 grams of LAY-4 molecular sieves（Butt 90wt%）, 44.44 grams of beta-molecular sieves（Crystal grain=250nm, SiO2/Al2O3=50, hole
Volume 0.45ml/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g butts 90wt%）, 142.7 grams of macroporous aluminium oxides
（Pore volume 1.0ml/g, specific surface area 400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid and aperture
The mol ratio of aluminum oxide is 0.4）Mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion bar dries 4 at 110 DEG C
Hour, then it is calcined 4 hours at 550 DEG C, obtains carrier ZS-4.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst Z C-4 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 4 ~ 6
As described in Example 6, change LAY-2 into LDAY-1, LDAY-2, LDAY-3 respectively, be made carrier DZS-1, DZS-2,
DZS-3 and catalyst DZC-1, DZC-2 and DZC-3, carrier and catalyst composition are shown in Table 2.
Embodiment 9 ~ 12
This embodiment describes catalyst Z C-1, ZC-2, ZC-3 and the ZC-4 prepared by carrier of the present invention Activity evaluation.
Evaluated on fixed bed hydrogenation experimental rig, appreciation condition is：React stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1250：1, liquid
When volume space velocity 1.5h-1, using one-stage serial once by technological process, use vacuum distillate（VGO）It is former as feedstock oil
Material oil nature is listed in table 3, and evaluation result is listed in table 4.
Comparative example 7 ~ 9
This comparative example describes catalyst DZC-1, DZC-2 and DZC-3 for being prepared by comparative example carrier of the present invention activity rating
As a result.Evaluated on fixed bed hydrogenation experimental rig, appreciation condition is：React stagnation pressure 15.0MPa, hydrogen to oil volume ratio
1250：1, volume space velocity 1.5h during liquid-1, using one-stage serial once by technological process, use vacuum distillate（VGO）As
Feedstock oil, raw material oil nature are listed in table 3, and evaluation result is listed in table 4.
The composition and physico-chemical property of the catalyst carrier of table 2 and catalyst
| Carrier forms and property | ||||
| Numbering | ZS-1 | ZS-2 | ZS-3 | ZS-4 |
| Composition | ||||
| Y type molecular sieve, wt% | 20 | 20 | 30 | 25 |
| Beta-molecular sieve, wt% | 10 | 15 | 5 | 20 |
| Aluminum oxide | Surplus | Surplus | Surplus | Surplus |
| Property | ||||
| Specific surface area, m2/g | 446 | 450 | 489 | 492 |
| Pore volume, mL/g | 0.67 | 0.66 | 0.68 | 0.64 |
| Catalyst forms and property | ||||
| Numbering | ZC-1 | ZC-2 | ZC-3 | ZC-4 |
| WO3, wt% | 25.51 | 25.53 | 25.35 | 25.37 |
| NiO, wt% | 6.92 | 6.84 | 6.86 | 6.93 |
| Specific surface area, m2/g | 322 | 3367 | 389 | 345 |
| Pore volume, mL/g | 0.47 | 0.42 | 0.43 | 0.44 |
Continued 2
| Carrier forms and property | |||
| Numbering | DZS-1 | DZS-2 | DZS-3 |
| Composition | |||
| Y type molecular sieve, wt% | 20 | 20 | 20 |
| Beta-molecular sieve, wt% | 15 | 15 | 15 |
| Aluminum oxide | Surplus | Surplus | Surplus |
| Property | |||
| Specific surface area, m2/g | 388 | 435 | 298 |
| Pore volume, mL/g | 0.55 | 0.53 | 0.42 |
| Catalyst forms and property | |||
| Numbering | DZC-1 | DZC-2 | DZC-3 |
| WO3, wt% | 25.61 | 25.67 | 25.69 |
| NiO, wt% | 6.92 | 6.97 | 6.55 |
| Specific surface area, m2/g | 256 | 234 | 196 |
| Pore volume, mL/g | 0.28 | 0.26 | 0.29 |
The raw material oil nature of table 3
| Feedstock oil | Vacuum distillate（VGO） |
| Density (20 DEG C), g/cm3 | 0.9072 |
| Boiling range, DEG C | |
| IBP/10% | 305/361 |
| 30%/50% | 394/417 |
| 70%/90% | 443/481 |
| 95%/EBP | 509/533 |
| Condensation point, DEG C | 34 |
| Sulphur, wt% | 1.98 |
| Nitrogen, μ g/g | 1228 |
| Carbon, wt% | 85.28 |
| Hydrogen, wt% | 12.46 |
| BMCI values | 45.0 |
The catalyst performance comparative evaluation's result of table 4
| Catalyst | ZC-1 | ZC-2 | ZC-3 | ZC-4 |
| Feedstock oil | Vacuum distillate（VGO） | Vacuum distillate（VGO） | Vacuum distillate（VGO） | Vacuum distillate（VGO） |
| Operating condition | ||||
| Volume space velocity during liquid, h-1 | 1.5 | 1.5 | 1.5 | 1.5 |
| React stagnation pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1250 | 1250 | 1250 | 1250 |
| Cracking zone reaction temperature, DEG C | 372 | 370 | 371 | 365 |
| Product yield and property | ||||
| Heavy naphtha | ||||
| Yield, wt% | 9.5 | 9.0 | 8.7 | 8.0 |
| Virtue is latent, wt% | 64.3 | 65.4 | 63.2 | 64.9 |
| Jet fuel | ||||
| Yield, wt% | 47.9 | 47.5 | 48.1 | 47.3 |
| Smoke point, mm | 28 | 28 | 29 | 27 |
| Aromatic hydrocarbons, v% | 5.1 | 4.1 | 3.3 | 4.3 |
| Diesel oil | ||||
| Yield, wt% | 21.6 | 22.6 | 21.2 | 23.5 |
| Condensation point, DEG C | -16 | -18 | -15 | -19 |
| Cetane number | 69.4 | 68.6 | 70.3 | 68.1 |
| Tail oil | ||||
| Yield, wt% | 15.3 | 16.1 | 16.3 | 16.0 |
| Condensation point, DEG C | 11 | 10 | 13 | 10 |
| BMCI values | 10.8 | 11.9 | 9.6 | 10.2 |
| Intermediate oil selectivity, wt% | 82.10 | 83.6 | 82.8 | 84.2 |
| Chemical hydrogen consumption, wt% | 2.48 | 2.45 | 2.46 | 2.47 |
Continued 4
| Catalyst | ZDC-1 | ZDC-2 | ZDC-3 |
| Feedstock oil | Vacuum distillate（VGO） | Vacuum distillate（VGO） | Vacuum distillate（VGO） |
| Operating condition | |||
| Volume space velocity during liquid, h-1 | 1.5 | 1.5 | 1.5 |
| React stagnation pressure, MPa | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1250 | 1250 | 1250 |
| Cracking zone reaction temperature, DEG C | 378 | 387 | 389 |
| Product yield and property | |||
| Heavy naphtha | |||
| Yield, wt% | 11.2 | 11.9 | 12.6 |
| Virtue is latent, wt% | 62.3 | 61.2 | 59.8 |
| Jet fuel | |||
| Yield, wt% | 44.9 | 43.8 | 42.0 |
| Smoke point, mm | 26 | 26 | 24 |
| Aromatic hydrocarbons, v% | 4.8 | 5.3 | 5.6 |
| Diesel oil | |||
| Yield, wt% | 22.5 | 23.5 | 21.6 |
| Condensation point, DEG C | -6 | -6 | -5 |
| Cetane number | 67.3 | 67.4 | 61.7 |
| Tail oil | |||
| Yield, wt% | 15.1 | 14.3 | 16.1 |
| Condensation point, DEG C | 19 | 21 | 20 |
| BMCI values | 14.6 | 14.9 | 15.3 |
| Intermediate oil selectivity, wt% | 80.6 | 78.6 | 77.0 |
| Chemical hydrogen consumption, wt% | 2.72 | 2.73 | 2.75 |
The hydrocracking catalyst prepared it can be seen from the evaluation result of table 4 using carrier of the present invention, intermediate oil selection
Property, yield and product quality are superior to reference catalyst.
Claims (21)
- A kind of 1. carrier of hydrocracking catalyst, comprising Modified Zeolite Y, beta-molecular sieve and aluminum oxide, wherein described modification Y type molecular sieve, its property are as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 55 ~ 100, and cell parameter is 2.425 ~ 2.435nm, total pore volume are 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume.
- 2. according to the catalyst carrier described in claim 1, it is characterised in that：The property of the Y type molecular sieve is as follows：Total hole body Product is 0.6 ~ 1.0mL/g, and mesoporous pore volume accounts for the 80% ~ 95% of total pore volume.
- 3. according to the catalyst carrier described in claim 1, it is characterised in that：The grain size of the Y type molecular sieve is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
- 4. according to the catalyst carrier described in claim 1, it is characterised in that：The mesoporous bore dia of the Y type molecular sieve is 2nm~10nm。
- 5. according to the catalyst carrier described in claim 1, it is characterised in that：The specific surface area of the Y type molecular sieve is 650m2/ g~1000m2/ g, preferably 750m2/g~1000m2/g。
- 6. according to the catalyst carrier described in claim 1, it is characterised in that：The infrared total acid content of the Y type molecular sieve is 0.1~0.5mmol/g。
- 7. according to the catalyst carrier described in claim 1, it is characterised in that：In the Y type molecular sieve, Na2O weight content For below 0.15wt%.
- 8. according to the catalyst carrier described in claim 1, it is characterised in that：The property of described beta-molecular sieve is as follows：Crystal grain is put down A diameter of 200 ~ 400nm, specific surface area are 600 ~ 800m2/ g, pore volume are 0.35 ~ 0.50mL/g, relative crystallinity 100% ~ 140%, infrared total acid content is 0.1 ~ 0.5mmoL/g, SiO2/Al2O3Mol ratio is 40 ~ 80.
- 9. according to the catalyst carrier described in claim 1, it is characterised in that：The property of the carrier of hydrocracking catalyst is such as Under：Specific surface area is 300 ~ 500m2/ g, pore volume are 0.5 ~ 1.0mL/g.
- 10. according to the catalyst carrier described in claim 1, it is characterised in that：Described carrier of hydrocracking catalyst, with On the basis of the weight of carrier, the content of Modified Zeolite Y is 10% ~ 40%, and the content of beta-molecular sieve is 5% ~ 20%, aluminum oxide Content is 40% ~ 85%.
- 11. the preparation method of any catalyst carrier of claim 1 ~ 10, including：By Modified Zeolite Y, beta-molecular sieve, Aluminum oxide mixes, and shaping, then dries and is calcined, and the preparation method of catalyst carrier, wherein Modified Zeolite Y, bag is made Include following steps：（1）NaY types molecular sieve with（NH4）2SiF6Aqueous solution contact is reacted, through filtering and drying after reaction；（2）To step（1）Gained Y type molecular sieve carries out hydro-thermal process；Hydrothermal conditions：Gauge pressure is 0.20 ~ 0.40MPa, temperature Spend for 600 ~ 800 DEG C, processing time is 0.5 ~ 5.0 hour, and preferably hydrothermal conditions are as follows：Gauge pressure is 0.25 ~ 0.40MPa, Temperature is 610 ~ 750 DEG C, and processing time is 1.0 ~ 3.0 hours；（3）By step（2）Gained Y type molecular sieve carries out hydrothermal crystallizing processing, Ran Houjing under the conditions of existing for organic formwork agent Filter and dry；（4）By step（3）The Y type molecular sieve of gained is calcined under low temperature oxygen-enriched atmosphere, and Modified Zeolite Y is made.
- 12. in accordance with the method for claim 11, it is characterised in that：Step（1）In, the property of NaY type molecular sieves is as follows：SiO2/Al2O3Mol ratio be 3 ~ 6, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm, relative crystallinity be 80% ~ 110%, cell parameter is 2.465 ~ 2.470nm, Na2O weight content is 6.0wt% ~ 8.0wt%, specific surface area is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4mL/g, and micropore pore volume accounts for more than the 75% of total pore volume.
- 13. in accordance with the method for claim 11, it is characterised in that：Step（1）In,（NH4）2SiF6Addition be NaY types 5wt% ~ 20wt% of molecular sieve butt weight.
- 14. in accordance with the method for claim 11, it is characterised in that：Step（1）In,（NH4）2SiF6The quality of the aqueous solution is dense Spend for 50 ~ 100g/L.
- 15. in accordance with the method for claim 11, it is characterised in that：Step（1）In, NaY types molecular sieve with（NH4）2SiF6Water The reaction condition that solution contact is reacted：Temperature is 80 ~ 150 DEG C, and the reaction time is 0.1 ~ 5.0 hour, preferred reaction conditions It is as follows：Temperature is 90 ~ 120 DEG C, and the reaction time is 1.0 ~ 3.0 hours.
- 16. in accordance with the method for claim 11, it is characterised in that：Step（1）In, dry condition is at 50 ~ 95 DEG C Dry 0.5 ~ 5.0 hour, the butt of the Y type molecular sieve of gained is 60wt% ~ 80wt% after drying.
- 17. in accordance with the method for claim 11, it is characterised in that：Step（3）In, organic formwork agent is tetraethyl hydroxide One or more in ammonium, TMAH, TPAOH.
- 18. in accordance with the method for claim 11, it is characterised in that：By step（2）In obtained Y type molecular sieve and organic mould Plate agent uniformly after mixing, carries out hydrothermal crystallizing, and process is as follows：By step（2）In obtained Y type molecular sieve in organic formwork agent water It is beaten in solution, solvent and solute weight ratio 3：1~8：1, temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and organic formwork agent is water-soluble The mass concentration of liquid is 3% ~ 10%, and mixed material then is placed in into crystallization in crystallizing kettle, and crystallization temperature is 80 ~ 120 DEG C, during crystallization Between be 4 ~ 10h, gauge pressure is 0.1 ~ 0.2MPa.
- 19. in accordance with the method for claim 11, it is characterised in that：Step（4）It is by step（3）Obtained Y type molecular sieve Be calcined under low temperature oxygen-enriched atmosphere, wherein oxygen-enriched atmosphere refers to that oxygen content is more than 50v%, and sintering temperature is 300 ~ 450 DEG C, Roasting time is 5 ~ 10h.
- 20. in accordance with the method for claim 11, it is characterised in that：Described aluminum oxide includes macroporous aluminium oxide and/or small Porous aluminum oxide, the property of described macroporous aluminium oxide are as follows：Pore volume is 0.6 ~ 1.3mL/g, and specific surface area is 300 ~ 450m2/ g；The property of described small porous aluminum oxide is as follows：Pore volume is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
- 21. in accordance with the method for claim 11, it is characterised in that：Process prepared by the carrier of hydrocracking catalyst For：Modified Zeolite Y, beta-molecular sieve, aluminum oxide are mixed, shaping, is then dried and is calcined, be prepared into carrier, institute The drying stated is dried 3 ~ 6 hours at a temperature of 80 DEG C ~ 150 DEG C, and roasting is calcined 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
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| CN103100417A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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| CN103100417A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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| CN114247421A (en) * | 2021-12-24 | 2022-03-29 | 商丘师范学院 | Modified molecular sieve purifying agent and preparation method and application thereof |
| CN114247421B (en) * | 2021-12-24 | 2023-11-21 | 商丘师范学院 | Modified molecular sieve purifying agent and preparation method and application thereof |
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