CN104646050B - Hydrogenation catalyst, preparation and application thereof - Google Patents
Hydrogenation catalyst, preparation and application thereof Download PDFInfo
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- CN104646050B CN104646050B CN201310597628.XA CN201310597628A CN104646050B CN 104646050 B CN104646050 B CN 104646050B CN 201310597628 A CN201310597628 A CN 201310597628A CN 104646050 B CN104646050 B CN 104646050B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002808 molecular sieve Substances 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 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 6
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 24
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000295 fuel oil Substances 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 18
- 238000005336 cracking Methods 0.000 abstract description 7
- 238000005470 impregnation Methods 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000002149 hierarchical pore Substances 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 101000688582 Homo sapiens SH3 domain-containing kinase-binding protein 1 Proteins 0.000 description 4
- 102100024244 SH3 domain-containing kinase-binding protein 1 Human genes 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 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 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000003113 dilution method Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polycyclic hydrocarbon Chemical class 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 239000010913 used oil Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a hydrogenation catalyst and a preparation method thereof; the active metal is a metal of VIB group and VIII group, the carrier is composed of a composite molecular sieve, alumina, silica and a binder, the composite molecular sieve is a hierarchical pore composite molecular sieve of mesoporous amorphous silica-alumina coated microporous Beta molecular sieve, (1) the composite molecular sieve, the alumina, the silica and the binder are uniformly mixed and molded; drying at 80-130 ℃ and roasting at 400-600 ℃; (2) preparing an impregnation solution by using a compound containing active metal component elements, impregnating the carrier, drying the impregnated carrier at 80-130 ℃, and calcining at 400-600 ℃; the catalyst is used for hydrocracking reaction of vacuum distillate oil, improves the reaction catalytic activity, promotes the selective generation of middle distillate oil, effectively inhibits secondary cracking side reaction, and reduces the yield of low-boiling fraction.
Description
Technical field
The invention belongs to a kind of hydrogenation catalyst and its preparation and application, specifically one kind is by mesoporous amorphous silica-alumina
The multi-stage porous composite molecular screen for coating micropore Beta molecular sieves is hydrogenation catalyst of acid constituent element and preparation method thereof.
Background technology
Hydrocracking technology is used as the important manufacturing process of heavy oil lighting, low grade oilses modification and Integrated Refinery And Petrochemical, tool
Have the advantages that production decision is flexible, adaptability to raw material is strong, purpose product selectivity is high, quality is good and tail oil added value is high.Hydrogenation
Cracking catalyst is the core of hydrocracking technology, therefore development, the development and application of hydrocracking catalyst are also that hydrogenation splits
Change the main contents of technological progress.Hydrocracking catalyst is typical bifunctional catalyst, and catalyst carrier material, which is provided, to be split
Change function, open loop, n-alkane are substantially carried out on acidic site and is hydrocracked, takes off alkyl, isomerization etc. is reacted.At present, for
Active metal component understanding and its load technology of preparing on a support material of the mechanism of action in hydrocracking catalyst shows
Be mature on the whole with it is perfect, and with more dominance can novel carriers material also just become grinding for hydrocracking catalyst technology
Heat generating spot.
VGO feedstock is mainly made up of saturated hydrocarbons, aromatic hydrocarbons and colloid etc..Make the big polycyclic cyclic hydrocarbon molecules of diameter with urging
Change activated centre contact, it is necessary that catalyst has good pore structure.Hydrocracking catalyst only possess big aperture,
Big pore volume, pore size distribution are uniform, pore system is opened and the pore structure feature such as unimpeded, can just make the big polycyclic hydrocarbon molecular proportion of diameter compared with
Catalyst duct is easily accessible, increase contacts the chance reacted with activated centre, improves ring-opening reaction speed；Diameter is small
Chain hydrocarbon can then be easier to depart from from duct, diffuse out, and reduce chain-breaking reaction speed.The acidity and pore structure of catalysis material
It is the principal element for determining hydrocracking catalyst.
Y types and Beta type molecular sieves are widely used in hydrocracking catalyst as acid centre.Y type molecular sieve has
The pore structure feature of three-dimensional supercage, tetrahedron trend and 12 yuan of rings macropores, counterincision solution cyclic hydrocarbon and raising selectivity of ring-opening have
Preferably effect.Beta type molecular sieves are 12 yuan of rings macropore straight passage structures, to cleavage of paraffin and straight-chain hydrocarbons stereoselectivity compared with
It is good.CN1296860 discloses a kind of preparation method of the hydrocracking catalyst containing particle diameter for 200~800nm Y molecular sieve,
Catalyst is prepared using the method for spray shaping.This catalyst is applied in catalytic cracking reaction, higher split is shown
Change activity, but liquid receives too low.CN102553638 discloses a kind of double microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41 and added
Hydrogen Cracking catalyst, the selectivity of its midbarrel is relatively low under conditions of catalyst greater activity is ensured, although double micropores point
The introducing of son sieve, which expands catalyst, can handle the scope of oil product, but the diffusional resistance that microporous molecular sieve structure is produced causes
The further cracking of midbarrel.CN103100412 discloses a kind of being hydrocracked based on SBA-15/Y composite molecular screens
Catalyst, the introducing of the regular mesoporous silicon oxide of pore structure promotes the diffusion of macromolecular, but the shortage in acid site is unfavorable
The cracking of macromolecular in oil product.In order to strengthen the diffusion of product, the Cracking Component of industrial hydrocracking catalyst is using tool
There is the modified Y molecular sieve of middle macroporous structure.CN103100403 discloses a kind of using modified Y molecular sieve and amorphous silicon aluminum
Standby hydrocracking catalyst, although improve cracking conversion rate, reduces reaction temperature, but modified Y molecular sieve is still suffered from
Pore structure is irregular, the disadvantage such as molecular sieve crystallinity decline and finite surface area, and hydrocracking catalyst is not solved fundamentally
Conversion ratio, selectivity and the stability problem of agent.
Crystallite molecular sieve is due to larger external surface area and higher micropore diffusion speed, being used as catalyst activity group
Point or support applications in catalytic cracking, be hydrocracked with the oil refining process such as isomerization, show the Y than stock size
The more superior performance of molecular sieve, is received more and more attention.CN103240114 discloses a kind of using small-grain Y molecular sieve
The application and preparation of the hydrocracking catalyst of preparation, catalyst has a greater activity, and shows tail oil high income and quality is good
Advantage.Therefore, the carrier of hydrocracking catalyst of a kind of greater activity and good stability is prepared to hydrocracking process
Development has important effect.
The content of the invention
It is an object of the invention to provide a kind of preparation method of hydrogenation catalyst.Hydrogenation catalyst, by hydrogenation active metals
With carrier composition.Hydrogenation active metals are vib and VIII metal, and vib metals are molybdenum and/or tungsten, VIII
Race's metal is cobalt and/or nickel；The content that vib metals are counted using oxide is 10~30wt%, and group VIII metal is with oxide
The content of meter is 3~10wt%.220~450m of catalyst specific surface2/ g, 0.30~0.65ml/g of total pore volume, meleic acid amount 0.20
The ratio of~0.50mmol/g, B acid and L acid is 0.05~1.0.
Catalyst carrier for hydrgenating of the present invention by weight percentage by 10~70wt% of composite molecular screen, aluminum oxide 10~
40wt%, 5~30wt% of silica, 10~30wt% of binding agent and 2~7wt% of extrusion aid mixing extrusion are formed.Used answers
It is the multi-stage porous composite molecular screen that the mesoporous amorphous silica-alumina of a class coats micropore Beta molecular sieves to close molecular sieve.The ratio table of molecular sieve
Area is 573~1082m2/ g, pore volume is 0.48~0.97cc/g, and meleic acid amount is 0.23~0.58mmol/g, B acid and L
The ratio of acid is maintained at 1.5~0.87:1.Multi-stage porous molecular sieve hydrocracking catalyst carrier specific surface area after extruded moulding
For 380~573m2/ g, pore volume is 0.63~0.94cc/g, and meleic acid amount is 0.10~0.45mmol/g, B acid and L acid ratio
It is worth for 2.3~0.9:1.
The aluminum oxide used is a class ball-type meso-porous alumina, and aperture is 8~35nm, and specific surface area is 95~320m2/
g.And involved silica is also unbodied mesoporous silicon oxide, aperture be 3~18nm, specific surface area be 260~
670m2/g。
The preparation method of the hydrogenation catalyst of the present invention, comprises the following steps：（1）By composite molecular screen, aluminum oxide, dioxy
SiClx and binding agent are well mixed, shaping；In dry 3~5h, 400~600 DEG C of 3~10h of roasting under 80~130 DEG C of atmosphere；（2）
Dipping solution is prepared with the compound of the element containing active metal component, and obtained carrier is impregnated, impregnated carrier
80~130 DEG C of dry 2~10h, 400~600 DEG C of 3~10h of calcining.
Wherein the molecular sieve mother liquor being synthesized by using the molecular sieve containing Beta of composite molecular screen, adds synthesising mesoporous nothing
Pore former required for amorphous silicon-alumina, the mass ratio for keeping pore former and Beta molecular sieve solids is 0.1~0.5:1, fully stir
Mix and reaction system is adjusted after 20~50 minutes to neutrality, the sial presoma mixing being added dropwise by prehydrolysis and mixed processing is molten
Liquid, silica alumina ratio is 45~280:1.At a temperature of 30~60 DEG C coat 1~5 hour, after aging at 60~140 DEG C
12~48 hours, washing separation and drying process are carried out to obtained product, product passes through 550 DEG C of high-temperature roastings 10 again after drying
The multi-stage porous composite molecular screen that hour processing is obtained.
The ingredient proportion of various raw materials is silica during synthesis Beta molecular sieves：Aluminum oxide：Sodium oxide molybdena：Template
Agent：Water=40~80：1:3~6:22~63：1400~2100, well mixed gel under 130~150 DEG C of high temperature crystallization 3~
The molecular sieve mother liquor of the molecular sieve containing Beta can be obtained within 5 days.
The catalyst of the present invention can be used in diesel oil hydrogenation, wax oil hydrogenation and heavy oil hydrogenation process, pre- using before needing to carry out
Vulcanizing treatment, process conditions are 330~400 DEG C of reaction temperature, and 6~15MPa of stagnation pressure, hydrogen to oil volume ratio 500~1500, volume is empty
Speed is 0.5~2.5h-1.Complex type molecular sieve in the present invention remains the pore passage structure of micro porous molecular sieve and unobstructed as much as possible
The linking of mesoporous micropore, pore distribution with gradient and acid site distribution are shown excellent in the catalytic cracking of heavy oil
Application prospect.
Embodiment
Embodiment 1
With Primogel ratio silica:Aluminum oxide:Sodium oxide molybdena:Template:Water=60:1:5:52:1950 will metering original
Material is mixed in order, and wherein silicon source is that Ludox, silicon source are that sodium metaaluminate, alkali lye are that sodium hydroxide, template are tetraethyl hydrogen
Amine-oxides, are sufficiently stirred for into gel, are then charged into the autoclave of polytetrafluoroethyllining lining, and crystallization temperature is set to 140
DEG C, thermostatic crystallization 72 hours.Solid product is by separation, and solid product, which is adopted, to be washed with deionized to neutrality, in 85 DEG C of air
Dried 24 hours in atmosphere, obtain Beta-1 molecular sieves.
Embodiment 2
With Primogel ratio silica:Aluminum oxide:Sodium oxide molybdena:Template:Water=40:1:3:28:1630 will metering original
Material is mixed in order, and wherein silicon source is that tetraethyl orthosilicate, silicon source are that sodium metaaluminate, alkali lye are that sodium hydroxide, template are tetrem
Base ammonium hydroxide, is sufficiently stirred for into gel, is then charged into the autoclave of polytetrafluoroethyllining lining, and crystallization temperature is set to
132 DEG C, thermostatic crystallization 120 hours.Solid product is by separation, and solid product, which is adopted, to be washed with deionized to neutrality, at 85 DEG C
Dried 24 hours in air atmosphere, obtain Beta-2 molecular sieves.
Embodiment 3
The Beta molecular sieve liquid for taking 1L to use the method in embodiment 1 to prepare, adds 19.5g pore formers cetyl three
Ammonio methacrylate, after being well mixed regulation solution ph to 6.8, be slowly added dropwise dilution process prehydrolysis and mixed processing just
The mixed solution of silester and aluminum nitrate, wherein keeping silicon source and the mol ratio of surfactant to be 1:0.26, silicon source and aluminium
The mol ratio in source is 80.At a temperature of 30 DEG C, coating reaction is carried out with 1000rpm rotating speed, continues 5 hours.By above solution
It is put into hydrothermal reaction kettle in aging 45 hours at 85 DEG C, whole ageing process is divided obtained molecular sieve solid after terminating
From washing and drying process, the surfactant that finally 550 DEG C of roastings are removed in molecular sieve pore passage for 3 hours in air atmosphere,
The Beta molecular sieves of mesoporous Si-Al cladding are obtained, ASABeta-1 is designated as.
Embodiment 4
The Beta molecular sieve liquid for taking 1L to use the method in embodiment 2 to prepare, adds 28.8g pore formers cetyl three
Ammonio methacrylate, after being well mixed regulation solution ph to 6.5, be slowly added dropwise dilution process prehydrolysis and mixed processing just
The mixed solution of silester and aluminum nitrate, wherein keeping silicon source and the mol ratio of surfactant to be 1:0.39, silicon source and aluminium
The mol ratio in source is 220.At a temperature of 55 DEG C, coating reaction is carried out with 1000rpm rotating speed, continues 1.5 hours.Will be molten above
Liquid is put into hydrothermal reaction kettle in aging 23 hours at 85 DEG C, and whole ageing process is carried out after terminating to obtained molecular sieve solid
Separating, washing and drying process, the surface-active that finally 550 DEG C of roastings are removed in molecular sieve pore passage for 3 hours in air atmosphere
Agent, obtains the Beta molecular sieves of mesoporous Si-Al cladding, is designated as ASABeta-2.
Embodiment 5
Prepare the NH that molar concentration is 0.5mol/L4NO3The aqueous solution, weighs the ASABeta-1 molecular sieves of 50g preparations, measures
1L0.5mol/L NH4NO3The aqueous solution, is exchanged 3 hours, washing separation, is repeated 3 times, afterwards afterwards after mixing under the conditions of 80 DEG C
It is dried overnight in 85 DEG C of air atmospheres, eventually passes the ASABeta-1 molecular sieves that H types are obtained after 550 DEG C of high-temperature roastings, be designated as
HSB-1；HSB-2 can be obtained by similar ion-exchange step.
HSB-1 and HSB-2 physical property is as shown in table 1.
Table 1 composite molecular screen HSB-1 and HSB-2 physical property
Embodiment 6
By 35g HSB-1 molecular sieves, 31g aluminum oxide（20~32nm of aperture, specific surface area 136m2/g）, 19g silica
（4~6nm of aperture, specific surface area 653m2/g）, 10g binding agents, 5g extrusion aids carry out roll extrusion, the cylinder bar of extrusion
120 DEG C dry 4 hours, then in Muffle furnace 550 DEG C be calcined 4 hours, be made carrier.
Obtained carrier 50g is weighed, the maceration extract of a certain amount of tungstenic and nickel, incipient impregnation is prepared.Precipitation 2h, 120
When DEG C drying 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst HC-1 is made.Embodiment 7
By 47g HSB-2 molecular sieves, 15g aluminum oxide（20~32nm of aperture, specific surface area 136m2/g）, 18g silica
（3~7nm of aperture, specific surface area 489m2/g）, 13g binding agents, 7g extrusion aids carry out roll extrusion, the cylinder of extrusion exists
100 DEG C of dryings 4 hours, then in Muffle furnace 500 DEG C be calcined 4 hours, carrier is made.
Obtained carrier 50g is weighed, the maceration extract of a certain amount of tungstenic and nickel, incipient impregnation is prepared.Precipitation 2h, 120
When DEG C drying 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst HC-2 is made.
The physical property of catalyst such as table 1.
Embodiment 8
Evaluated on fixed bed hydrogenation reaction unit, appreciation condition is：Reaction pressure 15.0MPa, hydrogen to oil volume ratio
800:1, volume space velocity 1.0h-1；Raw material oil nature such as table 2.Reaction evaluating result such as table 3.
Catalyst property obtained by table 1
| Catalyst | WO3, wt% | NiO, wt% | Than surface, m2/g | Pore volume, ml/g |
| C1 | 5.62 | 24.2 | 284.4 | 0.576 |
| C2 | 5.55 | 25.1 | 354.9 | 0.636 |
The raw materials used oil nature of table 2
The evaluating catalyst result of table 3
Claims (6)
1. a kind of hydrogenation catalyst, is made up of active metal and carrier, active metal is vib and VIII metal, its
Middle vib metals are molybdenum and/or tungsten, and group VIII metal is cobalt and/or nickel；Content of the vib metals in terms of oxide
For 10~30wt%, the content that group VIII metal is counted using oxide as 3~10wt%, carrier by composite molecular screen, aluminum oxide,
Silica and binding agent composition, wherein 10~70wt% of composite molecular screen, 10~40wt% of aluminum oxide, silica 5~
30wt%, remaining be binding agent；It is characterized in that：Hydrogenation catalyst is than 220~450m of surface2/ g, total pore volume 0.30~
The ratio of 0.65ml/g, meleic acid amount 0.20~0.50mmol/g, B acid and L acid is 0.05~1.0；Composite molecular screen is mesoporous
Amorphous silica-alumina coats the multi-stage porous composite molecular screen of micropore Beta molecular sieves, and the specific surface area of multi-stage porous composite molecular screen is
573~1082m2/ g, pore volume is 0.48~0.97cc/g, and meleic acid amount is 0.23~0.58mmol/g, B acid and L acid ratio
Value is maintained at 1.5~0.87:1；
The aluminum oxide used is a class ball-type meso-porous alumina, and aperture is 8~35nm, and specific surface area is 95~320m2/g；Two
Silica is unbodied mesoporous silicon oxide, and aperture is 3~18nm, and specific surface area is 260~670m2/g；Binding agent is by acid
It is prepared from aluminum oxide, the ratio of acid and aluminum oxide is 5%~25%；Wherein acid be nitric acid, acetic acid, phosphoric acid or citric acid,
The aperture of aluminum oxide is 3~10nm, and specific surface area is 100~300m2/g。
2. hydrogenation catalyst as claimed in claim 1, is further characterized in that：The specific surface area of catalyst carrier be 380~
573m2/ g, pore volume is 0.63~0.94cc/g, and meleic acid amount is 0.10~0.45mmol/g, and B acid and the sour ratios of L are 2.3
~0.9:1.
3. hydrogenation catalyst as claimed in claim 1, it is characterised in that：Hydrogenation catalyst outward appearance is cloverleaf pattern, cylinder
Or it is spherical.
4. a kind of preparation method of the hydrogenation catalyst described in claim 1, comprises the following steps：
(1) composite molecular screen, aluminum oxide, silica and binding agent are well mixed, are molded；In dry under 80~130 DEG C of atmosphere
Dry 3~5h, 400~600 DEG C of 3~10h of roasting；(2) dipping solution is prepared with the compound of the element containing active metal component, and it is right
Obtained carrier is impregnated, 80~130 DEG C of impregnated carrier dry 2~10h, 400~600 DEG C of 3~10h of calcining；It is special
Levy and be：The molecular sieve mother liquor being synthesized by using the molecular sieve containing Beta of composite molecular screen, is added synthesising mesoporous amorphous
Pore former required for sial, the mass ratio for keeping pore former and Beta molecular sieve solids is 0.1~0.5:1, it is sufficiently stirred for 20
Reaction system is adjusted after~50 minutes to neutrality, the sial precursor mixed solution by prehydrolysis and mixed processing, silicon is added dropwise
Al mole ratio is 45~280:1, at a temperature of 30~60 DEG C coat 1~5 hour, after aging 12 at 60~140 DEG C~
48 hours, washing separation and drying process are carried out to obtained product, product passes through 550 DEG C of high-temperature roastings 10 hours again after drying
Handle obtained multi-stage porous composite molecular screen.
5. the preparation method of hydrogenation catalyst according to claim 4, it is characterised in that：During synthesis Beta molecular sieves
The ingredient proportion of various raw materials is silica：Aluminum oxide：Sodium oxide molybdena：Template：Water=40~80：1:3~6:22~63：
1400~2100, the well mixed gel crystallization under 130~150 DEG C of high temperature can obtain point of the molecular sieve containing Beta for 3~5 days
Son sieve mother liquor.
6. a kind of application of the hydrogenation catalyst described in claim 1, it is characterised in that：Catalyst is used for diesel oil hydrogenation, wax oil
Hydrogenation and heavy oil hydrogenation process, process conditions be 330~400 DEG C of reaction temperature, 6~15MPa of stagnation pressure, hydrogen to oil volume ratio 500~
1500, volume space velocity is 0.5~2.5h-1。
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| CN106391105B (en) * | 2015-07-28 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of multi-stage porous hydrocracking catalyst and its application containing composite molecular screen |
| CN106391102B (en) * | 2015-07-28 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of multi-stage porous hydrocracking catalyst of the molecular sieve of type containing Beta and its application |
| CN106391103B (en) * | 2015-07-28 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of multi-stage porous hydrocracking catalyst of silicon-aluminum containing and its application |
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| TW201917097A (en) * | 2017-10-26 | 2019-05-01 | 大陸商中國石油化工科技開發有限公司 | Molecular sieve having mesopores, preparation method therefor, and application thereof particularly relating to a high silica-alumina ratio molecular sieve having mesopores |
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| CN111085250B (en) * | 2018-10-23 | 2022-06-28 | 中国石油化工股份有限公司 | Preparation method of metal-loaded catalyst |
| CN111085249B (en) * | 2018-10-23 | 2022-06-24 | 中国石油化工股份有限公司 | Preparation method of metal-loaded acidic material-containing catalyst |
| CN112844450A (en) * | 2021-01-25 | 2021-05-28 | 中国石油天然气股份有限公司 | Hydro-upgrading catalyst and application thereof |
| CN113000021B (en) * | 2021-02-18 | 2023-07-21 | 北京明星绿能化工科技有限公司 | Preparation and application methods of step hole molecular sieve for refining and separating phase-change wax |
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