CN117000295A - Catalyst regeneration method and regeneration system - Google Patents
Catalyst regeneration method and regeneration system Download PDFInfo
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- CN117000295A CN117000295A CN202210474594.4A CN202210474594A CN117000295A CN 117000295 A CN117000295 A CN 117000295A CN 202210474594 A CN202210474594 A CN 202210474594A CN 117000295 A CN117000295 A CN 117000295A
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- regenerator
- gas
- regeneration
- catalyst
- oxygen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 156
- 238000011069 regeneration method Methods 0.000 title claims abstract description 140
- 230000008929 regeneration Effects 0.000 title claims abstract description 130
- 239000002028 Biomass Substances 0.000 claims abstract description 67
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 48
- 230000008569 process Effects 0.000 claims abstract description 34
- 238000012545 processing Methods 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 198
- 239000012071 phase Substances 0.000 claims description 117
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 69
- 229910052760 oxygen Inorganic materials 0.000 claims description 69
- 239000001301 oxygen Substances 0.000 claims description 69
- 238000000855 fermentation Methods 0.000 claims description 54
- 239000000446 fuel Substances 0.000 claims description 49
- 230000004151 fermentation Effects 0.000 claims description 34
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 23
- 239000003546 flue gas Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 239000000571 coke Substances 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 238000003860 storage Methods 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 14
- 239000010865 sewage Substances 0.000 claims description 9
- 239000012808 vapor phase Substances 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000010813 municipal solid waste Substances 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004880 explosion Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000010871 livestock manure Substances 0.000 claims description 3
- 244000005700 microbiome Species 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 96
- 239000000047 product Substances 0.000 description 91
- 239000001569 carbon dioxide Substances 0.000 description 48
- 229910002092 carbon dioxide Inorganic materials 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000003921 oil Substances 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 15
- 239000010457 zeolite Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000000153 supplemental effect Effects 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 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 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 241000658379 Manihot esculenta subsp. esculenta Species 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 102100022929 Nuclear receptor coactivator 6 Human genes 0.000 description 1
- 101710115514 Nuclear receptor coactivator 6 Proteins 0.000 description 1
- 235000014676 Phragmites communis Nutrition 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 239000004202 carbamide Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- -1 rare earth hydrogen Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011514 vinification Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/20—Plural distinct oxidation stages
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/36—Means for collection or storage of gas; Gas holders
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M43/00—Combinations of bioreactors or fermenters with other apparatus
- C12M43/04—Bioreactors or fermenters combined with combustion devices or plants, e.g. for carbon dioxide removal
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M45/00—Means for pre-treatment of biological substances
- C12M45/02—Means for pre-treatment of biological substances by mechanical forces; Stirring; Trituration; Comminuting
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
- C12M47/14—Drying
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
Abstract
The present application relates to a catalyst regeneration method and a regeneration system comprising a biomass processing system and a regeneration unit. The regeneration system of the application introduces biomass into the regeneration system for energy supply, thereby fundamentally changing the energy source of the device, greatly reducing the carbon emission of the catalytic cracking unit, realizing the recycling of carbon elements and providing energy for other process units.
Description
Technical Field
The application relates to a method and a system for regenerating a carbon-containing catalyst in a hydrocarbon processing process. More particularly, the application relates to a catalyst regeneration method for realizing carbon dioxide emission reduction and strengthening energy supply of a regeneration system in a catalytic cracking process.
Background
Today, the development of the global oil refining industry faces many challenges such as new energy substitution, energy conservation and emission reduction requirements and the like. Flexible adjustment of cracking production schemes, reduction of carbon dioxide emissions, and reduction of climate change have become necessary routes for the refinery industry to change economic growth and maintain sustainable development. Therefore, the effective reduction of carbon emission in petroleum refining and chemical production processes is particularly important, and the research on a low-carbonization catalytic cracking scheme for reducing and increasing oil is an important task in the future of refineries. The carbon emission in the heavy oil processing process is mainly the energy consumption of catalytic cracking and burning, hydrogen production process, flue gas emission of equipment such as a boiler and the like. The catalytic cracking device is core equipment in a refinery, carbon emission caused by burning of a catalytic cracking regenerator accounts for 24-55% of carbon emission of the whole plant, the total carbon dioxide emission accounts for nearly 1% of the total national carbon dioxide emission, and the catalytic cracking device is important for carbon emission reduction in petrochemical industry.
CN103102937a discloses a catalytic cracking technology for reducing carbon dioxide emission, and the method adopts pure oxygen to regenerate the catalyst, so that the concentration of carbon dioxide in regenerated flue gas is higher, and the method is convenient for capturing and utilizing, and is favorable for solving the problems of capturing and economical utilization of carbon dioxide, but the method only focuses on treating the generated carbon dioxide, and does not fundamentally reduce the generation of carbon dioxide.
US5565089 discloses a catalytic cracking catalyst regeneration process, which comprises the steps of firstly burning with air, then recovering carbon dioxide in flue gas, recycling and gradually incorporating the carbon dioxide into an oxygen-containing gas stream until the temperature in a regenerator is normal, and finally injecting only oxygen and carbon dioxide for catalyst regeneration. The process focuses on the regeneration process air intake system and flue gas treatment, but the carbon dioxide produced by the energy supply is still all derived from fossil energy sources.
Catalytic cracking units are a cyclic heat supply and heat balance process, and the energy required for the reaction is derived from a regeneration system. When the scorching amount is insufficient to meet the energy consumption of the device, the method of recycling slurry oil, increasing the proportion of heavy oil in raw oil and the like is generally adopted to increase the coking amount, or the method of spraying and burning oil is adopted to increase the regeneration temperature. The three modes can meet the reaction heat balance, but the complementary energy comes from fossil energy, so that the carbon dioxide emission from the fossil energy is increased, and the utilization rate of petroleum resources is not improved. The energy utilization efficiency can be improved by optimizing the regeneration process, so that the emission of unit carbon dioxide is reduced to a certain extent; the discharged carbon dioxide is recycled, so that the discharge amount of the carbon dioxide can be reduced to a certain extent, but the cost is high, and the process is complex. However, the above ideas do not radically change the source of energy, and carbon dioxide is still derived from fossil energy.
Therefore, there is a need to develop a catalyst regeneration method that fundamentally reduces carbon dioxide emissions from fossil energy sources, reduces carbon dioxide emissions on the basis of satisfying the energy supply required for the apparatus, and achieves low carbonization development.
Disclosure of Invention
The application aims to provide a catalyst regeneration method and a catalyst regeneration system for fundamentally reducing carbon dioxide emission from fossil energy based on the prior art.
In one aspect, the present application provides a catalytic cracking catalyst regeneration system comprising:
a biomass processing system comprising:
a biomass pretreatment unit for pretreating biomass,
a biomass anaerobic fermentation unit for carrying out anaerobic fermentation treatment on the pretreated biomass to obtain a gas-phase fermentation product,
a gas phase product drying unit for drying the gas phase fermentation product obtained by the biomass anaerobic fermentation unit, and
a gas phase product storage tank for storing the gas phase product;
a regeneration unit, the regeneration unit comprising:
a regenerator in which:
an oxygen-containing gas inlet for inputting an oxygen-containing gas to the regenerator, the oxygen-containing gas inlet being disposed at the bottom of the regenerator;
A distribution plate configured to distribute an oxygen-containing gas input through the oxygen-containing gas inlet;
a gas phase fuel inlet arranged above the distribution plate for inputting gas phase fuel;
a gas distributor configured to distribute a gaseous fuel input through the gaseous fuel inlet;
a spent catalyst inlet for delivering spent catalyst of a catalytic cracking reactor to the interior of the regenerator; and
a regenerated catalyst outlet for delivering regenerated catalyst to a catalytic cracking reactor;
a heat extractor configured to deliver heat to an exterior of the regenerator;
wherein the vapor phase product storage tank is in communication with the vapor phase fuel inlet such that the vapor phase product is delivered to the interior of the regenerator.
In one embodiment, the regenerator is a dense bed, and the gas phase fuel inlet, gas distributor, and spent catalyst inlet are disposed in a lower portion of the dense bed.
In one embodiment, the regenerator comprises a char section and a regeneration section, wherein the regeneration section is in communication with the char Duan Liuti and is located above the char section; the regeneration section is spaced from the burn section by a fluid distribution plate;
The scorching section is provided with:
a first oxygen-containing gas inlet arranged at the bottom of the coke burning section for inputting a first oxygen-containing gas into the coke burning section;
a gas phase fuel inlet provided above the first oxygen-containing gas inlet for inputting gas phase fuel;
a gas distributor configured to distribute a gaseous fuel input through the gaseous fuel inlet; and
a spent catalyst inlet for conveying spent catalyst of a catalytic cracking reactor to the interior of the burn-in section;
the regeneration section is provided with:
a second oxygen-containing gas inlet provided at the bottom of the regeneration section for inputting a second oxygen-containing gas to the regeneration section; and
a regenerated catalyst outlet for delivering regenerated catalyst to the catalytic cracking reactor.
In one embodiment, the regeneration unit comprises:
a first regenerator, and
the second regenerator is provided with a second heat exchanger,
wherein the second regenerator is located downstream of the first regenerator, the first and second regenerators being connected by a catalyst transfer tube such that catalyst material of the first regenerator is transferred to the second regenerator;
The first regenerator is provided with:
a first oxygen-containing gas inlet provided at the bottom of the first regenerator for inputting a first oxygen-containing gas to the first regenerator;
a gas phase fuel inlet provided above the first oxygen-containing gas inlet for inputting gas phase fuel;
a gas distributor configured to distribute a gaseous fuel input through the gaseous fuel inlet;
a spent catalyst inlet for delivering spent catalyst of a catalytic cracking reactor to the interior of the first regenerator; and
a first flue gas outlet disposed at the top of the first regenerator;
the second regenerator is provided with:
a second oxygen-containing gas inlet provided at the bottom of the second regenerator for inputting a second oxygen-containing gas to the second regenerator;
a regenerated catalyst outlet for delivering regenerated catalyst from the second regenerator to the catalytic cracking reactor; and
and a second flue gas outlet arranged at the top of the second regenerator.
In another aspect, the present application provides a catalytic cracking catalyst regeneration process, the process being carried out in a regeneration system of the present application, the process comprising:
S1, conveying biomass to a biomass anaerobic fermentation unit for anaerobic fermentation treatment after pretreatment to obtain a gas-phase fermentation product;
s2, drying the gas-phase fermentation product, and storing the dried gas-phase product in a gas-phase product storage tank;
s3, conveying the gas phase product in the gas phase product storage tank to the inside of the regenerator through the gas distributor, and enabling the gas phase product to be in contact with a spent catalyst from a catalytic cracking reactor and an oxygen-containing gas so as to regenerate the spent catalyst.
In one embodiment, the biomass is selected from the group consisting of agricultural and forestry biomass, aquatic plants, energy crops, livestock manure, municipal solid waste, domestic sewage, and industrial organic sewage.
In one embodiment, the biomass pretreatment method comprises physical pretreatment, chemical pretreatment, biological pretreatment and the like, and specifically comprises one or more of grinding/extrusion/steam explosion/acid treatment/alkali treatment/microorganism pretreatment; the anaerobic fermentation process is carried out in a closed fermentation tank, and the fermentation temperature is not higher than 60 ℃;
in the gas phase product, the methane accounts for more than 40 percent based on the total volume of the gas phase product.
In one embodiment, the amount of gas phase product introduced into the regenerator is no more than 4% by volume of the oxygen-containing gas.
In one embodiment, the regenerator comprises a dense bed in which the catalyst has a bed density of 300 to 700kg/m 3 。
In one embodiment, the gas phase product is injected through a gas distributor from a level not below the level of the spent catalyst inlet.
In one embodiment, the regenerator is operated at a temperature of 550 to 750 ℃, the catalyst average residence time is 2.0 to 15.0 minutes, and the gas superficial linear velocity is 0.7 to 2.0m/s.
In one embodiment, the temperature of the regenerator bed is controlled via the heat extractor to not exceed 750 ℃, preferably 720 ℃.
Thus, compared with the existing catalytic cracking catalyst regeneration method, the main advantages of the invention are as follows:
(1) Biomass is cheap and easy to obtain, biomass energy belongs to renewable energy, carbon is derived from carbon dioxide captured by plants from air, and is not fossil energy, and the biomass energy is used as energy source, so that the energy source of the catalytic cracker can be fundamentally changed, the emission of fossil energy carbon dioxide is reduced, and the low carbonization development of oil refining is realized.
(2) The biomass anaerobic fermentation process is environment-friendly, low in energy consumption, pollution-free, high in methane content in gas-phase products, low in carbon emission in the whole life cycle, and energy consumed in the fermentation and drying processes is derived from renewable resources such as green electricity and solar energy.
(3) The gas phase fuel is used as a combustion medium, is uniformly mixed with the spent catalyst, and has stable combustion and heat conduction processes.
(4) The superfluous heat generated by the regeneration system can be used for generating high-pressure steam through the heat collector and outputting the steam to other devices.
Drawings
The accompanying drawings are included to provide a further understanding of the application, and are incorporated in and constitute a part of this specification, illustrate the application and together with the description serve to explain, without limitation, the application.
FIG. 1 shows a schematic diagram of one embodiment of a regeneration system of the present application;
FIG. 2 shows a schematic diagram of another embodiment of the regeneration system of the present application;
fig. 3 shows a schematic view of a third embodiment of the regeneration system of the present application.
Detailed Description
The application is further described in detail below by means of the figures and examples. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not collide with each other.
As shown in fig. 1, 2 and 3, the present application provides a catalytic cracking catalyst regeneration system comprising a biomass processing system 300 and regeneration units 200, 400, 500.
A catalytic cracking catalyst regeneration process may be performed in the regeneration system, the process comprising:
s1, conveying biomass to a biomass anaerobic fermentation unit for anaerobic fermentation treatment after pretreatment to obtain a gas-phase fermentation product;
s2, drying the gas-phase fermentation product, and storing the dried gas-phase product in a gas-phase product storage tank;
s3, conveying the gas phase product in the gas phase product storage tank to the inside of the regenerator through the gas distributor, and enabling the gas phase product to be in contact with a spent catalyst from a catalytic cracking reactor and an oxygen-containing gas so as to regenerate the spent catalyst.
The regeneration process of the present application is further described below in conjunction with the catalytic cracking catalyst regeneration system of the present application. The same applies to the regeneration system with respect to the embodiments of the regeneration method and vice versa.
As shown in fig. 1, 2 and 3, in the catalytic cracking reaction system 100, a catalytic cracking reactor 110 is used to perform a catalytic cracking reaction: the bottom inlet 102 of which is fed with a lifting medium to lift the regenerated catalyst (from regenerator 200) entering at regenerated catalyst inlet 103; the feedstock entering from feedstock inlet 101 contacts the catalyst to perform a catalytic cracking reaction. The reacted oil and gas products are separated by the oil agent separating device 120, and the separated oil and gas products are collected by the gas collection chamber 140 and then are input into the product separating device 150 for separation, thus obtaining various products. The separated spent catalyst is stripped by the stripping section 130 of the settler and then conveyed to the regeneration unit 200 for regeneration through the spent catalyst outlet 131, thereby realizing recycling. The catalytic cracking reactor 110 used in the present application may be various reactors commonly used in the art, such as a riser reactor, a fluidized bed reactor, a reducing reactor, a combination thereof, and the like.
The gas phase fuel used in the present application refers to a gas phase product obtained by passing biomass through a biomass processing system.
A biomass processing system 300 for producing the gas phase product comprising:
a biomass pretreatment unit 310 for pretreating biomass,
a biomass anaerobic fermentation unit 320 for performing anaerobic fermentation treatment on the pretreated biomass to obtain a gas-phase fermentation product,
a gas phase product drying unit 330 for drying the gas phase fermentation product obtained by the biomass anaerobic fermentation unit, and
a gas phase product storage tank 340 for storing the gas phase product.
In accordance with the present application, biomass includes, but is not limited to, agricultural and forestry biomass, aquatic plants, energy crops, livestock manure, municipal solid waste, domestic sewage, industrial organic sewage, and the like. The agricultural and forestry biomass comprises, but is not limited to, straw, chaff, cotton stalk and the like, the forestry biomass comprises, but is not limited to, firewood, fast-growing forest, forestry processing residues and the like, the aquatic plants comprise, but is not limited to, reed, algae and the like, the energy commercial crops comprise cassava, rape and the like, the municipal solid waste comprises household garbage, business service industry garbage and the like, and the domestic sewage and industrial organic sewage comprise organic sewage discharged by industries such as cooling water, kitchen drainage, wine making, food and the like.
According to the present invention, biomass pretreatment processes are well known to those skilled in the art, and biomass is pretreated by one or more of grinding/extrusion/steam explosion/acid treatment/alkali treatment/microorganism pretreatment. The process may be performed in the biomass pretreatment unit 310.
The biomass anaerobic fermentation process can be performed in a biomass anaerobic fermentation unit 320, such as a closed fermentation tank, and the fermentation substrate can be mixed biomass raw materials, and the fermentation temperature is not higher than 60 ℃. In a more preferred embodiment according to the invention urea, biomass charcoal or the like may be added to enhance the fermentation process.
According to the invention, the anaerobic fermentation products mainly comprise methane, carbon dioxide, water and the like, and the drying treatment is required because the water has adverse effects on the subsequent process. Drying may be performed in a gas phase product drying unit 330 to remove moisture from the fermentation product such that the moisture content is less than 1.0g/m 3 。
After drying, the dried vapor phase product is stored in vapor phase product storage tank 340 for subsequent processing. The methane may comprise more than 40%, for example 40-50%, up to more than 60% and up to more than 75% by weight of the total volume of the gas phase product after drying.
According to the invention, the energy consumed by the anaerobic fermentation process is derived from other products of the fermentation process or at least partially/totally derived from renewable energy sources such as solar energy, green electricity, nuclear energy and the like, so that the carbon emission in the whole life cycle is reduced.
Fig. 1 shows a schematic diagram of a section of regeneration. As shown in fig. 1, the regeneration unit 200 includes a regenerator 210, and the regenerator 210 is provided with:
an oxygen-containing gas inlet 211 for inputting an oxygen-containing gas to the regenerator, the oxygen-containing gas inlet 211 being provided at the bottom of the regenerator;
a distribution plate 212, the distribution plate 212 being configured to distribute oxygen-containing gas input through the oxygen-containing gas inlet 211;
a gas phase fuel inlet 214, said gas phase fuel inlet 214 being disposed above said distribution plate 212 for inputting gas phase fuel (gas phase product from gas phase product reservoir 340);
a gas distributor 213, the gas distributor 213 being configured to distribute a gas phase fuel input via the gas phase fuel inlet 214;
a spent catalyst inlet 216, wherein the spent catalyst inlet 216 is used for conveying spent catalyst of a catalytic cracking reactor into the regenerator;
a regenerated catalyst outlet 217, said regenerated catalyst outlet 217 being for delivering regenerated catalyst to a catalytic cracking reactor.
The vapor product reservoir 340 communicates with the vapor fuel inlet 214 such that vapor product is delivered to the interior of the regenerator, burned and regenerated from the spent catalyst.
The distribution plate 212 and the gas distributor 213 are both disposed inside the regenerator 210 to uniformly distribute the oxygen-containing gas and the gas phase fuel in the spent catalyst inside the regenerator, so that the catalyst can be uniformly combusted during the regeneration process, thereby avoiding local overheating. Typically, the distribution plate 212 and the gas distributor 213 are both disposed in a lower portion of the interior of the regenerator 210 so that the spent catalyst is in a fluidized state within the regenerator during regeneration within the regenerator.
The regenerator is a dense bed, and the bed density of the catalyst is 300-700kg/m 3 . Gas phase fuel (gas phase product) is injected through the gas distributor from a position never below the level of the spent catalyst inlet level. In this embodiment, a gas distributor 213 is provided in the lower portion of the dense bed section of the regenerator to better evenly distribute the gas phase product.
In one embodiment, the conditions of the regeneration process: the oxygen-containing gas is air, the regeneration temperature is 550-750 ℃, the average residence time of the catalyst is 1.0-15.0 minutes, and the apparent linear velocity of the gas is 0.7-2.0m/s.
According to the invention, the quantity of gaseous product introduced into the regeneration reactor is not higher than 4% by volume of the oxygen-containing gas consumed by the regeneration system. The gas phase product and the spent catalyst are conveyed to the bottom of the regenerator to be contacted with oxygen-containing gas for burning regeneration and energy supply.
A large amount of heat is generated during regeneration due to the injection of the gas phase product. If the temperature in the regenerator is too high, the activity of the catalyst may be adversely affected. Therefore, the regeneration unit 200 is further provided with a heat collector 215 for transporting heat to the outside of the regenerator. The heat extractors may be internal heat extractors (disposed inside the regenerator) or/and external heat extractors (disposed outside the regenerator), one or more of which may use excess energy generated by the regenerator to supply other devices. The heat collector can be used for generating high-pressure steam by using the surplus heat of the regeneration system and outputting the high-pressure steam to other devices for energy supply. In one embodiment, the regenerator bed temperature is controlled to not exceed 750 ℃, such as not exceeding 720 ℃, by providing a heat extractor.
As shown in fig. 1, the regeneration unit 200 further includes a cyclone 220, and the regenerated flue gas exits the regenerator through the cyclone 220 and enters the flue gas energy recovery system 230 to recover energy. The cyclone 220 may be disposed inside the regenerator 210.
The regeneration process can also adopt a two-stage regeneration mode. As shown in fig. 2, a diagram for performing two-stage regeneration is shown. The regeneration unit 400 comprises a regenerator 440, the regenerator 440 comprising a char section 410 and a regeneration section 450, wherein the regeneration section 450 is in fluid communication with the char section 410 and is located above the char section 410; the regeneration section 450 is spaced from the char section 410 by a fluid distribution plate 451. Thus, the regeneration section 450 and the char section 410 are connected together in series. After being distributed through the fluid distribution plate 451, the material from the burn section 410 enters the regeneration section 450 for complete regeneration.
The scorch section 410 is provided with:
a first oxygen-containing gas inlet 411 for inputting a first oxygen-containing gas to the char section, the oxygen-containing gas inlet being provided at the bottom of the char section;
a gas phase fuel inlet 414 provided above the oxygen-containing gas inlet for inputting gas phase fuel (gas phase product from gas phase product storage tank 340);
a gas distributor 413 configured to distribute the gas phase fuel input through the gas phase fuel inlet; and
a spent catalyst inlet 416 for delivering spent catalyst of the catalytic cracking reactor to the interior of the burn zone.
Thus, the spent catalyst is initially burned and the gas phase products are partially combusted within the burn section 410. The influence of water generated in the hydrogen combustion process on the hydrothermal deactivation of the catalyst can be avoided.
The regeneration section 450 is provided with:
a second oxygen-containing gas inlet 452 provided at the bottom of the regeneration section for inputting a second oxygen-containing gas to the regeneration section;
a regenerated catalyst outlet 417 for delivering regenerated catalyst to the catalytic cracking reactor; and
a flue gas outlet 432 disposed at the top of the regeneration section;
wherein the regeneration section 450 is further provided with a heat extractor 415 for delivering heat to the exterior of the regenerator.
In the regeneration operation, gas phase products from the gas phase product storage tank 340 are input to the coke burning section 410 through the gas phase fuel inlet 414 via the gas distributor 413, spent catalyst from the catalytic cracking reactor enters the coke burning section 410 through the spent catalyst inlet 416, contacts with first oxygen-containing gas entering through the oxygen-containing gas inlet 411, and transmits part of the coke burning reaction (first-stage regeneration) in the coke burning section; thereafter, after passing through the fluid distribution plate 451, it enters the regeneration section 450 for complete regeneration. At this time, the second oxygen-containing gas is supplied through the second oxygen-containing gas inlet 452 to contact the partially burnt catalyst, thereby further regenerating and burning the catalyst and the incompletely regenerated flue gas (second stage regeneration). After separation by cyclone 420, the regenerated catalyst falls back to the regeneration zone and exits through catalyst outlet 417 and is recycled back to the catalytic cracking reactor. The flue gas exiting through the flue gas outlet 432 is energy recovered by the flue gas energy recovery system 430.
A large amount of heat is generated during regeneration due to the injection of the gas phase product. If the temperature in the regenerator is too high, the activity of the catalyst may be adversely affected. Therefore, the regeneration unit 400 is also provided with a heat collector 415 for supplying heat to the outside of the regenerator. The heat extractors may be internal heat extractors (disposed inside the regenerator) or/and external heat extractors (disposed outside the regenerator), one or more of which may use excess energy generated by the regenerator to supply other devices. The heat collector can be used for generating high-pressure steam by using the surplus heat of the regeneration system and outputting the high-pressure steam to other devices for energy supply. In one embodiment, the regenerator bed temperature is controlled to not exceed 750 ℃, such as not exceeding 720 ℃, by providing a heat extractor.
In one embodiment, the operating conditions of the char section (first section) are: the temperature is 550-720 ℃, the average residence time of the catalyst is 15-120 seconds, 10.0-90.0 seconds, preferably 15.0-80.0 seconds, and the apparent linear velocity of the gas is 0.5-5.0m/s, preferably 1.0-3.0m/s.
In one embodiment, the operating conditions of the regeneration section (second section) are: the temperature is 600-750 ℃, the average residence time of the catalyst is 0.5-5.0 minutes, such as 1.0-5.0 minutes, preferably 1.0-3.0 minutes, and the apparent linear velocity of the gas is 0.4-1.5m/s, preferably 0.5-1.0m/s. The catalyst is completely regenerated in the regeneration section, and the gas phase product from the biomass is completely combusted in the regeneration section. In one embodiment, the regeneration zone is a dense bed having a catalyst density of from 300 kg/m to 700kg/m 3 。
In one embodiment, the first oxygen-containing gas and the second oxygen-containing gas are both air. The adoption of two-stage regeneration can improve the burning strength, reduce the catalyst inventory, and weaken the influence of water vapor on the catalyst in the regeneration process.
The regeneration process may also employ a dual regenerator regeneration scheme, as shown in fig. 3. The regeneration unit comprises two regenerators. The regeneration unit 500 includes a first regenerator 510 and a second regenerator 520. The two regenerators are connected in series, with the second regenerator 520 downstream of the first regenerator 510, connected by a catalyst transfer line 535, so that the catalyst material of the first regenerator is transferred to the second regenerator.
The first regenerator 510 is provided with:
a first oxygen-containing gas inlet 511 provided at the bottom of the first regenerator for inputting a first oxygen-containing gas thereto;
a gas phase fuel inlet 514 disposed above the first oxygen-containing gas inlet for inputting gas phase fuel;
a gas distributor 516 configured to distribute a gaseous fuel input through the gaseous fuel inlet; and
a spent catalyst inlet 518 (connected to a spent inclined tube) for delivering spent catalyst of a catalytic cracking reactor to the interior of the first regenerator;
A first flue gas outlet 519 provided at the top of the first regenerator;
the second regenerator 520 is provided with:
a second oxygen-containing gas inlet 521 provided at the bottom of the second regenerator for inputting a second oxygen-containing gas to the second regenerator;
a regenerated catalyst outlet 531 (connected to a regenerated inclined tube) for delivering regenerated catalyst to the catalytic cracking reactor; and
a second flue gas outlet 529, which is arranged at the top of the second regenerator.
In the regeneration operation, the gas-phase fuel is introduced into the first regenerator 510 from the gas-phase fuel inlet 514 through the gas distributor 516, the spent catalyst from the catalytic cracking reactor enters the first regenerator through the spent inclined tube (communicated with the spent catalyst outlet 131) and through the spent catalyst inlet 518, contacts with the first oxygen-containing gas entering from the first oxygen-containing gas inlet 511, and transmits partial burning reaction (first-stage regeneration) in the first regenerator; after being separated by the cyclone 513, the flue gas enters the flue gas energy recovery device 530 through a pipeline connected with the first flue gas outlet 519 to recover energy; the partially regenerated catalyst is transferred to the second regenerator 520 through a catalyst transfer pipe 535, and is brought into contact with the second oxygen-containing gas introduced through the second oxygen-containing gas inlet 521 to undergo a coke combustion reaction, thereby performing complete regeneration. The flue gas of the second regenerator is separated by the cyclone 523 and then enters the flue gas energy recovery device 530 through a pipeline connected with the second flue gas outlet 529 to recover energy. The regenerated catalyst is recycled back to the catalytic cracking reactor through the regenerated catalyst inlet 531 via a regeneration chute (in communication with the regenerated catalyst inlet 103).
The first regenerator operating conditions were: the temperature is 550-700 ℃, the average residence time of the catalyst is 0.5-5.0 minutes, and the apparent linear velocity of gas is 0.5-1.5m/s. The second regenerator operating conditions were: the temperature is 560-720 ℃, the average residence time of the catalyst is 1.0-8.0 minutes, and the apparent linear velocity of gas is 0.4-1.0m/s.
In one embodiment, the first oxygen-containing gas and the second oxygen-containing gas are both air. The adoption of the double regenerators for regeneration can improve the burning strength, reduce the catalyst inventory and weaken the influence of water vapor on the catalyst in the regeneration process.
A large amount of heat is generated during regeneration due to the injection of the gas phase product. If the temperature in the regenerator is too high, the activity of the catalyst may be adversely affected. Therefore, the regeneration unit 500 is also provided with heat extractors 515, 525 for delivering heat to the outside of the first and second regenerators. The heat extractors may be internal heat extractors (disposed inside the regenerator) or/and external heat extractors (disposed outside the regenerator), one or more of which may use the excess energy produced by the first regenerator and the second regenerator to supply other devices. The heat collector can be used for generating high-pressure steam by using the surplus heat of the regeneration system and outputting the high-pressure steam to other devices for energy supply. In one embodiment, by providing the heat extractor 515, the first regenerator bed temperature is controlled to not exceed 750 ℃, such as not exceeding 720 ℃, such as not exceeding 700 ℃. In one embodiment, the second regenerator bed temperature is controlled to not exceed 750 ℃, such as not exceeding 720 ℃, by providing a heat extractor 525.
The catalyst which can be used comprises zeolite, inorganic oxide and optional clay, wherein the components respectively account for the total weight of the catalyst: 1 to 50 weight percent of zeolite, 5 to 99 weight percent of inorganic oxide and 0 to 70 weight percent of clay. Wherein the zeolite is an active component and is selected from medium pore zeolite and/or optional large pore zeolite, the medium pore zeolite accounts for 10-100 wt% of the total weight of the zeolite, and the large pore zeolite accounts for 0-90 wt% of the total weight of the zeolite; the medium pore zeolite is selected from one or more of ZSM series zeolite and/or ZRP zeolite, and the zeolite can be modified by nonmetal such as phosphorus and/or transition metal such as iron, cobalt and nickel; the macroporous zeolite is one or more selected from hydrogen Y, rare earth hydrogen Y, ultrastable Y, etc.
The invention will be further illustrated by the following examples, but the invention is not limited thereby. The properties of the raw oils A and B used in the examples and comparative examples are shown in tables 1 and 2, respectively, and the composition of the raw material C is shown in Table 3.
Catalyst a is commercially available catalyst ASC-2, the properties of which are shown in Table 4;
catalyst b is catalyst TCC and is prepared as follows: 969 g of halloysite (Chinese kaolin company product, solid content 73%) is pulped by 4300 g of decationizing water, 781 g of pseudo-boehmite (Shandong Zibo aluminum stone plant product, solid content 64%) and 144 ml of hydrochloric acid (concentration 30% and specific gravity 1.56) are added to be stirred uniformly, the mixture is kept stand and aged for 1 hour at 60 ℃, the pH value is kept to be 2-4, the mixture is cooled to normal temperature, and then 5000 g of prepared high silica alumina ratio mesoporous shape-selective ZSM-5 zeolite slurry containing chemical water is added to be stirred uniformly, and free Na+ is washed off by spray drying, thus obtaining the catalyst. After aging, the product is used, and aging conditions are as follows: the properties are shown in Table 5 after steam aging for 15 hours at 800 ℃.
The preparation of catalyst c is as follows:
(1) 20 g NH 4 Cl is dissolved in 1000 g of water, 100 g (dry basis) of a crystallization product ZRP-1 molecular sieve (manufactured by Qilu petrochemical company catalyst plant, siO) is added into the solution 2 /Al 2 O 3 =30, rare earth content RE 2 O 3 =2.0 wt%) after 0.5 hours exchange at 90 deg.cFiltering to obtain a filter cake; 4.0 g of H are added 3 PO 4 (concentration 85%) and 4.5 g of Fe (NO) 3 ) 3 Dissolving in 90 g of water, mixing with the filter cake, soaking and drying; and roasting at 550 ℃ for 2 hours to obtain the MFI mesoporous molecular sieve containing phosphorus and iron. The elemental analysis chemistry of the resulting molecular sieve is: 0.1Na 2 O·5.1Al 2 O 3 ·2.4P 2 O 5 ·1.5Fe 2 O 3 ·3.8RE 2 O 3 ·88.1SiO 2 。
(2) Pulping 75.4 kg of multi-water kaolin (industrial product of Suzhou porcelain clay Co., ltd., solid content of 71.6 wt.%) with 250 kg of decationized water, adding 54.8 kg of pseudo-boehmite (industrial product of Dongnial Co., ltd., solid content of 63 wt.%) and adjusting pH to 2-4 with hydrochloric acid, stirring uniformly, standing at 60-70deg.C for aging for 1 hr, maintaining pH to 2-4, cooling to below 60deg.C, adding 41.5 kg of alumina sol (catalyst product of Qilu petrochemical Co., al) 2 O 3 The content was 21.7 wt%) and stirred for 40 minutes to obtain a mixed slurry.
(3) Adding the MFI medium pore molecular sieve (dry basis is 2 kg) containing phosphorus and iron prepared in the step (1) into the mixed slurry obtained in the step (2), stirring uniformly, spray drying to form, washing with monoammonium phosphate solution (phosphorus content is 1 wt%) and washing to remove free Na + And drying to obtain a sample of the catalytic conversion catalyst c. Based on the total weight of the dry basis of the catalyst c, the dry basis composition of the catalyst c comprises: 2 wt% MFI mesoporous molecular sieve containing phosphorus and iron, 36 wt% pseudo-boehmite and 8 wt% alumina sol, the balance being kaolin.
Example 1
Example 1 was carried out on a catalytic cracking unit as shown in figure 1,
the structure of the catalytic cracking reactor can be seen in the reactor 302 of fig. 4 of CN 111718230A.
Specific preparation process of gas phase product:
the biomass is pretreated in a pretreatment system through water washing or acid washing, crushing and grinding and the like, and the pretreated biomass is fermented in an anaerobic fermentation device at a fermentation temperature of 37 ℃. And (3) removing water from the fermentation product by a drying device to obtain a gas-phase product, wherein methane accounts for more than 40% (based on the volume of the gas-phase product), and storing the gas-phase product in a storage tank for later use.
The raw material A is used as a reaction raw material, and the catalytic conversion catalyst a is used as a catalyst. The method provided by the invention is used for regenerating the catalyst to be regenerated. The spent catalyst from the spent inclined tube contacts with the gas phase product and air introduced from the gas distributor at the bottom of the regenerator to generate coke burning reaction. The surplus energy generated by the regeneration system is used for supplying energy to the outside through the heat-taking system. The coke burning temperature of the regeneration reactor is 685 ℃, the average residence time of the catalyst and the biomass charcoal is 5 minutes, and the apparent linear velocity of gas is 1.0m/s. The regenerated catalyst enters a reactor and contacts with raw oil to carry out catalytic cracking reaction. The surplus energy is used to supply other devices through the heat extraction system. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in table 6.
Comparative example 1
Comparative example 1 was performed on the same apparatus as example 1, except that the biomass treatment system was not included, but instead fuel oil was injected into the regenerator with the fuel oil as a supplemental source of energy. The regenerator char temperature was 685 ℃. The average residence time of the catalyst was 5 minutes and the gas superficial linear velocity was 1.0m/s. The regenerated catalyst enters a reactor and contacts with raw oil to carry out catalytic cracking reaction. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in table 6.
From the data in Table 6, it can be seen that the example uses biomass gas phase product as a source of supplemental energy, and the regeneration system produces the same amount of energy, the amount of carbon dioxide emitted is significantly reduced as compared to the comparative example, and more energy can be delivered to other devices, which is advantageous for substantially reducing the amount of carbon dioxide emitted.
Example 2
Example 2 was carried out on a catalytic cracking unit as shown in figure 1,
the structure of the catalytic cracking reactor can be seen in the reactor 302 of fig. 4 of CN 111718230A.
Specific preparation process of gas phase product:
the biomass is pretreated in a pretreatment system through water washing or acid washing, crushing and grinding and the like, and the pretreated biomass is fermented in an anaerobic fermentation device at a fermentation temperature of 37 ℃. And (3) removing water from the fermentation product by a drying device to obtain a gas-phase product, wherein methane accounts for more than 40% (based on the volume of the gas-phase product), and storing the gas-phase product in a storage tank for later use.
The raw material B is used as a reaction raw material, and the catalytic conversion catalyst B is used as a catalyst. The method provided by the invention is used for regenerating the catalyst to be regenerated. The spent catalyst from the spent inclined tube contacts with the gas phase product and air introduced from the gas distributor at the bottom of the regenerator to generate coke burning reaction. The surplus energy generated by the regeneration system is used for supplying energy to the outside through the heat-taking system. The coke burning temperature of the regeneration reactor is 680 ℃, the average residence time of the catalyst and the biomass charcoal is 4.5 minutes, and the apparent linear velocity of gas is 1.2m/s. The regenerated catalyst enters a reactor and contacts with raw oil to carry out catalytic cracking reaction. The surplus energy is used to supply other devices through the heat extraction system. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in table 7.
Comparative example 2
The method and apparatus of example 2 were used, except that fuel oil was used as the supplemental energy source. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in table 7.
As can be seen from the data in table 7, the example uses the biomass gas phase product as a source of supplemental energy, and the regeneration system generates the same amount of energy, the amount of carbon dioxide emitted is significantly reduced as compared to the comparative example, which is advantageous for substantially reducing the amount of carbon dioxide emitted.
Example 3
Example 3 was carried out on a catalytic cracking unit as shown in figure 1,
the structure of the catalytic cracking reactor can be seen in the reactor 302 of fig. 4 of CN 111718230A.
Specific preparation process of gas phase product:
the biomass is pretreated in a pretreatment system through water washing or acid washing, crushing and grinding and the like, and the pretreated biomass is fermented in an anaerobic fermentation device at a fermentation temperature of 37 ℃. And (3) removing water from the fermentation product by a drying device to obtain a gas-phase product, wherein methane accounts for more than 40% (based on the volume of the gas-phase product), and storing the gas-phase product in a storage tank for later use.
The raw material C is used as a reaction raw material, and the catalytic conversion catalyst C is used as a catalyst. The method provided by the invention is used for regenerating the catalyst to be regenerated. The spent catalyst from the spent inclined tube contacts with the gas phase product and air introduced from the gas distributor at the bottom of the regenerator to generate coke burning reaction. The surplus energy generated by the regeneration system is used for supplying energy to the outside through the heat-taking system. The coke burning temperature of the regeneration reactor is 690 ℃, the average residence time of the catalyst and the biomass charcoal is 3 minutes, and the apparent linear velocity of gas is 1.5m/s. The regenerated catalyst enters a reactor and contacts with raw oil to carry out catalytic cracking reaction. The surplus energy is used to supply other devices through the heat extraction system. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in table 8.
Comparative example 3
The method and apparatus of example 3 were used, except that fuel oil was used as the supplemental energy source. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in table 8.
As can be seen from the data in table 8, the example uses the biomass gas phase product as a source of supplemental energy, and the regeneration system generates the same amount of energy, the amount of carbon dioxide emitted is significantly reduced as compared to the comparative example, which is advantageous for substantially reducing the amount of carbon dioxide emitted.
In the description of the present application, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "inner", "outer", "front", "rear", "left", "right", etc. are directions or positional relationships based on the operation state of the present application are merely for convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements to be referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present application.
In the description of the present application, it should be noted that the terms "mounted," "connected," and "connected" are to be construed broadly, unless otherwise specifically defined and limited. The specific meaning of the above terms in the present application will be understood in specific cases by those of ordinary skill in the art.
The application has been described above in connection with preferred embodiments, which are, however, exemplary only and for illustrative purposes. On this basis, the application can be subjected to various substitutions and improvements, and all fall within the protection scope of the application.
TABLE 1
| Feed Properties | Raw oil A |
| Density, kg/cubic meter (20 ℃ C.) | 890.5 |
| Kangshi carbon residue, weight percent | 2.94 |
| C, wt% | 86.48 |
| H, wt% | 13.18 |
| S, weight percent | 0.15 |
| N, wt% | 0.19 |
| Fe, microgram/gram | 9.1 |
| Na, micrograms/gram | 0.16 |
| Ni, microgram/gram | 5.4 |
| V, micrograms/gram | 16.49 |
| Initial point of distillation, DEG C | 261 |
| 10％，℃ | 439 |
| 30％，℃ | 501 |
| 50％，℃ | 550 |
TABLE 2
| Feed Properties | Raw oil B |
| Density, kg/cubic meter (20 ℃ C.) | 843.7 |
| C, wt% | 86.59 |
| H, wt% | 13.41 |
| S，μg/g | 5800 |
| N，μg/g | 62 |
| Initial point of distillation, DEG C | 226 |
| 50% distillation temperature, DEG C | 287 |
| Paraffin, weight percent | 40.5 |
| Naphthene, weight percent | 33.3 |
| Aromatic hydrocarbon, weight percent | 26.2 |
TABLE 3 raw material C
TABLE 4 Table 4
TABLE 5
TABLE 6
The calculation was performed based on 100g of the raw material processed.
The carbon dioxide emission index refers to the amount of carbon dioxide from fossil energy emitted per 1MJ energy produced by the coke burning of the regeneration system; the carbon dioxide produced by the biomass methane-rich gas is derived from carbon dioxide present in the atmosphere and is a neutral carbon emission process.
TABLE 7
The calculation was performed based on 100g of the raw material processed.
The carbon dioxide emission index refers to the amount of carbon dioxide from fossil energy emitted per 1MJ energy produced by the coke burning of the regeneration system; carbon dioxide produced by the biomass gas phase product is derived from carbon dioxide present in the atmosphere and is a neutral carbon emission process.
TABLE 8
The calculation was performed based on 100g of the raw material processed.
The carbon dioxide emission index refers to the amount of carbon dioxide from fossil energy emitted per 1MJ energy produced by the coke burning of the regeneration system; carbon dioxide produced by the biomass gas phase product is derived from carbon dioxide present in the atmosphere and is a neutral carbon emission process. />
Claims (12)
1. A catalytic cracking catalyst regeneration system comprising:
a biomass processing system comprising:
a biomass pretreatment unit for pretreating biomass,
a biomass anaerobic fermentation unit for carrying out anaerobic fermentation treatment on the pretreated biomass to obtain a gas-phase fermentation product,
a gas phase product drying unit for drying the gas phase fermentation product obtained by the biomass anaerobic fermentation unit to obtain a gas phase product, and
a gas phase product storage tank for storing the gas phase product;
a regeneration unit, the regeneration unit comprising:
a regenerator in which:
an oxygen-containing gas inlet for inputting an oxygen-containing gas to the regenerator, the oxygen-containing gas inlet being disposed at the bottom of the regenerator;
a distribution plate configured to distribute an oxygen-containing gas input through the oxygen-containing gas inlet;
A gas phase fuel inlet arranged above the distribution plate for inputting gas phase fuel;
a gas distributor configured to distribute a gaseous fuel input through the gaseous fuel inlet;
a spent catalyst inlet for delivering spent catalyst of a catalytic cracking reactor to the interior of the regenerator; and
a regenerated catalyst outlet for delivering regenerated catalyst to a catalytic cracking reactor;
a heat extractor configured to deliver heat to an exterior of the regenerator;
wherein the vapor phase product storage tank is in communication with the vapor phase fuel inlet such that the vapor phase product is delivered to the interior of the regenerator.
2. The regeneration system of claim 1, wherein the regenerator is a dense bed and the gas phase fuel inlet, gas distributor, and spent catalyst inlet are disposed in a lower portion of the dense bed.
3. The regeneration system of claim 1, wherein the regenerator comprises a char section and a regeneration section, wherein the regeneration section is in communication with and above the char Duan Liuti section; the regeneration section is spaced from the burn section by a fluid distribution plate;
The scorching section is provided with:
a first oxygen-containing gas inlet arranged at the bottom of the coke burning section for inputting a first oxygen-containing gas into the coke burning section;
a gas phase fuel inlet provided above the first oxygen-containing gas inlet for inputting gas phase fuel;
a gas distributor configured to distribute a gaseous fuel input through the gaseous fuel inlet; and
a spent catalyst inlet for conveying spent catalyst of a catalytic cracking reactor to the interior of the burn-in section;
the regeneration section is provided with:
a second oxygen-containing gas inlet provided at the bottom of the regeneration section for inputting a second oxygen-containing gas to the regeneration section; and
a regenerated catalyst outlet for delivering regenerated catalyst to the catalytic cracking reactor.
4. The regeneration system of claim 1, wherein the regeneration unit comprises
A first regenerator, and
the second regenerator is provided with a second heat exchanger,
wherein the second regenerator is located downstream of the first regenerator, the first and second regenerators being connected by a catalyst transfer tube such that catalyst material of the first regenerator is transferred to the second regenerator;
The first regenerator is provided with:
a first oxygen-containing gas inlet provided at the bottom of the first regenerator for inputting a first oxygen-containing gas to the first regenerator;
a gas phase fuel inlet provided above the first oxygen-containing gas inlet for inputting gas phase fuel;
a gas distributor configured to distribute a gaseous fuel input through the gaseous fuel inlet;
a spent catalyst inlet for delivering spent catalyst of a catalytic cracking reactor to the interior of the first regenerator; and
a first flue gas outlet disposed at the top of the first regenerator;
the second regenerator is provided with:
a second oxygen-containing gas inlet provided at the bottom of the second regenerator for inputting a second oxygen-containing gas to the second regenerator;
a regenerated catalyst outlet for delivering regenerated catalyst from the second regenerator to the catalytic cracking reactor; and
and a second flue gas outlet arranged at the top of the second regenerator.
5. A catalytic cracking catalyst regeneration process carried out in the regeneration system of any one of claims 1-4, the process comprising:
S1, conveying biomass to a biomass anaerobic fermentation unit for anaerobic fermentation treatment after pretreatment to obtain a gas-phase fermentation product;
s2, drying the gas-phase fermentation product to obtain a gas-phase product, and storing the gas-phase product in a gas-phase product storage tank;
s3, conveying the gas phase product in the gas phase product storage tank to the inside of the regenerator through the gas distributor, and enabling the gas phase product to be in contact with a spent catalyst from a catalytic cracking reactor and an oxygen-containing gas so as to regenerate the spent catalyst.
6. The method of claim 5, wherein the biomass is selected from the group consisting of agricultural and forestry biomass, aquatic plants, energy crops, livestock manure, municipal solid waste, domestic sewage, and industrial organic sewage.
7. The regeneration method according to claim 5, wherein the biomass pretreatment method comprises physical pretreatment, chemical pretreatment, biological pretreatment, etc., specifically comprises one or more of grinding/extrusion/steam explosion/acid treatment/alkali treatment/microorganism pretreatment; the anaerobic fermentation process is carried out in a closed fermentation tank, and the fermentation temperature is not higher than 60 ℃;
in the gas phase product, the methane accounts for more than 40 percent based on the total volume of the gas phase product.
8. The regeneration process of claim 5, wherein the amount of gas phase product introduced into the regenerator is no more than 4% by volume of the oxygen-containing gas.
9. The recycling party according to claim 5The method, wherein the regenerator comprises a dense bed in which the catalyst has a bed density of 300-700kg/m 3 。
10. The catalytic cracking catalyst regeneration method according to claim 8, wherein,
the gas phase product is injected through the gas distributor from a level not lower than the level of the spent catalyst inlet.
11. The method for regenerating a catalytic cracking catalyst according to claim 5, wherein the operation temperature of the regenerator is 550 to 750 ℃, the average residence time of the catalyst is 2.0 to 15.0 minutes, and the superficial linear velocity of the gas is 0.7 to 2.0m/s.
12. The catalytic cracking catalyst regeneration process of claim 5, wherein the temperature of the regenerator bed is controlled via the heat extractor to not exceed 750 ℃, preferably 720 ℃.
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|---|---|---|---|
| CN202210474594.4A CN117000295A (en) | 2022-04-29 | 2022-04-29 | Catalyst regeneration method and regeneration system |
| PCT/CN2023/091025 WO2023208083A1 (en) | 2022-04-29 | 2023-04-27 | Catalytic cracking catalyst regeneration method and system using bio-based gas-phase fuel |
| TW112115714A TW202342175A (en) | 2022-04-29 | 2023-04-27 | Catalytic cracking catalyst regeneration method and system using bio-based gas-phase fuel |
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