CN107008509A - Modified form H-G hydrocracking catalyst carrier and preparation method thereof - Google Patents
Modified form H-G hydrocracking catalyst carrier and preparation method thereof Download PDFInfo
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- CN107008509A CN107008509A CN201710264312.7A CN201710264312A CN107008509A CN 107008509 A CN107008509 A CN 107008509A CN 201710264312 A CN201710264312 A CN 201710264312A CN 107008509 A CN107008509 A CN 107008509A
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- molecular sieve
- hydrocracking catalyst
- modified form
- catalyst carrier
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 74
- 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 57
- 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 34
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000001994 activation Methods 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 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 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- AUBSNUSTVUZGCC-UHFFFAOYSA-N [NH4+].[Br-].C(C)[PH3+].[Br-] Chemical compound [NH4+].[Br-].C(C)[PH3+].[Br-] AUBSNUSTVUZGCC-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000002283 diesel fuel Substances 0.000 abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 6
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009415 formwork Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 230000003319 supportive effect Effects 0.000 abstract description 2
- 239000010457 zeolite Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000000499 gel Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- 230000008859 change Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
- B01J35/633—Pore volume less than 0.5 ml/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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of modified form H-G hydrocracking catalyst carrier and preparation method thereof, support material includes following components and percentage by weight：3~35% molecular sieve, 5~75% γ Al2O3, 15~75% amorphous silica-alumina and 7~40% binding agent；The specific surface area of the carrier is 200~450m2/ g, total pore volume is 0.35~0.75cm3/g.The present invention is added during molecular sieve and alumina composite material is prepared in the molecular sieve of not Template removal, mixed liquor, and aluminium salt reacts the NH4 of generation with ammoniacal liquor+Exchanged with the alkali Na+ of balance molecule sieve skeleton frame negative electrical charge, in roasting process, by the organic formwork agent and NH in molecular sieve4 +Removing; so as to which the ammonium that zeolite molecular sieve is completed in composite material is prepared is exchanged and Template removal; without individually carrying out Template removal and ammonium exchange to molecular sieve; template has support and protective effect to molecular sieve pore passage structure; the hydrocracking catalyst prepared with this carrier can be on the premise of ensureing diesel oil in high yield; the condensation point of diesel oil distillate is significantly reduced, the Cetane number of diesel oil is improved.
Description
Technical field
The present invention relates to catalyst carrier, in particular to a kind of modified form H-G hydrocracking catalyst carrier and its preparation
Method.
Background technology
With rapid development of economy, the demand rapid growth of oil product, China is hydrocracked working ability and also obtained
Swift and violent development.Gradually become weight however as China's oil quality that processes raw material, be deteriorated, the processing capacity of sour crude increases year by year,
Environmental protection to oil refining process in itself and petroleum product-quality require it is increasingly strict, this proposes higher to hydrocracking technology level
It is required that, and catalyst plays the role of a nucleus in hydrocracking reaction, the key of hydrocracking technology be catalyst development and
Improve.
The conventional preparation method of hydrocracking catalyst mainly has infusion process, coprecipitation, kneading method etc., wherein kneading method
Preparation technology it is most simple, the requirement to technique and catalyst dispensing is not high, but because its preparation process is more extensive, catalyst
The poor dispersion of middle each component, part metals hydrogenation sites are capped, it is impossible to preferably played its activity, usually added
Hydrogen performance requirement is not that very high catalyst is used；Coprecipitation technology of preparing preparation process is the most complicated, but in catalyst
Very well, the matching relationship between each component is good for the decentralization of each component, and hydrogenation and cracking activity center are uniformly divided in the catalyst
Cloth, makes catalyst hydrogenation have higher synergy with cracking activity center；Infusion process is to prepare hydrocracking catalyst most
Extensive application method, needs to prepare shape, mechanical strength, than the load that surface and acidity etc. meet catalyst performance requirement first
Body, then carries out carried metal component, metal component is enriched in catalyst, makes catalysis by saturation or supersaturated dipping method
Agent has higher mechanical strength, gives full play to its Hydrogenation.Therefore, carrier plays vital effect to catalyst,
The mechanical function of carrier is the skeleton as active component, plays a part of divided active component, and increase the intensity of catalyst
And heat endurance, it is important that it has a significant impact to catalyst activity and selectivity.
United States Patent (USP) US4738767 discloses a kind of hydrocracking catalyst, and main acidic components are amorphous silica-aluminas, carries
The preparation method of amorphous silica-alumina used in body is that by aluminum precipitation into Silica hydrogel, this results in the specific surface area and pore volume of sial
It is all smaller, the features such as acid measures low and skewness, catalyst activity is not high.CN1351121A discloses a kind of containing modified β points
Hydrocracking catalyst of son sieve and amorphous silicon aluminium and preparation method thereof, modified beta molecular sieve is by after synthesis in this method
Molecular sieve pulp directly carries out ammonium exchange, is then calcined de- ammonium, acid treatment and hydro-thermal process and obtains modified beta molecular sieve, due to big
Amount non-framework aluminum is trapped in molecular sieve pore passage, be have impact on the acidity and its diffusion of modified molecular screen, finally be have impact on bavin
The yield and property of oil product.CN1393521A discloses a kind of middle oil type hydrocracking catalyst and preparation method thereof, catalysis
Agent used carrier is amorphous silica-alumina, aluminum oxide and Y and the complex type molecular sieve of beta-molecular sieve, and wherein composite molecular screen is by β points
After being mixed after the former powder burning-off template of son sieve with modified Y molecular sieve, then carry out ammonium exchange processing and obtain, the catalysis of the catalyst is lived
Property it is not high, the product quality of the intermediate oil of boat coal and diesel oil is general, need to further improve.However, above-mentioned be hydrocracked is urged
All be that each component is easily reunited in simple mechanical mixture, catalyst between agent carrier component it is offspring so that activity
Component dispersiveness is poor, and then the catalyst prepared is difficult to play optimum performance.
The content of the invention
Present invention aim to provide a kind of modified form H-G hydrocracking catalyst carrier and preparation method thereof, make
The hydrocracking catalyst catalytic activity prepared with the catalyst carrier is high, can be on the premise of diesel yield is ensured, it will be apparent that
The condensation point of diesel oil distillate is reduced, the Cetane number of diesel oil is improved.
To achieve the above object, the technical solution adopted by the present invention is：A kind of modified form H-G hydrocracking catalyst is carried
Body, the support material includes following components and its percentage by weight：3~35% molecular sieve, 5~75% γ-Al2O3, 15
~75% amorphous silica-alumina and 7~40% binding agent；The specific surface area of the carrier is 200~450m2/ g, total pore volume is
0.35~0.75cm3/g。
Further, the support material includes following components and its percentage by weight：3.4~7.6% molecular sieve,
27.3~47.7% γ-Al2O3, 28.3~46.9% amorphous silica-alumina and 18~20% binding agent；The ratio of the carrier
Surface area is 362~383m2/ g, total pore volume is 0.52~0.63cm3/g；The carrier is in the form of a column, and length is 3~8mm.
Further, the molecular sieve is beta-molecular sieve, Y type molecular sieve, MOR molecular sieves, ZSM-5 molecular sieve, ZSM-22 point
One or more in son sieve and ZSM-23 molecular screen.
Further, the amorphous silica-alumina pore volume is 0.5~1.0cm3/ g, specific surface area is 300~500m2/g。
Further, containing the small porous aluminum oxide that mass percent is 10~40% in the binding agent, remaining is acid；It is described
Aperture aluminum oxide pore volume is 0.3~0.5cm3/ g, specific surface area is 200~350m2/ g, the described sour and aperture aluminum oxide
Amount ratio is 0.1~0.5.
Further, the beta-molecular sieve specific surface area is 624~643m2/ g, total pore volume is 0.32~0.35cm3/g。
A kind of preparation method of above-mentioned modified form H-G hydrocracking catalyst carrier, comprises the following steps：
1) tetraethylammonium bromide solution, sodium hydroxide, silicon source and water are mixed and stirred for settled solution, then add silicon
Source, continues stirring and obtains silica-alumina gel；
2) by step 1) gained silica-alumina gel progress crystallization, then through washing and drying process, obtain molecular sieve；
3) by step 2) obtained molecular sieve adds and precipitated in the mixed solution of aluminium salt and ammoniacal liquor, taken after fully precipitating
Slurries are evaporated, dried and calcination process successively, obtain molecular sieve and alumina composite material；
4) by step 3) gained molecular sieve and alumina composite material, amorphous silica-alumina and binding agent press the material rate
Mixed, the carrier of hydrocracking catalyst can be obtained after shaping.
Further, the step 1) in, silicon source, silicon source, sodium hydroxide, tetraethylammonium bromide solution and water rub by dispensing
You compare SiO2∶Al2O3∶Na2O: tetraethylammonium bromide: H2O adds for 50~70: 1: 5~8: 15~20: 1000~1200 ratio
Enter.
Further, the step 3) in, aluminium salt is 0.5~3.0mol/L aluminium chloride, the concentration of ammoniacal liquor for 0.5~
4mol/L。
Further, the step 3) in, the pore volume of molecular sieve and alumina composite material is 0.4~0.9cm3/ g, than
Surface area is 350~500m2/g。
Further, the step 2) in, molecular sieve is beta-molecular sieve, and crystallization temperature is 135~145 DEG C；It is washed to washing
Liquid pH is 6.5~7.5；Drying temperature is 90~110 DEG C, and drying time is 22~26h.
Further, the step 3) in, in precipitation process, temperature is 60~80 DEG C, and pH is 3~7；Drying temperature is 90
~120 DEG C, drying time is 2~3 hours；Sintering temperature is 300~600 DEG C, and roasting time is 2~8 hours.
Further, the step 4) in, it is dried successively and activation process after shaping, drying temperature is 100~120
DEG C, drying time is 18~22 hours, and activation temperature is 450~600 DEG C, and soak time is 4~6 hours.
Further, the step 3) in, the concentration of ammoniacal liquor is 1.0~2.0mol/L.
Further, the step 1) in, silicon source is one kind or several in boehmite, aluminum sulfate and sodium metaaluminate
Kind；Silicon source is the one or more in white carbon, Ludox and waterglass.
Compared with prior art, the present invention has advantages below：
First, the present invention adds the molecule of not Template removal during molecular sieve and alumina composite material is prepared
In sieve, mixed liquor, aluminium salt reacts the NH4 of generation with ammoniacal liquor+Swapped with the alkali Na+ of balance molecule sieve skeleton frame negative electrical charge,
In roasting process, while by organic formwork agent and NH in molecular sieve4 +Removing, the template of removing is mainly inside filling duct
And the TEA of balance molecule sieve skeleton frame negative electrical charge+, and NH4 +Then with NH3Form be removed, obtain H- beta-molecular sieves, thus system
The ammonium that zeolite molecular sieve is completed in standby composite material is exchanged and Template removal, without individually carrying out stripper plate to molecular sieve
Agent and ammonium are exchanged, and not only simplify preparation technology, and template has support and protective effect to molecular sieve pore passage structure, from
And molecular sieve pore passage structure is difficult to be destroyed, the mechanical strength of catalyst carrier is greatly improved.
Second, molecular sieve decentralization is high in catalyst carrier of the present invention, carrier has more uniform acidic site, aluminum oxide
What is contacted with molecular sieve is even closer, is conducive to reactant and product molecule quickly turning between acid centre and cracking center
Move, Cracking Component and hydrogenation component have obtained optimization and coordinated, hydrocracking catalyst its hydrogenation activity prepared using it is with splitting
Changing activity has synergy well.
Third, the hydrocracking catalyst prepared with carrier of the present invention is to the long side chain of long chain alkane, aromatic hydrocarbons and cycloalkane
Alkyl has suitable cracking and good isomerization, its hydrogenation sites and cracking activity center matching more adduction
Reason, the hydrocracking catalyst intermediate oil prepared using it is selectively good, can high-output qulified midbarrel oil product, and urge
Change activity very high, can be on the premise of ensureing diesel oil in high yield, it will be apparent that the condensation point of reduction diesel oil distillate, improve the 16 of diesel oil
Alkane value, is suitable for handling the catalytic process for being hydrocracked production fine-quality diesel oil of vacuum distillate.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, is easy to more clearly understand the present invention,
But they do not constitute to the present invention and limited.
In following examples, specific surface area and pore volume use low temperature N2Physisorphtion is determined, silica alumina ratio useization
Method is determined, and meleic acid amount, B acid amount and L acid amounts are determined using Pyridine adsorption IR spectra method, and molecular sieve relative crystallinity is used
XRD method is determined.
The preparation of carrier of hydrocracking catalyst is carried out as follows in following examples：
Molecular sieve pulp after crystallization is directly filtered, washed, being dried, and is handled after drying without Template removal, its
SiO2/Al2O3(mol ratio) is 20~60；Aluminum salt solution and alkali precipitation agent are mixed, the molecular sieve of above-mentioned not Template removal is added
Enter in mixed solution, stir, temperature control is at 60~80 DEG C, and pH value control is 3~7, in progress under 50~90 DEG C of temperature conditionss
Precipitation is calcined by evaporation, 100 DEG C of dryings, and sintering temperature is 300~600 DEG C, and roasting time is 2~6 hours, is divided
Son sieve and alumina composite material；According to catalyst carrier mixed proportion, by molecular sieve and alumina composite material, amorphous silicon
(small porous aluminum oxide pore volume is 0.3~0.5cm in the binding agent for aluminium and binding agent3/ g, specific surface area is 200~350m2/ g, is bonded
Acid and alumina ratio are 0.1~0.5 in agent, and acid is HNO3Or H3PO4) mixed, carry out rolling 20~60 in edge runner
Minute, extrusion is into column, and carrier lengths are 3~8nm, then strip carrier is dry 10~20 hours in 100~120 DEG C, 450~
It is calcined 4~6 hours at 600 DEG C, obtains carrier of hydrocracking catalyst.
Embodiment 1
Weigh 201.3g tetraethylammonium bromides (98wt%, technical grade), 27.39g sodium hydroxides, 7.2g boehmites
(70wt%, technical grade), 870g water is mixed and stirred for settled solution, and then lower that 180g is added into solution is white being stirred continuously
Carbon black (98wt%, technical grade), and continue stirring to obtain uniform silica-alumina gel, by silica-alumina gel in 145 DEG C of dynamic crystallizations 7
My god, beta-molecular sieve is obtained after being dried through separation of solid and liquid and washing, numbering is B1, and the main character of the beta-molecular sieve is shown in Table 1.
3000ml liquor alumini chloridis (concentration is 1.5mol/L) are added in 5000ml beakers, 19g B1 molecular sieves is (dry
Base 99%) add in mixed liquor, 70 DEG C of constant temperature, 2mol/L ammoniacal liquor is continuously added until pH value is 4, in evaporation (steaming at 80 DEG C
It can be 50~90 DEG C to send out temperature), the white solid of sucking-off is calcined at being dried 3 hours, 500 DEG C at 100 DEG C and divided within 4 hours
Son sieve and alumina composite material 273.7g (butt 93%), conversion ratio is 72.5%, and numbering is C1.
By 183.7g (butt 93%) C1, amorphous silica-alumina 172.7g (butt 88%), binding agent 240g (butt 30%)
Mixed, carry out rolling 40 minutes in edge runner, rolled as toothpaste-squeezable shape, extruded moulding, support shapes are column, length
It is calcined 5~6 hours for 3~8nm, then at strip carrier is dried 20 hours, 550 DEG C in 120 DEG C, obtains catalyst carrier Z-1,
Its property is shown in Table 2.
Embodiment 2
Weigh 201.3g tetraethylammonium bromides (98wt%, technical grade), 27.39g sodium hydroxides, 7.2g boehmites
(70wt%, technical grade), 870g water is mixed and stirred for settled solution, and then lower that 180g is added into solution is white being stirred continuously
Carbon black (98wt%, technical grade), and continue stirring to obtain uniform silica-alumina gel, by silica-alumina gel in 145 DEG C of dynamic crystallizations 7
My god, beta-molecular sieve is obtained after being dried through separation of solid and liquid and washing, numbering is B1, and the main character of the beta-molecular sieve is shown in Table 1.
3000ml liquor alumini chloridis (concentration is 1.5mol/L) are added in 5000ml beakers, 28g B1 molecular sieves is (dry
Base 99%) add in mixed liquor, 70 DEG C of constant temperature, 2mol/L ammoniacal liquor is continuously added up to pH value is 4.3, in evaporation at 85 DEG C,
By the white solid of sucking-off, roasting obtains molecular sieve and alumina composite material in 4 hours at being dried 3 hours, 500 DEG C at 100 DEG C
276.2g (butt 93%), conversion ratio is 73%, and numbering is C2.
By 225.1g (butt 93%) C2, amorphous silica-alumina 126.8g (butt 88%), binding agent 240g (butt 30%)
Mixed, carry out rolling 40 minutes in edge runner, rolled as toothpaste-squeezable shape, extruded moulding, support shapes are column, length
It is calcined 5~6 hours for 3~8nm, then at strip carrier is dried 20 hours, 550 DEG C in 120 DEG C, obtains catalyst carrier Z-2,
Its property is shown in Table 2.
Embodiment 3
Weigh 185.3g tetraethylammonium bromides (98wt%, technical grade), 22.65g sodium hydroxides, 10.3g boehmites
(70wt%, technical grade), 870g water is mixed and stirred for settled solution, and then lower that 180g is added into solution is white being stirred continuously
Carbon black (technical grade), and continue stirring to obtain uniform silica-alumina gel, by silica-alumina gel in 145 DEG C of dynamic crystallizations 7 days, through solid
Liquid separation and washing obtain beta-molecular sieve after drying, and numbering is B2, and the beta-molecular sieve obtains main character and is shown in Table 1.
3000ml liquor alumini chloridis (concentration is 1.5mol/L) are added in 5000ml beakers, by 60.5g B2 molecular sieves
(butt 99%) is added in mixed liquor, 70 DEG C of constant temperature, is continuously added 2mol/L ammoniacal liquor up to pH value is 4, in evaporation at 85 DEG C,
By the white solid of sucking-off, roasting obtains molecular sieve and alumina composite material in 4 hours at being dried 3 hours, 500 DEG C at 100 DEG C
296.4g (butt 93%), conversion ratio is 78.4%, and numbering is C3.
By 145.7g (butt 93%) C3, amorphous silica-alumina 210.7g (butt 88%), binding agent 240g (butt 30%)
Mixed, carry out rolling 40 minutes in edge runner, rolled as toothpaste-squeezable shape, extruded moulding, support shapes are column, length
It is calcined 5~6 hours for 3~8nm, then at strip carrier is dried 20 hours, 550 DEG C in 120 DEG C, obtains catalyst carrier Z-3,
Its property is shown in Table 2.
Embodiment 4
Weigh 185.3g tetraethylammonium bromides (98wt%, technical grade), 22.65g sodium hydroxides, 10.3g boehmites
(70wt%, technical grade), 870g water is mixed and stirred for settled solution, and then lower that 180g is added into solution is white being stirred continuously
Carbon black (technical grade), and continue stirring to obtain uniform silica-alumina gel, by silica-alumina gel in 145 DEG C of dynamic crystallizations 7 days, through solid
Liquid separation and washing obtain beta-molecular sieve after drying, and numbering is B2, and the beta-molecular sieve obtains main character and is shown in Table 1.
3000ml liquor alumini chloridis (concentration is 1.5mol/L) are added in 5000ml beakers, by 34.3g B2 molecular sieves
(butt 99%) is added in mixed liquor, 70 DEG C of constant temperature, is continuously added 2mol/L ammoniacal liquor until pH value is 4.8, in steaming at 85 DEG C
Hair, by the white solid of sucking-off, roasting obtains molecular sieve and alumina composite in 4 hours at being dried 3 hours, 500 DEG C at 100 DEG C
Material 285.3g (butt 93%), conversion ratio is 75.6%, and numbering is C4.
By 196.4g (butt 93%) C4, amorphous silica-alumina 159.6g (butt 88%), binding agent 240g (butt 30%)
Mixed, carry out rolling 40 minutes in edge runner, rolled as toothpaste-squeezable shape, extruded moulding, support shapes are column, length
It is calcined 5~6 hours for 3~8nm, then at strip carrier is dried 20 hours, 550 DEG C in 120 DEG C, obtains catalyst carrier Z-4,
Its property is shown in Table 2.
Embodiment 3 and the gained catalyst carrier of embodiment 4 carry out load hydrogenation metal using the method for supersaturation dipping, plus
Hydrogen metal uses tungsten-nickel system, and the catalyst numbering of preparation is respectively CZ-3, CZ-4, and its property is shown in Table 2.
The catalyst CZ-3 and CZ-4 that are prepared to embodiment 3 and the resulting vehicle of embodiment 4 catalytic activity add in fixed bed
Evaluated on hydrogen experimental provision, appreciation condition is：Reaction stagnation pressure is 10MPa, and hydrogen to oil volume ratio is 1000, volume space velocity
1.0h-1, the use of vacuum distillate (VGO) is feedstock oil, the raw material oil nature is shown in Table 3.By catalyst CZ-3, CZ-4 in identical
Evaluated under process conditions, evaluation result is shown in Table 4.As can be seen from Table 4, under identical process conditions, the present invention
Catalyst intermediate oil prepared by carrier is selectively good, it is ensured that on the premise of diesel yield, it will be apparent that reduction diesel oil distillate
Condensation point, improves the Cetane number of diesel oil.
Table 1
| Molecular sieve | B1 | B2 |
| Silica alumina ratio (Si/Al) | 31.5 | 22.6 |
| Relative crystallinity, % | 96 | 105 |
| Than surface, m2/g | 624 | 643 |
| Total pore volume, ml/g | 0.32 | 0.35 |
| Meleic acid amount, mmol/g | 0.29 | 0.31 |
| B acid/L acid | 0.56 | 0.48 |
Table 2
Table 3
| Feedstock oil | Vacuum distillate |
| Density (20 DEG C), kg/m3 | 912.3 |
| Boiling range, DEG C | |
| IBP/10% | 315/403 |
| 30%/50% | 442/461 |
| 70%/90% | 495/526 |
| 95%/EBP | 532/544 |
| Condensation point, DEG C | 32 |
| Nitrogen, μ g/g | 1568 |
| Carbon, wt% | 84.53 |
| Hydrogen, wt% | 11.72 |
| Carbon residue, wt% | 0.32 |
| BMCI values | 43 |
Table 4
Claims (15)
1. a kind of modified form H-G hydrocracking catalyst carrier, it is characterised in that：The support material include following components and
Its percentage by weight：3~35% molecular sieve, 5~75% γ-Al2O3, 15~75% amorphous silica-alumina and 7~40%
Binding agent；The specific surface area of the carrier is 200~450m2/ g, total pore volume is 0.35~0.75cm3/g。
2. modified form H-G hydrocracking catalyst carrier according to claim 1, it is characterised in that：The support material bag
Include following components and its percentage by weight：3.4~7.6% molecular sieve, 27.3~47.7% γ-Al2O3, 28.3~
46.9% amorphous silica-alumina and 18~20% binding agent；The specific surface area of the carrier is 362~383m2/ g, total pore volume
For 0.52~0.63cm3/g；The carrier is in the form of a column, and length is 3~8mm.
3. modified form H-G hydrocracking catalyst carrier according to claim 1, it is characterised in that：The molecular sieve is β
Molecular sieve, Y type molecular sieve, MOR molecular sieves, ZSM-5 molecular sieve, ZSM-22 molecular sieves and one kind or several in ZSM-23 molecular screen
Kind.
4. the modified form H-G hydrocracking catalyst carrier according to claim 1 or 2 or 3, it is characterised in that：The nothing is determined
Shape sial pore volume is 0.5~1.0cm3/ g, specific surface area is 300~500m2/g。
5. the modified form H-G hydrocracking catalyst carrier according to claim 1 or 2 or 3, it is characterised in that：The bonding
Containing the small porous aluminum oxide that mass percent is 10~40% in agent, remaining is acid；The aperture aluminum oxide pore volume be 0.3~
0.5cm3/ g, specific surface area is 200~350m2/ g, the described sour and aperture quality of alumina ratio is 0.1~0.5.
6. modified form H-G hydrocracking catalyst carrier according to claim 3, it is characterised in that：The beta-molecular sieve ratio
Surface area is 624~643m2/ g, total pore volume is 0.32~0.35cm3/g。
7. the preparation method of modified form H-G hydrocracking catalyst carrier described in a kind of claim 1, it is characterised in that：Including
Following steps：
1) tetraethylammonium bromide solution, sodium hydroxide, silicon source and water are mixed and stirred for settled solution, then add silicon source,
Continue stirring and obtain silica-alumina gel；
2) by step 1) gained silica-alumina gel progress crystallization, then through washing and drying process, obtain molecular sieve；
3) by step 2) obtained molecular sieve added and precipitated in the mixed solution of aluminium salt and ammoniacal liquor, and slurries are taken after fully precipitating
It is evaporated, dries and calcination process successively, obtains molecular sieve and alumina composite material；
4) by step 3) gained molecular sieve and alumina composite material, amorphous silica-alumina and binding agent be by material rate progress
Mixing, can obtain the carrier of hydrocracking catalyst after shaping.
8. the preparation method of modified form H-G hydrocracking catalyst carrier according to claim 7, it is characterised in that：It is described
Step 1) in, silicon source, silicon source, sodium hydroxide, tetraethylammonium bromide solution and water press dispensing mol ratio SiO2∶Al2O3∶Na2O: four
Ethyl phosphonium bromide ammonium: H2O adds for 50~70: 1: 5~8: 15~20: 1000~1200 ratio.
9. the preparation method of modified form H-G hydrocracking catalyst carrier according to claim 7, it is characterised in that：It is described
Step 3) in, aluminium salt is 0.5~3.0mol/L aluminium chloride, and the concentration of ammoniacal liquor is 0.5~4mol/L.
10. the preparation method of modified form H-G hydrocracking catalyst carrier according to claim 7 or 8 or 9, its feature exists
In：The step 3) in, the pore volume of molecular sieve and alumina composite material is 0.4~0.9cm3/ g, specific surface area be 350~
500m2/g。
11. the preparation method of modified form H-G hydrocracking catalyst carrier according to claim 7 or 8 or 9, its feature exists
In：The step 2) in, molecular sieve is beta-molecular sieve, and crystallization temperature is 135~145 DEG C；Be washed to cleaning solution pH for 6.5~
7.5；Drying temperature is 90~110 DEG C, and drying time is 22~26h.
12. the preparation method of modified form H-G hydrocracking catalyst carrier according to claim 7 or 8 or 9, its feature exists
In：The step 3) in, in precipitation process, temperature is 60~80 DEG C, and pH is 3~7；Drying temperature is 90~120 DEG C, when drying
Between be 2~3 hours；Sintering temperature is 300~600 DEG C, and roasting time is 2~8 hours.
13. the preparation method of modified form H-G hydrocracking catalyst carrier according to claim 7 or 8 or 9, its feature exists
In：The step 4) in, it is dried successively and activation process after shaping, drying temperature is 100~120 DEG C, and drying time is
18~22 hours, activation temperature was 450~600 DEG C, and soak time is 4~6 hours.
14. the preparation method of modified form H-G hydrocracking catalyst carrier according to claim 7 or 8 or 9, its feature exists
In：The step 3) in, the concentration of ammoniacal liquor is 1.0~2.0mol/L.
15. the preparation method of modified form H-G hydrocracking catalyst carrier according to claim 7 or 8 or 9, its feature exists
In：The step 1) in, silicon source is the one or more in boehmite, aluminum sulfate and sodium metaaluminate；Silicon source be white carbon,
One or more in Ludox and waterglass.
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| WO2018192517A1 (en) * | 2017-04-21 | 2018-10-25 | 武汉凯迪工程技术研究总院有限公司 | Improved diesel hydrocracking catalyst and method for preparing same |
| WO2018192516A1 (en) * | 2017-04-21 | 2018-10-25 | 武汉凯迪工程技术研究总院有限公司 | Improved diesel hydrocracking catalyst carrier and method for preparing same |
| RU2732243C1 (en) * | 2020-03-19 | 2020-09-14 | Акционерное общество «Газпромнефть - Омский НПЗ» (АО «Газпромнефть - ОНПЗ») | Method of preparing a diesel fuel hydrofining catalyst |
| RU2738080C1 (en) * | 2020-03-19 | 2020-12-07 | Акционерное общество «Газпромнефть - Омский НПЗ» (АО «Газпромнефть - ОНПЗ») | Hydrotreating catalyst support |
| RU2738076C1 (en) * | 2020-03-19 | 2020-12-07 | Акционерное общество «Газпромнефть - Омский НПЗ» (АО «Газпромнефть - ОНПЗ») | Method of preparing support for hydrotreating catalyst |
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| CN116020527B (en) * | 2021-10-25 | 2024-07-02 | 中国石油化工股份有限公司 | Pretreatment method of hydrocracking catalyst |
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