CN114453011B - Preparation method of hydrocracking catalyst, hydrocracking catalyst and application - Google Patents
Preparation method of hydrocracking catalyst, hydrocracking catalyst and application Download PDFInfo
- Publication number
- CN114453011B CN114453011B CN202011133043.9A CN202011133043A CN114453011B CN 114453011 B CN114453011 B CN 114453011B CN 202011133043 A CN202011133043 A CN 202011133043A CN 114453011 B CN114453011 B CN 114453011B
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- Prior art keywords
- molecular sieve
- beta
- sba
- hydrocracking catalyst
- catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000002808 molecular sieve Substances 0.000 claims abstract description 115
- 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 115
- 239000002131 composite material Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 58
- 238000001035 drying Methods 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011280 coal tar Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 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 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 8
- 238000004898 kneading Methods 0.000 claims abstract description 5
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- 238000002425 crystallisation Methods 0.000 claims description 45
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 37
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- 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 4
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 24
- 229910052911 sodium silicate Inorganic materials 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011294 coal tar pitch Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 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 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
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- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
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- 239000003292 glue Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of a hydrocracking catalyst, the hydrocracking catalyst and application. The preparation method of the hydrocracking catalyst comprises the following steps: (i) preparing a Beta/Al-SBA-15 composite molecular sieve; (ii) Kneading and molding the Beta/Al-SBA-15 composite molecular sieve, the Y molecular sieve and the alumina prepared in the step (i) to obtain a carrier precursor; (iii) Impregnating the carrier precursor obtained in the step (ii) with nano silicon dioxide dispersion liquid, and drying to obtain a hydrocracking catalyst carrier; (iv) And (3) impregnating the carrier obtained in the step (iii) with a solution containing an active metal component, and drying and roasting to obtain the hydrocracking catalyst. The hydrocracking catalyst prepared by the method is used for hydrocracking coal tar, and the cetane number and the condensation point of diesel oil can be improved to a great extent.
Description
Technical Field
The invention relates to a preparation method of a hydrocracking catalyst, in particular to a preparation method of a hydrocracking catalyst suitable for converting coal tar distillate into clean gasoline and diesel oil.
Background
Coal tar is an important byproduct in the pyrolysis and carbonization process of coal, black or blackish brown viscous liquid with pungent odor is a complex mixture of high-aromaticity hydrocarbon, and the coal tar can be divided into low-temperature coal tar and high-temperature coal tar according to different pyrolysis and carbonization temperatures and different process methods of coal. The coal tar raw material has the characteristics of high content of sulfur, nitrogen and other heteroatoms, high ash content, high content of polycyclic aromatic hydrocarbon, high content of colloid and asphaltene and the like.
The coal tar hydrogenation is carried out under high temperature and high pressure, the molecular structure of the coal tar is changed under the action of a catalyst, and heteroatoms such as S, N, O are removed, so that the effects of cleaning and lightening are achieved, and distillate fuels such as gasoline, diesel oil and kerosene are obtained. The method can not only improve the utilization rate of the non-renewable resources such as coal and reduce the resource waste, but also provide beneficial supplement for petroleum with shortage supply. The coal tar contains a large amount of aromatic compounds, the nitrogen content (0.45% -1.30%) and the sulfur content (0.29% -0.40%) of the coal tar are high, and a large amount of SO is generated when the coal tar is directly combusted X And NO X Does not meet the exhaust emission standard, and causes serious environmental pollution.
The main purpose of hydro-upgrading is to further change the molecular structure of each component in the coal tar, so that the product performance is fully improved. Compared with distillate oil hydrogenation, the coal tar has four high characteristics: high oxygen content; the content of colloid and carbon residue is high; high sulfur and nitrogen content; the content of aromatic hydrocarbon is high, and the developed hydrogenation catalyst has the characteristic of meeting the requirement of being suitable for coal tar refining.
CN101885984a discloses a combined process for producing clean fuel oil by hydrogenating coal tar and a catalyst thereof. The active components of the hydro-upgrading catalyst in the patent are metal oxides NiO and MoO of the VIII group and the VIB group 3 、CoO、WO 3 The carrier is acid modified kaolin. Because the acid modified kaolin is used as a carrier, the pore volume is small and the acidity is higher, and therefore, for coal tar raw materials with higher colloid and asphaltene contents, colloid and asphaltene cannot enter into a pore canal of a catalyst, and more carbon deposit is formed on the surface of the catalyst, so that the catalyst is easy to deactivate, and the operation period is short.
CN102029157a discloses a catalyst for coal tar pitch hydrocracking and lightening reaction, which is prepared by taking inorganic porous material as a carrier, selecting one of alumina, silica gel containing alumina, MCM-41 or SBA-15, loading one or two of metal elements Fe, ni, co, mo of active components on the carrier in the form of metal oxide or metal sulfide by a vacuum impregnation method, drying under nitrogen protection at normal pressure, and roasting. The catalyst prepared by the method has poor activity, more reaction coking, shorter service life, low yield of the cracked light oil and further needs to be improved in the conversion rate of the coal tar pitch.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a hydrocracking catalyst applicable to coal tar and a preparation method thereof. The hydrocracking catalyst prepared by the method is used for hydrocracking coal tar, and the cetane number and the condensation point of diesel oil can be improved to a great extent.
The first aspect of the invention provides a method for preparing a hydrocracking catalyst, which comprises the following steps:
(i) Preparing a Beta/Al-SBA-15 composite molecular sieve;
(ii) Kneading and molding the Beta/Al-SBA-15 composite molecular sieve, the Y molecular sieve and the alumina prepared in the step (i) to obtain a carrier precursor;
(iii) Impregnating the carrier precursor obtained in the step (ii) with nano silicon dioxide dispersion liquid, and drying to obtain a hydrocracking catalyst carrier;
(iv) And (3) impregnating the carrier obtained in the step (iii) with a solution containing an active metal component, and drying and roasting to obtain the hydrocracking catalyst.
Further, the medium strong acid content of the Beta/Al-SBA-15 composite molecular sieve is 0.6-1.2 mL/g, preferably 0.7-1.0 mL/g; the ratio of B acid to L acid is less than 0.80, preferably less than 0.75, more preferably less than 0.50, still more preferably more than 0.22, and may be specifically 0.25, 0.30, 0.35 or 0.40.
Further, in the Beta/Al-SBA-15 composite molecular sieve, the mass content of the alumina is 2% -85%, preferably 5% -82%, and more preferably 7.3% -77.5%. The mass content of the alumina of the Beta/Al-SBA-15 composite molecular sieve can be adjusted within a wide range, for example, 10.3%,15.5%,16.5%,18.6%,20.4%,25.5%,30.5%,32.5%,35.5%,40.5%,45.2%,50.5%,55.3%,60.5%,73.5%,77.5% and the like.
In the Beta/Al-SBA-15 composite molecular sieve, the mass content of the Beta molecular sieve is 10% -90%, preferably 25% -85%.
Further, in the Beta/Al-SBA-15 composite molecular sieve, the mass content of alumina in the Al-SBA-15 molecular sieve is as follows: 5% -75%. The mass content of the alumina in the Al-SBA-15 molecular sieve can be adjusted in a wide range, for example, 8%,10%,15%,18.3%, 25.0%, 28.5%, 33.1%, 54.5%, 65.5% and the like.
Further, the Beta/Al-SBA-15 composite molecular sieve has the following properties: siO (SiO) 2 /Al 2 O 3 The molar ratio is 25-150, the specific surface area is 500-950 m 2 Preferably 650-850 m 2 Per g, the total pore volume is 0.4-1.1 mL/g, preferably 0.48-0.85 mL/g.
The Beta/Al-SBA-15 composite molecular sieve has the following pore distribution: the pore volume occupied by the pores with the pore diameter of 4-15 nm is 42-72%, preferably 45-65%, and more preferably 55-65% of the total pore volume.
Further, the preparation method of the Beta/Al-SBA-15 composite molecular sieve comprises the following steps: the preparation method comprises the steps of taking amorphous silica-alumina dry gel as a raw material, adopting a P123 triblock copolymer as a template agent to perform first crystallization to synthesize an Al-SBA-15 molecular sieve, adding Beta molecular sieve slurry, and performing second crystallization to obtain the Beta/Al-SBA-15 composite molecular sieve.
Further, the amorphous silica alumina dry gel has the following properties: the specific surface area is 400-650 m 2 Preferably 450 to 600m 2 Per gram, pore volume of 0.52-1.8 ml/g, preferably 0.85-1.5 ml/g; pore volume with the pore diameter of 4-15 nm accounts for 85% -95% of the total pore volume, and pore volume with the diameter of more than 15nm accounts for less than 5% of the total pore volume.
Further, in the amorphous silica alumina dry gel, the mass content of the alumina is 2-85%. The mass content of alumina may be adjusted within a wide range, for example, 5%,10%,15%,16%,18%,20%,25%,30%,32%,35%,40%,45%,50%,55%,60%,70%,75%, etc.
Further, the specific preparation method of the Beta/Al-SBA-15 composite molecular sieve comprises the following steps:
(1) Mixing amorphous silica-alumina and deionized water, and pulping to form slurry;
(2) Preparing an acidic aqueous solution containing a P123 triblock copolymer;
(3) Mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), adding Beta molecular sieve slurry after first crystallization, and preparing the Beta/Al-SBA-15 composite molecular sieve after second crystallization.
Further, the Beta molecular sieve slurry can be prepared by pulping Beta molecular sieve with water, or can be crystallized Beta molecular sieve slurry, and the mass content of the Beta molecular sieve in the slurry is 20% -40%.
According to the method, the amorphous silicon aluminum in the step (1) is prepared by a carbonization method, and the amorphous silicon aluminum can be prepared by the following steps:
a. preparing sodium aluminate solution and sodium silicate solution respectively;
b. adding part or all of the sodium silicate solution into the sodium aluminate solution, and then introducing CO 2 Controlling the reaction temperature to be 10-40 ℃, preferably 15-35 ℃ and controlling the pH value of the prepared glue to be 8-11; wherein when CO is introduced 2 When the gas amount accounts for 40% -100% of the total inlet amount, preferably 50% -80%, adding the residual sodium silicate solution;
c. the mixture is ventilated and stabilized for 10 to 30 minutes under the control of the temperature and the pH value in the step b;
d. filtering the solid-liquid mixture obtained in the step c, and washing a filter cake;
e. Pulping the filter cake obtained in the step d, performing thermal cracking on the filter cake by water, filtering and drying to obtain the amorphous silica-alumina dry gel; the thermal cracking conditions of the water are as follows: cracking for 2-10 hours at 120-150 ℃ and 0.5-4.0 MPa water vapor pressure.
Further, in step a, the concentration of the sodium aluminate solution is 15 to 55gAl 2 O 3 The ratio of (C/L) may be 15-35 g Al 2 O 3 The concentration of the sodium silicate solution is 50-200 g SiO 2 The ratio of the component (A) to (L) may be 50 to 150g SiO 2 /L。
Further, part or all of the sodium silicate solution is added in the step b, namely 5-100 wt% of the total sodium silicate solution is added. The CO 2 The concentration of the gas is 30-60 v%. And (c) ventilating and stirring in the gelling process in the step b.
Further, the specific process of step b is the following cases: (1) Adding all sodium silicate into sodium aluminate, introducing CO 2 A gas; (2) After adding part of sodium silicate into sodium aluminate, introducing all CO 2 Gas, then adding the remaining sodium silicate solution to the mixture; (3) After adding part of sodium silicate into sodium aluminate, introducing part of CO 2 Gas, CO is introduced at the same time 2 The remaining sodium silicate solution was added while the gas was in.
Further, the slurry obtained in the step d is filtered and washed by deionized water with the temperature of 50-95 ℃ until the slurry is nearly neutral,
Further, the filter cake obtained in the step e is prepared according to a solid-liquid volume ratio of 8:1 to 12:1, adding water and pulping.
Further, the drying in step e may be performed by a conventional method, and may be performed at 110 to 130℃for 6 to 8 hours.
Further, the mass ratio of the amorphous silica alumina dry gel to water in the step (1) is 10: 90-30: 70, preferably 12: 88-25: 75.
further, the pH of the acidic aqueous solution in the step (2) is 1 to 5, preferably 1.2 to 2.3, and the mass content of the P123 triblock copolymer in the acidic aqueous solution is 0.5 to 5.0%, preferably 0.8 to 2.8%.
Further, in step (2), the P123 triblock copolymer is added to a dilute acid (such as dilute hydrochloric acid) at a concentration of H + 0.05 to 0.3mol/L, preferably 0.1 to 0.2 mol/L, more preferably 0.13 to 0.18 mol/L; in order to sufficiently dissolve the P123 triblock copolymer, the temperature system is controlled to 10 to 60 ℃, preferably 20 to 40 ℃, and more preferably 25 to 35 ℃.
Further, in the step (3), the slurry prepared in the step (1) is mixed with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), and the mass ratio of the P123 triblock copolymer to the amorphous silica alumina in the mixed system is 0.5:1 to 5:1, preferably 1:1 to 5:1, and more preferably 1:1 to 3:1.
Further, the conditions of the first crystallization in the step (3) are: the crystallization temperature is 80-120 ℃, preferably 90-110 ℃; the crystallization time is 10-35 h, preferably 16-24 h; the pH is controlled to be 2.0-5.0, preferably 3.2-4.8 during crystallization.
Further, the second crystallization condition in the step (3) is: the crystallization temperature is 80-130 ℃, preferably 90-120 ℃; the crystallization time is 4-20 h, preferably 10-15 h; the pH is controlled to be 2.0-5.0, preferably 4.2-5.0 during crystallization.
Further, after the crystallization step of step (3), the Beta/Al-SBA-15 composite molecular sieve may be separated from the obtained mixture by any conventionally known means, such as filtration, washing, drying, etc. The filtering can be suction filtration. The washing can be performed by adopting deionized water as a washing liquid. The drying may be at 80 to 150 ℃, preferably 90 to 130 ℃, and the drying time is 2 to 12 hours, preferably 3 to 6 hours. The drying may be performed at normal pressure.
Further, the composite molecular sieve prepared by the method can be roasted according to the requirement, so as to remove the template agent, water possibly existing and the like. The calcination may be carried out in any manner conventionally known in the art, the calcination temperature being controlled at 450 to 600 ℃, preferably 480 to 580 ℃, further preferably 500 to 560 ℃, and the calcination time being 2 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is typically performed under an oxygen-containing atmosphere, such as air or an oxygen atmosphere.
Further, the properties of the Y-type molecular sieve used in step (ii) are as follows: siO (SiO) 2 /Al 2 O 3 The molar ratio is 25-150, the specific surface area is 550-1000 m 2 And/g, wherein the total pore volume is 0.30-0.60 mL/g.
Further, the properties of the alumina in step (ii) are as follows: the specific surface area is 150-450 m 2 Preferably 230 to 340m 2 /g; the pore volume is 0.4-1.4 mL/g, preferably 0.8-1.2 mL/g, and the average pore diameter is 8-14 nm.
Further, the shaping in step (ii) may be performed by a method conventional in the art, such as extrusion molding, etc. Conventional molding aids, such as at least one of extrusion aids, peptizing acids, binders, and the like, may be added during the molding process. The peptizing acid may be at least one of citric acid and nitric acid, preferably citric acid and nitric acid. The binder may be a small pore alumina. The extrusion aid can be sesbania powder and the like. After forming, it is generally necessary to carry out a drying and firing process. The drying and roasting can be carried out by adopting a conventional method, the drying condition can be 80-150 ℃, the drying time is 2-12 h, the roasting condition can be 450-650 ℃, and the roasting time is 2-10 h.
Further, in the step (iii), the mass concentration of the nano silica dispersion liquid in the impregnation liquid is 20% -50%, preferably 25% -35%.
Further, the dispersion liquid containing nano-silica can be commercially available nano-silica dispersion liquid, and the particle size of the nano-silica is 10-20 nanometers.
Further, in step (iii), the impregnation may be carried out by conventional impregnation means in the art, such as isovolumetric impregnation, overdose impregnation, stepwise impregnation, co-impregnation, etc., preferably isovolumetric co-impregnation.
Further, in step (iii), the drying conditions are: the drying temperature is 60-150 ℃, preferably 80-120 ℃. The drying may be performed in an oxygen-containing atmosphere, and the oxygen concentration is not particularly limited, such as an air atmosphere or the like, or may be performed in an inert atmosphere, such as a nitrogen atmosphere or the like.
Further, in the step (iii), based on the weight of the hydrocracking catalyst carrier, the weight content of the Beta/Al-SBA-15 composite molecular sieve is 2% -20%, preferably 3% -18%, the weight content of the Y molecular sieve is 2% -15%, preferably 5% -12%, the weight content of the alumina is 65% -95%, preferably 75% -90%, and the content of the nano silica is 0.1% -20%, preferably 0.5% -18.0%, and more preferably 2% -15%.
Further, in the step (iii), the molar ratio of the hydroxyl group density on the surface of the hydrocracking catalyst carrier is 1.5-2.5, preferably 1.8-2.2.
Further, the impregnation in step (iv) may be carried out by methods conventional in the art, such as isovolumetric impregnation, supersaturation impregnation, stepwise impregnation, co-impregnation, etc., preferably isovolumetric co-impregnation.
Further, the drying conditions of step (iv) are as follows: the drying temperature is 60-220 ℃, preferably 90-180 ℃, and the drying time is 0.5-10 h, preferably 1-5 h. The roasting conditions are as follows: the roasting temperature is 350-500 ℃, preferably 380-480 ℃, and the roasting time is 0.5-10 h, preferably 1-5 h.
Further, the active metal component in step (iv) is a group viii and group vib metal, preferably Co and/or Ni, and the group vib metal is preferably W and/or Mo.
Further, the group VIII metal is present in an amount of from 1 to 15wt%, preferably from 4 to 10wt%, calculated as oxide, based on the weight of the catalyst; the content of the VI B metal in terms of oxide is 9-30wt%, preferably 15-28wt%, and the content of the hydrocracking catalyst carrier is 60-80wt%, preferably 65-75wt%.
In a second aspect the present invention provides a hydrocracking catalyst prepared by the process of the first aspect.
The hydrocracking catalyst has the following properties: the specific surface area is 120-350 m 2 Preferably 150 to 330 m per gram 2 The pore volume is 0.20 to 0.60mL/g, preferably 0.2 to 0.55mL/g.
The third aspect of the invention provides an application of the hydrocracking catalyst prepared by the method.
Further, the application is that the hydrocracking catalyst is applied to a coal tar distillate hydrocracking process, and is used for a hydrocracking method for converting coal tar into clean gasoline and diesel oil.
Further, the reaction conditions of the hydrocracking catalyst applied to the hydrocracking of the coal tar distillate are as follows: the total reaction pressure is 3.0-18.0 MPa, and the liquid hourly space velocity is 0.2h -1 ~4.0h -1 The volume ratio of hydrogen to oil is 200:1-2000:1, and the reaction temperature is 230-430 ℃.
Further, the properties of the coal tar are as follows: the density (20 ℃) is 1000kg/m 3 ~1200 kg/m 3 The nitrogen content is 0.8-1.5 wt%, the sulfur content is 0.2-0.8 wt%, and the aromatic component and colloid content are high.
Compared with the prior art, the hydrocracking catalyst carrier, the hydrocracking catalyst and the preparation method thereof have the following advantages:
(1) In the method, the Beta/Al-SBA-15 composite molecular sieve adopts amorphous silica-alumina dry gel as a raw material, al is synchronously and directly introduced into a framework in a form of Si-O-Al bond, and the Al is uniformly distributed, so that the agglomeration of Al on the surface of the molecular sieve is avoided, and the pore canal is smooth, thereby being beneficial to the reaction; the Beta/Al-SBA-15 composite molecular sieve synthesized by the method reacts in a weak acid environment, so that the framework structure damage of the Beta molecular sieve under the condition of long-time exposure to an acidic solution is avoided, the Beta/Al-SBA-15 composite molecular sieve has proper acid property and pore structure characteristics, and is matched with a specific Y molecular sieve, and the Beta/Al-SBA-15 composite molecular sieve is particularly suitable for being used in the hydrocracking process of coal tar fractions.
(2) The Beta/Al-SBA-15 composite molecular sieve still shows the regularity of mesoporous structure even under the condition of very high aluminum content, and the regularity can be characterized by the pore distribution (especially the pore volume ratio of the pores with the diameter of less than 4 nm) of the molecular sieve. As a surmise, according to the Beta/Al-SBA-15 composite molecular sieve, even if the mass percentage content of alumina in the chemical composition of the molecular sieve is widely changed from 2% to 85%, the pore volume occupied by pores with the diameters of 4-15 is still 42% -72%, and the integrity and regularity of a mesoporous structure are maintained, which are not possessed by the Beta/Al-SBA-15 composite molecular sieve manufactured by the prior art, so that the pore channel structure of the catalyst carrier can migrate towards the mesoporous direction after the Beta/Al-SBA-15 micro-mesoporous composite molecular sieve is added, and the macromolecular reaction in the coal tar fraction is benefited.
(3) In the method, the nano silicon dioxide dispersion liquid is used for modifying the carrier, and a large number of unsaturated bonds and hydroxyl groups in different bonding states exist on the surface of the nano silicon dioxide and are loaded on specific positions on the surface of the carrier, so that the hydroxyl density on the surface of the catalyst carrier is obviously increased, and the high dispersion of active components is facilitated; the slightly alkaline nano silicon dioxide dispersion liquid can adjust the acid amount on the surface of the carrier, so that the acid amount of the medium strong acid of the carrier is increased, the strong acid is reduced, the hydrogenation function and the acid function are more reasonably matched, the diesel oil yield is improved, and the product performance is improved.
(4) The catalyst prepared by the invention is used in the hydrocracking process of coal tar distillate, the yield of diesel oil is increased, the quality is obviously improved, especially the cetane number and the condensation point of the diesel oil are improved at the same time, and the requirements of different conditions can be met.
(5) The invention can also reduce the ammonia nitrogen wastewater discharge and the hydrochloric acid consumption in the existing preparation process of the industrial production composite molecular sieve, shorten the process flow and reduce the production cost.
Drawings
FIG. 1 is an XRD pattern of an Al-SBA-15 molecular sieve obtained in comparative example 4 of the present invention.
Detailed Description
In the present invention, al-SBA-15 molecular sieve means that aluminum atoms are introduced into SBA-15 molecular sieve, and the existence state of aluminum atoms in SBA-15 molecular sieve is not particularly limited, and part of aluminum atoms are generally distributed on the framework of SBA-15 molecular sieve.
In the invention, the determination of the L acid or the B acid is carried out by adopting an infrared spectrometry, an instrument is a Nicot Fourier infrared spectrometer-6700 in the United states, and the determination method is as follows: weighing 20mg of sample with granularity smaller than 200 meshes, pressing into sheet with diameter of 20mm, placing on sample rack of absorption cell, placing 200mg of sample into instrument suspension cup, connecting absorption cell and adsorption tube, vacuum-pumping and cracking to vacuum degree of 4×10 -2 In the case of Pa, the pressure of the gas,heating to 500 ℃ for 1 hour to remove adsorbate on the surface of a sample, cooling to room temperature, adsorbing pyridine to saturation, continuously heating to 160 ℃ for balancing for 1 hour, and desorbing physically adsorbed pyridine to obtain the acid amounts of infrared total acid, B acid and L acid, wherein the acid amounts of the B acid and the L acid are in mmol/L.
In the invention, the medium strong acid amount is NH 3 The TPD method is used, and the instrument is an Auto-Chem II 2920 type chemical adsorption instrument of microphone instrument company. Ammonia is used as an adsorption and desorption medium, helium is used as carrier gas, and the temperature programming desorption and chromatographic analysis are adopted to obtain the acid quantity of different desorption temperature areas, wherein the ammonia desorption temperature corresponding to the acid quantity of the medium strong acid is 250-400 ℃, and the acid quantity unit is as follows: mL/g is the amount of ammonia adsorbed per gram of molecular sieve.
In the invention, the specific surface area, pore volume and pore distribution are measured by adopting an ASAP2405 physical adsorption instrument, and the measuring method comprises the following steps: after the sample is cracked, liquid N 2 As an adsorbate, the adsorption temperature was-196 ℃ and analytical tests were performed. Wherein the specific surface area is calculated by BET method, and the pore volume and pore distribution are calculated by BJH method.
The method for measuring the density of the surface hydroxyl groups of the catalyst carrier comprises the following steps: first, 0.5g of a sample of the catalyst support was weighed and ground to a particle size of less than 1 micron for use. Weighing 10mg of sample, tabletting, placing the sample in an in-situ cell of an in-situ infrared spectrometer, and vacuum-measuring at 10 -3 And heating the sample in the in-situ cell under the condition of Pa, wherein the heating rate is 10 ℃/min, heating to 500 ℃, keeping the temperature for 2 hours, and then cooling to room temperature under the vacuum condition. Collecting spectrum by using an in-situ infrared spectrometer, wherein the peak position of the peak of the surface hydroxyl of the sample is 3600-3850 cm -1 The catalyst prepared by the invention and SB powder (pore volume is 0.5 mL/g) imported from Germany are respectively measured for the area of the surface hydroxyl group peak under the same condition, and the ratio of the peak areas of the two figures is the molar ratio of the surface hydroxyl group density of the two samples.
In the present invention, XRD was measured by using a D/max2500 type X-ray diffractometer manufactured by Japanese national institute of technology, under the following test conditions: the voltage is 40KV, the current is 80mA, a CuK alpha target is selected, and the incident wavelength is 0.15405 nm.
The following examples and comparative examples further illustrate the operation and effect of the technical scheme of the present invention, but the present invention should not be construed as being limited to the specific examples, and the following examples and comparative examples of the present invention are given by mass percent unless otherwise specified.
Example 1
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica-alumina dry gel powder A1 and slurry: concentration of sodium aluminate solution 15gAl 2 O 3 Concentration of sodium silicate solution 82SiO 2 Adding 0.85L sodium aluminate solution into a colloid forming tank, adding 0.30L sodium silicate solution, controlling the reaction temperature to 20 ℃, and introducing CO with concentration of 35v% 2 Gas is introduced into CO 2 When the gas accounts for 65% of the total inlet amount, 0.30L sodium silicate solution is added while ventilation is carried out, the pH value of the gel is controlled to be 9.5, then ventilation is stabilized for 20 minutes, slurry is filtered and washed to be neutral by deionized water at 65 ℃, water is added into a filter cake according to the solid-liquid volume ratio of 10:1 for pulping, cracking is carried out for 3 hours under the water vapor pressure of 3.5MPa at 130 ℃, after drying is carried out for 6 hours at 120 ℃, the amorphous silicon aluminum product A1 is obtained by crushing and sieving. The properties of the amorphous silica alumina dry gel powder A1 are shown in Table 1. Mixing the prepared amorphous silicon aluminum A1 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica alumina dry gel to the water is 21:79;
(2) Preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of the dilute hydrochloric acid solution is 0.12mol/L, the pH of an acidic aqueous solution containing the P123 triblock copolymer is 1.6, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 26 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.8wt%;
(3) Mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silicon aluminum in the mixed system is 1.2:1, the crystallization temperature is 102 ℃, and the crystallization time is 18 hours; the pH is controlled to be 3.3 in the crystallization process,
(4) A slurry containing 36.5Beta molecular sieve (wherein the Beta molecular sieve has the following properties: specific surface area 793 m 2 Per g, pore volume 0.52 mL.g -1 ，SiO 2 /Al 2 O 3 The molar ratio is 65, the Beta molecular sieve slurry is prepared by pulping Beta molecular sieve and water, pumping the Beta molecular sieve slurry into a mixed system prepared in the step (3) by a vacuum pump, drying the Beta molecular sieve slurry for 3 hours at 100 ℃ after the pH value is 4.3 and the temperature is 95 ℃ and the crystallization time is 12 hours, and roasting the Beta molecular sieve slurry for 3 hours at 550 ℃ to obtain the finished product BetaAS-1. The properties are shown in Table 2.
(ii) Preparation of the Carrier
Weighing alumina dry gel powder (specific surface area 308 m) 2 Per gram, pore volume of 0.81mL/g, average pore diameter of 8.8 nm), 80g, 15g of BetaAS-1 composite molecular sieve, and Y molecular sieve (SiO 2 /Al 2 O 3 Molar ratio of 30, specific surface area of 650m 2 Per gram, total pore volume of 0.48 mL/g) 5g, sesbania powder of 4g, adding 120mL (the amount of nitric acid is 12.6g, the amount of citric acid is 4.5 g) of aqueous solution containing nitric acid and citric acid, kneading, rolling, extruding, shaping, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 4 hours to obtain a carrier precursor Z0.
Impregnating a carrier precursor with an impregnating solution (product property: appearance transparent liquid, silica mass concentration 30%, particle diameter 10 nm) containing a nano silica dispersion, wherein the nano silica dispersion is used in an amount of 5% by weight of the carrier and has a pH value of 8.0, and drying at 120 ℃ for 2 hours to obtain the hydrocracking catalyst carrier, number Z1. The molar ratio of hydroxyl groups on the surface of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
Z1 was impregnated with an impregnation solution containing W, ni in an equal volume, dried at 130℃for 2 hours and calcined at 430℃for 3 hours, and the finally obtained catalyst was designated as C-1. The catalyst composition and properties are shown in Table 3.
Catalyst C-1 was subjected to a catalyst activity evaluation experiment, specifically: the catalyst was presulfided prior to evaluation on a 200mL small hydrogenation unit. The properties of the raw oil used are shown in Table 4. The activity evaluation conditions were as follows: reaction TotalPressure 14.5MPa, liquid hourly space velocity 0.5h -1 Hydrogen oil volume ratio 1500:1, the reaction temperature was 382 ℃. The results of the catalyst activity test are shown in Table 5.
Example 2
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica-alumina dry gel powder A2 and slurry: sodium aluminate solution concentration 35gAl 2 O 3 Concentration of sodium silicate solution/L125 gSiO 2 Adding 0.85L sodium aluminate solution into a colloid forming tank, adding 0.2L sodium silicate solution, controlling the reaction temperature at 22deg.C, and introducing CO with concentration of 48v% 2 Gas is introduced into CO 2 When the gas accounts for 55% of the total inlet amount, 0.25L of sodium silicate solution is added while ventilation is carried out, the pH value of the gel is controlled to be 9.8, then ventilation is stabilized for 20 minutes, slurry is filtered and washed to be neutral by deionized water at 75 ℃, water is added into a filter cake according to the solid-liquid volume ratio of 8:1 for pulping, cracking is carried out for 3 hours at the temperature of 110 ℃ and the water vapor pressure of 3.0MPa, after drying for 8 hours at the temperature of 120 ℃, the amorphous silica-alumina product A2 is obtained by crushing and sieving, and the properties of the amorphous silica-alumina dry gel powder A2 are shown in the table 1. Mixing the prepared amorphous silicon aluminum A2 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica alumina dry gel to the water is 23:77;
(2) Preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of the dilute hydrochloric acid solution is 0.15mol/L, the pH of an acidic aqueous solution containing the P123 triblock copolymer is 1.2, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 28 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.5wt%;
(3) Mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silicon aluminum in the mixed system is 1.5:1, the crystallization temperature is 95 ℃, and the crystallization time is 18 hours; the pH is controlled to be 3.6 in the crystallization process,
(4) Will contain 31.4g Beta molecular sieve slurry (wherein the Beta molecular sieve has the following properties: ratioSurface area 821 m 2 Per g, pore volume 0.56 mL.g -1 ，SiO 2 /Al 2 O 3 The molar ratio is 55, the Beta molecular sieve slurry is prepared by pulping Beta molecular sieve and water, pumping the Beta molecular sieve slurry into the mixed system prepared in the step (3) by a vacuum pump, drying the Beta molecular sieve slurry for 4 hours at 110 ℃ and roasting the Beta molecular sieve slurry for 3 hours at 530 ℃ after the pH value is 2.8 and the temperature is 115 ℃ and the crystallization time is 13 hours, thus obtaining the finished product BetaAS-2. The properties are shown in Table 2.
(ii) Preparation of the Carrier
Weighing aluminum oxide dry gel powder (specific surface area 328 m) 2 Per gram, pore volume of 1.2mL/g, average pore diameter of 8.8 nm) 76g, betaAS-2 composite molecular sieve 16g, Y molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 35, the specific surface area is 660m 2 Per gram, the total pore volume is 0.50 mL/g) 12g sesbania powder 4g, 120mL of aqueous solution containing nitric acid and citric acid (the amount of nitric acid is 12.6g, the amount of citric acid is 4.5 g) is added, and the carrier precursor is obtained by kneading, rolling, extruding, shaping, drying at 120 ℃ for 3 hours and roasting at 550 ℃ for 4 hours.
Impregnating a carrier precursor with an impregnating solution (product property: appearance transparent liquid, silica mass concentration 30%, particle diameter 15 nm) containing a nano silica dispersion, wherein the nano silica dispersion is used in an amount of 8% by weight of the carrier and has a pH value of 8.2, and drying at 100 ℃ for 4 hours to obtain the hydrocracking catalyst carrier, number Z2. The hydroxyl group density molar ratio of the carrier surface is shown as 3.
(iii) Preparation of the catalyst
The catalyst was prepared in the same manner as in example 1 except that the carrier Z1 was replaced with the carrier Z2 to obtain a hydrocracking catalyst, number C-2. The catalyst composition and properties are shown in Table 3.
Catalyst C-2A catalyst activity evaluation experiment was carried out in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity test are shown in Table 5.
Example 3
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica alumina dry gel powder A3 and slurry: concentration of sodium aluminate solution 22gAl 2 O 3 Concentration of sodium silicate working solution 80gSiO 2 1.08L of sodium aluminate solution is taken and placed in a gel forming tank, then 0.25L of sodium silicate solution is added, the reaction temperature is controlled at 32 ℃, and CO with the concentration of 55v percent is introduced 2 Stopping gas when the pH value reaches 9.8, then ventilating and stabilizing for 20 minutes, washing to be neutral, adding water into a filter cake according to the solid-liquid volume ratio of 8:1 for pulping, cracking for 2.5 hours at 130 ℃ and the water vapor pressure of 3.9MPa, drying for 8 hours at 120 ℃, crushing and sieving to obtain an amorphous silicon aluminum product A3. The properties of the amorphous silica alumina dry powder A3 are shown in Table 1. Mixing the prepared amorphous silicon aluminum A3 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica alumina dry gel to the water is 18:82;
(2) Preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of the dilute hydrochloric acid solution is 0.17mol/L, the pH of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.1wt%;
(3) Mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silicon aluminum in the mixed system is 1.8:1, the crystallization temperature is 98 ℃, and the crystallization time is 12 hours; the pH is controlled to be 3.6 in the crystallization process;
(4) Will contain 35.9g Beta molecular sieve slurry (wherein the Beta molecular sieve has the following properties: specific surface area 778m 2 Per g, pore volume 0.53 mL.g -1 ，SiO 2 /Al 2 O 3 And (3) pumping Beta molecular sieve slurry into the mixed system prepared in the step (3) by using a vacuum pump, drying at 110 ℃ for 4h and roasting at 540 ℃ for 3h after the pH value is 4.5 and the temperature is 95 ℃ and the crystallization time is 10h, thereby obtaining the finished product BetaAS-3. The properties are shown in Table 2.
(ii) Preparation of the Carrier
Weighing alumina dry gel powder (specific surface area)Is 338m 2 Per gram, pore volume of 1.1mL/g, average pore diameter of 10 nm), 80g, 12g of BetaAS-3 composite molecular sieve, 12g of Y molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 40, the specific surface area is 680m 2 Per gram, total pore volume is 0.50 mL/g), sesbania powder is 4g, 120mL (the amount of nitric acid is 12.6g, the amount of citric acid is 4.5 g) of aqueous solution containing nitric acid and citric acid is added, and the mixture is kneaded, rolled, extruded, molded, dried at 120 ℃ for 3 hours and baked at 550 ℃ for 4 hours to obtain a carrier precursor.
Impregnating a carrier precursor with an impregnating solution (product property: apparent transparent liquid, silica mass concentration 35%, particle diameter 10 nm) containing a nano silica dispersion, wherein the nano silica dispersion is used in an amount of 10% by weight of the carrier, the pH value is 8.2, and drying at 90 ℃ for 4 hours to obtain the hydrocracking catalyst carrier, number Z3. The molar ratio of hydroxyl groups on the surface of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
The catalyst was prepared in the same manner as in example 1 except that the carrier Z1 was replaced with the carrier Z3 to obtain a hydrocracking catalyst, number C-3. The catalyst composition and properties are shown in Table 3.
Catalyst C-3A catalyst activity evaluation experiment was carried out in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity test are shown in Table 5.
Example 4
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica alumina dry gel powder A4 and slurry: concentration of sodium aluminate solution 22gAl 2 O 3 Concentration of sodium silicate solution/L55 gSiO 2 Placing 0.60L sodium aluminate solution into a colloid forming tank, adding 0.15L sodium silicate solution, controlling the reaction temperature to 35 ℃, and introducing CO with concentration of 52v% 2 Stopping gas when the pH value reaches 9.5, then ventilating and stabilizing for 20 minutes, washing to be neutral, adding water into a filter cake according to the solid-liquid volume ratio of 8:1 for pulping, cracking for 2.5 hours at 130 ℃ and the water vapor pressure of 3.2MPa, drying for 8 hours at 120 ℃, crushing and sieving to obtain an amorphous silicon aluminum product A4. The properties of the amorphous silica alumina dry powder A4 are shown in Table 1. Will be preparedMixing the prepared amorphous silicon aluminum A4 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica alumina dry gel to the water is 24:76;
(2) Preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of the dilute hydrochloric acid solution is 0.16mol/L, the pH of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.9wt%;
(3) Mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silicon aluminum in the mixed system is 1.7:1, the crystallization temperature is 98 ℃, and the crystallization time is 13h; the pH is controlled to be 3.5 in the crystallization process;
(4) Will contain 20g of Beta molecular sieve slurry (wherein the Beta molecular sieve has the following properties: specific surface area 769 m 2 Per g, pore volume 0.55 mL.g -1 ，SiO 2 /Al 2 O 3 The molar ratio is 68, the Beta molecular sieve slurry is prepared by pulping Beta molecular sieve and water, pumping the Beta molecular sieve slurry into the mixed system prepared in the step (3) by a vacuum pump, drying the Beta molecular sieve slurry for 4 hours at 110 ℃ and roasting the Beta molecular sieve slurry for 4 hours at 550 ℃ after the pH value is 4.7 and the temperature is 98 ℃ and the crystallization time is 13 hours, thus obtaining the finished product BetaAS-4. The properties are shown in Table 2.
(ii) Preparation of the Carrier
Weighing aluminum oxide dry gel powder (specific surface area 328 m) 2 Per gram, pore volume of 1.1mL/g, average pore diameter of 12 nm), 76g, 14g of BetaAS-4 composite molecular sieve, and Y molecular sieve (SiO 2 /Al 2 O 3 The molar ratio is 38, the specific surface area is 650m 2 Per gram, total pore volume is 0.52 mL/g), sesbania powder is 4g, 120mL (the amount of nitric acid is 12.6g, the amount of citric acid is 4.5 g) of aqueous solution containing nitric acid and citric acid is added, and the mixture is kneaded, rolled, extruded, molded, dried at 120 ℃ for 3 hours and baked at 550 ℃ for 4 hours to obtain a carrier precursor.
Impregnating a carrier precursor with an impregnating solution (product property: appearance transparent liquid, silica mass concentration 30%, particle diameter 10 nm) containing a nano silica dispersion, wherein the nano silica dispersion is used in an amount of 12% by weight of the carrier, the pH value is 8.0, and drying at 110 ℃ for 5 hours to obtain the hydrocracking catalyst carrier, number Z4. The molar ratio of hydroxyl groups on the surface of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
The catalyst was prepared in the same manner as in example 1 except that the carrier Z1 was replaced with the carrier Z4 to obtain a hydrocracking catalyst, number C-4. The catalyst composition and properties are shown in Table 3.
Catalyst C-4A catalyst activity evaluation experiment was carried out in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity test are shown in Table 5.
Comparative example 1
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
Respectively weighing a template agent triblock copolymer P123 and silicon source ethyl orthosilicate, wherein the mass of the template agent P123 is 5.5g, and the mass of the ethyl orthosilicate is 10.2g; adding a template agent and a silicon source into an HCl solution with the pH of 2.8, and fully stirring for 30 hours at the temperature of 28 ℃; standing and crystallizing the stirred mixture for 20 hours at 120 ℃, washing with deionized water, and drying to obtain SBA-15. Pulping the obtained SBA-15 molecular sieve, adding the SBA-15 molecular sieve into a hydrochloric acid solution containing 23g of aluminum isopropoxide, heating to 100 ℃, stirring for 20 hours, and cooling to room temperature to obtain a mixed system E.
Pumping 34.3g beta molecular sieve slurry (the same as in example 1) into a mixed system of mixed liquid F by a vacuum pump, drying at 110 ℃ for 4h and roasting at 550 ℃ for 4h after the pH value is 3.5 and the temperature is 110 ℃ and the crystallization time is 12h, thus obtaining the finished product BetaAS-5. The properties are shown in Table 2.
(ii) Preparation of the Carrier
The preparation method of the carrier precursor is the same as in example 1, except that the BetaAS-1 composite molecular sieve is replaced with a BetaAS-5 composite molecular sieve.
The carrier precursor was impregnated with an impregnation solution containing a nano silica dispersion (same as in example 1) in an amount of 2% by weight of the carrier and at a pH of 8.4, and then dried at 100 ℃ for 4 hours to obtain the hydrocracking catalyst carrier, no. Z5. The molar ratio of hydroxyl groups on the surface of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
The catalyst was prepared in the same manner as in example 1 except that the carrier Z1 was replaced with the carrier Z5 to obtain a hydrocracking catalyst, number C-5. The catalyst composition and properties are shown in Table 3.
Catalyst C-5A catalyst activity evaluation experiment was carried out in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity test are shown in Table 5.
Comparative example 2
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
5g of P123 are added into 2mol/L125mL of hydrochloric acid solution, and stirred at 40 ℃ until P123 is completely dissolved; adding 8.5g of tetraethoxysilane into a hydrochloric acid solution containing P123, stirring for 4 hours, adding aluminum nitrate to enable the silicon aluminum molar ratio to be 35, continuously stirring for 20 hours, adding the solution into a 250mL reaction kettle, stirring for 48 hours at the temperature of 100 ℃, cooling to room temperature, adjusting the pH value to 7.5 by using 4mol of ammonia water solution, continuously stirring, heating to the temperature of 100 ℃, stirring for 72 hours, and cooling to the temperature of 40 ℃ to obtain a solution A for standby.
Pumping 34.3g beta molecular sieve slurry (same as in example 1) into the mixed system of A by a vacuum pump, drying at 110 ℃ for 4h and roasting at 550 ℃ for 4h after the pH value is 3.4 and the temperature is 100 ℃ and the crystallization time is 13h, thus obtaining the finished product BetaAS-6. The properties are shown in Table 2.
(ii) Preparation of the Carrier
The preparation method of the carrier precursor is the same as in example 1, except that the BetaAS-1 composite molecular sieve is replaced with a BetaAS-6 composite molecular sieve.
The carrier precursor was impregnated with an impregnation solution containing a nano silica dispersion (same as in example 1) in an amount of 3% by weight of the carrier and at a pH of 8.0, and then dried at 100 ℃ for 4 hours to obtain the hydrocracking catalyst carrier, no. Z6. The molar ratio of hydroxyl groups on the surface of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
The catalyst was prepared in the same manner as in example 1 except that the carrier Z1 was replaced with the carrier Z6 to obtain a hydrocracking catalyst having a number of C-6. The catalyst composition and properties are shown in Table 3.
Catalyst C-6A catalyst activity evaluation experiment was carried out in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity test are shown in Table 5.
Comparative example 3
(i) Preparation of the Carrier
18 g of Y molecular sieve (SiO 2 /Al 2 O 3 Molar ratio of 30, specific surface area of 650m 2 Per gram, total pore volume of 0.48 mL/g), 12 grams of beta molecular sieve (SiO 2 /Al 2 O 3 Molar ratio of 45 and specific surface area of 630m 2 Per gram, total pore volume of 0.50mL/g, 130 g macroporous alumina (pore volume of 0.9mLg, specific surface area of 355 m) 2 Per g), 4g microcrystalline cellulose, and a mixed acidic aqueous solution containing 4g guar gum and dilute nitric acid (wherein the concentration of nitric acid is 3.0%) were put into a roller to be mixed and ground into paste, extruded into strips, the extruded strips were dried at 120 ℃ for 4 hours, and then calcined at 500 ℃ for 4 hours, to obtain carrier Z7. The molar ratio of hydroxyl groups on the surface of the carrier is shown in Table 3.
(ii) Preparation of the catalyst
Z7 was impregnated with an impregnation solution containing W, ni in an equal volume, dried at 130℃for 2 hours and calcined at 450℃for 3 hours, and the finally obtained catalyst was designated as C-7. The catalyst composition and properties are shown in Table 3.
Catalyst C-7A catalyst activity evaluation experiment was carried out in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity test are shown in Table 5.
Comparative example 4
This comparative example to illustrate that the composite molecular sieve prepared in example 1 is a Beta/Al-SBA-15 composite molecular sieve, the Al-SBA-15 molecular sieve was synthesized directly without adding Beta molecular sieve slurry, as compared to example 1, specifically as follows:
(1) Preparation of amorphous silica-alumina dry gel powder A1 and slurry: concentration of sodium aluminate solution 15gAl 2 O 3 Concentration of sodium silicate solution 82SiO 2 Adding 0.85L sodium aluminate solution into a colloid forming tank, adding 0.30L sodium silicate solution, controlling the reaction temperature to 20 ℃, and introducing CO with concentration of 35v% 2 Gas is introduced into CO 2 When the gas accounts for 65% of the total inlet amount, 0.30L sodium silicate solution is added while ventilation is carried out, the pH value of the gel is controlled to be 9.5, then ventilation is stabilized for 20 minutes, slurry is filtered and washed to be neutral by deionized water at 65 ℃, water is added into a filter cake according to the solid-liquid volume ratio of 10:1 for pulping, cracking is carried out for 3 hours under the water vapor pressure of 3.5MPa at 130 ℃, after drying is carried out for 6 hours at 120 ℃, the amorphous silicon aluminum product A1 is obtained by crushing and sieving. The properties of the amorphous silica alumina dry gel powder A1 are shown in Table 1. Mixing the prepared amorphous silicon aluminum A1 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica alumina dry gel to the water is 21:79;
(2) Preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of the dilute hydrochloric acid solution is 0.12mol/L, the pH of an acidic aqueous solution containing the P123 triblock copolymer is 1.6, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 26 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.8wt%;
(3) Mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the Al-SBA-15 molecular sieve is prepared after crystallization, filtration, drying and roasting, and the number of the molecular sieve is A-S-1. The mass ratio of the P123 triblock copolymer to the amorphous silicon aluminum in the mixed system is 1.2:1, the crystallization temperature is 102 ℃, and the crystallization time is 18 hours; the pH value is controlled to be 3.3 in the crystallization process, and the finished Al-SBA-15 molecular sieve is obtained after the process of drying at 100 ℃ for 3 hours and roasting at 550 ℃ for 3 hours. XRD patterns of the A-S-1 molecular sieve obtained in comparative example 4 are shown in FIG. 1, and characteristic peaks of the Al-SBA-15 molecular sieve are shown.
The Beta/Al-SBA-15 composite molecular sieves prepared in examples 1-4 of the invention all contain XRD patterns similar to those of comparative example 4, which indicates that the composite molecular sieves prepared in examples 1-4 are Beta/Al-SBA-15 composite molecular sieves.
TABLE 1 Properties of amorphous silica-alumina
| Project | A1 | A2 | A3 | A4 |
| Specific surface area, m 2 /g | 485 | 516 | 508 | 520 |
| Pore volume, ml/g | 1.31 | 1.28 | 1.33 | 1.30 |
| Pore distribution, percent | ||||
| 4～15nm | 91 | 86.5 | 88.3 | 91.2 |
| ＞15nm | 2.5 | 4.3 | 2.8 | 4.1 |
Table 2 properties of the composite pore molecular sieves obtained in examples and comparative examples
| Project | BetaAS-1 | BetaAS-2 | BetaAS-3 | BetaAS-4 | BetaAS-5 | BetaAS-6 |
| Alumina content, wt% | 23.53 | 37.59 | 56.97 | 63.98 | 19.80 | 15.55 |
| Alumina content in Al-SBA-15 molecular sieve, wt% | 20.98 | 34.59 | 54.30 | 61.54 | 17.25 | 13.0 |
| Specific surface area, m 2 /g | 758 | 764 | 775 | 769 | 712 | 719 |
| Pore volume, mL/g | 0.58 | 0.63 | 0.59 | 0.65 | 0.48 | 0.45 |
| Relative crystallinity after calcination at 900 ℃ percent | 98 | 98 | 97 | 99 | 88 | 85 |
| Amount of medium strong acid, mL/g | 0.71 | 0.72 | 0.75 | 0.76 | 0.52 | 0.48 |
| B/L | 0.226 | 0.228 | 0.234 | 0.255 | 1.05 | 1.25 |
| Pore distribution, percent | ||||||
| 4～15nm | 55.38 | 56.35 | 64.88 | 56.65 | 30.47 | 35.32 |
| ＞15nm | 4.92 | 4.85 | 4.33 | 3.56 | 11.34 | 14.03 |
TABLE 3 composition and physicochemical Properties of the catalysts
| Project | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | C-7 |
| Specific surface area, m 2 /g | 324 | 325 | 321 | 335 | 232 | 245 | 220 |
| Pore volume, mL/g | 0.43 | 0.44 | 0.42 | 0.43 | 0.32 | 0.33 | 0.31 |
| WO 3 ，wt% | 23.1 | 23.6 | 22.9 | 23.3 | 22.8 | 23.2 | 23.5 |
| NiO，wt% | 5.94 | 5.92 | 5.91 | 5.96 | 5.87 | 5.83 | 5.78 |
| Density molar ratio of hydroxyl groups on the surface of the catalyst support | 1.62 | 1.65 | 1.68 | 1.73 | 1.41 | 1.43 | 0.81 |
| W/Al | 0.18 | 0.19 | 0.18 | 0.17 | 0.12 | 0.11 | 0.08 |
| Ni/Al | 0.07 | 0.08 | 0.08 | 0.09 | 0.03 | 0.04 | 0.03 |
TABLE 4 Properties of raw oil
| Analysis item | Coal tar |
| Density (20 ℃ C.) kg/m 3 | 1120 |
| Nitrogen, μg/g | 12600 |
| Distillation range/. Degree.C | |
| IBP/10%/30%/50% | 170/230/305/340 |
| 70%/90%/95%/EBP | 370/415/435/466 |
| Saturation fraction | 0.6 |
| Aromatic components | 67 |
| Colloid | 32.2 |
| Asphaltenes | 0.2 |
| Moisture content of% | 1.86 |
| Carbon residue, percent | 0 .83 |
| Flash point (closed) and C | 98 |
| Ni，μg/g | 0.025 |
| V ，μg/g | 0 |
| Fe ，μg/g | 1.488 |
| Na ，μg/g | 0 |
Table 5 catalyst evaluation results
| Project | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | C-7 |
| Heavy naphtha | |||||||
| Yield, wt% | 12.2 | 11.8 | 13.3 | 12.5 | 14.3 | 15.5 | 19.2 |
| Sulfur, μg/g | 7.5 | 8.2 | 7.6 | 8.3 | 20 | 16 | 14 |
| Diesel oil | |||||||
| Yield, wt% | 73.3 | 76.5 | 77.8 | 75.6 | 52.5 | 60.2 | 60.8 |
| Aromatic hydrocarbon, wt% | 27.5 | 28.6 | 28.2 | 29.3 | 38.6 | 33.3 | 42.3 |
| Cetane number | 60 | 63 | 65 | 67 | 48 | 47 | 43 |
| Condensation point, DEG C | -31 | -30 | -29 | -32 | -14 | -16 | -13 |
As is clear from the evaluation results in Table 5, the coal tar hydrocracking catalyst of the present invention has better selectivity and good product properties than those of the comparative catalyst.
Claims (18)
1. A preparation method of a hydrocracking catalyst is characterized in that: the method comprises the following steps:
(i) Preparing a Beta/Al-SBA-15 composite molecular sieve;
(ii) Kneading and molding the Beta/Al-SBA-15 composite molecular sieve, the Y molecular sieve and the alumina prepared in the step (i) to obtain a carrier precursor;
(iii) Impregnating the carrier precursor obtained in the step (ii) with nano silicon dioxide dispersion liquid, and drying to obtain a hydrocracking catalyst carrier;
(iv) Impregnating the carrier obtained in the step (iii) with a solution containing an active metal component, and drying and roasting to obtain a hydrocracking catalyst;
in the Beta/Al-SBA-15 composite molecular sieve, the mass content of alumina is 2% -85%;
in the Beta/Al-SBA-15 composite molecular sieve, the mass content of the Beta molecular sieve is 10% -90%;
in the Beta/Al-SBA-15 composite molecular sieve, the mass content of alumina in the Al-SBA-15 molecular sieve is as follows: 5% -75%;
the medium strong acid amount of the Beta/Al-SBA-15 composite molecular sieve is 0.6-1.2 mL/g; the ratio of the acid B to the acid L is less than 0.80;
the preparation method of the Beta/Al-SBA-15 composite molecular sieve comprises the following steps:
(1) Mixing amorphous silica-alumina and deionized water, and pulping to form slurry;
(2) Preparing an acidic aqueous solution containing a P123 triblock copolymer;
(3) Mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), adding Beta molecular sieve slurry after first crystallization, and preparing the Beta/Al-SBA-15 composite molecular sieve after second crystallization.
2. A method according to claim 1, characterized in that: in the Beta/Al-SBA-15 composite molecular sieve, the mass content of the alumina is 5% -82%.
3. A method according to claim 1, characterized in that: in the Beta/Al-SBA-15 composite molecular sieve, the mass content of the Beta molecular sieve is 25% -85%.
4. A method according to claim 1, characterized in that: the medium strong acid amount of the Beta/Al-SBA-15 composite molecular sieve is 0.7-1.0 mL/g.
5. A method according to claim 1, characterized in that: the conditions for the first crystallization in step (3) are: the crystallization temperature is 80-120 ℃, the crystallization time is 10-35 h, the pH value in the crystallization process is controlled to be 2.0-5.0, and the second crystallization condition in the step (3) is as follows: the crystallization temperature is 80-130 ℃, the crystallization time is 4-20 h, and the pH is controlled to be 2.0-5.0 in the crystallization process.
6. A method according to claim 1, characterized in that: the properties of the Y-type molecular sieve used in step (ii) are as follows: siO (SiO) 2 /Al 2 O 3 The molar ratio is 25-150, the specific surface area is 550-1000 m 2 And/g, wherein the total pore volume is 0.30-0.60 mL/g.
7. A method according to claim 1, characterized in that: the properties of the alumina in step (ii) are as follows: the specific surface area is 150-450 m 2 /g; the pore volume is 0.4-1.4 mL/g, and the average pore diameter is 8-14 nm.
8. The method of claim 7, wherein: the properties of the alumina in step (ii) are as follows: the specific surface area is 230-340 m 2 /g; the pore volume is 0.8-1.2 mL/g.
9. A method according to claim 1, characterized in that: in the step (iii), the mass concentration of the nano silicon dioxide dispersion liquid in the impregnating solution is 20% -50%; the particle size of the nano silicon dioxide is 10-20 nanometers.
10. A method according to claim 1, characterized in that: the active metal component in the step (iv) is a metal in the VIII family and a metal in the VIB family, wherein the metal in the VIII family is Co and/or Ni, and the metal in the VIB family is W and/or Mo; the content of the group VIII metal in terms of oxide is 1-15 wt% based on the weight of the catalyst; the content of the VI B group metal calculated by oxide is 9-30wt%, and the content of the hydrocracking catalyst carrier is 60-80wt%.
11. The method of claim 10, wherein: the content of the group VIII metal in terms of oxide is 4-10wt% based on the weight of the catalyst; the content of the VI B group metal calculated by oxide is 15-28 wt%, and the content of the hydrocracking catalyst carrier is 65-75 wt%.
12. A method according to claim 1, characterized in that: the density molar ratio of the hydroxyl groups on the surface of the hydrocracking catalyst carrier is 1.5-2.5.
13. The method of claim 12, wherein: the density molar ratio of the hydroxyl groups on the surface of the hydrocracking catalyst carrier is 1.8-2.2.
14. A hydrocracking catalyst prepared by the process of any one of claims 1 to 13.
15. The catalyst of claim 14, wherein: the hydrocracking catalyst has the following properties: specific surface area of 120-350 m 2 Per g, the pore volume is 0.20-0.60 mL/g.
16. The catalyst of claim 15, wherein: the hydrocracking catalyst has the following properties: specific surface area of 150-330 m 2 The pore volume is 0.2-0.55 mL/g.
17. The application of the hydrocracking catalyst in the coal tar hydrocracking process is characterized in that: the catalyst is a hydrocracking catalyst prepared according to the process of any one of claims 1 to 13 or a hydrocracking catalyst according to any one of claims 14 to 16.
18. The use according to claim 17, characterized in that: the properties of the coal tar are as follows: the density is 1000-1200 kg/m 3 The nitrogen content is 0.8-1.5 wt% and the sulfur content is 0.2-0.8 wt%.
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| CN103100427A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier containing beta molecular sieve and preparation method thereof |
| WO2013149014A1 (en) * | 2012-03-29 | 2013-10-03 | Wayne State University | Bimetal catalysts |
| CN106140287A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
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| MX352582B (en) * | 2012-11-06 | 2017-11-07 | Mexicano Inst Petrol | Mesoporous composite of molecular meshes for the hydrocracking of heavy crude oil and residues. |
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| WO2013149014A1 (en) * | 2012-03-29 | 2013-10-03 | Wayne State University | Bimetal catalysts |
| CN106140287A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
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Effective date of registration: 20231214 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |