CN119264924A - Biomass pyrolysis system coupled with catalytic cracking unit and rotary furnace and method for producing biogas - Google Patents
Biomass pyrolysis system coupled with catalytic cracking unit and rotary furnace and method for producing biogas Download PDFInfo
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- CN119264924A CN119264924A CN202310834190.6A CN202310834190A CN119264924A CN 119264924 A CN119264924 A CN 119264924A CN 202310834190 A CN202310834190 A CN 202310834190A CN 119264924 A CN119264924 A CN 119264924A
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 136
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 121
- 239000002028 Biomass Substances 0.000 title claims abstract description 106
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000007789 gas Substances 0.000 claims abstract description 46
- 239000007790 solid phase Substances 0.000 claims abstract description 42
- 239000012071 phase Substances 0.000 claims abstract description 40
- 239000003345 natural gas Substances 0.000 claims abstract description 31
- 238000009833 condensation Methods 0.000 claims abstract description 18
- 230000005494 condensation Effects 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000012075 bio-oil Substances 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
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- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 66
- 239000003921 oil Substances 0.000 description 47
- 238000005303 weighing Methods 0.000 description 27
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- 238000004458 analytical method Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- 238000011069 regeneration method Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 240000008042 Zea mays Species 0.000 description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 8
- 235000005822 corn Nutrition 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 239000010902 straw Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
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- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000007701 flash-distillation Methods 0.000 description 4
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- 230000008878 coupling Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
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- 241000196324 Embryophyta Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
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- 230000029553 photosynthesis Effects 0.000 description 1
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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 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/06—Flash distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
- B01D45/02—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by utilising gravity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a biomass pyrolysis system with a catalytic cracking device and a rotary furnace coupled and a method for producing biological natural gas, wherein the system comprises a catalytic cracking settler, a catalytic cracking regenerator, a catalytic cracking fractionating tower, a rotary furnace, a condensation cooler and a flash tower; the catalytic cracking settler and the catalytic cracking regenerator are communicated with the rotary furnace through pipelines, the rotary furnace is provided with a settling chamber for gas-solid separation, the settling chamber is provided with a pyrolysis product gas phase outlet and a pyrolysis product solid phase outlet, the pyrolysis product gas phase outlet is sequentially communicated with the condensation cooler, the flash tower and the catalytic cracking fractionating tower, and the pyrolysis product solid phase outlet is communicated with the catalytic cracking settler. The invention uses the regenerated catalyst of the catalytic cracking device as a heat source, introduces the regenerated catalyst into the rotary furnace of the biomass pyrolysis reactor, and saves the investment and the operation cost of the biomass single pyrolysis equipment.
Description
Technical Field
The invention relates to a biomass pyrolysis system with a catalytic cracking device and a rotary furnace coupled and a method for producing biological natural gas, belonging to the field of petroleum refining.
Background
Biomass energy is produced by photosynthesis of plants. Biomass can absorb, store, and convert solar energy into chemical energy itself. Past statistics indicate that the total biomass energy reserves are listed at position 4 of all energy reserves, and the annual consumed biomass energy accounts for 14% of the total world energy consumption. Compared with other renewable energy sources, the biomass energy is the only energy source capable of generating gas and liquid products, and the biomass oil can be effectively used as the supplement of petroleum resources after being upgraded, so that the utilization of the petroleum resources is effectively supplemented.
The biomass energy in China is rich, and the biomass energy can be directly combusted, but the direct combustion mode only singly utilizes the heat generated in the biomass combustion process, so that the biomass energy cannot be fully utilized, the waste of the biomass energy is caused, and meanwhile, the requirements of the development of the current society and the clean energy utilization of human beings are not met. Moreover, currently utilized biomass resources are mainly agriculture and forestry biomass, which has periodic growth, large storage occupation area and is easy to damp and rot, and great inconvenience is caused to the supply of raw materials for practical continuous industrial application. Therefore, the clean and efficient biomass energy utilization technology is adopted to directly convert biomass energy into the biomass natural gas which is easy to store and utilize, so that the biomass energy storage device meets the market requirements.
At present, the contradiction between the ecological environment and fossil energy is increasingly aggravated, and the development and the utilization of renewable and novel clean energy are urgent. The development and utilization modes of biomass energy are various, and mainly include three main types of physical conversion technology, thermochemical conversion technology and biochemical conversion technology. The physical conversion technology is mainly compression molding technology, and biomass raw material density, strength and granularity uniformity after conversion by the compression molding technology are improved, so that biomass energy is more convenient to store and transport, and biomass treated by the method is mainly used for direct combustion. The main purpose of the thermochemical conversion technology is to obtain the products of high-grade energy sources such as charcoal, biomass fuel oil, biological natural gas and the like. The method mainly comprises the steps of directly putting biomass into equipment for combustion, directly burning or carrying out mixed combustion with minerals such as coal, and reusing the generated energy.
Biomass pyrolysis technology is one of the thermochemical conversion technologies, and pyrolysis refers to the process of breaking endothermic macromolecules of biomass to produce small molecules in the absence of oxygen. The purpose of pyrolysis is to obtain biological natural gas, biological oil and biological carbon, and the pyrolysis can effectively and fully convert biomass raw materials with low energy density into gas, liquid and solid tri-state products with high energy density, and has high energy yield ratio. Therefore, the development and utilization of biomass energy are important contents of energy production and consumption revolution, and are important tasks of improving environmental quality and developing recycling economy.
The catalytic cracking technology is a mature petroleum secondary processing technology and has advantages in investment, operation cost, technical reliability, raw material adaptability, conversion depth, investment recovery rate and the like. The typical process of catalytic cracking consists of a reaction-regeneration, fractionation, absorption-stabilization system, uses a molecular sieve catalyst, operates a fluidized bed, and recycles the catalyst after the catalyst is burned to recover the activity.
Biomass pyrolysis is an endothermic reaction, which is a process in which endothermic macromolecules of biomass break down to produce small molecules. The catalytic cracking catalyst generates excessive heat in the regeneration process in the regenerator, and besides meeting the heat requirement of the catalytic cracking reaction, an external heat collector is generally adopted to remove the heat, so that the heat balance of the catalytic cracking reaction-regeneration system is met.
Disclosure of Invention
Pyrolysis refers to the process of breaking biomass endothermic macromolecules to produce small molecules in the absence of oxygen. The purpose of pyrolysis is to obtain three high-valued products of bio-oil, biochar and biogas, and the pyrolysis can effectively and fully convert biomass raw materials with low energy density into gas, liquid and solid tri-state products with high energy density, so that the biomass raw materials have high energy yield ratio.
The invention uses the catalyst in the catalytic cracking regenerator as a biomass pyrolysis heat source to realize biomass pyrolysis in the rotary furnace, and pyrolysis products are subjected to subsequent treatment by an original reaction-regeneration and fractionation system of the catalytic cracking device, so that the biomass is treated by the coupling process of the catalytic cracking device and the rotary furnace, and the biological natural gas is finally produced.
In one aspect, the invention provides a biomass pyrolysis system with a catalytic cracking device and a rotary furnace coupled, the biomass pyrolysis system comprises a catalytic cracking settler, a catalytic cracking regenerator, a catalytic cracking fractionating tower, a rotary furnace, a condensation cooler and a flash tower, the catalytic cracking settler and the catalytic cracking regenerator are communicated with the rotary furnace through pipelines, the rotary furnace is provided with a settling chamber for gas-solid separation, the settling chamber is provided with a pyrolysis product gas phase outlet and a pyrolysis product solid phase outlet, the pyrolysis product gas phase outlet is sequentially communicated with the condensation cooler, the flash tower and the catalytic cracking fractionating tower, and the pyrolysis product solid phase outlet is communicated with the catalytic cracking settler.
As a preferred embodiment, the rotary kiln has a feed end and a discharge end, the catalytic cracking regenerator is in communication with the feed end of the rotary kiln, and the settling chamber is located at the discharge end of the rotary kiln.
The catalytic cracking device in the invention is a conventional and universal device in the technical field of petroleum secondary processing, and generally comprises a catalytic cracking settler, a catalytic cracking regenerator and a catalytic cracking fractionating tower, the specific structure is not limited, and a fluid catalytic cracking device is preferably adopted.
In the technical field of petroleum secondary processing, a catalytic cracking settler, a catalytic cracking regenerator and a catalytic cracking fractionating tower are conventional and universal equipment, are main component parts of the catalytic cracking device, and the specific structure is not limited.
Optionally, the rotary furnace is of a cylindrical structure, rotary seals are arranged at two ends of the rotary furnace, and the cylinder can rotate along a central shaft. The included angle between the central axis of the cylinder body and the horizontal line is 2-5 degrees.
Optionally, 1-10 trays without overflow weirs are arranged from the feeding end of the flash distillation tower to the top of the tower.
Optionally, a stirring device is arranged at the bottom of the flash tower and is used for preventing a small amount of carbon deposition catalyst from depositing.
Optionally, the catalytic cracking settler has a steam stripping section.
As a preferred embodiment, the outlet of the catalytic cracking settler is in communication with the first catalytic cracking regenerator.
Optionally, the settling chamber is provided with 1-10 groups of cyclone separators for gas-solid separation.
On the other hand, the invention provides a method for producing biogas by pyrolyzing biomass by adopting a catalytic cracking device and a rotary furnace, wherein the biomass and a regenerated catalyst from the catalytic cracking device are subjected to catalytic pyrolysis reaction in the rotary furnace to obtain a solid-phase pyrolysis product and a gas-phase pyrolysis product, the gas-phase pyrolysis product is subjected to flash evaporation to obtain a gas-phase substance and a liquid-phase substance, the liquid-phase substance is fed into the rotary furnace to be subjected to catalytic pyrolysis reaction in a circulating manner, and the gas-phase substance is the biogas. The main component of the liquid phase in the flash tower is liquid biological oil and also contains a small amount of water.
Optionally, the gas phase comprises hydrocarbons of H 2、C1～C4.
Preferably, the hot product in the gas phase is condensed and cooled and then enters a flash tower for flash evaporation.
Optionally, the gas phase is boosted at the top of the flash tower and then enters a catalytic cracking fractionating tower to fractionate C 1～C4 hydrocarbons.
Optionally, the liquid phase enters the rotary kiln from the bottom of the flash tower, and the catalytic pyrolysis reaction is circularly carried out.
Optionally, the pyrolysis product of the solid phase is sent to a catalytic cracking settler of a catalytic cracking device to be stripped by water vapor and then sent to a catalytic cracking regenerator to burn off carbon deposit, and the carbon deposit is recycled as a regenerated catalyst.
Optionally, the rotary furnace is of a cylindrical structure, rotary seals are arranged at two ends of the rotary furnace, an included angle of 2-5 degrees is formed between the central axis of the cylinder and the horizontal line, and the cylinder rotates along the central axis.
Optionally, the liquid phase comprises bio-oil and water, wherein the bio-oil comprises C 5～C30 hydrocarbon and C 5～C30 oxygen-containing organic compound.
Optionally, the regenerated catalyst is from a catalytic cracking regenerator.
Optionally, the temperature of the regenerated catalyst is 650-750 ℃.
Optionally, the particle size of the biomass is 1-10 mm, and the water content is 0-20wt%.
Optionally, the amount of the regenerated catalyst is 5-10 times that of biomass.
Optionally, when the liquid phase matters exist in the rotary furnace, the consumption of the regenerated catalyst is 5-10 times of the total mass of the biomass and the liquid phase matters.
Optionally, the gas phase speed of the inlet of the cyclone separator is 15-25 m/s.
Optionally, the reaction conditions in the rotary furnace comprise the pressure of 5-10 KPa (g) and the catalytic pyrolysis reaction time of 60-120 minutes.
Optionally, the conditions for the gas-liquid separation of the flash evaporation (conditions in the flash evaporation tower) comprise the temperature of 40-60 ℃ and the pressure of 5-10 KPa (g).
Optionally, the conditions that the gas phase substances enter the catalytic cracking fractionating tower for fractionation after being boosted at the top of the flash tower comprise the temperature of 40-60 ℃ and the pressure of 0.10-0.25 MPa (g).
Optionally, steam stripping is carried out after the pyrolysis product of the solid phase enters a catalytic cracking settler, wherein the steam stripping condition comprises that the temperature of the pyrolysis product of the solid phase is 400-550 ℃ and the pressure is 0.12-0.25 MPa (g), the steam temperature is 250-350 ℃ and the pressure is 0.3-0.8 MPa (g), and the steam consumption is 3-5% of the mass of the pyrolysis product of the solid phase.
Optionally, the pyrolysis product of the solid phase is sent to a catalytic cracking regenerator to burn off carbon deposit after steam stripping in a catalytic cracking settler, and is recycled as a regenerated catalyst.
The invention discloses a biomass pyrolysis system with a catalytic cracking device and a rotary furnace coupled, which utilizes a regenerated catalyst of the catalytic cracking device as a heat source to introduce the regenerated catalyst into the rotary furnace of a biomass pyrolysis reactor. In the rotary kiln, the catalyst and biomass undergo a pyrolysis reaction. A pyrolysis product gas phase and a pyrolysis product solid phase are produced. The gas phase of pyrolysis product is condensed and cooled and then enters a flash tower, the gas phase at the top of the flash tower is boosted and then enters a catalytic cracking fractionating tower, and the liquid-phase biological oil at the bottom of the flash tower is sent into a rotary furnace for pyrolysis in a circulating way. The solid phase of the pyrolysis product is sent to a catalytic cracking device settler, and is sent to a catalytic cracking regenerator to burn off carbon deposit after steam stripping, and is used as a regenerated catalyst for recycling.
Compared with a single pyrolysis method of biomass in a fixed bed or a rotary furnace, the single pyrolysis method of biomass requires adding 3-10% of active Al 2O3 and other catalysts to obtain the biological natural gas, and the Al 2O3 catalysts and the biochar are mixed together, so that the biochar cannot be fully utilized, for example, the catalyst is regenerated to burn off the biochar, and heat loss of the biochar is caused. According to the invention, the catalytic cracking device and the rotary furnace are coupled to carry out biomass pyrolysis, so that the dosage of the catalyst can be increased to 5-10 times of the biological quality, the natural gas can be produced more easily, the problem of catalyst regeneration is solved, the heat released during catalyst regeneration is recovered by an external heat-taking system of the catalytic cracking regenerator, or the heat required by the catalytic cracking regeneration system can be supplemented, and the heat of biochar is effectively utilized. The invention also effectively solves the problems of high yield and low utilization rate of the conventional biomass pyrolysis bio-oil.
Compared with the fluidized bed biomass pyrolysis method, the method has the advantages that the catalytic cracking device is coupled with the rotary furnace to carry out biomass pyrolysis, so that the investment and the running cost of independent biomass pyrolysis equipment are saved.
Drawings
FIG. 1 biomass is coupled to a rotary kiln via a catalytic cracking unit;
In fig. 1, 1a first catalytic cracking regenerator, 2a second catalytic cracking regenerator, 3a rotary kiln, 3a settling chamber, 4 condensing cooler, 5 flash tower, 6 catalytic cracking fractionating tower and 7 catalytic cracking settling device.
Detailed Description
The following examples further illustrate the effects of the present invention.
Pyrolysis system with equipment for coupling catalytic cracking device with rotary furnace
The invention utilizes a pyrolysis system with a catalytic cracking device and a rotary furnace coupled to pyrolyze biomass, and the process of producing biological natural gas comprises the steps that biomass particles enter the rotary furnace of a biomass pyrolysis reactor through a feed end by a screw conveyor and are mixed with a regenerated catalyst from a second catalytic cracking regenerator. The rotary furnace is of a cylindrical rotary structure, the included angle between the central axis of the cylinder and the horizontal line is 3 degrees, the regenerated catalyst and biomass forward in the rotary furnace and complete pyrolysis reaction, and the consumption of the regenerated catalyst is 5-10 times of the total mass of biomass and bio-oil.
As shown in figure 1, the pyrolysis system with the coupling of the catalytic cracking device and the rotary furnace comprises a catalytic cracking settler 7, a catalytic cracking regenerator 2, a catalytic cracking fractionating tower 6, a rotary furnace 3, a condensation cooler 4 and a flash distillation tower 5, wherein the catalytic cracking settler 7, the catalytic cracking regenerator 2 and the rotary furnace 3 are communicated through pipelines, the rotary furnace is provided with a settling chamber 3a for gas-solid separation, the settling chamber 3a is provided with a pyrolysis product gas phase outlet and a pyrolysis product solid phase outlet, the pyrolysis product gas phase outlet is sequentially communicated with the condensation cooler 4, the flash distillation tower 5 and the catalytic cracking fractionating tower 6, and the pyrolysis product solid phase outlet is communicated with the catalytic cracking settler 7.
A steel cylinder with the diameter of 89 multiplied by 500mm is adopted as a rotary furnace 3, and rotary seals are arranged at two ends of the cylinder. The feeding end of the rotary furnace 3 adopts a double-screw conveyor for feeding, and the discharging end is provided with a settling chamber 3a. The upper end of the sedimentation chamber is connected with a condensation cooler 4. A regenerated catalyst second catalytic cracking regenerator 2 (a first hopper) and a first catalytic cracking regenerator 1 (a second hopper) are arranged at the upper part of the outer sleeve of the screw conveyor, and the mixture of the regenerated catalyst and biomass particles/biological oil is respectively filled.
And heating the regenerated catalyst in the first hopper to 650-750 ℃, respectively starting spiral feeding of the two hoppers, pushing the materials in the two hoppers into the rotary furnace 3 through the feeding end of the rotary furnace 3 after air is replaced by water vapor in advance, and performing pyrolysis reaction. The pressure of the system is regulated by the opening of a pyrolysis gas phase outlet valve, the reaction time is regulated by the rotating speed of the rotary furnace 3, and the quality of the catalyst and biomass/bio-oil is regulated by the spiral feeding speed of two hoppers.
Along with the rotation of the rotary furnace, the regenerated catalyst and biomass forward and carry out pyrolysis reaction to generate gas-phase pyrolysis products and solid-phase pyrolysis products, wherein the residence time of the regenerated catalyst and biomass in the rotary furnace, namely the reaction time, is 60-120 minutes. The rear end of the rotary kiln is provided with a settling chamber 3a for separating the pyrolysis products of the gas phase and the pyrolysis products of the solid phase. In the settling chamber, the pyrolysis product of the gas phase enters a condensing cooler 4 from the top of the settling chamber 3a, is cooled to 40-60 ℃ and then enters a flash tower.
The solid-phase pyrolysis product obtained from the bottom of the settling chamber is a mixture formed by adsorbing biochar generated by biomass pyrolysis on a catalyst, and is sent into a catalytic cracking settling device by a screw conveyor, wherein a stripping section is subjected to steam stripping and then enters a first catalytic cracking regenerator and a second catalytic cracking regenerator for burning, and the burnt catalyst is recycled. The first catalytic cracking regenerator and the second catalytic cracking regenerator are connected in series, which is common in the art.
The pyrolysis product of the gas phase enters a condensation cooler 4 from the top of a settling chamber 3a, is cooled to 40-60 ℃ and enters a flash tower 5. Transferring the biological natural gas at the top of the flash tower 5 into a gas collecting bag for weighing and metering at 5-10 Kpa (g), separating the biological oil and water at the bottom of the flash tower 5, respectively loading the separated biological oil and water into a collecting bottle for weighing and metering, stripping the pyrolysis product of the solid phase at the bottom of the settling chamber 3a by using water vapor with the pressure of 0.3-0.8 MPa (g) at the temperature of 250-350 ℃ at the temperature of 400-550 ℃, cooling to 50 ℃, weighing and metering, and subtracting the weight of the original catalytic cracking catalyst to obtain the weight of the biological carbon.
And (3) obtaining the biological natural gas at the top of the flash distillation tower, increasing the pressure to 0.10-0.25 MPa (g), and entering the catalytic cracking fractionating tower 6 through a pipeline communicated with the fractionating tower. Biological oil and water are obtained at the bottom of the flash tower, wherein the biological oil is returned to the feed end of the rotary furnace 3 for cyclic pyrolysis.
The biomass particle size is 3mm in diameter, the water content is 10wt%, and the catalyst is a regenerated catalyst of a 130 ten thousand ton/year catalytic cracking device.
Examples 1 to 8 of the present invention:
the test method of the product comprises the following steps:
The testing of biogas is performed using multidimensional gas chromatography.
The bio-oil is tested by gas chromatography-mass spectrometry.
The yield was calculated by:
The yield of the biological natural gas is calculated as the mass of the biological natural gas/(biomass mass+biological oil mass).
The yield of the bio-oil is calculated as mass/(biomass mass+bio-oil mass).
The yield of the biochar is calculated as the mass of the biochar/(biomass mass+bio-oil mass).
Calculation formula of yield of pyrolysis water, mass of pyrolysis water/(mass of biomass+mass of bio-oil).
Example 1
By adopting a system of equipment, the naturally sun-dried corn straw is taken as a biomass raw material and crushed into biomass particles with the size of 3mm, wherein the water content is 10wt%.
250G of catalytic cracking regeneration catalyst is filled in the first hopper, and 50g of biomass particles is filled in the second hopper.
The regenerated catalyst in the first hopper is heated to 650 ℃, spiral feeding of the two hoppers is started respectively, materials in the two hoppers are pushed into the rotary furnace 3 after air is replaced by water vapor in advance, and pyrolysis reaction is carried out. At a pressure of 5Kpa (g) and a rotational speed of the rotary kiln 3 of 2.0 rpm, the time for which the pyrolysis product of the solid phase was entirely introduced into the settling chamber 3a was 60 minutes.
The pyrolysis product of the gas phase enters the condensation cooler 4 from the top of the settling chamber 3a, is cooled to a temperature of 40 ℃ and enters the flash column 5. Transferring the biological natural gas at the top of the flash tower 5 into a gas collecting bag for weighing and metering at 5Kpa (g), separating the biological oil and water at the bottom of the flash tower 5, respectively loading the separated biological oil and water into a collecting bottle for weighing and metering, stripping the pyrolysis product of the solid phase at the bottom of the settling chamber 3a by using water vapor with the pressure of 0.3MPa (g) at the temperature of 250 ℃ at the temperature of 400 ℃, cooling to 50 ℃, weighing and metering, and subtracting the weight of the original catalytic cracking catalyst to obtain the weight of the biochar. The yields obtained are shown in Table-1.
TABLE 1 biomass pyrolysis yield
| Yield of cyclic pyrolysis products | Yield, wt% |
| Biological natural gas | 18.10% |
| Biological oil | 41.80% |
| Biochar | 30.10% |
| Water and its preparation method | 10.00% |
| Totalizing | 100.00% |
The composition analysis was performed on biogas, which contains hydrocarbons of H 2、C1～C4.
The composition analysis was performed on a bio-oil comprising C 5～C30 hydrocarbons and oxygenated organic compounds.
Example 2
By adopting a system of equipment, the naturally sun-dried corn straw is taken as a biomass raw material and crushed into 3mm particles, wherein the water content is 10wt%.
400G of catalytic cracking regeneration catalyst is filled in the first hopper, and 25g of biomass particles and 25g of biological oil are filled in the second hopper.
The regenerated catalyst in the first hopper is heated to 650 ℃, spiral feeding of the two hoppers is started respectively, materials in the two hoppers are pushed into the rotary furnace 3 after air is replaced by water vapor in advance, and pyrolysis reaction is carried out. At a pressure of 8Kpa (g) and a rotational speed of the rotary kiln 3 of 2.0 rpm, the time for the pyrolysis product solid phase to completely enter the settling chamber 3a was 60 minutes.
The pyrolysis product gas phase enters the condensation cooler 4 from the top of the settling chamber 3a, is cooled to a temperature of 45 ℃ and enters the flash column 5. Transferring the biological natural gas at the top of the flash tower 5 into a gas collecting bag for weighing and metering at 8Kpa (g), separating the biological oil and water at the bottom of the flash tower 5, respectively loading the separated biological oil and water into a collecting bottle for weighing and metering, stripping the pyrolysis product solid phase at the bottom of the settling chamber 3a by using water vapor with the pressure of 0.5MPa (g) at the temperature of 300 ℃ at the temperature of 450 ℃, cooling to 50 ℃, weighing and metering, and subtracting the weight of the original catalytic cracking catalyst to obtain the biological carbon weight. The yields obtained are shown in Table-2.
TABLE 2 pyrolysis yield of biomass+biological oil
| Yield of cyclic pyrolysis products | Yield, wt% |
| Biological natural gas | 41.43% |
| Biological oil | 7.72% |
| Biochar | 40.85% |
| Water and its preparation method | 10.00% |
| Totalizing | 100.00% |
The composition analysis was performed on biogas, which contains hydrocarbons of H 2、C1～C4.
The composition analysis was performed on a bio-oil comprising C 5～C30 hydrocarbons and oxygenated organic compounds.
Example 3
By adopting a system of equipment, the naturally sun-dried corn straw is taken as a biomass raw material and crushed into 3mm particles, wherein the water content is 10wt%.
500G of catalytic cracking regenerated catalyst is filled in the first hopper, and 25g of biomass particles and 25g of biological oil are filled in the second hopper.
The regenerated catalyst in the first hopper is heated to 650 ℃, spiral feeding of the two hoppers is started respectively, materials in the two hoppers are pushed into the rotary furnace 3 after air is replaced by water vapor in advance, and pyrolysis reaction is carried out. At a pressure of 10Kpa (g) and a rotational speed of the rotary kiln 3 of 2.0 rpm, the time for the pyrolysis product solid phase to completely enter the settling chamber 3a was 60 minutes.
The pyrolysis product gas phase enters the condensation cooler 4 from the top of the settling chamber 3a, is cooled to a temperature of 45 ℃ and enters the flash column 5. Transferring the biological natural gas at the top of the flash tower 5 into a gas collecting bag for weighing and metering at 10Kpa (g), separating the biological oil and water at the bottom of the flash tower 5, respectively loading the separated biological oil and water into a collecting bottle for weighing and metering, stripping the pyrolysis product solid phase at the bottom of the settling chamber 3a by using water vapor with the pressure of 0.8MPa (g) at the temperature of 500 ℃, cooling to 50 ℃, weighing and metering, and subtracting the weight of the original catalytic cracking catalyst to obtain the biological carbon weight. The yields obtained are shown in Table-3.
TABLE 3 pyrolysis yield of biomass+biological oil
| Yield of cyclic pyrolysis products | Yield, wt% |
| Biological natural gas | 43.66% |
| Biological oil | 5.34% |
| Biochar | 41.00% |
| Water and its preparation method | 10.00% |
| Totalizing | 100.00% |
The composition analysis was performed on biogas, which contains hydrocarbons of H 2、C1～C4.
The composition analysis was performed on a bio-oil comprising C 5～C30 hydrocarbons and oxygenated organic compounds.
Example 4
By adopting a system of equipment, the naturally sun-dried corn straw is taken as a biomass raw material and crushed into 3mm particles, wherein the water content is 10wt%.
250G of catalytic cracking regenerated catalyst is filled in the first hopper, and 25g of biomass particles and 25g of biological oil are filled in the second hopper.
The regenerated catalyst in the first hopper is heated to 700 ℃, spiral feeding of the two hoppers is started respectively, materials in the two hoppers are pushed into the rotary furnace 3 after air is replaced by water vapor in advance, and pyrolysis reaction is carried out. At a pressure of 8Kpa (g) and a rotational speed of the rotary kiln 3 of 2.0 rpm, the time for the pyrolysis product solid phase to completely enter the settling chamber 3a was 60 minutes.
The pyrolysis product gas phase enters the condensation cooler 4 from the top of the settling chamber 3a, is cooled to a temperature of 50 ℃ and enters the flash column 5. Transferring the biological natural gas at the top of the flash tower 5 into a gas collecting bag for weighing and metering at 8Kpa (g), separating the biological oil and water at the bottom of the flash tower 5, respectively loading the separated biological oil and water into a collecting bottle for weighing and metering, stripping the pyrolysis product solid phase at the bottom of the settling chamber 3a by using water vapor with the pressure of 0.8MPa (g) at the temperature of 450 ℃, cooling to 50 ℃, weighing and metering, and subtracting the weight of the original catalytic cracking catalyst to obtain the biological carbon weight. The yields obtained are shown in Table-4.
TABLE 4 pyrolysis yield of biomass+biological oil
| Yield of cyclic pyrolysis products | Yield, wt% |
| Biological natural gas | 42.57% |
| Biological oil | 5.84% |
| Biochar | 41.60% |
| Water and its preparation method | 10.00% |
| Totalizing | 100.00% |
The composition analysis was performed on biogas, which contains hydrocarbons of H 2、C1～C4.
The composition analysis was performed on a bio-oil comprising C 5～C30 hydrocarbons and oxygenated organic compounds.
Example 5
By adopting a system of equipment, the naturally sun-dried corn straw is taken as a biomass raw material and crushed into 3mm particles, wherein the water content is 10wt%.
400G of catalytic cracking regeneration catalyst is filled in the first hopper, and 25g of biomass particles and 25g of biological oil are filled in the second hopper.
The regenerated catalyst in the first hopper is heated to 700 ℃, spiral feeding of the two hoppers is started respectively, materials in the two hoppers are pushed into the rotary furnace 3 after air is replaced by water vapor in advance, and pyrolysis reaction is carried out. At a pressure of 5Kpa (g) and a rotational speed of the rotary kiln 3 of 2.0 rpm, the time for the pyrolysis product solid phase to completely enter the settling chamber 3a was 60 minutes.
The pyrolysis product gas phase enters the condensation cooler 4 from the top of the settling chamber 3a, is cooled to a temperature of 60 ℃ and enters the flash column 5. Transferring the biological natural gas at the top of the flash tower 5 into a gas collecting bag for weighing and metering at 5Kpa (g), separating the biological oil and water at the bottom of the flash tower 5, respectively loading the separated biological oil and water into a collecting bottle for weighing and metering, stripping the pyrolysis product solid phase at the bottom of the settling chamber 3a by using water vapor with the pressure of 0.3MPa (g) at the temperature of 450 ℃, cooling to 50 ℃, weighing and metering, and subtracting the weight of the original catalytic cracking catalyst to obtain the biological carbon weight. The yields obtained are shown in Table-5.
TABLE 5 pyrolysis yield of biomass+biological oil
The composition analysis was performed on biogas, which contains hydrocarbons of H 2、C1～C4.
The composition analysis was performed on a bio-oil comprising C 5～C30 hydrocarbons and oxygenated organic compounds.
Example 6
By adopting a system of equipment, the naturally sun-dried corn straw is taken as a biomass raw material and crushed into 3mm particles, wherein the water content is 10wt%.
500G of catalytic cracking regenerated catalyst is filled in the first hopper, and 25g of biomass particles and 25g of biological oil are filled in the second hopper.
The regenerated catalyst in the first hopper is heated to 700 ℃, spiral feeding of the two hoppers is started respectively, materials in the two hoppers are pushed into the rotary furnace 3 after air is replaced by water vapor in advance, and pyrolysis reaction is carried out. At a pressure of 10Kpa (g) and a rotational speed of the rotary kiln 3 of 2.0 rpm, the time for the pyrolysis product solid phase to completely enter the settling chamber 3a was 60 minutes.
The pyrolysis product gas phase enters the condensation cooler 4 from the top of the settling chamber 3a, is cooled to a temperature of 60 ℃ and enters the flash column 5. Transferring the biological natural gas at the top of the flash tower 5 into a gas collecting bag for weighing and metering at 10Kpa (g), separating the biological oil and water at the bottom of the flash tower 5, respectively loading the separated biological oil and water into a collecting bottle for weighing and metering, stripping the pyrolysis product solid phase at the bottom of the settling chamber 3a by using water vapor with the pressure of 0.5MPa (g) at the temperature of 250 ℃, cooling to 50 ℃, weighing and metering, and subtracting the weight of the original catalytic cracking catalyst to obtain the biological carbon weight. The yields obtained are shown in Table-6.
TABLE 6 pyrolysis yield of biomass+biological oil
| Yield of cyclic pyrolysis products | Yield, wt% |
| Biological natural gas | 43.74% |
| Biological oil | 3.69% |
| Biochar | 42.58% |
| Water and its preparation method | 10.00% |
| Totalizing | 100.00% |
The composition analysis was performed on biogas, which contains hydrocarbons of H 2、C1～C4.
The composition analysis was performed on a bio-oil comprising C 5～C30 hydrocarbons and oxygenated organic compounds.
Example 7
By adopting a system of equipment, the naturally sun-dried corn straw is taken as a biomass raw material and crushed into 3mm particles, wherein the water content is 10wt%.
400G of catalytic cracking regeneration catalyst is filled in the first hopper, and 25g of biomass particles and 25g of biological oil are filled in the second hopper.
The regenerated catalyst in the first hopper is heated to 700 ℃, spiral feeding of the two hoppers is started respectively, materials in the two hoppers are pushed into the rotary furnace 3 after air is replaced by water vapor in advance, and pyrolysis reaction is carried out. At a pressure of 8Kpa (g) and a rotational speed of the rotary kiln 3 of 1.5 rpm, the time for the pyrolysis product solid phase to completely enter the settling chamber 3a was 90 minutes.
The pyrolysis product gas phase enters the condensation cooler 4 from the top of the settling chamber 3a, is cooled to a temperature of 50 ℃ and enters the flash column 5. Transferring the biological natural gas at the top of the flash tower 5 into a gas collecting bag for weighing and metering at 8Kpa (g), separating the biological oil and water at the bottom of the flash tower 5, respectively loading the separated biological oil and water into a collecting bottle for weighing and metering, stripping the pyrolysis product solid phase at the bottom of the settling chamber 3a by using steam with the pressure of 0.5MPa (g) at the temperature of 300 ℃ at the temperature of 500 ℃, cooling to 50 ℃, weighing and metering, and subtracting the weight of the original catalytic cracking catalyst to obtain the biological carbon. The yields obtained are shown in Table-7.
TABLE 7 pyrolysis yield of biomass+biological oil
| Yield of cyclic pyrolysis products | Yield, wt% |
| Biological natural gas | 43.98% |
| Biological oil | 2.82% |
| Biochar | 43.20% |
| Water and its preparation method | 10.00% |
| Totalizing | 100.00% |
The composition analysis was performed on biogas, which contains hydrocarbons of H 2、C1～C4.
The composition analysis was performed on a bio-oil comprising C 5～C30 hydrocarbons and oxygenated organic compounds.
Example 8
By adopting a system of equipment, the naturally sun-dried corn straw is taken as a biomass raw material and crushed into 3mm particles, wherein the water content is 10wt%.
400G of catalytic cracking regeneration catalyst is filled in the first hopper, and 25g of biomass particles and 25g of biological oil are filled in the second hopper.
The regenerated catalyst in the first hopper is heated to 700 ℃, spiral feeding of the two hoppers is started respectively, materials in the two hoppers are pushed into the rotary furnace 3 after air is replaced by water vapor in advance, and pyrolysis reaction is carried out. At a pressure of 10Kpa (g) and a rotational speed of the rotary kiln 3 of 1.0 rpm, the time for the pyrolysis product solid phase to completely enter the settling chamber 3a was 120 minutes.
The pyrolysis product gas phase enters the condensation cooler 4 from the top of the settling chamber 3a, is cooled to a temperature of 50 ℃ and enters the flash column 5. Transferring the biological natural gas at the top of the flash tower 5 into a gas collecting bag for weighing and metering at 10Kpa (g), separating the biological oil and water at the bottom of the flash tower 5, respectively loading the separated biological oil and water into a collecting bottle for weighing and metering, stripping the pyrolysis product solid phase at the bottom of the settling chamber 3a by using water vapor with the pressure of 0.5MPa (g) at the temperature of 500 ℃, cooling to 50 ℃, weighing and metering, and subtracting the weight of the original catalytic cracking catalyst to obtain the biological carbon weight. The yields obtained are shown in Table-8.
TABLE 8 pyrolysis yield of biomass+biological oil
| Yield of cyclic pyrolysis products | Yield, wt% |
| Biological natural gas | 44.16% |
| Biological oil | 2.31% |
| Biochar | 43.52% |
| Water and its preparation method | 10.00% |
| Totalizing | 100.00% |
The composition analysis was performed on biogas, which contains hydrocarbons of H 2、C1～C4.
The composition analysis was performed on a bio-oil comprising C 5～C30 hydrocarbons and oxygenated organic compounds.
The foregoing is a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (10)
1.A biomass pyrolysis system with a catalytic cracking device and a rotary furnace coupled is characterized in that,
The biomass pyrolysis system comprises a catalytic cracking settler, a catalytic cracking regenerator, a catalytic cracking fractionating tower, a rotary furnace, a condensation cooler and a flash tower;
The catalytic cracking settler and the catalytic cracking regenerator are communicated with the rotary furnace through pipelines;
The rotary furnace is provided with a settling chamber for gas-solid separation, and the settling chamber is provided with a pyrolysis product gas phase outlet and a pyrolysis product solid phase outlet;
the gas phase outlet of the pyrolysis product is sequentially communicated with a condensation cooler, a flash tower and a catalytic cracking fractionating tower;
And the solid phase outlet of the pyrolysis product is communicated with a catalytic cracking settler.
2. The biomass pyrolysis system according to claim 1, wherein the rotary kiln is of a cylindrical structure, a central axis of the cylindrical structure forms an included angle of 2-5 degrees with a horizontal line, and the cylindrical structure rotates along the central axis;
And/or 1-10 trays without overflow weirs are arranged from the feeding end of the flash evaporation tower to the top of the tower;
and/or the bottom of the flash tower is provided with a stirring device;
And/or the settling chamber is provided with 1-10 groups of cyclone separators for gas-solid separation, and the gas phase speed of the inlet of the cyclone separators is preferably 15-25 m/s.
3. A method for producing biological natural gas by adopting a catalytic cracking device and a rotary furnace is characterized in that,
Carrying out catalytic pyrolysis reaction on biomass and a regenerated catalyst from a catalytic cracking device in a rotary furnace to obtain a solid-phase pyrolysis product and a gas-phase pyrolysis product;
The gas phase pyrolysis product is subjected to flash evaporation, and a gas phase material and a liquid phase material are returned to the rotary furnace for carrying out catalytic pyrolysis reaction in a circulating way;
The gas phase organisms are bio-natural gas.
4. The method of claim 3, wherein the step of,
The gas phase comprises hydrocarbons of H 2、C1～C4;
And/or the liquid phase comprises bio-oil and water, wherein the bio-oil comprises C 5～C30 hydrocarbon and C 5～C30 oxygen-containing organic compound;
The rotary furnace is of a cylindrical structure, and the cylinder body rotates along a central shaft, preferably, the central shaft of the cylinder body and the horizontal line form an included angle of 2-5 degrees;
And/or the gas phase material enters a catalytic cracking fractionating tower of the catalytic cracking device after flash evaporation;
And/or, the pyrolysis product of the solid phase is sent to a catalytic cracking settler of a catalytic cracking unit.
5. The method according to claim 3 or 4, wherein,
The regenerated catalyst is from a catalytic cracking regenerator;
and/or the temperature of the regenerated catalyst is 650-750 ℃;
And/or the particle size of the biomass is 1-10 mm, and the water content is 0-20wt%;
and/or the dosage of the regenerated catalyst is 5-10 times of biomass;
And/or when the liquid phase matters exist in the rotary furnace, the consumption of the regenerated catalyst is 5-10 times of the total mass of the biomass and the liquid phase matters.
6. The method according to claim 3, 4 or 5, wherein,
The reaction conditions in the rotary furnace comprise the pressure of 5-10 KPa (g) and the time of the catalytic pyrolysis reaction of 60-120 minutes.
7. The method according to any one of claims 3 to 6, wherein the conditions for the flash evaporation gas-liquid separation comprise a temperature of 40 to 60 ℃ and a pressure of 5 to 10kpa (g).
8. The method according to claim 4, wherein the conditions for the vapor phase to enter the catalytic cracking fractionating tower for fractionation after flash evaporation and pressure boosting include a temperature of 40-60 ℃ and a pressure of 0.10-0.25 MPa (g).
9. The method according to claim 4, wherein the pyrolysis product of the solid phase enters a catalytic cracking settler and is subjected to steam stripping, and the steam stripping condition comprises that the pyrolysis product of the solid phase is 400-550 ℃ and the pressure is 0.12-0.25 MPa (g), the steam temperature is 250-350 ℃ and the pressure is 0.3-0.8 MPa (g), and the steam consumption is 3-5% of the mass of the pyrolysis product of the solid phase.
10. The method according to claim 9, wherein the pyrolysis product of the solid phase is sent to a catalytic cracking regenerator to burn off carbon deposit after steam stripping in a catalytic cracking settler, and is recycled as regenerated catalyst.
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