CN113908817B - Carrier for catalyst and preparation method thereof, pour point depressing catalyst and preparation method and application thereof - Google Patents
Carrier for catalyst and preparation method thereof, pour point depressing catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 230000000881 depressing effect Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 21
- 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 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 49
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 32
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000011959 amorphous silica alumina Substances 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000001935 peptisation Methods 0.000 claims description 11
- 229910001679 gibbsite Inorganic materials 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 4
- 238000010304 firing Methods 0.000 claims 2
- 238000006317 isomerization reaction Methods 0.000 abstract description 18
- 238000005336 cracking Methods 0.000 abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002283 diesel fuel Substances 0.000 description 40
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 27
- 239000002808 molecular sieve Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 241000219793 Trifolium Species 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- -1 carbonium ion Chemical class 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/647—
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
Abstract
The invention relates to the field of catalysts, and discloses a carrier for a catalyst and a preparation method thereof, a pour point depressing catalyst and a preparation method and application thereof. The carrier for the catalyst comprises silicon oxide and aluminum oxide, wherein, based on the total weight of the carrier, siO 2 The content of the silicon oxide is 4-36wt%, calculated as Al 2 O 3 The content of the alumina is 64-96wt%; in the carrier, the silicon oxide and the aluminum oxide are amorphous; the acidity of the carrier is 1.1-3.25mmol/g. The surface of the carrier for the catalyst belongs to medium-strength acid, and the diesel pour point depressing catalyst prepared from the catalyst has larger specific surface area, wider mesoporous pore size distribution and excellent isomerization catalytic activity, can prepare a high-isomerization diesel product, and is suitable for Fischer-Tropsch synthesis with cracking hydrogenation reaction.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a carrier for a catalyst and a preparation method thereof, a pour point depressing catalyst and a preparation method and application thereof.
Background
In northern areas of China, the demand for low-freezing diesel oil is large in winter, while diesel oil produced by a 400-ten thousand ton indirect liquefying device for Ningcoal is mainly paraffin, and diesel oil fraction has high freezing point and poor low-temperature fluidity, and needs to be subjected to pour point depressing treatment to improve the low-temperature fluidity of the diesel oil. In the diesel dewaxing process, the hydrogenation pour point depressing technology has the advantages of low investment, low operation cost, mild operation condition and the like, and has obvious technical advantages.
The diesel oil hydrogenation pour point depressing principle is that under the existence of hydrogen, normal paraffins with short side chains, naphthenes with long side chains, aromatics with long side chains and other components with high pour point in raw oil are subjected to hydroisomerization reaction on a catalyst with shape selective isomerization performance to generate isoparaffins or isoparaffins with long side chains with lower pour point, so that the purpose of reducing the pour point is achieved. The key of the diesel oil hydrogenation pour point depressing technology is a hydrogenation pour point depressing catalyst. The hydrogenation pour point depressing catalyst is a double-function catalyst, the metal component provides hydrogenation dehydrogenation active center, and the molecular sieve provides acid center.
CN107570206a discloses a diesel oil hydrogenation pour point depressing catalyst, which is prepared by adopting TON/MFI shape selective isomerism in-situ composite molecular sieve, adding a small amount of adhesive, extruding and molding to prepare a carrier, drying/roasting the carrier, and loading metal active components. Wherein, TON/MFI shape selective isomerism in situ composite molecular sieve is synthesized in situ by sol-gel method, the mol ratio of silicon-aluminum oxide is 30-180, and the TON structure accounts for 1-60%. The catalyst is suitable for the hydrogenation pour point depressing process of diesel oil, and has the characteristics of high yield of diesel oil products, large reduction range of the pour point, and the like.
CN1448475a discloses a catalyst for producing low-freezing point clean diesel oil, modified beta zeolite is used as an acidic component, a modification method of zeolite uses silicon-containing organic matters with larger kinetic diameters to contact with zeolite under certain conditions, so that the silicon-containing organic matters are combined with acid centers on the outer surface of the zeolite to be passivated, the acid centers inside zeolite pore channels are reserved, and the obtained catalyst is used for producing low-freezing point clean diesel oil and has the advantages of high diesel oil product yield and cetane number, low sulfur and nitrogen content and freezing point and the like.
CN1952074a discloses a diesel fraction pour point depressing catalyst, which comprises a modified molecular sieve carrier and a hydrogenation metal component, wherein the modified molecular sieve is modified by a VIB group metal, the weight of the modifier in the modified molecular sieve is 1% -40% in terms of oxidation state, the weight content of the molecular sieve in the catalyst is 10% -90%, and the weight content of the hydrogenation active metal in terms of oxide is 0.1% -40%. The modifier can modify the acid property and the pore size of the surface of the molecular sieve, is good in matching of the isomerization function and the shape selective cracking function of the catalyst, is carried out according to a key reaction mechanism, and can be suitable for the shape selective cracking reaction, so that the excessive cracking is prevented, the property of diesel oil is improved, and the yield of the diesel oil is improved.
However, in the above-mentioned technologies, molecular sieves are used as carriers of catalysts, resulting in a decrease in the yield of heterogeneous diesel.
Disclosure of Invention
The invention aims to solve the problem of low yield of heterogeneous diesel oil in the Fischer-Tropsch synthetic oil cracking process in the prior art, and provides a carrier for a catalyst, a preparation method thereof, a pour point depressing catalyst, a preparation method thereof and application thereof. The carrier surface for the catalyst belongs to medium-strength acid, and the diesel pour point depressing catalyst prepared from the catalyst has larger specific surface area, wider mesoporous pore size distribution and excellent isomerization catalytic activity, can prepare a high-isomerization diesel product, and is suitable for Fischer-Tropsch synthesis with cracking hydrogenation reaction.
In order to achieve the above object, a first aspect of the present invention provides a carrier for a catalyst, wherein the carrier comprises silica and alumina, wherein the silica is formed of SiO 2 The content of the silicon oxide is 4-36wt%, calculated as Al 2 O 3 The content of the alumina is 64-96wt%; in the carrier, the silicon oxide and the aluminum oxide are amorphous, and the acidity of the carrier is 1.1-3.25mmol/g。
Preferably in SiO 2 The content of the silicon oxide is 8-32wt%, preferably 12-28wt%; with Al 2 O 3 The alumina content is 68-92wt%, preferably 72-88wt%.
Preferably, the acidity of the support is from 2.6 to 3mmol/g.
The second aspect of the present invention provides a method for producing the carrier for a catalyst of the present invention, wherein the method comprises: mixing amorphous silicon aluminum with a binder, stirring, adding a nitric acid solution, kneading, forming, drying and roasting to obtain the carrier for the catalyst.
Preferably, the binder is selected from at least one of pseudoboehmite, silica sol, alumina sol and water glass, preferably pseudoboehmite.
Preferably, the pseudo-boehmite has a peptization index of at least 90wt%; more preferably, the pseudo-boehmite has a peptization index of at least 95% by weight.
Preferably, the gibbsite content in the pseudo-boehmite is at most 5wt%; more preferably, the gibbsite content in the pseudo-boehmite is at most 2wt%.
Preferably, the specific surface area of the amorphous silica-alumina is 200-500m 2 Preferably 400-500m 2 /g。
Preferably, the amorphous silica alumina has a pore volume of 1 to 1.6mL/g, preferably 1.4 to 1.6mL/g.
Preferably, siO in the amorphous silica-alumina 2 The content of (C) is 20-70wt%, preferably 30-50wt%.
Preferably, the nitric acid solution is used in an amount of 4 to 10g, preferably 4 to 7g, relative to 100g of the total weight of amorphous silica alumina and binder.
Preferably, the method of forming comprises at least one of drop forming, extrusion forming and tablet forming, preferably extrusion forming.
Preferably, the drying conditions include: the drying temperature is 40-180deg.C, preferably 100-150deg.C; the drying time is 0.5 to 24 hours, preferably 1 to 8 hours.
Preferably, the roasting conditions include: the roasting temperature is 350-700 ℃, preferably 400-600 ℃; the calcination time is 0.5 to 24 hours, preferably 4 to 8 hours.
In a third aspect the present invention provides a pour point depressing catalyst, wherein the catalyst comprises a support and a metal active component, wherein the support is a support according to the present invention or a support made by a process according to the present invention.
Preferably, the support is present in an amount of from 60 to 80wt% based on the total weight of the catalyst, and the metal active component is present in an amount of from 20 to 40wt% calculated as metal oxide.
Preferably, the support is present in an amount of from 65 to 75wt% based on the total weight of the catalyst, and the metal active component is present in an amount of from 25 to 35wt% calculated as metal oxide.
Preferably, the metallic active component comprises group VIII and group VIB metal elements.
Preferably, the group VIII metal element is present in an amount of 1 to 15wt%, preferably 4 to 8wt%, calculated as oxide, based on the total weight of the catalyst; the content of the group VIB metal element is 10-35wt%, preferably 20-28wt%.
More preferably, the group VIII metal element is cobalt and/or nickel and the group VIB metal element is molybdenum and/or tungsten.
The fourth aspect of the invention provides a method for preparing the pour point depressing catalyst, which comprises the steps of immersing a carrier in an impregnating solution containing active metal components, drying and roasting to obtain the diesel pour point depressing catalyst.
Preferably, the impregnation comprises at least one of saturation impregnation, spray impregnation, excess impregnation and isovolumetric impregnation, preferably isovolumetric impregnation.
Preferably, the drying conditions include: the drying temperature is below 200deg.C, preferably 80-150deg.C; the drying time is 1-10h.
Preferably, the roasting conditions include: the roasting temperature is 350-700 ℃, preferably 450-550 ℃; the calcination time is 0.5 to 24 hours, preferably 4 to 8 hours.
In a fifth aspect the present invention provides the use of a pour point depressing catalyst according to the invention or obtainable by a process according to the invention in the cracking of Fischer-Tropsch synthetic oils.
Through the technical scheme, the carrier for the catalyst, the preparation method of the carrier, the pour point depressing catalyst, the preparation method and the application of the pour point depressing catalyst have the following beneficial effects:
1. the carrier for the catalyst provided by the invention does not use a molecular sieve as a carrier, but uses amorphous silicon aluminum as a carrier, the surface of the carrier is provided with medium-strength acid, the prepared catalyst has large specific surface area and wider mesoporous pore size distribution, the diffusion of raw materials and products is easy, the adverse effect of the molecular sieve on the reduction of the yield of diesel oil caused by the secondary cracking of the raw materials is reduced, and the production of high-isomerization diesel oil products is facilitated;
2. the diesel oil pour point depressing catalyst provided by the invention uses non-noble metal as an active metal component, so that the production cost of the catalyst is greatly reduced.
Drawings
FIG. 1 is an XRD pattern for the catalysts provided in examples 1-2 and comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a carrier for a catalyst, wherein the carrier comprises silica and alumina, wherein SiO is used as a carrier based on the total weight of the carrier 2 The content of the silicon oxide is 4-36wt%, calculated as Al 2 O 3 The content of the alumina is 64-96wt%; in the carrier, the silicon oxide and the aluminum oxide are amorphous, and the acidity of the carrier is 1.1-3.25mmol/g.
In the invention, the acidity of the carrier is obtained by pyridine infrared test at 100 ℃.
Because the cracking hydrogenation raw material Fischer-Tropsch heavy diesel oil has a narrow distillation range, the main fraction range is 280-370 ℃, no aromatic hydrocarbon, no carbon residue, no sulfur and no nitrogen are generated, and more than 90% of the structure is alkane.
For the cleavage reaction of alkanes, the occurrence of concomitant isomerization is unavoidable. Both isomerization and cracking are carried out by means of a carbonium ion intermediate under the acid catalyst conditions, the carbonium ion being extremely reactive and only transiently present, and once produced, rapidly undergoing isomerization and cracking reactions. It follows that the step of desorption of the olefin at the acid sites and adsorption to the metal active sites during the alkane cleavage reaction is very important.
Therefore, the residence time of the isomerism carbo-ion in the acid center is reduced, so that the isomerism carbo-ion is desorbed from the acid center before beta-fracture occurs, the cracking reaction can be inhibited, the isomerism reaction is promoted, and the isomerism reaction of the Fischer-Tropsch heavy diesel is facilitated to prepare the diesel.
In the prior art, when hydroisomerization pour point depressing reaction is performed on Fischer-Tropsch heavy diesel oil to produce diesel oil, a catalyst using a molecular sieve as a carrier is generally used.
The inventor researches and discovers that the catalyst taking the molecular sieve as the carrier in the prior art has high cracking activity due to the strong acidity of the molecular sieve, so that the yield of the catalyst for catalyzing the Fischer-Tropsch heavy diesel oil to isomerize to prepare diesel oil is lower and cannot meet the actual requirements.
In the present invention, however, the inventors have employed amorphous oxides, particularly amorphous aluminosilicates (e.g., siO 2 -A1 2 O 3 ) The carrier is used for replacing the molecular sieve in the prior art, and compared with the molecular sieve, the amorphous silica-alumina has weaker acidity, so that the ratio of the metal and the acidity of the catalyst can be greatly improved, the metal/acid value on the hydroisomerization catalyst is improved, the generation of high-isomerization products is facilitated, the pour point depressing effect is remarkably improved, and the yield of diesel oil is improved.
Further, when the acidity of the carrier is 2.6 to 3mmol/g, the catalyst has more excellent catalytic effect.
Meanwhile, the inventor has studied the amorphous silica-alumina and the amount of binder in the carrier, and has shown that when SiO is used 2 The content of the silicon oxide is 8 to 32 weight percent, calculated as Al 2 O 3 When the content of the alumina is 68-92wt%, the provided carrier has more proper surface acidity, more proper pore size distribution and specific surface area, and is beneficial to improving the yield of diesel oil.
Further, based on the total weight of the carrier, in SiO 2 The content of the silicon oxide is 12-28wt%, calculated as Al 2 O 3 The content of the alumina is 72-88wt%.
The second aspect of the present invention provides a method for preparing the carrier for a catalyst according to the present invention, wherein the method comprises: mixing amorphous silicon aluminum with a binder, stirring, adding a nitric acid solution, kneading, forming, drying and roasting to obtain the carrier for the catalyst.
According to the invention, the nitric acid solution is added into the mixed amorphous silicon aluminum and binder, so that the binder, particularly the sol of pseudo-boehmite, can be promoted, the binding performance of the amorphous silicon aluminum is remarkably improved, and the carrier for the catalyst with more excellent comprehensive performance is obtained.
According to the invention, the binder is at least one selected from the group consisting of pseudo-boehmite, silica sol, alumina sol and water glass, preferably pseudo-boehmite.
The inventors have found that the use of pseudo-boehmite as a binder has a significant effect on improving the surface acidity of the support, improving the pore size distribution of the support, etc. According to the invention, the peptization index of the pseudo-boehmite is at least 90wt%, the content of the gibbsite in the pseudo-boehmite is not more than 5wt%, the obtained carrier can be ensured to have excellent performance, and adverse effects of the gibbsite in the pseudo-boehmite on the carrier structure are reduced.
Specifically, when the peptization index of pseudo-boehmite is too low, the binding function of pseudo-boehmite becomes weak, which is unfavorable for the binding of amorphous silica-alumina powder, and when the content of gibbsite in pseudo-boehmite is too high, the performance of the catalyst becomes poor.
Further, in the present invention, the pseudo-boehmite has a peptization index of at least 95% by weight, and the pseudo-boehmite contains at most 2% by weight.
In the present invention, the inventors have found that amorphous silica-alumina has a specific surface area, pore volume and SiO 2 The content of (2) has important influence on the surface activity, pore size distribution and the like of the carrier, and further has obvious influence on the yield of the Fischer-Tropsch heavy diesel oil isomerized diesel oil. It has been found that, in order to ensure the yield of the Fischer-Tropsch heavy diesel oil isomerised to diesel oil, the specific surface area of the amorphous silica-alumina is 400-500m 2 Preferably 450-500m 2 /g; the pore volume of the amorphous silicon aluminum is 0.5-1.6mL/g, preferably 0.8-1.6mL/g; siO in the amorphous silicon aluminum 2 The content of (C) is 20-70wt%, preferably 30-70wt%.
Such as specific surface area, pore volume and SiO of amorphous silica-alumina 2 When the content of the catalyst does not fall into the range defined by the invention, the comprehensive performance of the prepared carrier is poor, the yield of the catalyst for preparing diesel oil by catalyzing Fei Tuochong diesel oil isomerization is low, and the actual requirement cannot be met.
According to the invention, the nitric acid solution is used in an amount of 4 to 10g, preferably 4 to 7g, relative to 100g of the total weight of amorphous silica alumina and binder.
In the present invention, the amount of the nitric acid solution is calculated based on the mass of nitric acid contained in the nitric acid solution.
According to the present invention, the molding method includes at least one of drop molding, extrusion molding, and tablet molding, preferably extrusion molding.
According to the invention, the drying conditions include: the drying temperature is 40-180deg.C, preferably 100-150deg.C; the drying time is 0.5 to 24 hours, preferably 1 to 8 hours.
According to the invention, the conditions of the calcination include: the roasting temperature is 350-700 ℃, preferably 400-600 ℃; the calcination time is 0.5 to 24 hours, preferably 4 to 8 hours.
The third aspect of the invention provides a pour point depressing catalyst, wherein the catalyst comprises a carrier and a metal active component, wherein the carrier is the carrier or the carrier prepared by the method.
In the invention, the catalyst prepared by matching the carrier provided by the invention with the active metal component has excellent diesel oil pour point depressing effect, and can obviously improve the yield of diesel oil when being used for isomerization of Fischer-Tropsch heavy diesel oil.
Meanwhile, the carrier amorphous silicon aluminum used in the invention has weak sensitivity to temperature, so that the reaction temperature is easy to control when the prepared catalyst is subjected to catalytic reaction, and the requirement on production devices is reduced.
According to the invention, the support is present in an amount of 60 to 80% by weight, based on the total weight of the catalyst, and the metal active component is present in an amount of 20 to 40% by weight, calculated as metal oxide.
According to the invention, the support is present in an amount of 67 to 75% by weight, based on the total weight of the catalyst, and the metal active component is present in an amount of 25 to 33% by weight, calculated as metal oxide.
According to the invention, the metallic active component comprises metallic elements of groups VIII and VIB.
In the invention, the content of the VIII group metal element is 1-15wt% and the content of the VIB group metal element is 10-35wt% calculated by oxide, when the content of the metal element in the metal active component does not meet the above range, the obtained catalyst has weak metallicity and the isomerization degree of the product is low.
Further, the content of the group VIII metal element is preferably 4 to 8wt% in terms of oxide; the content of the group VIB metal element is preferably 20 to 28wt%. The catalyst prepared by the method has more excellent isomerization catalytic activity, and can prepare a high isomerization diesel product.
Preferably, the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten.
In the invention, the acidity of the carrier is weakened, so that the catalyst can be matched with non-noble metal as a metal active component of the catalyst when the catalyst is prepared, and the production cost of the catalyst can be obviously reduced on the premise of ensuring the isomerism catalytic activity of the catalyst.
The fourth aspect of the invention provides a method for preparing the pour point depressing catalyst, which comprises the steps of immersing a carrier in an impregnating solution containing an active metal component, drying and roasting to obtain the diesel pour point depressing catalyst.
According to the invention, the impregnation comprises at least one of saturated impregnation, spray impregnation, excess impregnation and isovolumetric impregnation, preferably isovolumetric impregnation.
According to the invention, the drying conditions include: the drying temperature is below 200deg.C, preferably 80-150deg.C; the drying time is 1-10h.
According to the invention, the conditions of the calcination include: the roasting temperature is 350-700 ℃, preferably 450-550 ℃; the calcination time is 0.5 to 24 hours, preferably 4 to 8 hours.
In a fifth aspect, the invention provides the use of a pour point depressing catalyst according to the invention or a diesel pour point depressing catalyst obtainable by a process according to the invention in the cracking of Fischer-Tropsch synthetic oils.
The present invention will be described in detail by examples. In the following examples, N is used as the specific surface area, pore volume and pore distribution of the catalyst 2 Adsorption (BET) measurement;
the strength of the catalyst is measured by an intelligent particle strength tester;
the peptization index of pseudo-boehmite was measured by EDTA method;
the content of gibbsite in pseudo-boehmite is measured by XRD method;
the XRF is adopted to test the content of each component in the carrier;
pyridine infrared (1540 cm) at 100deg.C was used -1 ) Testing the acid amount of the surface of the carrier and the amorphous silicon aluminum powder;
XRD was used to characterize the crystalline morphology of the catalyst.
The physicochemical parameters of the amorphous silica-alumina used in the examples and comparative examples are shown in Table 1;
TABLE 1
| Amorphous silicon aluminum | PA-1 | 3903 | A |
| Specific surface, m 2 /g | 320.1 | 193.97 | 498 |
| Pore volume, mL/g | 0.81 | 0.64 | 1.6 |
| Acid amount, mmol/g | 1.781 | 1.344 | 4.927 |
Pseudo-boehmite I is purchased from Shandong catalytic technology Co., ltd, has a peptization index of 95wt%, a gibbsite content of 2wt%, a pore volume of 0.45mL/g, and a specific surface area of 200m 2 /g；
Pseudo-boehmite II is purchased from Shandong catalytic technology Co., ltd, has a peptization index of 90wt%, a gibbsite content of 4wt%, a pore volume of 0.45mL/g, and a specific surface area of 200m 2 /g；
Pseudo-boehmiteIII available from Shandong Chemicals Co., ltd, having a peptization index of 85% by weight, a gibbsite content of 6% by weight, a pore volume of 0.45mL/g and a specific surface area of 200m 2 /g。
Example 1
147g of amorphous silicon aluminum I (ASA) and 74g of pseudo-boehmite I (SB, not baked), mixing uniformly, adding aqueous solution of nitric acid under stirring, kneading into clusters by a mixer, extruding clover with the maximum diameter of 2mm by a strip extruder, drying at 120 ℃ for 4h, and baking at 500 ℃ for 4h to obtain a carrier A, wherein SiO is used as a carrier A 2 The content of the silicon oxide is 26wt%, calculated as Al 2 O 3 The alumina content was 74wt%. Carrier A was subjected to an acidity test, the results of which are shown in Table 3.
Taking 20g of ammonium metatungstate and 18 g of nickel nitrate to prepare an impregnating solution, taking 50g of the obtained carrier A, adding the carrier A into the impregnating solution, impregnating the carrier A in a rotary evaporator at 80 ℃ for 2 hours, and roasting the carrier A at 500 ℃ for 2 hours to prepare the catalyst A, wherein the content of the nickel element of the VIII group is 5wt% and the content of the tungsten element of the VIB group is 17.5wt% in terms of oxide. The composition is shown in Table 3.
As can be seen from the XRD pattern of the catalyst shown in fig. 1, catalyst a exhibited an amorphous shape and the surface support B did not contain molecular sieves.
Example 2
126g of amorphous silicon aluminum I (ASA) and 98g of pseudo-boehmite I (SB, not baked), mixing uniformly, adding nitric acid aqueous solution under stirring, kneading into clusters by a mixer, extruding clover with the maximum diameter of 2mm by a strip extruder, drying at 120 ℃ for 4h, and baking at 500 ℃ for 4h to obtain a carrier B, wherein SiO is used as a carrier B 2 The content of the silicon oxide is 22wt%, calculated as Al 2 O 3 The alumina content was 78wt%. Carrier B was subjected to an acidity test, the results of which are shown in Table 3.
Taking 20g of ammonium metatungstate and 18 g of nickel nitrate to prepare an impregnating solution, taking 50g of the obtained carrier B, adding the carrier B into the impregnating solution, impregnating the carrier B in a rotary evaporator at 80 ℃ for 2 hours, and roasting the carrier B at 500 ℃ for 2 hours to prepare the catalyst B, wherein the content of the VIII group metal nickel element is 5wt% and the content of the VIB group metal tungsten element is 17.5wt% in terms of oxide. The composition is shown in Table 3.
As can be seen from the XRD pattern of catalyst B shown in fig. 1, catalyst B exhibited an amorphous shape, and the surface support B did not contain molecular sieves.
Example 3
The carrier was prepared in the same manner as in example 1 except that: the amorphous silicon aluminum II is used to replace the amorphous silicon aluminum I to prepare a carrier C, wherein, siO is used as the carrier 2 The content of the silicon oxide is 26wt%, calculated as Al 2 O 3 The alumina content was 74wt% and catalyst C was prepared in the same manner as in example 1. Carrier C was subjected to an acidity test, and the results are shown in Table 3. The composition of catalyst C is shown in Table 3.
Example 4
The carrier was prepared in the same manner as in example 1 except that: a support D was prepared using pseudo-boehmite II instead of pseudo-boehmite I, and a catalyst D was prepared in the same manner as in example 1. Carrier D was subjected to an acidity test, and the results are shown in Table 3. Catalyst D had the composition shown in table 3.
Example 5
The carrier was prepared in the same manner as in example 1 except that: the catalyst E is prepared by using 10g of ammonium tungstate and 5.5 g of nickel nitrate, wherein the content of the nickel element of the VIII group metal is 2wt% and the content of the tungsten element of the VIB group metal is 13wt% in terms of oxide. The carrier E was subjected to an acidity test, and the results are shown in Table 3. The composition of catalyst E is shown in Table 3.
Example 6
The carrier was prepared in the same manner as in example 1 except that: a support F was prepared using pseudo-boehmite III instead of pseudo-boehmite I, and a catalyst F was prepared in the same manner as in example 1, wherein SiO 2 The content of the silicon oxide is 26wt%, calculated as Al 2 O 3 The alumina content was 74wt%. Carrier F was subjected to an acidity test, the results of which are shown in Table 3. The composition of catalyst F is shown in Table 3.
Comparative example 1
147g of amorphous silicon aluminum I (ASA), 54g of pseudo-boehmite I (SB, not baked) and 20g of beta molecular sieve (Si/Al=25) are uniformly mixed, nitric acid aqueous solution is added under the stirring state, after the mixture is kneaded into a mass, the mass is put into a strip extruder to extrude clover with the maximum diameter of 2mm, and then the mixture is dried for 4 hours at 120 ℃ and baked for 4 hours at 500 ℃ to obtain a carrier D1, wherein SiO is used as the carrier D1 2 The content of the silicon oxide is 38wt%, calculated as Al 2 O 3 The alumina content was 62wt%. The carrier D1 was subjected to an acidity test, and the results are shown in Table 3.
Taking 20g of ammonium metatungstate and 18 g of nickel nitrate to prepare an impregnating solution, taking 50g of the obtained carrier D, adding the carrier D into the impregnating solution, impregnating the carrier D in a rotary evaporator at 80 ℃ for 2 hours, and roasting the carrier D at 500 ℃ for 2 hours to prepare the catalyst D1, wherein the content of the VIII group metal nickel element is 5wt% and the content of the VIB group metal tungsten element is 17.5wt% in terms of oxide. Catalyst D1 had the composition shown in Table 3.
The XRD spectrum of catalyst D1 obtained in comparative example 1 is shown in FIG. 1. As can be seen from fig. 1, a distinct peak appears at 2θ=22.4°, representing the presence of molecular sieves.
Comparative example 2
147g of amorphous silicon aluminum I (ASA), 62g of pseudo-boehmite I (SB, not baked) and 12g of beta molecular sieve (Si/Al=25) are uniformly mixed, nitric acid aqueous solution is added under the stirring state, after the mixture is kneaded into a mass, the mass is put into a strip extruder to extrude clover with the maximum diameter of 2mm, and then dried for 4 hours at 120 ℃ and baked for 4 hours at 500 ℃ to obtain an A catalyst carrier D2, wherein SiO is used as a catalyst carrier D2 2 The content of the silicon oxide is 33wt%, calculated as Al 2 O 3 The alumina content was 67wt%. Carrier D2 was subjected to an acidity test, and the results are shown in Table 3.
Taking 20g of ammonium metatungstate and 18 g of nickel nitrate to prepare an impregnating solution, taking 50g of the obtained carrier D2, adding the carrier D2 g into the impregnating solution, impregnating the carrier D2 g in a rotary evaporator at 80 ℃ for 2 hours, and roasting the carrier D2 g at 500 ℃ for 2 hours to prepare a contrast agent D2, wherein the content of the VIII group metal nickel element is 5wt% and the content of the VIB group metal tungsten element is 17.5wt% based on oxide. Catalyst D2 had the composition shown in table 3.
Comparative example 3
The carrier was prepared in the same manner as in example 1 except that: a carrier D3 was prepared using amorphous silica alumina III instead of amorphous silica alumina I, and a catalyst D3 was prepared in the same manner as in example 1, wherein SiO 2 The content of the silicon oxide is 26wt%, calculated as Al 2 O 3 The alumina content was 74wt%. The carrier D3 was subjected to an acidity test, and the results are shown in Table 3. Catalyst D3 had the composition shown in Table 3.
N carrying out the catalyst B prepared in example 2 of the present invention and the FC-14 pour point depressing catalyst (commercially available) 2 The adsorption method (BET) and the strength measurement, and the obtained structural parameters are shown in Table 2.
TABLE 2 structural parameters of catalyst B and FC pour point depressing catalyst prepared in example 2 of the invention
| FC series | Example 2 | |
| Specific surface area, m 2 /g | 179.44 | 253.3 |
| Pore volume, ml/g | 0.37 | 0.5 |
| Pore distribution (in dV/dlogD)% | ||
| <4nm | 13.12 | 11.23 |
| 4-6nm | 25.1 | 22.46 |
| 6-12nm | 49.05 | 62.96 |
| >12nm | 12.74 | 3.35 |
| Average pore diameter, nm | 8.24 | 7.97 |
| Catalyst particle strength | 20 | 19.5 |
TABLE 3 composition of support, acidity, composition of catalyst
Evaluation example
The hydrofined Fischer-Tropsch heavy firewood is used as a raw material, and the physical and chemical parameters are shown in table 4, so that hydroisomerization and pour point depressing reactions are carried out. Catalyst A-F, D1-D3 are respectively filled in a 30mL hydrogenation device for reverse reactionThe conditions are as follows: hydrogen-oil ratio 800, reaction pressure 7MPa, volume space velocity 1.00h -1 The reaction temperature is 320-360 ℃.
TABLE 4 physicochemical parameters of Fischer-Tropsch heavy firewood
Testing the condensation point of the hydroisomerization product by adopting a condensation point pour point tester; the conversion of hydroisomerization reactions and the yield of diesel were calculated using data from simulated distillation. The results are shown in tables 5 and 6. TABLE 5 product congealing Point and Diesel yield at the same conversion for different catalysts (cracking conversion 15%)
| Temperature, DEG C | Full distillate product set point, DEG C | Diesel oil yield% | |
| D1 | 320 | -35 | 60 |
| D2 | 330 | -30 | 65 |
| D3 | 360 | -15 | 70 |
| A | 348 | -35 | 85 |
| B | 353 | -30 | 83 |
| C | 356 | -20 | 80 |
| D | 348 | -30 | 80 |
| E | 348 | -10 | 70 |
| F | 348 | -25 | 73 |
TABLE 6 Diesel yield with the same catalyst at the same product congealing point
As can be seen from Table 2, the catalyst provided by the invention has a larger specific surface area, the carrier provided by the invention has a wider mesoporous pore size distribution, and the diesel oil pour point depressing catalyst prepared from the catalyst has excellent isomerization catalytic activity.
As can be seen from Table 3, the acid effect of the various amorphous silica-alumina and molecular sieves on the support is great, and the larger the acid, the lower the product yield is, which is disadvantageous for the improvement of the product yield.
As can be seen from Table 5, the diesel oil pour point depressing catalyst provided by the invention has a lower pour point when catalyzing hydroisomerization pour point depressing reaction at the same conversion rate (15%). In comparative examples 1-2, in which molecular sieves were added to the carrier, the congealing point of the whole fraction product was low (but the congealing point of the diesel fraction was not lowered) due to the cracking into naphtha, and with the increase in the amount of molecular sieves, the naphtha content in the whole fraction product was increased, resulting in further lowering of the congealing point (but the congealing point of the diesel fraction was not lowered), the addition of molecular sieves, and the diesel yield was greatly lowered, indicating that the increase in the molecular sieve content in the catalyst carrier was unfavorable for the isomerization reaction.
As can be seen from Table 6, the yield of the diesel oil is remarkably improved when the diesel oil pour point depressing catalyst provided by the invention catalyzes the hydroisomerization pour point depressing reaction on the premise of ensuring that the products of the hydroisomerization pour point depressing reaction have the same condensation point. The catalyst containing amorphous silicon aluminum as a carrier is more beneficial to improving the yield of the product diesel oil compared with the catalyst containing molecular sieve as the carrier.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (25)
1. Use of a diesel pour point depressing catalyst for hydroisomerization pour point depressing reactions of fischer-tropsch heavy diesel, the catalyst comprising a carrier and a metal active component;
the carrier comprises silicon oxide and aluminum oxide, wherein, based on the total weight of the carrier, siO 2 The content of the silicon oxide is 8 to 32 weight percent, calculated as Al 2 O 3 The content of the alumina is 68-92wt%; in the carrier, the silicon oxide and the aluminum oxide are amorphous;
the acidity of the carrier is 1.1-3.25mmol/g;
the preparation method of the carrier comprises the following steps: mixing amorphous silicon aluminum with a binder, stirring, adding a nitric acid solution, kneading, forming, drying and roasting to obtain the carrier;
the binder is pseudo-boehmite;
the pseudo-boehmite has a peptization index of at least 90wt%, and the pseudo-boehmite contains at most 5wt%;
wherein the specific surface area of the amorphous silicon aluminum is 200-500m 2 /g；
The pore volume of the amorphous silicon aluminum is 1-1.6mL/g;
SiO in the amorphous silicon aluminum 2 The content of (C) is 20-70wt%.
2. Use according to claim 1, wherein the carrier is based on the total weight of the carrier, in SiO 2 The content of the silicon oxide is 12-28wt%; with Al 2 O 3 The content of the alumina is 72-88wt%.
3. Use according to claim 1 or 2, wherein the acidity of the carrier is 2.6-3mmol/g.
4. Use according to claim 1 or 2, wherein the pseudo-boehmite has a peptization index of at least 95% by weight.
5. Use according to claim 1 or 2, wherein the gibbsite content of the pseudo-boehmite is at most 2wt%.
6. The use according to claim 1 or 2, wherein the amorphous silica-alumina has a specific surface area of 400-500m 2 /g。
7. The use according to claim 1 or 2, wherein the amorphous silica alumina has a pore volume of 1.4-1.6mL/g.
8. Use according to claim 1 or 2, wherein the amorphous silicon-aluminum SiO 2 The content of (C) is 30-50wt%.
9. Use according to claim 1 or 2, wherein the nitric acid solution is used in an amount of 4-10g relative to 100g of the total weight of amorphous silica alumina and binder.
10. The use according to claim 1 or 2, wherein the shaping method comprises at least one of drop shaping, extrusion shaping and tabletting shaping.
11. The use according to claim 1 or 2, wherein the drying conditions comprise: the drying temperature is 40-180 ℃; the drying time is 0.5-24h.
12. The use according to claim 1 or 2, wherein the firing conditions comprise: the roasting temperature is 350-700 ℃; the roasting time is 0.5-24h.
13. Use according to claim 1 or 2, wherein the nitric acid solution is used in an amount of 4-7g relative to 100g of the total weight of amorphous silica alumina and binder.
14. Use according to claim 1 or 2, wherein the molding method is extrusion molding.
15. The use according to claim 1 or 2, wherein the drying conditions comprise: the drying temperature is 100-150 ℃ and the drying time is 1-8h.
16. The use according to claim 1 or 2, wherein the firing conditions comprise: the roasting temperature is 400-600 ℃, and the roasting time is 4-8h.
17. Use according to claim 1 or 2, wherein the support is present in an amount of 60-80wt%, calculated as metal oxide, of 20-40wt% of the metal active component, based on the total weight of the catalyst.
18. Use according to claim 1 or 2, wherein the support is present in an amount of 67-75wt%, calculated as metal oxide, of 25-33wt% of the metal active component, based on the total weight of the catalyst.
19. Use according to claim 1 or 2, wherein the metallic active component comprises group VIII and group VIB metal elements.
20. Use according to claim 19, wherein the content of the group VIII metal element, calculated as oxide, is 1-15wt%, based on the total weight of the catalyst; the content of the VIB group metal element is 10-35wt%.
21. Use according to claim 19, wherein the content of the group VIII metal element, calculated as oxide, is 4-8wt%, based on the total weight of the catalyst; the content of the VIB group metal element is 20-28wt%.
22. The use according to claim 19, wherein the group VIII metal element is cobalt and/or nickel and the group VIB metal element is molybdenum and/or tungsten.
23. The use according to claim 1 or 2, wherein the preparation method of the diesel pour point depressing catalyst comprises the steps of immersing a carrier in an impregnating solution containing a metal active component, drying and roasting to obtain the diesel pour point depressing catalyst.
24. The use of claim 23, wherein the impregnation comprises at least one of saturated impregnation, spray impregnation, excess impregnation, and isovolumetric impregnation;
the drying conditions include: the drying temperature is below 200 ℃; the drying time is 1-10h;
the roasting conditions include: the roasting temperature is 350-700 ℃; the roasting time is 0.5-24h.
25. The use according to claim 24, wherein the impregnation is an isovolumetric impregnation;
the drying conditions include: the drying temperature is 80-150 ℃;
the roasting conditions include: the roasting temperature is 450-550 ℃; the roasting time is 4-8h.
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| CN103316710A (en) * | 2013-07-11 | 2013-09-25 | 中科合成油内蒙古有限公司 | Hydroisomerization/cracking catalyst, and preparation method and application thereof |
| CN105582972A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Isomerization pour point depression catalyst, preparation method and application thereof, and a Fischer-Tropsch synthetic wax isomerization pour point depression method |
| CN105771970A (en) * | 2014-12-23 | 2016-07-20 | 神华集团有限责任公司 | Hydroisomerization catalyst and preparation method thereof, and method for producing base oil of lubricating oil from hydrocarbon oil or Fischer-Tropsch synthesis oil |
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| CN107570207A (en) * | 2016-07-04 | 2018-01-12 | 中国石油天然气股份有限公司 | Base metal distillate hydrogenation heterogeneous catalyst and preparation method thereof |
| CN107661756A (en) * | 2016-07-29 | 2018-02-06 | 神华集团有限责任公司 | The method that hydrocracking catalyst of coproduction lube base oil and its preparation method and application and Fischer-Tropsch wax are hydrocracked |
| CN110433819A (en) * | 2018-05-04 | 2019-11-12 | 国家能源投资集团有限责任公司 | The method that Fischer Tropsch waxes hydrocracking catalyst and preparation method thereof and Fischer Tropsch waxes are hydrocracked |
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