CN116273012A - Iron-based core-shell catalyst for residual oil suspension bed hydrocracking and preparation method thereof - Google Patents
Iron-based core-shell catalyst for residual oil suspension bed hydrocracking and preparation method thereof Download PDFInfo
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- CN116273012A CN116273012A CN202310159620.9A CN202310159620A CN116273012A CN 116273012 A CN116273012 A CN 116273012A CN 202310159620 A CN202310159620 A CN 202310159620A CN 116273012 A CN116273012 A CN 116273012A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 239000011258 core-shell material Substances 0.000 title claims abstract description 66
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 50
- 239000012053 oil suspension Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims description 43
- 239000003921 oil Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical group [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- -1 iron ions Chemical class 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229960004011 methenamine Drugs 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 14
- 239000000571 coke Substances 0.000 abstract description 11
- 239000003502 gasoline Substances 0.000 abstract description 10
- 239000002283 diesel fuel Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 11
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- 239000000295 fuel oil Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 229910000856 hastalloy Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Images
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
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses an iron-based core-shell catalyst for residual oil suspension bed hydrocracking and a preparation method thereof, wherein a hydrothermal-coprecipitation method is adopted to prepare SiO with a core-shell structure in situ 2 Roasting an iron-based catalyst material of ZnFe-LDHs binary hydrotalcite-like compound in an air atmosphere to obtain an iron-based core-shell catalyst (SiO) 2 @ ZnFe-LMOs). The prepared catalyst has low granularity, can be highly dispersed in residual oil medium, has larger specific surface area of the catalytic material, and is favorable for full contact between residual oil and the catalyst. Application of the catalyst to residual oil suspensionThe floating bed hydrocracking has higher hydrogenation activity, effectively inhibits the generation of gas micromolecules and coke, improves the utilization rate of residual oil molecules, has the yield of gasoline and diesel oil of products higher than 50 percent, has higher conversion rate and liquid yield, and has good application prospect in industry.
Description
Technical Field
The invention belongs to the technical field of energy and chemical industry, and particularly relates to an iron-based core-shell catalyst material, a preparation method thereof and application thereof in the production of light oil by residual oil suspension bed hydrocracking.
Background
Since the 21 st century, the world's conventional crude oil resources have been increasingly scarce, and crude oil resources have exhibited a very significant tendency to be heavy and poor. Today, the world's remaining petroleum resources are about 100000 billions of barrels, with heavy oil resources accounting for seven components and conventional petroleum resources only three components. In recent years, the world heavy oil production cost is continuously reduced under the improvement of development technology and operation management level, and the growth speed of global conventional crude oil development and production is far lower than that of heavy oil development and production. In the future the commercial production scale of heavy oils will be an increasing proportion of the refinery industry.
The residual oil hydrogenation technology is favored by the characteristics of high conversion rate, high light oil yield, good product quality, good device benefit and excellent environmental protection performance. Therefore, the residual oil hydrogenation process is still a main treatment means of the inferior heavy oil processing technology in the future, and is also the most reasonable and effective method for solving the deep processing of heavy oil. Currently, industrial residuum suspension bed hydrocracking catalysts are largely classified into homogeneous catalysts (water-soluble catalysts and oil-soluble catalysts) and solid powder catalysts.
CN 110237851 A,CN 110237866A and CN 107469837B disclose one or more homogeneously dispersed catalysts for inferior heavy oil and residual oil, which can obtain higher hydrogenation conversion rate, have higher selectivity and stability, and can effectively inhibit coking in the reaction process, but these catalysts have the problems of complex process, higher cost, and the like in preparation, and meanwhile, the catalyst is difficult to recycle.
CN 103769196B discloses a residual oil hydrocracking catalyst which can be prepared by adopting a coprecipitation method, the catalyst contains 2-20wt% of hydrated ferric oxide, 27-wt% of molecular sieve and 30-70 wt% of heat-resistant inorganic oxide carrier, and is suitable for the hydrocracking process of super heavy oil and inferior residual oil with high asphaltene and metal content, and has the advantages of simple preparation method, no noble metal, low cost and high light oil yield. CN 101491764B discloses a residuum hydrocracking catalyst prepared by kaolin modified loading active components (active components include active metal components of VIB and VIII, the VIII metal is Ni or Co, the VIB metal is W or Mo), and the prepared catalyst can be used in the fields of hydrodemetallization, hydrodesulfurization, hydroconversion, etc. of heavy oil or residuum, and has good usability.
Hydrotalcite (LDH) is used as a functional material with a layered structure, has excellent catalytic performance, and has great advantages in the aspect of residual oil hydrocracking. Silicon dioxide (SiO) 2 ) Is an inorganic substance which is used as one of common carriers, has larger specific surface area and rich void structure, has stable chemical property and is favorable for loading and dispersing active metals. CN 107115853A discloses a MgAl hydrotalcite-like catalyst for treating heavy oil, which can be directly used for producing high-quality gasoline and diesel oil by conventional catalytic cracking; the catalyst has strong water-heat resistance, the adopted gasification regeneration technology takes the mixture of water vapor and air as regeneration gas to obtain the synthesis gas with the H/C ratio of about 1, and the synthesis gas can be used for the production of diesel oil production technology or chemical products such as olefin, aromatic hydrocarbon and the like by a one-step method, thereby realizing the maximum utilization of resource value. However, the liquid yield is low, and a large amount of solid coke is generated, so that the deactivation of the catalyst is accelerated.
At present, the light oil production by the residuum hydrocracking technology mainly uses a fixed bed reaction process, however, the residuum raw material used in the residuum hydrocracking process does not contain a large amount of impurities and toxic substances, so that the deactivation of the catalyst is accelerated, the catalyst stability is very challenging, and coke is produced in the reaction process. The concentration of impurities, poisons and coke on the surface of the catalyst severely reduces the activity of the catalyst, resulting in rapid catalyst deactivation. Therefore, the development of a novel process for hydrocracking residual oil has a great significance. The suspension bed reaction process is characterized in that the catalyst and raw materials pass through the reactor once, and the problem of catalyst deactivation caused by the existence of impurities and coke is well avoided. Based on the characteristics of the suspension bed hydrogenation reaction, the catalyst is required to have the characteristics of high activity, low price and good stability.
In view of the above, there is a great need for residuum processing to develop a high activity, good hydrogenation performance, low cost, and good stability suspension hydrocracking catalyst. The key is how to select the material with high hydrocracking activity and low price as the active component, and prepare the catalyst with high dispersion and high stability. In order to achieve the effect, the invention discloses an iron-based core-shell catalytic material for lightening residual oil, the preparation process of the material is green and simple, the raw materials are cheap, and the application of the iron-based core-shell catalytic material in the field of the hydrocracking production of residual oil suspension bed is freshly reported, so that the material has very important guiding significance and practical value for the lightening production of residual oil.
Disclosure of Invention
The invention aims to apply an iron-based core-shell catalytic material to the production of residual oil suspension bed hydrocracking. SiO with core-shell structure 2 The @ ZnFe-LDHs binary hydrotalcite-like iron-based catalytic material is used as a precursor, and after calcination, the iron-based core-shell catalytic material (SiO) wrapped by the composite metal oxide with tightly packed and stable crystal units can be generated 2 @ZnFe-LMOs) which have metal active sites and oxygen vacancies, are favorable for the hydrocracking reaction, have good stability, have relatively large specific surface area and are favorable for the macromolecular agglomeration in the raw materialsAnd (5) combining. The catalyst has excellent catalytic performance in the residual oil suspension bed hydrocracking reaction, and has high residual oil conversion rate and high gasoline and diesel oil yield. The prepared iron-based core-shell catalyst material has good application prospect in the residual oil suspension bed hydrocracking reaction.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation process of iron-base core-shell catalyst for hydrocracking residual oil in suspension bed includes hydrothermal coprecipitation to produce carbonate and hydroxide with mixed alkali to react with zinc and iron metal salt ion to produce SiO 2 The combined carbonate intercalation binary hydrotalcite-like compound (ZnFe-LDHs) is calcined in air atmosphere to obtain the iron-based core-shell catalyst material (SiO) with highly dispersed active components and good stability 2 @ ZnFe-LMOs). The method specifically comprises the following steps:
(1) Mixing metal ferric salt and zinc salt according to a certain molar ratio, dissolving in deionized water, and stirring until the metal ferric salt and the zinc salt are completely dissolved to form a mixed metal salt solution;
(2) Mixing alkaline substances according to a certain molar ratio, dissolving the alkaline substances in deionized water, and stirring the mixture until the alkaline substances are completely dissolved to form alkaline solution;
(3) Slowly adding alkaline solution dropwise into mixed metal salt solution under vigorous stirring, and adding SiO 2 Forming uniform suspension, and then vigorously stirring and aging for 0.5-12 h at normal temperature;
(4) Transferring the aged suspension in the step (3) into a stainless steel water heating kettle with a polytetrafluoroethylene lining, carrying out static crystallization at 70-180 ℃ for 6-48h, taking out and cooling to room temperature, filtering and washing a precipitate, and then drying in a baking oven at 80-180 ℃ for several hours to obtain a binary hydrotalcite-like iron-zinc core-shell catalyst precursor;
(5) Roasting the binary hydrotalcite-like iron-zinc core-shell catalyst precursor obtained in the step (4) under the air atmosphere of 300-800 ℃ for 2-12 h, and cooling to obtain the iron-based core-shell catalyst.
Further, in the step (1), the metal ferric salt is any one of ferric nitrate, ferric acetate, ferric chloride, ferric oxalate or ferric sulfate; the zinc precursor is any one of zinc nitrate, zinc sulfate, zinc chloride or zinc acetate.
Further, the ratio of the amount of zinc ions to the amount of iron ions in the step (1) is 1:0.1-10.
Further, the alkaline substance in the step (2) is NaOH, KOH, liOH, ammonia water and Na 2 CO 3 ，K 2 CO 3 ，Li 2 CO 3 ，(NH 4 ) 2 CO 3 ，NH 4 HCO 3 At least one of urea, water and hydrazine, hexamethylene tetramine.
Further, the mixed metal salt solution in the steps (1) and (2) has an amount concentration of 0.1 to 10 mol/L and the alkaline solution has an amount concentration of 0.1 to 20 mol/L.
Further, the speed of intense stirring in the step (3) is 300-1500 r/min, and the ageing time is 0.5-12 h.
Further, in the step (4), the crystallization temperature is 70-180 ℃ and the crystallization time is 6-48 h;
further, in the step (5), the roasting atmosphere is air, the roasting temperature is 300-800 ℃, and the time is 2-12 h.
The iron-based core-shell catalyst for residual oil suspension bed hydrocracking is applied to the production of light oil by residual oil hydrocracking. The specific application method comprises the following steps: vacuum residuum and the iron-based core-shell catalyst are put into a hastelloy reaction kettle of a simulated suspension bed reactor, nitrogen is used for purging air in the reactor and a pipeline, and then high-purity hydrogen is filled into the suspension bed reactor for hydrocracking reaction, wherein the reaction conditions are as follows: the temperature is 350-430 ℃ (preferably 400-430 ℃), the hydrogen pressure is 5-11MPa (preferably 7-9 MPa), the stirring speed is 300-1000 rpm/min (preferably 300-800 rpm/min), the catalyst dosage is 0.5-5%, and the hydrocracking reaction product is filtered, distilled and separated to obtain naphtha, gasoline, diesel oil and wax oil. The residual oil is one of industrial production residual oil.
The innovation of the invention is that:
(1) The preparation process of the iron-based core-shell catalyst material provided by the invention is green and simple, the catalyst raw material cost and the preparation cost are low, the prepared catalyst has metal active sites and oxygen defect sites, the hydrocracking reaction is facilitated, the stability is good, the active components are not easy to run off, the specific surface area is large, and the combination of macromolecules in the raw material is facilitated.
(2) The catalyst prepared by the invention is firstly applied to the residual oil suspension bed hydrocracking process, has higher residual oil conversion rate and higher gasoline and diesel oil yield, and has good application prospect in industry.
（3）SiO 2 Can obviously improve the SiO content of active metal by adding 2 Dispersing the surface, reducing the agglomeration of the active metal, the reduction of the agglomeration of the metal reduces the catalyst particle size, and simultaneously the non-metallic SiO 2 The addition of the catalyst powder obviously reduces the density of the catalyst powder and improves the dispersibility and stability of the catalyst in residual oil. Without addition of SiO 2 When the bi-metal oxide is used in residual oil suspension bed hydrocracking reaction, the gas coke formation inhibiting performance is greatly reduced, although the gasoline and diesel oil yield and SiO are 2 The @ ZnFe-LMOs iron-based core-shell catalyst is equivalent, but the gas coke yield is obviously increased, and the catalyst is rapidly deactivated by mass production of coke, so that the industrial utilization of residual oil suspension bed hydrocracking is not facilitated.
(4) The preparation method of the catalyst is also applicable to other metals, and in general, divalent metal ion M which can be allowed to enter a water-skid layer 2+ With trivalent metal ions M 3+ Should have similar ionic radii, when M 3+ Is Fe 3+ When M is 2+ May also be Cu 2+ 、Ni 2+ 、Co 2+ 、Zn 2+ 、Mg 2+ Etc., siO 2 Can be of different particle sizes and specifications. In the application of hydrocracking of residual oil suspended bed, znFe bimetallic shows better hydrogenation activity and gas coke inhibition performance.
Drawings
FIG. 1 is SiO of example 1 2 SEM image of the powder material.
Fig. 2 is an SEM image of the iron-based core-shell catalyst material prepared in example 1.
Table 1 shows the conversion and gasoline and diesel yields of the iron-based core-shell catalysts prepared in examples 1-6 for use in suspension hydrocracking reactions.
Table 2 shows the iron-based core-shell catalyst prepared in example 1 without SiO addition 2 The prepared pure hydrotalcite-like material is used for comparing the gasoline and diesel oil yield and the coke yield of the suspension bed hydrocracking reaction.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
The raw materials are all reagent grade. The prepared catalyst is used for residual oil suspension bed hydrogenation reaction, and after the reaction is finished, the reaction product is subjected to experimental evaluation by vacuum distillation: quantitatively analyzing the distillation sections at the temperature of 180 ℃ to 180 ℃ and 350 ℃ to 500 ℃ and at the temperature of more than 500 ℃ to calculate the residual oil conversion rate, the liquid yield, the gasoline and diesel oil yield and the gas coke yield of the reaction.
Example 1
0.006 mol of Zn (NO 3 ) 2 •6H 2 O and 0.014 mol Fe (NO) 3 ) 3 •9H 2 O was dissolved in 100 ml deionized water to form a solution A, 0.04 mol NaOH and 0.007 mol Na 2 CO 3 Adding the solution into 80 ml deionized water to obtain a clear solution B, slowly adding the solution B into the solution A which is vigorously stirred dropwise to form a uniform suspension, adding silicon dioxide powder, vigorously stirring and ageing for 1 h at normal temperature, transferring the aged suspension into a stainless steel water heating kettle with a polytetrafluoroethylene lining, statically crystallizing for 12 h at 120 ℃, taking out and cooling to room temperature, filtering the precipitate, washing and drying in a baking oven at 120 ℃ for several hours to obtain a binary hydrotalcite-like iron-zinc core-shell catalyst precursor, and then placing the obtained binary hydrotalcite-like iron-zinc core-shell catalyst precursor in a muffle furnace to bake for 6 h at 500 ℃ to obtain the iron-based core-shell catalyst material.
40 g residual oil and 1.2 g iron-based core-shell catalyst material are taken to be filled into a hastelloy reactor of a simulated suspension bed reactor, nitrogen is used for purging the air in the reactor and a pipeline, and then 6 MPa high-purity hydrogen is filled into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature was 430℃and the hydrogen pressure was 6 MPa, the stirring rate was 600 rpm/min, and the product after hydrocracking was separated by filtration and analyzed for the liquid phase product.
Example 2
0.002 mol of Zn (NO 3 ) 2 •6H 2 O and 0.018 mol Fe (NO) 3 ) 3 •9H 2 O was dissolved in 100 ml deionized water to form a solution A, 0.04 mol NaOH and 0.009 mol Na 2 CO 3 Adding into 80 ml deionized water to obtain a clear solution B, slowly adding the solution B into the solution A with vigorous stirring dropwise to form a uniform suspension, adding silicon dioxide powder, vigorously stirring at normal temperature for ageing for 1 h, transferring the aged suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing into an oven, carrying out static crystallization at 120 ℃ for 12 h, taking out, cooling to room temperature, filtering, washing the precipitate, placing the precipitate into the oven, drying the precipitate to constant weight at 120 ℃ to obtain a binary hydrotalcite-like iron-zinc core-shell catalyst precursor, placing the obtained binary hydrotalcite-like iron-zinc core-shell catalyst precursor into a muffle furnace, and roasting at 500 ℃ for 6 h to obtain the iron-based core-shell catalyst material.
40 g residual oil and 1.2 g iron-based core-shell catalyst material are taken to be filled into a hastelloy reactor of a simulated suspension bed reactor, nitrogen is used for purging the air in the reactor and a pipeline, and then 6 MPa high-purity hydrogen is filled into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature was 430℃and the hydrogen pressure was 6 MPa, the stirring rate was 600 rpm/min, and the product after hydrocracking was separated by filtration and analyzed for the liquid phase product.
Example 3
0.01 mol of Zn (NO) 3 ) 2 •6H 2 O and 0.01 mol Fe (NO) 3 ) 3 •9H 2 O was dissolved in 100 ml deionized water to form a solution A, 0.04 mol NaOH and 0.005 mol Na 2 CO 3 Adding into 80 ml deionized water to obtainThe clear solution B is slowly added into the solution A with vigorous stirring dropwise to form uniform suspension, silicon dioxide powder is added, then the suspension is vigorously stirred and aged at normal temperature for 1 h, the aged suspension is transferred into a stainless steel reactor with polytetrafluoroethylene lining, static crystallization is carried out at 120 ℃ for 12 h, the precipitate is taken out and cooled to room temperature, the precipitate is filtered, washed and placed in a baking oven at 120 ℃ for drying for a plurality of hours to obtain a binary hydrotalcite-like iron-zinc core-shell catalyst precursor, and then the obtained binary hydrotalcite-like iron-zinc core-shell catalyst precursor is placed in a muffle furnace for roasting at 500 ℃ for 6 h to obtain the iron-based core-shell catalyst material.
40 g residual oil and 1.2 g iron-based core-shell catalyst material are taken to be filled into a hastelloy reactor of a simulated suspension bed reactor, nitrogen is used for purging the air in the reactor and a pipeline, and then 6 MPa high-purity hydrogen is filled into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature was 430℃and the hydrogen pressure was 6 MPa, the stirring rate was 600 rpm/min, and the product after hydrocracking was separated by filtration and analyzed for the liquid phase product.
Example 4
0.006 mol of Zn (NO 3 ) 2 •6H 2 O and 0.014 mol Fe (NO) 3 ) 3 •9H 2 O was dissolved in 100 ml deionized water to form a solution A, 0.04 mol NaOH and 0.007 mol Na 2 CO 3 Adding the solution into 80 ml deionized water to obtain a clear solution B, slowly adding the solution B into the solution A which is vigorously stirred dropwise to form a uniform suspension, adding silicon dioxide powder, vigorously stirring and ageing for 1 h at normal temperature, transferring the aged suspension into a stainless steel water heating kettle with a polytetrafluoroethylene lining, statically crystallizing for 12 h at 140 ℃, taking out and cooling to room temperature, filtering the precipitate, washing, drying in a baking oven at 120 ℃ for several hours to obtain a binary hydrotalcite-like iron-zinc core-shell catalyst precursor, then placing the obtained binary hydrotalcite-like iron-zinc core-shell catalyst precursor into a muffle furnace, and roasting for 6 h at 500 ℃ to obtain the iron-based core-shell catalyst material.
40 g residual oil and 1.2 g iron-based core-shell catalyst material are taken to be filled into a hastelloy reactor of a simulated suspension bed reactor, nitrogen is used for purging the air in the reactor and a pipeline, and then 6 MPa high-purity hydrogen is filled into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature was 430℃and the hydrogen pressure was 6 MPa, the stirring rate was 600 rpm/min, and the product after hydrocracking was separated by filtration and analyzed for the liquid phase product.
Example 5
0.006 mol of Zn (NO 3 ) 2 •6H 2 O and 0.014 mol Fe (NO) 3 ) 3 •9H 2 O was dissolved in 100 ml deionized water to form a solution A, 0.04 mol NaOH and 0.007 mol Na 2 CO 3 Adding the solution into 80 ml deionized water to obtain a clear solution B, slowly adding the solution B into the solution A which is vigorously stirred dropwise to form a uniform suspension, adding silicon dioxide powder, vigorously stirring and ageing for 1 h at normal temperature, transferring the aged suspension into a stainless steel water heating kettle with a polytetrafluoroethylene lining, statically crystallizing for 12 h at 160 ℃, taking out and cooling to room temperature, filtering the precipitate, washing and drying in a baking oven at 120 ℃ for several hours to obtain a binary hydrotalcite-like iron-zinc core-shell catalyst precursor, then placing the obtained binary hydrotalcite-like iron-zinc core-shell catalyst precursor in a muffle furnace, and roasting for 6 h at 500 ℃ to obtain the iron-based core-shell catalyst material.
40 g residual oil and 1.2 g iron-based core-shell catalyst material are taken to be filled into a hastelloy reactor of a simulated suspension bed reactor, nitrogen is used for purging the air in the reactor and a pipeline, and then 6 MPa high-purity hydrogen is filled into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature was 430℃and the hydrogen pressure was 6 MPa, the stirring rate was 600 rpm/min, and the product after hydrocracking was separated by filtration and analyzed for the liquid phase product.
Example 6
0.006 mol of Zn (NO 3 ) 2 •6H 2 O and 0.014 mol Fe (NO) 3 ) 3 •9H 2 O was dissolved in 100 ml deionized water to form a solution A, 0.04 mol NaOH and 0.007 mol Na 2 CO 3 Adding into 80 ml deionized water to obtain clear solution B, slowly adding dropwise into vigorously stirred solution A to give a clear solution BAnd (3) forming a uniform suspension, adding silicon dioxide powder, then vigorously stirring and ageing 1 h at normal temperature, transferring the aged suspension into a stainless steel water heating kettle with a polytetrafluoroethylene lining, statically crystallizing 24 h at 120 ℃, taking out and cooling to room temperature, filtering a precipitate, washing, drying in a baking oven at 120 ℃ for several hours to obtain a binary hydrotalcite-like iron-zinc core-shell catalyst precursor, then placing the obtained binary hydrotalcite-like iron-zinc core-shell catalyst precursor in a muffle furnace, and roasting 6 h at 500 ℃ to obtain the iron-based core-shell catalyst material.
40 g residual oil and 1.2 g iron-based core-shell catalyst material are taken to be filled into a hastelloy reactor of a simulated suspension bed reactor, nitrogen is used for purging the air in the reactor and a pipeline, and then 6 MPa high-purity hydrogen is filled into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature was 430℃and the hydrogen pressure was 6 MPa, the stirring rate was 600 rpm/min, and the product after hydrocracking was separated by filtration and analyzed for the liquid phase product.
FIG. 1 is a SiO having a particle size of 400-500 and 500 nm 2 SEM pictures of spherical powders, it can be seen that the surface is very smooth.
FIG. 2 shows the use of SiO with a particle size of 400-500 and 500 nm 2 The spheres are cores, and the SEM image of the iron-based core-shell catalyst synthesized by the method of the patent can be seen in SiO 2 The fine lamellar metal oxide growing on the surface of the sphere wraps the sphere and has a similar core-shell structure.
Table 1 shows the conversion and gasoline and diesel yields of the iron-based core-shell catalysts prepared in examples 1-6 for residuum suspension bed hydrocracking.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. The preparation method of the iron-based core-shell catalyst for residual oil suspension bed hydrocracking is characterized by comprising the following steps of: the method comprises the following steps:
(1) Mixing metal ferric salt and zinc salt, dissolving in deionized water, and stirring until the metal ferric salt and the zinc salt are completely dissolved to form a mixed metal salt solution;
(2) Mixing alkaline substances, dissolving the alkaline substances in deionized water, and stirring the mixture until the alkaline substances are completely dissolved to form alkaline solution;
(3) Slowly adding alkaline solution dropwise into the mixed metal salt solution with intense stirring, adding silicon dioxide powder to form uniform suspension, intense stirring at normal temperature, and aging for 0.5-12 h;
(4) Transferring the aged suspension in the step (3) into a hydrothermal kettle, statically crystallizing 6-48 and h, taking out, cooling to room temperature, filtering and washing a precipitate, and drying in an oven at 80-180 ℃ to obtain a binary hydrotalcite-like iron-zinc core-shell catalyst precursor;
(5) Roasting the binary hydrotalcite-like iron-zinc core-shell catalyst precursor obtained in the step (4) at 300-800 ℃ in air atmosphere for 2-12 h, and cooling to obtain the iron-based core-shell catalyst for residual oil suspension bed hydrocracking.
2. The method for preparing the iron-based core-shell catalyst for residual oil suspension bed hydrocracking as claimed in claim 1, wherein: the metal ferric salt in the step (1) is any one of ferric nitrate, ferric acetate, ferric chloride, ferric oxalate and ferric sulfate; the zinc salt is any one of zinc nitrate, zinc sulfate, zinc chloride and zinc acetate.
3. The method for preparing the iron-based core-shell catalyst for residual oil suspension bed hydrocracking as claimed in claim 1, wherein: in the step (1), the molar ratio of zinc ions to iron ions is 1:0.1-10, and the mass concentration of the mixed metal salt solution substance is 0.1-10 mol/L.
4. According to claimThe method for preparing the iron-based core-shell catalyst for residual oil suspension bed hydrocracking, which is characterized in that: the alkaline substances in the step (2) are NaOH, KOH, liOH, ammonia water and Na 2 CO 3 ，K 2 CO 3 ，Li 2 CO 3 ，(NH 4 ) 2 CO 3 ，NH 4 HCO 3 Urea, at least one of hexamethylene tetramine.
5. The method for preparing the iron-based core-shell catalyst for residual oil suspension bed hydrocracking as claimed in claim 1, wherein: the concentration of the alkaline solution substance in the step (2) is 0.1-20 mol/L.
6. The method for preparing the iron-based core-shell catalyst for residual oil suspension bed hydrocracking as claimed in claim 1, wherein: the stirring speed in the step (3) is 300-1500 rpm/min, and the aging time is 0.5-12 h.
7. The method for preparing the iron-based core-shell catalyst for residual oil suspension bed hydrocracking as claimed in claim 1, wherein: the crystallization temperature in the step (4) is 80-300 ℃ and the crystallization time is 6-48h.
8. The method for preparing the iron-based core-shell catalyst for residual oil suspension bed hydrocracking as claimed in claim 1, wherein: the roasting temperature in the step (5) is 300-800 ℃ and the time is 2-12 h.
9. An iron-based core-shell catalyst for resid suspension bed hydrocracking prepared by the process of any one of claims 1-8.
10. Use of the iron-based core-shell catalyst for resid suspension bed hydrocracking as claimed in claim 9 in the production of light oil by resid hydrocracking, characterized in that: vacuum residuum and the iron-based core-shell catalyst are put into a suspension bed reactor, and high-purity hydrogen is filled into the suspension bed reactor for hydrocracking reaction under the following reaction conditions: the temperature is 350-430 ℃, the hydrogen pressure is 5-11MPa, the stirring speed is 300-1000 rpm/min, and the dosage of the iron-based core-shell catalyst is 0.5-5wt% of the vacuum residue.
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