CN107008509B - Improved diesel hydrocracking catalyst carrier and preparation method thereof - Google Patents
Improved diesel hydrocracking catalyst carrier and preparation method thereof Download PDFInfo
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- CN107008509B CN107008509B CN201710264312.7A CN201710264312A CN107008509B CN 107008509 B CN107008509 B CN 107008509B CN 201710264312 A CN201710264312 A CN 201710264312A CN 107008509 B CN107008509 B CN 107008509B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 81
- 239000002808 molecular sieve Substances 0.000 claims abstract description 79
- 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 35
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000011148 porous material Substances 0.000 claims abstract description 28
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 239000002283 diesel fuel Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000002156 mixing Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910001845 yogo sapphire 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
- 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
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 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
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 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
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010457 zeolite Substances 0.000 abstract description 3
- 230000002633 protecting effect Effects 0.000 abstract description 2
- 230000008093 supporting effect Effects 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 239000000499 gel Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 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
- 239000000969 carrier Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 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
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator 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
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer 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 an improved diesel hydrocracking catalyst carrier and a preparation method thereof, wherein the carrier comprises the following raw materials in percentage by weight: 3-35% of molecular sieve and 5-75% of gamma-Al2O315-75% of amorphous silica-alumina and 7-40% of binder; the specific surface area of the carrier is 200-450 m2Per g, total pore volume of 0.35-0.75 cm3(ii) in terms of/g. In the invention, a molecular sieve without a template agent is added in the process of preparing the molecular sieve and alumina composite material, and in the mixed solution, NH4 generated by the reaction of aluminum salt and ammonia water+Exchanging with alkali Na + for balancing negative charge of molecular sieve skeleton, and calcining organic template agent and NH in molecular sieve4 +The removal is carried out, so that the ammonium exchange and the template agent of the zeolite molecular sieve are completed in the process of preparing the composite material, the template agent does not need to carry out the ammonium exchange and the template agent separately on the molecular sieve, the template agent has supporting and protecting functions on the pore structure of the molecular sieve, and the hydrocracking catalyst prepared by using the carrier can obviously reduce the condensation point of diesel oil fraction and improve the cetane number of the diesel oil on the premise of ensuring high yield of the diesel oil.
Description
Technical Field
The invention relates to a catalyst carrier, in particular to an improved diesel hydrocracking catalyst carrier and a preparation method thereof.
Background
With the rapid development of economy and the rapid increase of the demand of petroleum products, the hydrocracking processing capacity of our country is also rapidly developed. However, as the quality of raw oil processed in China gradually gets heavier and worse, the processing amount of high-sulfur crude oil increases year by year, the environmental protection has increasingly strict requirements on the quality of an oil refining process and petroleum products, which puts higher requirements on the hydrocracking technical level, and the catalyst plays a central role in hydrocracking reaction, and the key point of the hydrocracking technology lies in the development and improvement of the catalyst.
The conventional preparation method of the hydrocracking catalyst mainly comprises an impregnation method, a coprecipitation method, a kneading method and the like, wherein the kneading method has the simplest preparation process and has low requirements on the process and the catalyst ingredients, but because the preparation process is relatively extensive, the dispersibility of each component in the catalyst is poor, part of metal hydrogenation active centers are covered, the activity of the metal hydrogenation active centers cannot be better exerted, and the conventional preparation method is usually adopted by the catalyst with the requirement on hydrogenation performance which is not high; the preparation process of the coprecipitation method is the most complex, but the dispersity of each component in the catalyst is good, the matching relationship among the components is good, and the hydrogenation and cracking active centers are uniformly distributed in the catalyst, so that the hydrogenation and cracking active centers of the catalyst have higher synergistic effect; the impregnation method is the most widely used method for preparing the hydrocracking catalyst, and firstly, a carrier with the shape, mechanical strength, specific surface, acidity and the like meeting the performance requirements of the catalyst needs to be prepared, and then a saturated or supersaturated impregnation method is used for loading metal components, and the metal components are enriched in the catalyst, so that the catalyst has higher mechanical strength and the hydrogenation performance of the catalyst is fully exerted. Therefore, the carrier plays an important role in the catalyst, the mechanical function of the carrier is to serve as a framework for the active component, to serve the function of dispersing the active component, and to increase the strength and thermal stability of the catalyst, and it is important that it has a great influence on the activity and selectivity of the catalyst.
The U.S. Pat. No. 4,4738767 discloses a hydrocracking catalyst, the main acidic component of which is amorphous silica-alumina, the amorphous silica-alumina used as the carrier is prepared by precipitating aluminum into silica gel, which results in smaller specific surface area and pore volume of silica-alumina, low acid content, uneven distribution and the like, and the catalyst activity is not high, CN1351121A discloses a hydrocracking catalyst containing a modified β molecular sieve and amorphous silica-alumina and a preparation method thereof, wherein the modified β molecular sieve is prepared by directly performing ammonium exchange on synthesized molecular sieve slurry, and then roasting, deammoniation, acid treatment and hydrothermal treatment to obtain a modified β molecular sieve, and a large amount of non-framework aluminum is retained in the pore channels of the molecular sieve, so that the acidity and the diffusion performance of the modified molecular sieve are affected, and finally the yield and the properties of a diesel oil product are affected.
Disclosure of Invention
The invention aims to provide an improved diesel hydrocracking catalyst carrier and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: an improved diesel hydrocracking catalyst carrier comprises the following raw materials in percentage by weight: 3-35% of molecular sieve and 5-75% of gamma-Al2O315-75% of amorphous silica-alumina and 7-40% of binder; the specific surface area of the carrier is 200-450 m2Per g, total pore volume of 0.35-0.75 cm3/g。
Further, the carrier raw material comprises the following components in percentage by weight: 3.4 to 7.6 percent of molecular sieve and 27.3 to 47.7 percent of gamma-Al2O328.3-46.9% of amorphous silica-alumina and 18-20% of binder; the specific surface area of the carrier is 362-383 m2(ii) a total pore volume of 0.52 to 0.63cm3(ii)/g; the carrier is columnar, and the length is 3-8 mm.
Further, the molecular sieve is one or more of β molecular sieve, Y-type molecular sieve, MOR molecular sieve, ZSM-5 molecular sieve, ZSM-22 molecular sieve and ZSM-23 molecular sieve.
Further, the amorphous silica-alumina pore volume is 0.5-1.0 cm3A specific surface area of 300 to 500 m/g2/g。
Further, the binder contains 10-40% by mass of small-pore alumina, and the balance of acid; the pore volume of the small-pore alumina is 0.3-0.5 cm3A specific surface area of 200 to 350 m/g2The mass ratio of the acid to the small-pore alumina is 0.1-0.5.
Furthermore, the specific surface area of the β molecular sieve is 624-643 m2Per g, total pore volume of 0.32-0.35 cm3/g。
The preparation method of the improved diesel hydrocracking catalyst carrier comprises the following steps:
1) mixing and stirring tetraethyl ammonium bromide solution, sodium hydroxide, an aluminum source and water to obtain a clear solution, then adding a silicon source, and continuously stirring to obtain silicon-aluminum gel;
2) crystallizing the silicon-aluminum gel obtained in the step 1), and then washing and drying to obtain a molecular sieve;
3) adding the molecular sieve obtained in the step 2) into a mixed solution of aluminum salt and ammonia water for precipitation, taking slurry after full precipitation, and sequentially evaporating, drying and roasting to obtain a molecular sieve and alumina composite material;
4) mixing the molecular sieve obtained in the step 3) with an alumina composite material, amorphous silica-alumina and a binder according to the raw material proportion, and forming to obtain the hydrocracking catalyst carrier.
Further, in the step 1), a silicon source, an aluminum source, sodium hydroxide, a tetraethylammonium bromide solution and water are mixed according to a molar ratio of SiO2∶Al2O3∶Na2O tetraethylammonium bromide H2O is added in a ratio of 50-70: 1: 5-8: 15-20: 1000-1200.
Further, in the step 3), the aluminum salt is 0.5-3.0 mol/L aluminum chloride, and the concentration of ammonia water is 0.5-4 mol/L.
Further, in the step 3), the pores of the molecular sieve and alumina composite materialThe volume is 0.4-0.9 cm3A specific surface area of 350 to 500 m/g2/g。
Further, in the step 2), the molecular sieve is β molecular sieve, the crystallization temperature is 135-145 ℃, the washing is carried out until the pH of the washing liquid is 6.5-7.5, the drying temperature is 90-110 ℃, and the drying time is 22-26 hours.
Further, in the step 3), the temperature is 60-80 ℃ and the pH is 3-7 in the precipitation process; the drying temperature is 90-120 ℃, and the drying time is 2-3 hours; the roasting temperature is 300-600 ℃, and the roasting time is 2-8 hours.
Further, in the step 4), drying and activating treatment are sequentially carried out after forming, wherein the drying temperature is 100-120 ℃, the drying time is 18-22 hours, the activating temperature is 450-600 ℃, and the activating time is 4-6 hours.
Further, in the step 3), the concentration of ammonia water is 1.0-2.0 mol/L.
Furthermore, in the step 1), the aluminum source is one or more of pseudo-boehmite, aluminum sulfate and sodium metaaluminate; the silicon source is one or more of white carbon black, silica sol and water glass.
Compared with the prior art, the invention has the following advantages:
firstly, the invention adds the molecular sieve without the template agent in the process of preparing the molecular sieve and alumina composite material, and NH4 generated by the reaction of aluminum salt and ammonia water is added in the mixed solution+Exchanging with alkali Na + for balancing the negative charge of the molecular sieve skeleton, and simultaneously adding organic template agent and NH in the molecular sieve during roasting4 +The removed template agent is mainly TEA for filling the inside of the pore canal and balancing the negative charge of the framework of the molecular sieve+And NH is4 +Then with NH3The form of the zeolite is removed to obtain the H- β molecular sieve, so that the ammonium exchange and the template agent of the zeolite molecular sieve are completed in the process of preparing the composite material, the template agent and the ammonium exchange are not needed to be carried out on the molecular sieve independently, the preparation process is simplified, and the template agent has supporting and protecting effects on the pore structure of the molecular sieve, so that the pore structure of the molecular sieve is not easy to damage, and the catalyst loading capacity is greatly improvedMechanical strength of the body.
Secondly, the catalyst carrier has high dispersity of molecular sieve, more uniform acid sites, more compact contact between alumina and the molecular sieve, and is beneficial to rapid transfer of reactant and product molecules between an acid center and a cracking center, cracking components and hydrogenation components are optimally matched, and the hydrocracking catalyst prepared by using the catalyst carrier has good synergistic effect on hydrogenation activity and cracking activity.
The hydrocracking catalyst prepared by the carrier has proper cracking effect and good isomerization effect on long-chain alkane, aromatic hydrocarbon and long-side chain alkyl of naphthenic hydrocarbon, the matching of the hydrogenation activity center and the cracking activity center is more reasonable, the hydrocracking catalyst prepared by the hydrocracking catalyst has good middle distillate oil selectivity, high catalytic activity, can produce high-quality middle distillate oil products, can obviously reduce the condensation point of diesel oil fraction on the premise of ensuring high yield of the diesel oil, improves the cetane number of the diesel oil, and is suitable for the catalytic process of producing high-quality diesel oil by hydrocracking for processing vacuum distillate oil.
Detailed Description
The present invention will be described in further detail with reference to specific examples to facilitate the clear understanding of the invention, but the present invention is not limited thereto.
In the following examples, low temperatures N were used for specific surface area and pore volume2And (3) measuring by a physical adsorption method, wherein the molar ratio of silicon to aluminum is measured by a chemical method, the infrared acid amount, the B acid amount and the L acid amount are measured by a pyridine adsorption infrared spectrometry method, and the relative crystallinity of the molecular sieve is measured by an XRD method.
The preparation of the hydrocracking catalyst support in the following examples was carried out as follows:
the crystallized molecular sieve slurry is directly filtered, washed and dried, and the dried molecular sieve slurry is not treated by a stripping agent, namely SiO2/Al2O3(molar ratio) is 20-60; mixing an aluminum salt solution and an alkali precipitator, adding the molecular sieve without removing the template agent into the mixed solution, stirring, controlling the temperature at 60-80 ℃, controlling the pH value at 3-7, and carrying out temperature strip at 50-90 DEG CEvaporating under the condition, drying at 100 ℃, and roasting the precipitate at the roasting temperature of 300-600 ℃ for 2-6 hours to obtain the molecular sieve and alumina composite material; according to the mixing proportion of a catalyst carrier, a molecular sieve, an alumina composite material, amorphous silica-alumina and a binder (the pore volume of the small-pore alumina in the binder is 0.3-0.5 cm)3A specific surface area of 200 to 350 m/g2The ratio of acid to alumina in the binder is 0.1-0.5, and the acid is HNO3Or H3PO4) Mixing, rolling in an edge runner mill for 20-60 minutes, extruding strips into columns, drying the strip-shaped carriers at 100-120 ℃ for 10-20 hours, and roasting at 450-600 ℃ for 4-6 hours to obtain the hydrocracking catalyst carrier, wherein the length of the carrier is 3-8 nm.
Example 1
Weighing 201.3g of tetraethylammonium bromide (98 wt%, industrial grade), 27.39g of sodium hydroxide, 7.2g of pseudo-boehmite (70 wt%, industrial grade) and 870g of water, mixing and stirring to obtain a clear solution, then adding 180g of white carbon black (98 wt%, industrial grade) into the solution under continuous stirring, continuously stirring to obtain uniform silica-alumina gel, dynamically crystallizing the silica-alumina gel at 145 ℃ for 7 days, and carrying out solid-liquid separation, washing and drying to obtain β molecular sieve with the number of B1, wherein the β molecular sieve has the main properties shown in Table 1.
Adding 3000ml of aluminum chloride solution (the concentration is 1.5mol/L) into a 5000ml beaker, adding a 19g B1 molecular sieve (dry basis is 99%) into the mixed solution, keeping the temperature at 70 ℃, continuously adding 2mol/L ammonia water until the pH value is 4, evaporating at 80 ℃ (the evaporation temperature can be 50-90 ℃), drying the sucked white solid at 100 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain 273.7g of the molecular sieve and alumina composite material (dry basis is 93%), wherein the conversion rate is 72.5%, and the number is C1.
183.7g (dry basis 93%) of C1, 172.7g (dry basis 88%) of amorphous silica-alumina and 240g (dry basis 30%) of a binder are mixed, the mixture is rolled for 40 minutes in an edge runner mill to be extruded into paste, the paste is extruded into strips, the shape of the carrier is columnar, the length of the carrier is 3-8 nm, then the strip-shaped carrier is dried for 20 hours at 120 ℃, and the calcined for 5-6 hours at 550 ℃, so that the catalyst carrier Z-1 is obtained, and the properties of the catalyst carrier are shown in Table 2.
Example 2
Weighing 201.3g of tetraethylammonium bromide (98 wt%, industrial grade), 27.39g of sodium hydroxide, 7.2g of pseudo-boehmite (70 wt%, industrial grade) and 870g of water, mixing and stirring to obtain a clear solution, then adding 180g of white carbon black (98 wt%, industrial grade) into the solution under continuous stirring, continuously stirring to obtain uniform silica-alumina gel, dynamically crystallizing the silica-alumina gel at 145 ℃ for 7 days, and carrying out solid-liquid separation, washing and drying to obtain β molecular sieve with the number of B1, wherein the β molecular sieve has the main properties shown in Table 1.
Adding 3000ml of aluminum chloride solution (the concentration is 1.5mol/L) into a 5000ml beaker, adding 28g B1 molecular sieve (dry basis is 99%) into the mixed solution, keeping the temperature at 70 ℃, continuously adding 2mol/L ammonia water until the pH value is 4.3, evaporating at 85 ℃, drying the sucked white solid at 100 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain 276.2g of the molecular sieve and alumina composite material (dry basis is 93%), wherein the conversion rate is 73%, and the number is C2.
225.1g (dry basis 93%) of C2, 126.8g (dry basis 88%) of amorphous silica-alumina and 240g (dry basis 30%) of a binder are mixed, the mixture is rolled for 40 minutes in a wheel mill to be extruded into paste, the paste is extruded into strips, the shape of the carrier is columnar, the length of the carrier is 3-8 nm, then the strip-shaped carrier is dried for 20 hours at 120 ℃, and the calcined for 5-6 hours at 550 ℃, so that the catalyst carrier Z-2 is obtained, and the properties of the catalyst carrier are shown in Table 2.
Example 3
185.3g tetraethylammonium bromide (98 wt%, industrial grade), 22.65g sodium hydroxide, 10.3g pseudo-boehmite (70 wt%, industrial grade) and 870g water are weighed, mixed and stirred to obtain a clear solution, then 180g white carbon black (industrial grade) is added into the solution under continuous stirring, stirring is continued to obtain uniform silica-alumina gel, the silica-alumina gel is dynamically crystallized for 7 days at 145 ℃, and after solid-liquid separation, washing and drying, β molecular sieve with the number of B2 is obtained, and the main properties of the β molecular sieve are shown in Table 1.
Adding 3000ml of aluminum chloride solution (with the concentration of 1.5mol/L) into a 5000ml beaker, adding 60.5g B2 molecular sieve (99% dry basis) into the mixed solution, keeping the temperature at 70 ℃, continuously adding 2mol/L ammonia water until the pH value is 4, evaporating at 85 ℃, drying the sucked white solid at 100 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain 296.4g of the molecular sieve and alumina composite material (93% dry basis), wherein the conversion rate is 78.4%, and the number is C3.
145.7g (dry basis 93%) of C3, 210.7g (dry basis 88%) of amorphous silica-alumina and 240g (dry basis 30%) of a binder are mixed, the mixture is rolled for 40 minutes in an edge runner mill to be extruded into paste, the paste is extruded into strips, the shape of the carrier is columnar, the length of the carrier is 3-8 nm, then the strip-shaped carrier is dried for 20 hours at 120 ℃, and the baking is carried out for 5-6 hours at 550 ℃, so that the catalyst carrier Z-3 is obtained, and the properties of the catalyst carrier are shown in Table 2.
Example 4
185.3g tetraethylammonium bromide (98 wt%, industrial grade), 22.65g sodium hydroxide, 10.3g pseudo-boehmite (70 wt%, industrial grade) and 870g water are weighed, mixed and stirred to obtain a clear solution, then 180g white carbon black (industrial grade) is added into the solution under continuous stirring, stirring is continued to obtain uniform silica-alumina gel, the silica-alumina gel is dynamically crystallized for 7 days at 145 ℃, and after solid-liquid separation, washing and drying, β molecular sieve with the number of B2 is obtained, and the main properties of the β molecular sieve are shown in Table 1.
Adding 3000ml of aluminum chloride solution (with the concentration of 1.5mol/L) into a 5000ml beaker, adding 34.3g B2 molecular sieve (99% dry basis) into the mixed solution, keeping the temperature at 70 ℃, continuously adding 2mol/L ammonia water until the pH value is 4.8, evaporating at 85 ℃, drying the sucked white solid at 100 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain 285.3g of the molecular sieve and alumina composite material (93% dry basis), wherein the conversion rate is 75.6%, and the number is C4.
196.4g (dry basis 93%) of C4, 159.6g (dry basis 88%) of amorphous silica-alumina and 240g (dry basis 30%) of a binder are mixed, the mixture is rolled for 40 minutes in an edge runner mill to be extruded into paste, the paste is extruded into strips, the shape of the carrier is columnar, the length of the carrier is 3-8 nm, then the strip-shaped carrier is dried for 20 hours at 120 ℃, and the baking is carried out for 5-6 hours at 550 ℃, so that the catalyst carrier Z-4 is obtained, and the properties of the catalyst carrier are shown in Table 2.
The catalyst carriers obtained in the example 3 and the example 4 adopt a supersaturated impregnation method to load hydrogenation metal, the hydrogenation metal adopts a tungsten-nickel system, the prepared catalysts are CZ-3 and CZ-4 in serial number, and the properties are shown in the table 2.
The catalytic activity of the CZ-3 and CZ-4 catalysts prepared by the carrier obtained in example 3 and example 4 was evaluated on a fixed bed hydrogenation experimental device under the following conditions: the total reaction pressure is 10MPa, the volume ratio of hydrogen to oil is 1000, and the volume airspeed is 1.0h-1Vacuum distillate (VGO) was used as the feedstock, and the properties of the feedstock are shown in Table 3. The catalysts CZ-3 and CZ-4 were evaluated under the same process conditions, and the evaluation results are shown in Table 4. As can be seen from the data in Table 4, under the same process conditions, the catalyst prepared by the carrier has good middle distillate selectivity, and obviously reduces the condensation point of diesel oil fraction and improves the cetane number of the diesel oil on the premise of ensuring the yield of the diesel oil.
TABLE 1
| Molecular sieves | B1 | B2 |
| Molar ratio of silicon to aluminum (Si/Al) | 31.5 | 22.6 |
| Relative degree of crystallinity,% | 96 | 105 |
| Specific surface area, m2/g | 624 | 643 |
| Total pore volume, ml/g | 0.32 | 0.35 |
| Amount of Infrared acid mmol/g | 0.29 | 0.31 |
| B acid/L acid | 0.56 | 0.48 |
TABLE 2
TABLE 3
| Raw oil | Vacuum distillate |
| Density (20 ℃), kg/m3 | 912.3 |
| Distillation range, deg.C | |
| IBP/10％ | 315/403 |
| 30％/50％ | 442/461 |
| 70％/90％ | 495/526 |
| 95％/EBP | 532/544 |
| Freezing point, deg.C | 32 |
| Nitrogen,. mu.g/g | 1568 |
| Carbon, wt.% | 84.53 |
| Hydrogen, wt.% | 11.72 |
| Carbon residue in wt% | 0.32 |
| BMCI value | 43 |
TABLE 4
Claims (11)
1. An improvement type diesel oil hydrocracking catalyst carrier which characterized in that:
the carrier raw material comprises the following components in percentage by weight: 3.4 to 7.6 percent of molecular sieve and 27.3 to 47.7 percent of gamma-Al2O328.3-46.9% of amorphous silica-alumina and 18-20% of binder; the specific surface area of the carrier is 362-383 m2(ii) a total pore volume of 0.52 to 0.63cm3(ii)/g; the carrier is columnar and 3-8 mm in length;
the molecular sieve is one or more of β molecular sieve, Y-type molecular sieve, MOR molecular sieve, ZSM-5 molecular sieve, ZSM-22 molecular sieve and ZSM-23 molecular sieve;
the binder contains 10-40% by mass of small-pore alumina and the balance of acid; the pore volume of the small-pore alumina is 0.3-0.5 cm3A specific surface area of 200 to 350 m/g2The mass ratio of the acid to the small-pore alumina is 0.1-0.5;
the amorphous silica-alumina pore volume is 0.5-1.0 cm3A specific surface area of 300 to 500 m/g2/g。
2. The improved diesel hydrocracking catalyst carrier as set forth in claim 1, wherein the β molecular sieve has a specific surface area of 624-643 m2Per g, total pore volume of 0.32-0.35 cm3/g。
3. A method for preparing the improved diesel hydrocracking catalyst carrier as claimed in claim 1, which is characterized in that: the method comprises the following steps:
1) mixing and stirring tetraethyl ammonium bromide solution, sodium hydroxide, an aluminum source and water to obtain a clear solution, then adding a silicon source, and continuously stirring to obtain silicon-aluminum gel;
2) crystallizing the silicon-aluminum gel obtained in the step 1), and then washing and drying to obtain a molecular sieve;
3) adding the molecular sieve obtained in the step 2) into a mixed solution of aluminum salt and ammonia water for precipitation, taking slurry after full precipitation, and sequentially evaporating, drying and roasting to obtain a molecular sieve and alumina composite material;
4) mixing the molecular sieve obtained in the step 3) with an alumina composite material, amorphous silica-alumina and a binder according to the raw material proportion, and forming to obtain the hydrocracking catalyst carrier.
4. The method for preparing the improved diesel hydrocracking catalyst carrier as claimed in claim 3, wherein: in the step 1), a silicon source, an aluminum source, sodium hydroxide and tetraethyl bromideThe ammonium solution and the water are SiO according to the molar ratio of the ingredients2∶Al2O3∶Na2O tetraethylammonium bromide H2O is added in a ratio of 50-70: 1: 5-8: 15-20: 1000-1200.
5. The method for preparing the improved diesel hydrocracking catalyst carrier as claimed in claim 3, wherein: in the step 3), the aluminum salt is 0.5-3.0 mol/L aluminum chloride, and the concentration of ammonia water is 0.5-4 mol/L.
6. The method for preparing the improved diesel hydrocracking catalyst carrier as claimed in claim 3, 4 or 5, wherein: in the step 3), the pore volume of the molecular sieve and alumina composite material is 0.4-0.9 cm3A specific surface area of 350 to 500 m/g2/g。
7. The preparation method of the improved diesel hydrocracking catalyst carrier as claimed in claim 3, 4 or 5, wherein in the step 2), the molecular sieve is β molecular sieve, the crystallization temperature is 135-145 ℃, the washing liquid is washed with water until the pH of the washing liquid is 6.5-7.5, the drying temperature is 90-110 ℃, and the drying time is 22-26 hours.
8. The method for preparing the improved diesel hydrocracking catalyst carrier as claimed in claim 3, 4 or 5, wherein: in the step 3), the temperature is 60-80 ℃ and the pH is 3-7 in the precipitation process; the drying temperature is 90-120 ℃, and the drying time is 2-3 hours; the roasting temperature is 300-600 ℃, and the roasting time is 2-8 hours.
9. The method for preparing the improved diesel hydrocracking catalyst carrier as claimed in claim 3, 4 or 5, wherein: in the step 4), drying and activating treatment are sequentially carried out after forming, wherein the drying temperature is 100-120 ℃, the drying time is 18-22 hours, the activating temperature is 450-600 ℃, and the activating time is 4-6 hours.
10. The method for preparing the improved diesel hydrocracking catalyst carrier as claimed in claim 3, 4 or 5, wherein: in the step 3), the concentration of ammonia water is 1.0-2.0 mol/L.
11. The method for preparing the improved diesel hydrocracking catalyst carrier as claimed in claim 3, 4 or 5, wherein: in the step 1), the aluminum source is one or more of pseudo-boehmite, aluminum sulfate and sodium metaaluminate; the silicon source is one or more of white carbon black, silica sol and water glass.
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| RU2738080C1 (en) * | 2020-03-19 | 2020-12-07 | Акционерное общество «Газпромнефть - Омский НПЗ» (АО «Газпромнефть - ОНПЗ») | Hydrotreating catalyst support |
| RU2732243C1 (en) * | 2020-03-19 | 2020-09-14 | Акционерное общество «Газпромнефть - Омский НПЗ» (АО «Газпромнефть - ОНПЗ») | Method of preparing a diesel fuel hydrofining catalyst |
| RU2738076C1 (en) * | 2020-03-19 | 2020-12-07 | Акционерное общество «Газпромнефть - Омский НПЗ» (АО «Газпромнефть - ОНПЗ») | Method of preparing support for hydrotreating catalyst |
| 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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