CN116004276B - Method for pretreatment and hydrogen production of inferior heavy oil - Google Patents
Method for pretreatment and hydrogen production of inferior heavy oil Download PDFInfo
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- CN116004276B CN116004276B CN202111229733.9A CN202111229733A CN116004276B CN 116004276 B CN116004276 B CN 116004276B CN 202111229733 A CN202111229733 A CN 202111229733A CN 116004276 B CN116004276 B CN 116004276B
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 104
- 239000001257 hydrogen Substances 0.000 title claims abstract description 104
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 64
- 239000000295 fuel oil Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000003921 oil Substances 0.000 claims abstract description 47
- 239000007789 gas Substances 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 230000008929 regeneration Effects 0.000 claims abstract description 22
- 238000011069 regeneration method Methods 0.000 claims abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005243 fluidization Methods 0.000 claims abstract description 16
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 14
- 239000003546 flue gas Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- -1 rare earth hydrogen Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 8
- 239000012495 reaction gas Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000004231 fluid catalytic cracking Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000007795 chemical reaction product Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000003345 natural gas Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000003245 coal Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005261 decarburization Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- GZGREZWGCWVAEE-UHFFFAOYSA-N chloro-dimethyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(C)Cl GZGREZWGCWVAEE-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 102100028099 Thyroid receptor-interacting protein 6 Human genes 0.000 description 1
- 101710084345 Thyroid receptor-interacting protein 6 Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method for pretreating inferior heavy oil and preparing hydrogen comprises the steps of mixing the inferior heavy oil with steam, contacting with regenerated catalyst, and carrying out catalytic pretreatment reaction to obtain reactant flow and catalyst with carbon; the reactant stream is separated into a reactant gas, light oil and heavy oil; the light oil is sent to a hydrogen production reactor to obtain reaction gas and a catalyst with carbon; the reaction gas obtained by separation of the pretreatment reactor and the hydrogen production reactor is sent to a separation unit for further separation into hydrogen, CO 2 and light hydrocarbon; and (3) sending the obtained catalyst with carbon to a regenerator for regeneration, returning the deactivated catalyst to the fluidization reactor for recycling after the burnt regeneration, and separating the regenerated flue gas into CO and CO 2 by a separation unit. The invention adopts the fluid catalytic cracking method to pretreat the inferior heavy oil, thereby improving the quality of the catalytic cracking raw material and simultaneously producing hydrogen to realize the high-efficiency utilization of the inferior heavy oil.
Description
Technical Field
The invention relates to a method for pretreating inferior heavy oil and producing hydrogen, in particular to a method for pretreating inferior heavy oil by fluid catalytic cracking and producing hydrogen.
Background
The crude oil quality shows an inferior trend year by year, and is mainly characterized by higher crude oil density, higher viscosity, higher heavy metal content, sulfur content, nitrogen content, colloid and asphaltene content and acid value. The traditional heavy oil processing is mainly divided into two types, namely a hydrogenation process mainly comprising hydrotreating and hydrofining; and the decarburization process mainly comprises solvent deasphalting, delayed coking and heavy oil catalytic cracking. Inferior heavy oils can be converted to lower boiling point compounds by increasing the hydrogen to carbon ratio by these process techniques. When the inferior heavy oil is treated by adopting a decarburization process, the contents of sulfur, nitrogen and heavy metals and the contents of aromatic hydrocarbon, colloid and asphaltene in the inferior heavy oil have great influence on the decarburization process, the deficiencies of the decarburization process can be made up by a hydrotreating process, the yield of liquid products is high after the inferior heavy oil is hydrotreated, the product properties are good, but the hydrotreating mode tends to have great investment and consume hydrogen sources. Although the catalytic cracking process is difficult to treat the inferior heavy oil with high carbon residue and high metal content, the operation flexibility is high, and the process is hopeful to bear the heavy duty of the pretreatment of the inferior residual oil.
The hydrogen energy is an ideal novel energy source, and is used as a green energy source with rich reserves, high heat value, large energy density and various sources. The existing main hydrogen production modes are mature in three technical routes, namely reforming hydrogen production by fossil energy sources such as coal, natural gas and the like, high-temperature decomposition reforming hydrogen production by chemical raw materials represented by an alcohol pyrolysis hydrogen production technology and water electrolysis hydrogen production; technical routes such as photolysis water and biomass gasification hydrogen production are still in experimental and development stages, and related technologies are difficult to break through, and the requirement of large-scale hydrogen production is not met. At present, domestic natural gas reforming hydrogen production and high-temperature pyrolysis hydrogen production are mainly applied to the large-scale hydrogen production industry. The raw material gas in the hydrogen production process of the natural gas is also fuel gas, and transportation is not needed, but the hydrogen production investment of the natural gas is relatively high, so that the method is suitable for large-scale industrial production. The natural gas hydrogen production process is more economical when the hydrogen production scale is more than 5000m 3/h. In addition, the natural gas raw material accounts for more than 70% of the hydrogen production cost, the natural gas price is an important factor for determining the hydrogen price, and the energy characteristics of rich coal, lack of oil and less gas in China restrict the implementation of natural gas hydrogen production in China. Coal gasification hydrogen production is the first choice for industrial large-scale hydrogen production and is also the mainstream fossil energy hydrogen production method in China. The technical route of coal hydrogen production is mature and efficient, hydrogen can be stably prepared on a large scale, but the power energy consumption of the coal hydrogen production fuel is higher than that of natural gas hydrogen production, the requirements on system steam and electric power are high, and enterprises need matched boilers. In addition, the environmental protection problem is outstanding, the environmental requirements of the existing urban refinery are harsh, and the coal transportation restriction factors are many, so that the application of the technology in modern refineries is limited.
With the development of oil refining technology, particularly the heavy/inferior trend of crude oil is aggravated, and the quality of oil is improved, so that the hydrogenation technology is widely applied, and the hydrogen demand is greatly promoted. The annual increase in global refinery hydrogen demand was statistically more than 4%. Hydrogen from refineries comes mainly from process plant byproducts, refinery gas recovery, existing refinery hydrogen production facilities, and the hydrogen production from refineries will have difficulty meeting future hydrogen growth demands, thus, more flexible and feasible hydrogen supply strategies need to be explored. The method has great practical value if a non-critical inferior heavy oil pretreatment technology can be developed and hydrogen can be produced.
Disclosure of Invention
The invention aims to provide a method for pretreating inferior heavy oil and producing hydrogen.
The method for pretreating inferior heavy oil and producing hydrogen provided by the invention comprises the following steps:
Mixing inferior heavy oil with steam, introducing the mixture into a fluidization reactor, contacting with a regenerated catalyst, and carrying out pretreatment reaction to obtain a reactant flow and a catalyst with carbon; carrying out gas-solid separation on the reaction oil gas obtained by the pretreatment reaction and the catalyst with carbon; and (3) enabling the separated reaction oil gas to enter a fractionating tower, further separating the reaction oil gas into gas, light oil and heavy oil according to a distillation range, and taking the separated heavy oil as a raw material of a conventional catalytic cracking device.
Mixing the separated light oil with water vapor, and then sending the mixture into a hydrogen production reactor to contact with a regenerated catalyst and produce hydrogen production reaction to obtain a reactant flow and a catalyst with carbon; carrying out gas-solid separation on the reaction oil gas obtained by the hydrogen production reaction and the catalyst with carbon;
And (3) sending the reaction oil gas obtained by separating the fluidization reactor and the hydrogen production reactor into a separation unit, and further separating the reaction oil gas into H 2、CO、CO2 and light hydrocarbon.
And (3) sending the obtained fluidized reactor and the carbon-containing catalyst of the hydrogen production reactor to a regenerator for oxygen-enriched regeneration, returning the carbon-containing catalyst to the fluidized reactor for recycling after burning and regenerating, and separating the regenerated flue gas into carbon monoxide and carbon dioxide by a separation unit.
The inferior heavy oil is selected from one or more of a density greater than 940 kg/m 3, a char greater than 8 wt%, a hydrogen content less than 11.8 wt%, and a heavy metal content greater than 50 mg/kg based on the total weight of nickel and vanadium.
The catalyst comprises the following components in percentage by weight: 5 to 65 percent of natural mineral, 10 to 60 percent of oxide, 20 to 60 percent of macroporous zeolite, and 0.1 to 30 percent, preferably 0.5 to 20 percent of metal active component by weight. The metal active component is selected from one or more compounds of transition metal elements.
The carbon monoxide obtained by the separation unit can be used as a raw material for water gas shift to further produce hydrogen and carbon dioxide; and the waste heat of the flue gas can be recycled by the carbon monoxide boiler so as to generate high-quality steam.
The invention carries out catalytic cracking pretreatment reaction on the inferior heavy oil under a relatively mild condition, and the generated light oil is used as a raw material for hydrogen production, thereby providing a cheap raw material for hydrogen production. The generated heavy oil is used as a catalytic cracking raw material, so that the quality of the catalytic cracking raw material is improved, and the efficient utilization of the raw material is realized.
The invention couples the catalytic cracking reaction of the inferior heavy oil and the hydrogen production reaction of the light oil together, and in the reaction process, metals in the inferior heavy oil are deposited on the catalyst and can play a role of dehydrogenation active center in the hydrogen production reaction process, thereby strengthening the dehydrogenation reaction of the light oil and producing more hydrogen.
The invention adopts the fluidization reactor to produce hydrogen, can utilize the characteristic of high coke formation of the catalytic cracking reaction of inferior heavy oil, transfers a large amount of heat for the hydrogen production reaction, greatly reduces the energy required to be consumed in the hydrogen production process, and realizes the process economy.
The invention preferably adopts a low-temperature incomplete regeneration technology, so that the CO/CO 2 ratio in the regenerated flue gas is high, and the invention can provide cheap raw gas for the water gas shift process and realize the optimal utilization of resources. Meanwhile, oxygen-containing gas used in the regeneration process is preferably oxygen-enriched gas, so that the concentration of CO 2 in the flue gas is greatly improved, the large-scale production of CO 2 can be realized, and then the carbon emission is reduced through the technologies of trapping, utilizing and sealing, so that the production of blue hydrogen is realized. Therefore, the invention not only brings hydrogen energy, but also is beneficial to carbon capture, and can bring great economic and social benefits for petrochemical industry.
Drawings
FIG. 1 is a process flow diagram of an embodiment of a method for pretreating inferior heavy oil and producing hydrogen, provided by the invention.
Detailed Description
A method for pretreating and producing hydrogen from a poor heavy oil, the method comprising the steps of:
Mixing inferior heavy oil with steam, introducing the mixture into a fluidization reactor, contacting with a regenerated catalyst, and carrying out pretreatment reaction to obtain a reactant flow and a catalyst with carbon; carrying out gas-solid separation on the reaction oil gas obtained by the pretreatment reaction and the catalyst with carbon; the separated reaction oil gas enters a fractionating tower and is further separated into gas, light oil and heavy oil according to distillation ranges; the heavy oil obtained by separation is used as a raw material of a conventional catalytic cracking device.
Mixing the separated light oil with water vapor, and then sending the mixture into a hydrogen production reactor to contact with a regenerated catalyst and produce hydrogen production reaction to obtain a reactant flow and a catalyst with carbon; carrying out gas-solid separation on the reaction oil gas obtained by the hydrogen production reaction and the catalyst with carbon;
And (3) sending the reaction oil gas obtained by separating the fluidization reactor and the hydrogen production reactor into a separation unit, and further separating the reaction oil gas into H 2、CO、CO2 and light hydrocarbon.
And (3) sending the obtained fluidized reactor and the carbon-containing catalyst of the hydrogen production reactor to a regenerator for oxygen-enriched regeneration, returning the carbon-containing catalyst to the fluidized reactor for recycling after burning and regenerating, and separating the regenerated flue gas into carbon monoxide and carbon dioxide by a separation unit.
The inferior heavy oil is selected from one or more of a density greater than 940 kg/m 3, a char greater than 8 wt%, a hydrogen content less than 11.8 wt%, and a heavy metal content greater than 50 mg/kg based on the total weight of nickel and vanadium.
The catalyst comprises the following components in percentage by weight:
a) 5 to 65 percent of natural mineral substances,
B) 10 to 60 percent of oxide,
C) 20 to 60 percent of macroporous zeolite, and
D) 0.1 to 30 percent of metal active component.
According to the method provided by the invention, the catalytic cracking pretreatment reactor and the hydrogen production reactor of the inferior heavy oil are selected from fluidization reactors. The fluidized reactor is selected from one or a combination of a plurality of turbulent bed, fast bed and dilute phase conveying bed. The fluidization reactor comprises a pre-lifting section and at least one reaction zone fluidization reactor from bottom to top in sequence, and in order to enable the raw oil to fully react, and according to different target product quality requirements, the number of the reaction zones can be 2-8, preferably 2-3.
According to the method provided by the invention, the pretreatment conditions of the inferior heavy oil comprise: the fluidization reactor has a reaction temperature of 450-600 ℃, preferably 480-550 ℃, a reaction time of 0.5-8 seconds, preferably 1-6 seconds, and a weight ratio of catalyst to inferior heavy oil of 1-30, preferably 5-20; the weight ratio of water vapor to inferior heavy oil is 0.01-1, preferably 0.05-0.3.
According to the method provided by the invention, the conditions of the light oil hydrogen production reactor comprise: the reaction temperature is 600-1000 ℃, preferably 650-900 ℃, the reaction time is 1-10, preferably 2-8 seconds, and the weight ratio of the catalyst to the light oil is 5-100, preferably 20-50; the weight ratio of water vapor to light oil is 0.1-50, preferably 1-20.
According to the method provided by the invention, the carbon-containing catalyst and the reaction oil gas are separated in the inferior heavy oil pretreatment reactor and the hydrogen production reactor to obtain the carbon-containing catalyst and the reaction oil gas, then the obtained reaction oil gas is separated into fractions such as hydrogen, CO 2, CO, light hydrocarbon and the like through a subsequent separation unit, and the method for separating the hydrogen, CO 2, CO, light hydrocarbon and the like from the reaction product is similar to the conventional technical method in the field, and the method is not limited in this invention and is not described in detail herein. The CO obtained in the separation unit may be used as feed for water gas shift.
In the method provided by the invention, the optimized carbon-bearing catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the carbon-bearing catalyst are stripped by steam, and the stripped carbon-bearing catalyst enters a regenerator.
In the process provided by the invention, the coked catalyst can be regenerated in a conventional regenerator, either a single regenerator or multiple regenerators can be used. In the regeneration process, oxygen-containing gas is generally introduced from the bottom of the regenerator, after the oxygen-containing gas is introduced into the regenerator, the catalyst with carbon contacts with oxygen for burning regeneration, the flue gas generated after the catalyst is burnt for regeneration is subjected to gas-solid separation at the upper part of the regenerator, and the flue gas enters a water gas conversion unit. The method for regenerating the catalyst with carbon adopts oxygen-enriched regeneration. The concentration of oxygen in the oxygen-containing gas at the bottom of the regenerator is 22 to 100% by volume, preferably 25 to 80% by volume.
In the method provided by the invention, low-temperature incomplete regeneration is preferable, and the operation conditions are as follows: the temperature is 550-700 ℃, preferably 600-650 ℃; the gas superficial linear velocity is 0.2 to 1.2 m/s, preferably 0.4 to 0.8 m/s, and the average residence time of the catalyst with carbon is 1 to 10 minutes, preferably 2 to 6 minutes.
In the method provided by the invention, the natural mineral substances in the catalyst are selected from one or more of kaolin, halloysite, montmorillonite, kieselguhr, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite, wherein the content of the natural mineral substances is 5-65 wt%, preferably 15-60 wt% on a dry basis; the oxide is one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and amorphous silicon aluminum, and the content of the oxide is 10-60 wt%, preferably 10-30 wt%, more preferably 12-28 wt% based on the total catalyst weight. The zeolite comprises large pore zeolite, and the large pore zeolite is one or more selected from rare earth Y, rare earth hydrogen Y, ultrastable Y and high silicon Y.
The metal active component content is 0.1 to 30 wt%, preferably 0.5 to 20 wt%, based on the weight of the catalyst. The metal active component is selected from one or more of compounds of transition metal elements, preferably one or more of nickel, cobalt, iron, tungsten, molybdenum, manganese, copper, zirconium and chromium.
In the method provided by the invention, the catalyst preparation method adopts a preparation method of a conventional catalytic cracking catalyst, which is a preparation method well known to a person skilled in the art. The metal supported on the catalyst may be impregnated or slurry mixed, preferably impregnated, as known to those skilled in the art.
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure.
As shown in fig. 1, the regenerated catalyst from line 7 enters the pretreatment reactor 1, moves up the reactor with acceleration, and after being mixed with steam from line 6 via line 5, the inferior heavy oil is injected into the fluidization reactor 1 to contact the regenerated catalyst, and the inferior heavy oil undergoes a pretreatment reaction on the hot catalyst and moves up with acceleration. After the generated reaction product and the catalyst to be generated with carbon are separated, the reaction product enters the fractionating tower 3 through a pipeline 8, and the reaction product is separated into reaction gas, light oil and heavy oil according to the distillation range. Heavy oil is fed out of the unit via line 14 and can be fed to a conventional catalytic cracker.
The light oil is mixed with steam from a pipeline 21 through a pipeline 13 and then sent to a hydrogen production reactor 4, and contacts with a regenerated catalyst entering the bottom of the hydrogen production reactor through a pipeline 22 to generate hydrogen production reaction, and the generated reaction gas 16 is mixed with the reaction gas 12 from the fractionating tower and then sent to a separation unit 23 to be separated into hydrogen 17, carbon dioxide 18, carbon monoxide 19 and light hydrocarbon 20.
The catalyst 9 with carbon of the pretreatment reactor and the catalyst 15 with carbon of the hydrogen production reactor enter the regenerator 2, contact oxygen-enriched gas from the pipeline 10, burn coke on the spent catalyst, regenerate the spent catalyst with carbon, the regenerated flue gas enters the separation unit 23 through the flue gas pipeline 11, the hydrogen 17, the carbon dioxide 18, the carbon monoxide 19 and the light hydrocarbon 20 are separated, and the regenerated catalyst after regeneration is respectively circulated to the bottom of the pretreatment reactor 1 and the bottom of the hydrogen production reactor 4 for recycling through the regeneration pipeline 7 and the pipeline 22.
The following examples further illustrate the invention, but are not intended to limit it.
The feeds used in the examples and comparative examples were vacuum residuum, the properties of which are shown in Table 1. The commercial catalysts used in the comparative examples, commercially available under the trade designation CDOS, have the properties shown in Table 2.
The catalyst preparation used in the examples is briefly described as follows:
1) Pulping 75.4 kg of kaolin (solid content: 71.6 wt%) with 250 kg of decationizing water, adding 54.8 kg of pseudo-boehmite (solid content: 63 wt%) and adjusting the pH to 2-4 with hydrochloric acid, stirring uniformly, standing and aging at 60-70deg.C for 1 hr, maintaining the pH at 2-4, cooling to below 60deg.C, adding 41.5 kg of alumina sol (Al 2O3 content: 21.7 wt%) and stirring for 40min to obtain mixed slurry.
2) ZRP-1 (2 kg dry basis) and DASY zeolite (22.5 kg dry basis) were added to the resulting mixed slurry, stirred well, spray dried to shape, washed with monoammonium phosphate solution (phosphorus content 1 wt%), washed to remove free Na +, and calcined to obtain a molecular sieve catalyst sample.
3) 3 Kg of Ni (NO 3)2 is dissolved in 5.5 kg of water to prepare Ni (NO 3)2·6H2 O water solution), 10 kg of molecular sieve catalyst sample is immersed in Ni (NO 3)2·6H2 O water solution), the obtained mixture is dried at 180 ℃ for 4 hours and baked at 600 ℃ for 2 hours, and the immersion, drying and baking are repeated to ensure that the Ni content loaded on the catalyst sample reaches 2 weight percent, thus obtaining the catalyst A of the embodiment.
Example 1
The test was carried out according to the flow of FIG. 1, the pretreatment reaction test of the atmospheric residuum was carried out on the riser reactor, the atmospheric residuum was introduced into the lower portion of the riser reactor, contacted with the hot regenerated catalyst and subjected to the pretreatment reaction, the reaction product and the spent catalyst were introduced into the closed cyclone separator from the outlet of the reactor, the reaction product and the spent catalyst were rapidly separated, and the reaction product was separated into gas, light oil and heavy oil in the separation system according to the distillation range.
The light oil enters the lower part of another riser hydrogen production reactor, contacts with the hot regenerated catalyst and carries out hydrogen production reaction, and the reaction product and the spent catalyst enter a closed cyclone separator from the outlet of the reactor, so that the reaction product and the spent catalyst are rapidly separated.
The spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped spent catalyst enters a regenerator to be contacted with air rich in oxygen for regeneration; the regenerated catalyst is returned to the riser reactor for recycling. The operating conditions and product distribution are listed in Table 3.
As can be seen from the results in Table 3, the hydrogen yield is as high as 5.65%, the heavy oil yield is 78.63%, the heavy oil property is obviously improved, the density is 928.6 kg/m 3, the hydrogen content is increased to 12.08% by weight, and the requirements of the conventional catalytic cracking raw materials are met. The concentration of CO 2 in the regeneration flue gas was 32.07% by volume.
Comparative example 1
The test was carried out on a medium-sized riser unit with the same atmospheric residuum feed as in example 1 with catalyst a.
The atmospheric residuum enters a hot re-heavy catalyst under a riser reactor to contact and carry out pretreatment reaction, reaction products and spent catalyst enter a closed cyclone separator from an outlet of the reactor, the reaction products and the spent catalyst are rapidly separated, and the reaction products are separated into products such as gas, liquid and the like in a separation system according to a distillation range.
The spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped spent catalyst enters a regenerator to be in contact with air for regeneration; the regenerated catalyst is returned to the riser reactor for recycling; the operating conditions and product distribution are listed in Table 3.
As can be seen from the results of Table 3, the hydrogen yield was 1.69%, the heavy oil yield was 77.51%, and the heavy oil properties were significantly improved, the density was 928.9 kg/m 3, and the hydrogen content was increased to 12.0% by weight. The concentration of CO 2 in the regeneration flue gas was 31.79% by volume.
Comparative example 2
The test was carried out on a medium-sized apparatus for a riser, with the catalytic diesel feedstock being the same as in example 1, the catalyst being CDOS.
The catalytic diesel oil enters a hot re-heavy catalyst under a riser reactor to be contacted and subjected to pretreatment reaction, a reaction product and a spent catalyst enter a closed cyclone separator from an outlet of the reactor, the reaction product and the spent catalyst are rapidly separated, and the reaction product is separated into products such as gas, liquid and the like in a separation system according to a distillation range.
The spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped spent catalyst enters a regenerator to be in contact with air for regeneration; the regenerated catalyst is returned to the riser reactor for recycling; the operating conditions and product distribution are listed in Table 3.
As can be seen from the results of Table 3, the hydrogen yield was only 0.75%, the heavy oil yield was 74.43%, and the heavy oil properties were slightly improved, the density was 946.3 kg/m 3, the hydrogen content was increased to 11.6% by weight, and the cracking performance was still relatively poor. The concentration of CO 2 in the regeneration flue gas was 31.87% by volume.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the present invention can be made, as long as it does not depart from the gist of the present invention, which is also regarded as the content of the present invention.
TABLE 1
| Name of the name | Atmospheric residuum |
| Density (20 ℃ C.)/(kg/m 3) | 974.7 |
| Viscosity (100 ℃ C.)/(mm 2/s) | 62.75 |
| Carbon residue value/wt% | 10.34 |
| Element content/wt% | |
| Carbon (C) | 84.30 |
| Hydrogen gas | 11.06 |
| Sulfur (S) | 4.18 |
| Nitrogen and nitrogen | 0.24 |
| Four component composition/wt% | |
| Saturation fraction | 31.0 |
| Aromatic components | 46.8 |
| Colloid | 18.8 |
| Asphaltenes | 3.4 |
| Metal content/(micrograms/gram) | |
| Ca | 1.7 |
| Fe | 2.9 |
| Ni | 21.1 |
| V | 60.5 |
TABLE 2
TABLE 3 Table 3
Claims (9)
1. A method for pretreating and producing hydrogen from a poor heavy oil, the method comprising the steps of:
Mixing inferior heavy oil with steam, introducing the mixture into a fluidization reactor to contact with regenerated catalyst and perform pretreatment reaction, wherein the pretreatment conditions comprise: the reaction temperature is 450-600 ℃, the reaction time is 0.5-8 seconds, the weight ratio of the catalyst to the inferior heavy oil is 1-30, and the weight ratio of the water vapor to the inferior heavy oil is 0.01-1, so as to obtain a reactant flow and a catalyst with carbon; carrying out gas-solid separation on the reaction oil gas obtained by the pretreatment reaction and the catalyst with carbon; the separated reaction oil gas enters a fractionating tower and is further separated into gas, light oil and heavy oil according to a distillation range, and the separated heavy oil is used as a raw material of a conventional catalytic cracking device; the inferior heavy oil is selected from one or more indexes of density greater than 940 kg/m 3, carbon residue greater than 8 wt%, hydrogen content less than 11.8 wt%, and heavy metal content greater than 50 mg/kg based on total weight of nickel and vanadium; based on the dry basis weight of the catalyst, the catalyst comprises 5% -65% of natural minerals, 10% -60% of oxides, 20% -60% of zeolite and 0.1% -30% of metal active components; the zeolite comprises large pore zeolite, the large pore zeolite is one or more selected from rare earth Y, rare earth hydrogen Y, ultrastable Y and high silicon Y, the natural mineral is one or more selected from kaolin, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite, the oxide is one or more selected from silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and amorphous silicon aluminum, and the metal active component is one or more selected from compounds of transition metal elements;
Mixing the separated light oil with water vapor, and then sending the mixture into a hydrogen production reactor, wherein the hydrogen production reactor is contacted with a regenerated catalyst and is subjected to hydrogen production reaction, and the conditions of the hydrogen production reactor for the light oil include: the reaction temperature is 600-1000 ℃, the reaction time is 1-10 seconds, and the weight ratio of the catalyst to the light oil is 5-100; the weight ratio of the water vapor to the light oil is 0.1-50, and a reactant stream and a catalyst with carbon are obtained; carrying out gas-solid separation on the reaction oil gas obtained by the hydrogen production reaction and the catalyst with carbon;
The reaction oil gas obtained by separating the fluidization reactor and the hydrogen production reactor is sent to a separation unit to be further separated into H 2、CO、CO2 and light hydrocarbon;
The obtained fluidized reactor and the catalyst with carbon of the hydrogen production reactor are sent to a regenerator for regeneration, the oxygen concentration in the oxygen-containing gas at the bottom of the regenerator is 22-100 vol%, and the regeneration operation conditions are as follows: the temperature is 550-700 ℃; the apparent linear velocity of the gas is 0.2-1.2 m/s, the average residence time of the catalyst with carbon is 1-10 minutes, the catalyst with carbon is returned to the fluidization reactor for recycling after being burnt and regenerated, and the regenerated flue gas enters a separation unit to be separated to obtain CO and CO 2.
2. The method of claim 1, wherein the metal active component is present in an amount of 0.5 to 20 wt%; the metal active component is one or more selected from nickel, cobalt, iron, tungsten, molybdenum, manganese, copper, zirconium and chromium.
3. The method of claim 1, wherein the fluidization reactor is selected from one or a combination of several of a turbulent bed, a fast bed, and a dilute phase transport bed.
4. The method of claim 1, wherein the fluidization reactor includes at least one or more reaction zones in series.
5. The method of claim 1, wherein the hydrogen production reactor is selected from the group consisting of a fluidized reactor selected from the group consisting of a turbulent bed, a fast bed, and a dilute phase transport bed.
6. The method of claim 1, wherein the conditions for the pretreatment of the inferior heavy oil comprise: the reaction temperature is 480-550 ℃, the reaction time is 1-6 seconds, and the weight ratio of the catalyst to the inferior heavy oil is 5-20; the weight ratio of water vapor to inferior heavy oil is 0.05-0.3.
7. The method of claim 1, wherein the conditions of the light oil hydrogen production reactor comprise: the reaction temperature is 650-900 ℃, the reaction time is 2-8 seconds, and the weight ratio of the catalyst to the light oil is 20-50; the weight ratio of the water vapor to the light oil is 1-20.
8. The method of claim 1, wherein the concentration of oxygen in the oxygen-containing gas at the bottom of the regenerator is 25-80% by volume.
9. The method of claim 1, wherein the regeneration operating conditions are: the temperature is 600-650 ℃; the apparent linear velocity of the gas is 0.4-0.8 m/s, and the average residence time of the catalyst with carbon is 2-6 minutes.
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