CN117000296A - Catalytic cracking catalyst regeneration method and regeneration system - Google Patents
Catalytic cracking catalyst regeneration method and regeneration system Download PDFInfo
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- CN117000296A CN117000296A CN202210475997.0A CN202210475997A CN117000296A CN 117000296 A CN117000296 A CN 117000296A CN 202210475997 A CN202210475997 A CN 202210475997A CN 117000296 A CN117000296 A CN 117000296A
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- regenerator
- alcohol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 238000011069 regeneration method Methods 0.000 title claims abstract description 77
- 230000008929 regeneration Effects 0.000 title claims abstract description 66
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000000446 fuel Substances 0.000 claims abstract description 123
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000003546 flue gas Substances 0.000 claims abstract description 65
- 239000002028 Biomass Substances 0.000 claims abstract description 62
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 55
- 239000001301 oxygen Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 34
- 238000000855 fermentation Methods 0.000 claims description 28
- 230000004151 fermentation Effects 0.000 claims description 28
- 230000007062 hydrolysis Effects 0.000 claims description 26
- 238000006460 hydrolysis reaction Methods 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- 238000003860 storage Methods 0.000 claims description 23
- 239000000413 hydrolysate Substances 0.000 claims description 20
- 238000004891 communication Methods 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 15
- 238000004064 recycling Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 208000005156 Dehydration Diseases 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 6
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 5
- 241000894006 Bacteria Species 0.000 claims description 3
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- 244000005700 microbiome Species 0.000 claims description 3
- 230000007071 enzymatic hydrolysis Effects 0.000 claims description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 94
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 49
- 239000001569 carbon dioxide Substances 0.000 abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052799 carbon Inorganic materials 0.000 abstract description 19
- 238000000926 separation method Methods 0.000 abstract description 16
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 22
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 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
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- 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
- 239000002699 waste material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
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- 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 2
- 239000011268 mixed slurry Substances 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 240000000385 Brassica napus var. napus Species 0.000 description 1
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- 241000195493 Cryptophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 102100028099 Thyroid receptor-interacting protein 6 Human genes 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 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
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- 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
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 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
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000000813 microbial effect Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
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- -1 rare earth hydrogen Chemical class 0.000 description 1
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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
- C12M21/12—Bioreactors or fermenters specially adapted for specific uses for producing fuels or solvents
-
- 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
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
Abstract
The application relates to a catalytic cracking catalyst regeneration method and a regeneration system, wherein the method comprises the following steps: injecting biomass alcohol-based fuel into a first regenerator through a first distributor, and contacting with a spent catalyst from a catalytic cracking reactor and oxygen to partially burn the spent catalyst; the catalyst from the first regenerator enters the second regenerator and contacts with oxygen injected into the second regenerator through the second oxygen inlet and the alcohol-based fuel optionally injected through the second distributor to completely regenerate the catalyst. The method of the application uses the biomass-derived alcohol-based fuel as the energy supply of the catalytic cracking device, reasonably utilizes the biomass energy, radically changes the energy source of the device, can greatly reduce the carbon emission of the catalytic cracking unit, and can also provide energy for other process units; the concentration of carbon dioxide in the flue gas is higher, which is beneficial to separation and trapping.
Description
Technical Field
The application relates to a method for regenerating a catalyst in a hydrocarbon processing process. More particularly, the application relates to a catalyst regeneration method and a regeneration system for realizing carbon dioxide emission reduction and strengthening energy supply of a regeneration device 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 low-carbonization catalytic cracking schemes 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 flue gas emission of equipment such as catalytic cracking and burning, hydrogen production process, boilers and the like and the energy consumption in the technical process. 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 a key point of carbon emission reduction in petrochemical industry.
CN113877397a discloses a method for incompletely regenerating a catalyst by pure oxygen, wherein carbon monoxide in the obtained flue gas is used as a chemical raw material, and carbon dioxide is used for sealing or displacing oil, so that carbon emission is reduced. However, the process mainly involves the post-treatment process of the flue gas, and has high cost. The method relates to separation of carbon monoxide, carbon dioxide, oxygen and other wastes, the separation process is complex, the chemical energy of carbon deposit is not utilized to the maximum extent even though the carbon deposit is not completely regenerated, and the accumulated carbon dioxide is stored in a sealing way, so that the resource waste is caused.
CN1600431a discloses an incomplete regeneration flue gas combustion technology, which adopts a method of supplementing air in the incomplete regeneration flue gas to enable CO in the non-regenerated flue gas to continue to burn, raise the temperature of the flue gas, improve the recovery efficiency of the flue gas machine, and furthest recover the pressure energy of the flue gas, thereby reducing the energy consumption of the device. The method can improve the energy utilization efficiency, but can not effectively reduce the carbon dioxide emission.
The reaction-regeneration system of a catalytic cracker is a cyclic heat-taking-exothermic heat balance process, the energy of which derives from the scorching exotherm of the catalyst in the regeneration system. Under the current development trend, the production mode of oil reduction and increase is beneficial to promote the sustainable development of the oil refining industry, but more reaction heat is needed to meet the heat balance under the mode. When the amount of scorching is insufficient to meet the energy consumption of the device, additional fuel is usually needed for heat compensation, and the compensated energy is derived from fossil energy, so that the carbon dioxide emission amount from the fossil energy is increased, and the resource waste is also caused. The optimization of the regeneration process or the recycling of the discharged carbon dioxide can also reduce the discharge amount of the carbon dioxide to a certain extent, but the cost is higher, and the process is more complex. And the source of energy is not changed fundamentally, 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 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 process, the process being carried out in a regeneration system,
wherein the regeneration system comprises:
a biomass processing unit comprising:
a biomass pretreatment device for pretreating biomass, and
the biomass hydrolysis device is used for carrying out hydrolysis treatment on the pretreated biomass to obtain hydrolysate,
the hydrolysate fermentation device is used for carrying out fermentation treatment on the hydrolysate to obtain a liquid-phase product;
the dehydration device is used for carrying out dehydration treatment on the liquid-phase product to obtain an alcohol-based fuel;
a storage tank for storing the alcohol-based fuel;
a regeneration unit, the regeneration unit comprising:
a regenerator, the regenerator comprising:
the first regenerator is provided with a first set of heat exchangers,
a second regenerator, and
wherein the first regenerator is in communication with the second regenerator such that catalyst material of the first regenerator may enter the second regenerator;
wherein, be provided with in the first regenerator:
a first alcohol-based fuel inlet for inputting alcohol-based fuel from the storage tank to the first regenerator;
a first distributor configured to distribute an alcohol-based fuel input via the first alcohol-based fuel inlet;
a first oxygen inlet provided at the bottom of the first regenerator for inputting oxygen to the first regenerator;
a spent catalyst inlet for delivering spent catalyst of a catalytic cracking reactor to the interior of the first regenerator; and
a first recycle flue gas inlet for recycling a portion of flue gas exiting a first regenerator back into the first regenerator;
wherein the storage tank is in communication with the alcohol-based fuel inlet such that the alcohol-based fuel is delivered to the interior of the first regenerator;
wherein, be provided with in the second regenerator:
a second alcohol-based fuel inlet for inputting alcohol-based fuel from the storage tank to the second regenerator;
a second distributor configured to distribute alcohol-based fuel input via the second alcohol-based fuel inlet;
the second oxygen inlet is arranged at the bottom of the second regenerator and is used for inputting oxygen into the second regenerator;
a second recycle flue gas inlet for recycling a portion of the flue gas exiting the first regenerator back into the second regenerator; and
a regenerated catalyst outlet for delivering regenerated catalyst to a catalytic cracking reactor;
the method comprises the following steps:
s1, conveying biomass to a hydrolysis device for hydrolysis treatment after pretreatment to obtain hydrolysate;
s2, conveying the hydrolysate to a fermentation device, fermenting to generate a liquid-phase product, dehydrating to obtain alcohol-based fuel, and conveying the alcohol-based fuel to a storage tank;
s3, injecting alcohol-based fuel into a first regenerator through a first distributor, and contacting with a spent catalyst from a catalytic cracking reactor and oxygen to partially burn the spent catalyst;
s4, the catalyst from the first regenerator enters the second regenerator, and is contacted with oxygen injected into the second regenerator through a second oxygen inlet and the optional alcohol-based fuel injected through a second distributor, so that the catalyst is completely regenerated.
In one embodiment, the first regenerator is located above the second regenerator, the first regenerator being in communication with the second regenerator via an external circulation line such that catalyst material of the first regenerator may enter the second regenerator via the external circulation line;
the first regenerator is spaced from the second regenerator by a flue gas distribution plate such that flue gas generated by the second regenerator enters the first regenerator via the flue gas distribution plate.
In one embodiment, the hydrolysis treatment is an acid hydrolysis treatment or an enzymatic hydrolysis treatment;
the temperature of the hydrolysis liquid in the fermentation process is not higher than 50 ℃, and the microorganism in the fermentation process is selected from bacteria, fungi and saccharomycetes.
In one embodiment, the alcohol-based fuel comprises more than 90% ethanol, no more than 5% water, and the balance methanol and C 3-5 Saturated monohydric alcohols, and the like, based on the total weight of the alcohol-based fuel.
In one embodiment, the weight ratio of spent catalyst to introduced alcohol-based fuel is from 10 to 400:1, the alcohol-based fuel introduced into the first regenerator comprising from 60 to 100 weight percent of the total amount of alcohol-based fuel introduced into the regeneration unit.
In one embodiment, the operating conditions of the first regenerator are: the temperature is 570-720 ℃, the average residence time of the catalyst is 1.0-7.0 minutes, and the apparent linear velocity of gas is 0.4-1.0m/s.
In one embodiment, the operating conditions of the second regenerator are: the temperature is not higher than 750 ℃, the average residence time of the catalyst is 1.0-5.0 minutes, and the apparent linear velocity of gas is 0.3-0.8m/s.
In one embodiment, the oxygen concentration in the first regenerator is no more than 28% by volume; in the second regenerator, the oxygen concentration does not exceed 28% by volume.
In one embodiment, the burn rate in the first regenerator is from 30 to 50%; the second regenerator has a char ratio of 50-70%.
In another aspect, the present application provides a catalytic cracking catalyst regeneration system comprising:
a biomass processing unit comprising:
a biomass pretreatment device for pretreating biomass, and
the biomass hydrolysis device is used for carrying out hydrolysis treatment on the pretreated biomass to obtain hydrolysate,
the hydrolysate fermentation device is used for carrying out fermentation treatment on the hydrolysate to obtain a liquid-phase product;
the dehydration device is used for carrying out dehydration treatment on the liquid-phase product to obtain an alcohol-based fuel;
a storage tank for storing the alcohol-based fuel;
a regeneration unit, the regeneration unit comprising:
a regenerator, the regenerator comprising:
the first regenerator is provided with a first set of heat exchangers,
a second regenerator, and
wherein the first regenerator is in communication with the second regenerator such that catalyst material of the first regenerator may enter the second regenerator;
wherein, be provided with in the first regenerator:
a first alcohol-based fuel inlet for inputting alcohol-based fuel from the storage tank to the first regenerator;
a first distributor configured to distribute an alcohol-based fuel input via the first alcohol-based fuel inlet;
a first oxygen inlet provided at the bottom of the first regenerator for inputting oxygen to the first regenerator;
a spent catalyst inlet for delivering spent catalyst of a catalytic cracking reactor to the interior of the first regenerator; and
a first recycle flue gas inlet for recycling a portion of flue gas exiting a first regenerator back into the first regenerator;
wherein the storage tank is in communication with the alcohol-based fuel inlet such that the alcohol-based fuel is delivered to the interior of the first regenerator;
wherein, be provided with in the second regenerator:
a second alcohol-based fuel inlet for inputting alcohol-based fuel from the storage tank to the second regenerator;
a second distributor configured to distribute alcohol-based fuel input via the second alcohol-based fuel inlet;
the second oxygen inlet is arranged at the bottom of the second regenerator and is used for inputting oxygen into the second regenerator;
a second recycle flue gas inlet for recycling a portion of the flue gas exiting the first regenerator back into the second regenerator; and
a regenerated catalyst outlet for delivering regenerated catalyst to the catalytic cracking reactor.
Thus, compared with the existing catalytic cracking catalyst regeneration method, the main advantages of the application are as follows:
(1) Biomass is cheap and easy to obtain, biomass energy belongs to renewable energy, and carbon is derived from carbon dioxide captured by plants from air; biomass energy is introduced into a catalytic cracking regeneration system in a proper mode to replace the original fossil fuel energy supply, so that the emission of carbon dioxide can be reduced, and the low carbonization development of oil refining is realized.
(2) The biomass can be converted into the alcohol-based fuel through the hydrolysis fermentation process, the process is mild, the energy consumption is low, the consumed energy sources are derived from renewable energy sources such as solar energy, green electricity and the like, the alcohol-based fuel can be introduced into a regeneration system for supplying energy, and the reduction of the carbon dioxide emission in the whole life cycle of catalytic cracking is realized.
(3) The alcohol-based fuel can be used as fuel for energy supply without separation and purification, so that the process is simplified, the cost is saved, and the utilization mode and the way of biomass energy are expanded.
(4) The surplus heat generated by the regeneration system can be used for generating high-pressure steam to supply other devices; after the generated flue gas is subjected to energy recovery, carbon dioxide in the flue gas can be separated and trapped, so that carbon dioxide emission is realized.
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 is a schematic diagram of one embodiment of a regeneration system.
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.
The application provides a catalytic cracking catalyst regeneration system and a regeneration method performed in the regeneration system. 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, the present application provides a catalytic cracking catalyst regeneration system for reducing carbon dioxide emissions, comprising: a biomass processing unit 300 and a regeneration unit 200.
The present application provides a catalytic cracking catalyst regeneration process which may be performed in the regeneration system of the present application, the process comprising:
s1, conveying biomass to a hydrolysis device for hydrolysis treatment after pretreatment to obtain hydrolysate;
s2, conveying the hydrolysate to a fermentation device, fermenting to generate a liquid-phase product, dehydrating to obtain alcohol-based fuel, and conveying the alcohol-based fuel to a storage tank;
s3, injecting alcohol-based fuel into a first regenerator through a first distributor, and contacting with a spent catalyst from a catalytic cracking reactor and oxygen to partially burn the spent catalyst;
s4, the catalyst from the first regenerator enters the second regenerator, and is contacted with oxygen injected into the second regenerator through a second oxygen inlet and the optional alcohol-based fuel injected through a second distributor, so that the catalyst is completely regenerated.
As shown in fig. 1, in the catalytic cracking reaction system 100, a catalytic cracking reactor 110 is used to perform catalytic cracking reaction: the bottom inlet 102 of which is fed with a lifting medium to lift the regenerated catalyst (from the regeneration unit 200) entering the 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 biomass processing unit 300 for providing an alcohol-based fuel includes:
a biomass pretreatment device 310 for pretreating biomass, and
a biomass hydrolysis device 320 for hydrolyzing the pretreated biomass to obtain a hydrolysate,
a hydrolysate fermentation device 330 for fermenting the hydrolysate to obtain a liquid phase product;
a dehydration device 340, configured to dehydrate the liquid phase product to obtain an alcohol-based fuel;
and
a storage tank 350 for storing the alcohol-based fuel.
As shown in fig. 1, biomass may be conveyed to a pretreatment device 310, pretreated, and then conveyed to a hydrolysis system 320 to obtain a hydrolysate; the hydrolysate is sent to a fermentation device 330, and the liquid phase product obtained by fermentation is sent to a dehydration device 340 to remove water and is sent to a storage tank 350 for subsequent regeneration treatment.
In accordance with the present application, biomass includes, but is not limited to, agroforestry biomass, forestry biomass, aquatic plants, energy crops, waste, domestic sewage, industrial organic sewage, and the like. For example, agricultural and forestry biomass including but not limited to straw, chaff, cotton stalks, and the like, forestry biomass including but not limited to firewood, fast-growing forest, forestry processing residues, and the like, aquatic plants including but not limited to reed, algae, and the like, energy crops including cassava, canola, and the like, waste including but not limited to waste paper, and domestic and industrial organic sewage including but not limited to organic sewage discharged from industries such as cooling water, kitchen drainage, wine making, food products, and the like.
According to the application, the biomass pretreatment process aims at breaking the connection between cellulose, hemicellulose and lignin and improving the efficiency of the hydrolysis process, and the pretreatment method can be selected from a plurality of major categories such as physical pretreatment, chemical pretreatment, biological pretreatment, physicochemical pretreatment and the like, and the specific method is one or more selected from ball milling treatment, microwave treatment, acid treatment, alkali treatment, steam explosion, carbon dioxide explosion, microbial degradation and the like.
According to the present application, the biomass hydrolysis process may employ an acid hydrolysis process or an enzyme hydrolysis process. The temperature of the acid hydrolysis process is not higher than 200 ℃, and the temperature of the enzyme hydrolysis process is not higher than 70 ℃.
According to the application, the temperature of the hydrolysis liquid fermentation process is not more than 50 ℃, microorganisms in the fermentation process are selected from bacteria, fungi and saccharomycetes, and the liquid phase product obtained by fermentation is dehydrated to obtain the alcohol-based fuel which is directly used as the fuel without separation.
According to the application, the energy consumed in the process of preparing alcohol fuel by biomass is at least partially or completely derived from renewable energy sources such as solar energy, green electricity, nuclear energy and the like.
According to the application, the alcohol-based fuel is mainly ethanol, and also comprises a small amount of methanol and saturated monohydric alcohol with 3-5 carbon atomsClass, organic acids, ethers, esters, ketones, aldehydes, and the like. In one embodiment, the alcohol-based fuel comprises more than 90% ethanol, no more than 5% water, the balance methanol and C 3-5 Saturated monohydric alcohols, and the like, based on the total weight of the alcohol-based fuel.
The regeneration unit 200 of the present application is suitable for the above-described catalytic cracking reaction system 100, for regenerating the spent catalyst passing through the catalytic cracking reaction system, and for transferring the regenerated catalyst back to the catalytic cracking reaction system 100, thereby realizing the recycling of the catalyst.
As shown in fig. 1, the regeneration unit 200 includes:
the first regenerator 210 is provided with a first set of filters,
a second regenerator 250, and
wherein the first regenerator 210 is in communication with the second regenerator 250 such that catalyst material of the first regenerator may enter the second regenerator.
In one embodiment, the first regenerator 210 is positioned above the second regenerator 250, the first regenerator being in communication with the second regenerator via an outer circulation pipe 255 such that catalyst material of the first regenerator may enter the second regenerator 250 via the outer circulation pipe 255; the first regenerator is spaced from the second regenerator by a flue gas distribution plate 256 such that flue gas generated by the second regenerator enters the first regenerator via the flue gas distribution plate 256. The flue gas distribution plate 256 may allow the flue gas produced by the second regenerator to pass, but not the catalyst; the catalyst material of the first regenerator enters the second regenerator via an external circulation line 255.
The first regenerator 210 is provided with:
a first alcohol-based fuel inlet 214 for inputting alcohol-based fuel from the tank to the first regenerator;
a first sparger 2101 configured to distribute an alcohol-based fuel input through the first alcohol-based fuel inlet;
a first oxygen inlet 218 provided at the bottom of the first regenerator for inputting oxygen thereto;
a spent catalyst inlet 216 for delivering spent catalyst of a catalytic cracking reactor to the interior of the first regenerator; and
a first recycle flue gas inlet 2102 for recycling a portion of the flue gas exiting the first regenerator back into the first regenerator interior;
wherein the reservoir 350 is in communication with the first alcohol-based fuel inlet 214 such that the alcohol-based fuel is delivered to the interior of the first regenerator.
The second regenerator 250 is provided with:
a second alcohol-based fuel inlet 251 for inputting alcohol-based fuel from the reservoir to the second regenerator;
a second distributor 252 configured to distribute alcohol-based fuel input via the second alcohol-based fuel inlet;
a second oxygen inlet 211 provided at the bottom of the second regenerator for inputting oxygen to the second regenerator;
a second recycle flue gas inlet 253 for recycling a portion of the flue gas exiting the first regenerator back into the second regenerator; and
a regenerated catalyst outlet 217 for delivering regenerated catalyst to the catalytic cracking reactor,
wherein the storage tank 350 is in communication with the second alcohol-based fuel inlet 251 such that the alcohol-based fuel may be delivered to the interior of the second regenerator.
In one embodiment, the weight ratio of spent catalyst to introduced alcohol-based fuel is from 10 to 400:1, the alcohol-based fuel introduced into the first regenerator comprising from 60 to 100 weight percent of the total amount of alcohol-based fuel introduced into the regeneration unit.
In performing a regeneration operation, the alcohol-based fuel in the tank 350 is introduced into the first regenerator 210 to contact the oxygen introduced through the oxygen-containing gas inlet 218 and through the first sparger 2101, and a partial burn reaction occurs in the first regenerator 210; thereafter, the mixture enters the second regenerator 250 for complete regeneration. At this time, pure oxygen is supplied through the second oxygen inlet 253, and the catalyst is brought into contact with the partially burnt catalyst, thereby further regenerating and burning the catalyst. Optionally, a storage tank 350 may be in communication with the second base fuel inlet 251 such that alcohol base fuel may be delivered to the second regenerator interior via the second base fuel inlet 251 and the second distributor 252. The regenerated catalyst may be withdrawn through catalyst outlet 217 and recycled back to the catalytic cracking reactor. The flue gas discharged from the first regenerator through the flue gas outlet 232 after being separated by the cyclone separator 220, part of the flue gas is recovered by the flue gas energy recovery system 230, and then is separated by the carbon dioxide separation system 260, so that the capture of carbon dioxide is realized; and the other part of the flue gas is recycled to the first regenerator and the second regenerator.
In one embodiment, the gases input through the first oxygen inlet 211 and the second oxygen inlet 253 are both oxygen. However, the oxygen input through the first oxygen inlet 211 is mixed with the recycled flue gas after entering the first regenerator to form an oxy-carbon dioxide mixture, and the amount of oxygen and/or recycled flue gas is controlled such that the oxygen concentration in the mixture does not exceed 28% by volume. Similarly, the oxygen input through the second oxygen inlet 252 is mixed with the recycled flue gas and the like after entering the second regenerator to form an oxy-carbon dioxide mixed gas, and the amount of oxygen and/or recycled flue gas is controlled so that the oxygen concentration in the mixed gas is not higher than 28 vol%. The scorching is carried out in the atmosphere, so that the scorching strength is improved; the air inlet does not contain nitrogen, so that the energy consumed by preheating the air can be reduced; and the carbon dioxide concentration of the flue gas at the outlet of the regenerator is higher, so that the separation and the capture of the carbon dioxide are convenient.
In one embodiment, the operating conditions of the first regenerator are: the temperature is 570-720 ℃, the average residence time of the catalyst is 1.0-7.0 minutes, and the apparent linear velocity of gas is 0.4-1.0m/s.
In one embodiment, the operating conditions of the second regenerator are: the temperature is not higher than 750 ℃, the average residence time of the catalyst is 1.0-5.0 minutes, and the apparent linear velocity of gas is 0.3-0.8m/s.
In one embodiment, the burn rate in the first regenerator is from 30 to 50%; the second regenerator has a char ratio of 50-70%. The application adopts pure oxygen regeneration, and the regenerated flue gas only contains carbon dioxide and oxygen, thereby being convenient for separating and capturing the carbon dioxide for further conversion and utilization and realizing carbon emission.
In one embodiment, the alcohol-based fuel is introduced directly into the first regenerator and optionally the second regenerator via a distributor, contacts the catalyst and undergoes a combustion reaction, the alcohol-based fuel being introduced into the first regenerator in a ratio of 60 to 100% by weight. The distributor is selected from a nozzle and a distributing pipe. In one embodiment, the ratio of spent catalyst to introduced alcohol-based fuel is from 10 to 400:1 by weight.
A large amount of heat is generated during the regeneration in the first regenerator and the second regenerator. If the temperature in the first regenerator and the second regenerator is too high, the activity of the catalyst may be adversely affected. Therefore, the regeneration unit is further provided with a heat extractor 215 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 generated by the first and second regenerators 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 first and second regenerator bed temperatures are controlled to not exceed 750 ℃, such as not exceeding 720 ℃, by providing a heat extractor.
In the present application, 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 application uses the energy of burning the alcohol-based fuel generated by biomass to maintain the operation of the catalytic cracking device, which is an indirect solar energy utilization process in nature, wherein carbon in the biomass is derived from carbon dioxide captured by plants from the atmosphere, rather than fossil energy, and the energy consumed by the whole process is derived from solar energy. Therefore, biomass energy utilization is also recycling of carbon element, and is a neutral emission process of carbon.
The application can also use the energy generated by the regeneration system of the catalytic cracking device to supply other operation units to become a power center of the refinery, thereby fundamentally reducing the carbon emission of the refinery. According to the application, biomass is introduced into the power center of the catalytic cracking device, the biomass energy supply device is operated, and the discharged carbon dioxide is not derived from fossil energy, so that the energy source can be radically changed, and the carbon emission reduction is realized.
The application will be further illustrated by the following examples, but the application is not limited thereby. The properties of the raw oil a and the raw oil B used in examples and comparative examples are shown in tables 1 and 2.
The catalyst a is TCC, and the preparation process is as follows: pulping 969 g of halloysite (product of China Kaolin Co., ltd., solid content of 73%) with 4300 g of decationizing water, adding 781 g of pseudo-boehmite (product of Shandong Zibo Ala mill, solid content of 64%) and 144 ml of hydrochloric acid (concentration of 30%, specific gravity of 1.56), stirring uniformly, standing at 60deg.C for aging for 1 hr, maintaining pH at 2-4, cooling to room temperature, adding 5000 g of prepared mesoporous shape-selective ZSM-5 zeolite slurry with high silica-alumina ratio containing chemical water, stirring uniformly, spray drying, and washing free Na + Used after aging, the aging process: aging in water vapor at 800℃for 15 hours gave the properties shown in Table 3.
The catalyst b was prepared as follows:
(1) 20 g NH 4 Cl is dissolved in 1000 g of water, 100g (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%) and after 0.5 hours exchange at 90 ℃, filtering 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 b, the dry basis composition of the catalyst b 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
The example was carried out on the apparatus shown in fig. 1, in which,
the structure of the catalytic cracking reactor can be seen in the reactor 302 of fig. 4 of CN 111718230A.
The biomass alcohol-based fuel production process comprises the following steps:
the processing unit 300 includes: biological preparationPerforming steam explosion pretreatment on the biomass, performing acid hydrolysis on the pretreated biomass, conveying the hydrolysate to a fermentation device, fermenting at 35 ℃ to obtain fermentation liquor, and performing dehydration treatment on the fermentation liquor to obtain the alcohol-based fuel, wherein the ethanol content is 90%, the water content is 3%, and the balance is methanol and C 3-5 Saturated monohydric alcohols, based on the total weight of the alcohol-based fuel.
The raw oil A is used as a reaction raw material, the catalytic conversion catalyst a is used as a catalyst, and the method provided by the application is used for regenerating the catalyst to be regenerated: the spent catalyst is conveyed to the first regenerator from the inclined pipe, contacts with alcohol-based fuel (the weight ratio of the spent catalyst to the alcohol-based fuel is 65:1) and pure oxygen gas which are introduced into the first regenerator from the bottom of the first regenerator through the distribution pipe, generates combustion reaction, and the flue gas enters the flue gas energy recovery system after cyclone separation. The partially regenerated catalyst enters the second regenerator through the outer circulating pipe and then contacts with pure oxygen gas for continuous regeneration, and the flue gas enters the flue gas energy recovery system after cyclone separation, and is then introduced into the carbon dioxide separation system for separation and recovery. Part of the flue gas is recycled to the regeneration system, and the oxygen content of the first regenerator and the second regenerator is controlled to be not more than 28 percent. The surplus energy generated by the regenerator is used for supplying energy to the outside through a heat collector.
The first regenerator temperature was 630 c with a residence time of 1.5 minutes, the second regenerator temperature was 660 c with a residence time of 3.5 minutes. The regenerated catalyst is circulated back to the reactor and is contacted with raw oil to carry out catalytic cracking reaction. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in table 4.
Comparative example 1
Comparative example 1 was performed on the same apparatus as example 1, except that no biomass treatment unit was included, with fuel oil as a supplemental source of energy, introduced from the first regenerator. The first regenerator temperature was 630 c with a residence time of 1.5 minutes, the second regenerator temperature was 660 c with a residence time of 3.5 minutes. The regenerated catalyst is circulated back to the reactor and is contacted with raw oil to carry out catalytic cracking reaction. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in table 4.
Example 2
The example was carried out on the apparatus shown in fig. 1, in which,
the structure of the catalytic cracking reactor can be seen in the reactor 302 of fig. 4 of CN 111718230A.
The biomass alcohol-based fuel production process comprises the following steps:
the processing unit 300 includes: carrying out steam explosion pretreatment on biomass, carrying out acid hydrolysis on the pretreated biomass, conveying the hydrolysate to a fermentation device, fermenting at 35 ℃ to obtain fermentation liquor, and carrying out dehydration treatment on the fermentation liquor to obtain the alcohol-based fuel, wherein the ethanol content is 90%, the water content is 3%, and the balance is methanol and C 3-5 Saturated monohydric alcohols, based on the total weight of the alcohol-based fuel.
The raw material B is used as a reaction raw material, the catalytic conversion catalyst B is used as a catalyst, and the method provided by the application is used for regenerating the spent catalyst: the spent catalyst is conveyed to the first regenerator from the inclined pipe, contacts with the alcohol-based fuel (the weight ratio of the spent catalyst to the alcohol-based fuel is 152:1) which is introduced into the first regenerator from the bottom of the first regenerator through the distribution pipe and the oxygen diluted by the circulating flue gas, generates a combustion reaction, and the flue gas enters the flue gas energy recovery system after cyclone separation. The partially regenerated catalyst enters the second regenerator through the outer circulating pipe for continuous regeneration, and the flue gas enters the flue gas energy recovery system after cyclone separation, and is then introduced into the carbon dioxide separation system for separation and recovery. Part of the flue gas is recycled to the regeneration system, and the oxygen content of the first regenerator and the second regenerator is controlled to be not more than 28 percent. The surplus energy generated by the regenerator is used for supplying energy to the outside through a heat collector.
The first regenerator temperature was 630 ℃ and residence time 1.5 minutes, the second regenerator temperature was 665 ℃ and residence time 3.0 minutes. The regenerated catalyst is circulated back to the reactor and is contacted with raw oil to carry out catalytic cracking reaction. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in table 5.
Comparative example 2
Comparative example 2 was performed on the same exemplary apparatus as example 2, except that no biomass processing unit was included, with fuel oil as a supplemental source of energy, introduced from the first regenerator. The first regenerator temperature was 630 ℃ and residence time 1.5 minutes, the second regenerator temperature was 665 ℃ and residence time 3.0 minutes. The regenerated catalyst is circulated back to the reactor and is contacted with raw oil to carry out catalytic cracking reaction. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in table 5.
From the data in tables 4 and 5, it can be seen that the example uses biomass-derived alcohol-based fuel as a source of supplemental energy, and that the amount of carbon dioxide emitted is significantly reduced when the regeneration system generates equivalent energy 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.) | 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 2 raw material B
TABLE 3 Table 3
TABLE 4 Table 4
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 biomass alcohol-based fuels is derived from carbon dioxide present in the atmosphere and is a neutral carbon emission process.
TABLE 5
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 biomass alcohol-based fuels is derived from carbon dioxide present in the atmosphere and is a neutral carbon emission process. />
Claims (10)
1. A catalytic cracking catalyst regeneration process, which is carried out in a regeneration system,
wherein the regeneration system comprises:
a biomass processing unit comprising:
a biomass pretreatment device for pretreating biomass, and
the biomass hydrolysis device is used for carrying out hydrolysis treatment on the pretreated biomass to obtain hydrolysate,
the hydrolysate fermentation device is used for carrying out fermentation treatment on the hydrolysate to obtain a liquid-phase product;
the dehydration device is used for carrying out dehydration treatment on the liquid-phase product to obtain an alcohol-based fuel;
a storage tank for storing the alcohol-based fuel;
a regeneration unit, the regeneration unit comprising:
a regenerator, the regenerator comprising:
the first regenerator is provided with a first set of heat exchangers,
a second regenerator, and
wherein the first regenerator is in communication with the second regenerator such that catalyst material of the first regenerator may enter the second regenerator;
wherein, be provided with in the first regenerator:
a first alcohol-based fuel inlet for inputting alcohol-based fuel from the storage tank to the first regenerator;
a first distributor configured to distribute an alcohol-based fuel input via the first alcohol-based fuel inlet;
a first oxygen inlet provided at the bottom of the first regenerator for inputting oxygen to the first regenerator;
a spent catalyst inlet for delivering spent catalyst of a catalytic cracking reactor to the interior of the first regenerator; and
a first recycle flue gas inlet for recycling a portion of flue gas exiting a first regenerator back into the first regenerator;
wherein the storage tank is in communication with the alcohol-based fuel inlet such that the alcohol-based fuel is delivered to the interior of the first regenerator;
wherein, be provided with in the second regenerator:
a second alcohol-based fuel inlet for inputting alcohol-based fuel from the storage tank to the second regenerator;
a second distributor configured to distribute alcohol-based fuel input via the second alcohol-based fuel inlet;
the second oxygen inlet is arranged at the bottom of the second regenerator and is used for inputting oxygen into the second regenerator;
a second recycle flue gas inlet for recycling a portion of the flue gas exiting the first regenerator back into the second regenerator; and
a regenerated catalyst outlet for delivering regenerated catalyst to a catalytic cracking reactor;
the method comprises the following steps:
s1, conveying biomass to a hydrolysis device for hydrolysis treatment after pretreatment to obtain hydrolysate;
s2, conveying the hydrolysate to a fermentation device, fermenting to generate a liquid-phase product, dehydrating to obtain alcohol-based fuel, and conveying the alcohol-based fuel to a storage tank;
s3, injecting alcohol-based fuel into a first regenerator through a first distributor, and contacting with a spent catalyst from a catalytic cracking reactor and oxygen to partially burn the spent catalyst;
s4, the catalyst from the first regenerator enters the second regenerator, and is contacted with oxygen injected into the second regenerator through a second oxygen inlet and the optional alcohol-based fuel injected through a second distributor, so that the catalyst is completely regenerated.
2. The regeneration process of claim 1, wherein the first regenerator is positioned above the second regenerator, the first regenerator being in communication with the second regenerator via an external circulation line such that catalyst material of the first regenerator can enter the second regenerator via the external circulation line;
the first regenerator is spaced from the second regenerator by a flue gas distribution plate such that flue gas generated by the second regenerator enters the first regenerator via the flue gas distribution plate.
3. The regeneration method according to claim 1, wherein the hydrolysis treatment is an acid hydrolysis treatment or an enzymatic hydrolysis treatment;
the temperature of the hydrolysis liquid in the fermentation process is not higher than 50 ℃, and the microorganism in the fermentation process is selected from bacteria, fungi and saccharomycetes.
4. The method of claim 1, wherein the alcohol-based fuel comprises greater than 90% ethanol, no greater than 5% water, based on the total weight of the alcohol-based fuel.
5. The method of claim 1, wherein the weight ratio of spent catalyst to introduced alcohol-based fuel is 10-400:1, the alcohol-based fuel introduced into the first regenerator comprising 60-100 wt% of the total amount of alcohol-based fuel introduced into the regeneration unit.
6. The method of claim 1, wherein the operating conditions of the first regenerator are: the temperature is 570-720 ℃, the average residence time of the catalyst is 1.0-7.0 minutes, and the apparent linear velocity of gas is 0.4-1.0m/s.
7. The method of claim 1, wherein the operating conditions of the second regenerator are: the temperature is not higher than 750 ℃, the average residence time of the catalyst is 1.0-5.0 minutes, and the apparent linear velocity of gas is 0.3-0.8m/s.
8. The method of claim 1, wherein the oxygen concentration in the first regenerator is no more than 28% by volume; in the second regenerator, the oxygen concentration does not exceed 28% by volume.
9. The process of claim 1, wherein the char ratio in the first regenerator is 30-50%; the second regenerator has a char ratio of 50-70%.
10. A catalytic cracking catalyst regeneration system comprising:
a biomass processing unit comprising:
a biomass pretreatment device for pretreating biomass, and
the biomass hydrolysis device is used for carrying out hydrolysis treatment on the pretreated biomass to obtain hydrolysate,
the hydrolysate fermentation device is used for carrying out fermentation treatment on the hydrolysate to obtain a liquid-phase product;
the dehydration device is used for carrying out dehydration treatment on the liquid-phase product to obtain an alcohol-based fuel;
a storage tank for storing the alcohol-based fuel;
a regeneration unit, the regeneration unit comprising:
a regenerator, the regenerator comprising:
the first regenerator is provided with a first set of heat exchangers,
a second regenerator, and
wherein the first regenerator is in communication with the second regenerator such that catalyst material of the first regenerator may enter the second regenerator;
wherein, be provided with in the first regenerator:
a first alcohol-based fuel inlet for inputting alcohol-based fuel from the storage tank to the first regenerator;
a first distributor configured to distribute an alcohol-based fuel input via the first alcohol-based fuel inlet;
a first oxygen inlet provided at the bottom of the first regenerator for inputting oxygen to the first regenerator;
a spent catalyst inlet for delivering spent catalyst of a catalytic cracking reactor to the interior of the first regenerator; and
a first recycle flue gas inlet for recycling a portion of flue gas exiting a first regenerator back into the first regenerator;
wherein the storage tank is in communication with the alcohol-based fuel inlet such that the alcohol-based fuel is delivered to the interior of the first regenerator;
wherein, be provided with in the second regenerator:
a second alcohol-based fuel inlet for inputting alcohol-based fuel from the storage tank to the second regenerator;
a second distributor configured to distribute alcohol-based fuel input via the second alcohol-based fuel inlet;
the second oxygen inlet is arranged at the bottom of the second regenerator and is used for inputting oxygen into the second regenerator;
a second recycle flue gas inlet for recycling a portion of the flue gas exiting the first regenerator back into the second regenerator; and
a regenerated catalyst outlet for delivering regenerated catalyst to the catalytic cracking reactor.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210475997.0A CN117000296A (en) | 2022-04-29 | 2022-04-29 | Catalytic cracking catalyst regeneration method and regeneration system |
| PCT/CN2023/091038 WO2023208085A1 (en) | 2022-04-29 | 2023-04-27 | Catalytic cracking catalyst regeneration method and system using bio-based liquid-phase fuel |
| TW112115713A TW202342173A (en) | 2022-04-29 | 2023-04-27 | Catalytic cracking catalyst regeneration method and system using bio-based liquid-phase fuel |
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| CN202210475997.0A CN117000296A (en) | 2022-04-29 | 2022-04-29 | Catalytic cracking catalyst regeneration method and regeneration system |
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| CN117000296A true CN117000296A (en) | 2023-11-07 |
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| CN202210475997.0A Pending CN117000296A (en) | 2022-04-29 | 2022-04-29 | Catalytic cracking catalyst regeneration method and regeneration system |
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