CN104059682A - Apparatus and method for preparing aircraft fuel through biomass selectivity pyrolysis-cascaded conversion - Google Patents
Apparatus and method for preparing aircraft fuel through biomass selectivity pyrolysis-cascaded conversion Download PDFInfo
- Publication number
- CN104059682A CN104059682A CN201410287728.7A CN201410287728A CN104059682A CN 104059682 A CN104059682 A CN 104059682A CN 201410287728 A CN201410287728 A CN 201410287728A CN 104059682 A CN104059682 A CN 104059682A
- Authority
- CN
- China
- Prior art keywords
- aromatic hydrocarbon
- biomass
- pyrolysis
- oligomerisation
- alkane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an apparatus and a method for preparing aircraft fuel through biomass selectivity pyrolysis-cascaded conversion. The apparatus comprises a biomass selectivity pyrolysis system, a light olefins oligomerization hydrogenation system as well as a aromatic hydrocarbon and alkane mixing system; the inlet of the biomass selectivity pyrolysis system is the biomass inlet of the apparatus, the gas phase outlet is connected to the inlet of an alkene catalysis oligomerization hydrogenation reactor in the light olefins oligomerization hydrogenation system, the oil phase outlet of the biomass selectivity pyrolysis system is connected to the inlet of an aromatic hydrocarbon diverter in the aromatic hydrocarbon and alkane mixing system; the alkane liquid outlet in the light olefins oligomerization hydrogenation system is connected to the inlet of a stirring mixer in the alkane mixing system; and the liquid outlet of aromatic hydrocarbon and alkane mixing system is the aromatic hydrocarbon and aviation kerosene outlet of the apparatus. The cascaded conversion method combines the biomass selectivity pyrolysis and alkene oligomerization hydrogenation reaction, so that biomass utilization rate is enhanced.
Description
Technical field
The invention belongs to solid fuel pyrolysis and olefin oligomerization field of hydrogenation, relate to biomass by selective pyrolysis and prepared olefin oligomerization method of hydrotreating and device.
Background technology
Due to the aggravation of the day by day exhausted of fossil fuel resource and the problem of environmental pollution that brought by it, it is further important that renewable energy source becomes.Biomass are as unique a kind of renewable carbon source, and having made up sun power and nuclear energy cannot prepare liquid fuel and the chemical industry defect of producing, and has become a kind of starting material of important petroleum replacing.Biomass can be prepared the products such as aromatic hydrocarbon and low-carbon alkene by the mode of catalyse pyrolysis, this process is carried out under normal pressure and middle temperature, and technique is simple, and target product productive rate is higher.In this process, aromatic hydrocarbon can be collected by condensation, but alkene in gas-phase product, because pyrolysis also can produce CO and CO2 gas, concentration of olefin is not high in gaseous product, and complicated component, is difficult to separated use.
Aviation Fuel there are certain requirements the length of carbochain, perhaps meets certain anti-knocking property, volatility, mobility, erosion resistance and degree of cleaning simultaneously.Alkane and aromatic hydrocarbon that aviation spirit is mainly C10-C16 by carbon chain lengths form according to a certain percentage, and wherein aromatic hydrocarbon is mainly used to increase the octane value of gasoline, strengthen its anti-knocking property.Aviation Fuel mainly forms by oil rectifying refining at present.China's oil scarcity of resources, petroleum import amount has surpassed 50% barrier line in continuous 4 years, and Chinese energy safety in serious threat.How adopting renewable energy source petroleum replacing to prepare aviation fuel is the focus of studying at present.In renewable energy source, biomass are the unique a kind of origin of organic carbons that can prepare aviation fuel.At present from biomass, preparing aviation is mainly the alkane of producing wherein with oil, and the technique of employing is to be first hydrolyzed to prepare saccharide compound, then to saccharide compound at high pressure, noble metal catalyst Pt/Al
2o
3or Ru/Al
2o
3deng effect, descend Hydrogenation for alkane.This technology has hydrolysis cycle length, complex process, equipment and takes up an area shortcoming wide and that catalyzer cost is higher, never by industrial applications.
Therefore, adopt novel method to overcome the shortcoming of prior art, total composition is prepared Aviation Fuel, very urgent.
Technology only can be prepared the alkane component in oil for aviation from biomass at present, and alkane component is to obtain by high-pressure hydrogenation under biomass by hydrolyzation, noble metal catalyst effect, this Period Process length, complex process, equipment are taken up an area the shortcomings such as wide and cost of investment is high.Need the development process cycle badly short, technique is simple, can prepare the new technology of total composition Aviation Fuel.
Summary of the invention
Technical problem: the object of this invention is to provide a kind of biomass by selective pyrolysis-step and transform the device and method of preparing Aviation Fuel, adopt the method for catalytic pyrolysis of biomass to prepare aromatic hydrocarbon and low-carbon alkene, this process is carried out under normal pressure, and biomass can change into target product within 1 minute, treatment cycle is short, and technique is simple.Low-carbon alkene completes oligomerisation in a reactor simultaneously and hydrogenation reaction is prepared alkane, then alkane and aromatic hydrocarbon is mixed with to total composition Aviation Fuel, and the step of realizing biomass transforms.
Technical scheme: for achieving the above object, the technical scheme that the present invention uses is as follows:
A kind of biomass by selective pyrolysis of the present invention-step transforms the device of preparing Aviation Fuel, and this device comprises:
Biomass by selective pyrolysis system for being prepared by catalytic pyrolysis of biomass to aromatic hydrocarbon and low-carbon alkene, realizes the regeneration of catalyzer and the supply of pyrolysis heat simultaneously;
Low-carbon alkene oligomerisation hydrogenation system, the low-carbon alkene oligomerisation Hydrogenation that is used for biomass by selective pyrolysis system to produce, for alkane fuel, is realized the regeneration of oligomerisation hydrogenation catalyst simultaneously;
Aromatic hydrocarbon and alkane mixing system, for proportionally, fully mixed arenes and alkane, make oil for aviation;
The import of described biomass by selective pyrolysis system is the biomass inlet of this device, gaseous phase outlet is connected with the olefin catalytic oligomerisation hydrogenator entrance in low-carbon alkene oligomerisation hydrogenation system, and the entrance of the oil phase outlet of biomass by selective pyrolysis system and aromatic hydrocarbon and aromatic hydrocarbon splitter in alkane mixing system is connected; The entrance of the alkane liquid exit in low-carbon alkene oligomerisation hydrogenation system and aromatic hydrocarbon and stirring mixer in alkane mixing system is connected; The liquid exit of described aromatic hydrocarbon and alkane mixing system is aromatic hydrocarbon and the aviation kerosene outlet of this device.
Described biomass by selective pyrolysis system comprises selectivity pyrolysis reactor, cyclonic separator, catalyst regeneration reactor, product condenser and water-and-oil separator, the wherein import of selectivity pyrolysis reactor (1) import of matter selective pyrolysis system (I) of making a living, selectivity pyrolysis reactor outlet is connected with the entrance of cyclonic separator, the upper outlet of cyclonic separator is connected with the entrance of product condenser, the liquid-phase outlet of product condenser is connected with the entrance of water-and-oil separator, the lower outlet of cyclonic separator is connected with the entrance of catalyst regeneration reactor, the outlet of catalyst regeneration reactor is connected with the catalyst inlet of selectivity pyrolysis reactor, the make a living gaseous phase outlet of matter selective pyrolysis system of the gaseous phase outlet of product condenser, the oil phase of water-and-oil separator (5) exports the oil phase outlet of the matter selective pyrolysis system (I) of making a living.
Described low-carbon alkene oligomerisation hydrogenation system comprises olefin catalytic oligomerisation hydrogenator, gas-liquid-solid three-phase separator, catalyst regeneration reactor, catalyzer storage tank, hydrogen-holder and hydrogen gas compressor, wherein the import of olefin catalytic oligomerisation hydrogenator is the gas phase import of low-carbon alkene oligomerisation hydrogenation system, the import of hydrogen gas compressor connects hydrogen-holder, outlet connects the import of olefin catalytic oligomerisation hydrogenator, the outlet of olefin catalytic oligomerisation hydrogenator connects the import of gas-liquid-solid three-phase separator, the liquid-phase outlet of gas-liquid-solid three-phase separator is the liquid-phase outlet of low-carbon alkene oligomerisation hydrogenation system, the gaseous phase outlet of gas-liquid-solid three-phase separator is the mixed gas outlet of low-carbon alkene oligomerisation hydrogenation system, the solid phase outlet of gas-liquid-solid three-phase separator connects the import of catalyst regeneration reactor, and the outlet of catalyst regeneration reactor connects the entrance of catalyzer storage tank, and the outlet of catalyzer storage tank connects olefin catalytic oligomerisation hydrogenator catalyst inlet.
Described aromatic hydrocarbon and alkane mixing system comprise aromatic hydrocarbon splitter and stirring mixer, the import of aromatic hydrocarbon splitter is the aromatic hydrocarbon entrance of aromatic hydrocarbon and alkane mixing system, the alkane import of the outlet of aromatic hydrocarbon splitter and aromatic hydrocarbon and alkane mixing system connects stirring mixer and mixes, by stirring mixer output aviation kerosene.
In described biomass by selective pyrolysis system, adopt zeolite micropore class catalyzer, pressure is normal pressure, and temperature is between 500-650 ℃.
Described zeolite micropore class catalyzer is HZSM-5, SAPO-34, Fe/HZSM-5, Cu/HZSM-5 or Ga/HZSM-5.
In described low-carbon alkene oligomerisation hydrogenation system, adopt Fe, Cu, Ni as active element, HZSM-5 and MCM-41 or HZSM-5 and Al
2o
3be made into combined multi-stage duct carrier, be prepared into Fe/HZSM-5/MCM-41, Cu/HZSM-5/MCM-41, Ni/HZSM-5/MCM-41 or Cu/HZSM-5/Al
2o
3catalyzer is as the catalyzer of native system, and working pressure is 2-5MPa, and temperature is between 150-300 ℃.
Biomass by selective pyrolysis of the present invention-step transforms the device of preparing Aviation Fuel to be prepared the method for Aviation Fuel and comprises the steps: first to be prepared by catalytic pyrolysis of biomass aromatic hydrocarbon and low-carbon alkene, then aromatic hydrocarbon is separated with low-carbon alkene, low-carbon alkene is completed to oligomerisation Hydrogenation for alkane process in a reactor, then aromatic hydrocarbon and alkene are hybridly prepared into Aviation Fuel according to aviation by oil ratio example.
The device of described the method based on being formed by biomass by selective pyrolysis system, low-carbon alkene oligomerisation hydrogenation system and aromatic hydrocarbon and alkane mixing system, biomass by selective pyrolysis system comprises selectivity pyrolysis reactor, cyclonic separator, catalyst regeneration reactor, product condenser and water-and-oil separator; Low-carbon alkene oligomerisation hydrogenation system comprises olefin catalytic oligomerisation hydrogenator, gas-liquid-solid three-phase separator, catalyst regeneration reactor, catalyzer storage tank, hydrogen-holder and hydrogen gas compressor; Aromatic hydrocarbon and alkane mixing system comprise aromatic hydrocarbon splitter and stirring mixer, and concrete steps are as follows:
First biomass are added to selectivity pyrolysis under normal pressure, normal temperature and catalyzer from pyrolysis reactor bottom; Biomass pyrolysis reactor outlet product enters cyclonic separator, the separated catalyst regeneration reactor that enters of catalyzer wherein and coke solid matter, this reactor passes into air, the coke heatable catalyst that burning generates on the one hand, burn off catalyst surface coking on the other hand, make its regeneration, come back in pyrolysis reactor, realization recycles;
Cyclonic separator gas is out through condenser condenses, water and aromatic product are wherein condensed, through water-and-oil separator, isolate aromatic hydrocarbon, aromatic hydrocarbon is through aromatic hydrocarbon part flow arrangement, alkane prepared by part aromatic hydrocarbon and low-carbon alkene oligomerisation hydrogenation system is hybridly prepared into Aviation Fuel, and remaining aromatic hydrocarbon is as chemical products;
The gas that biomass by selective pyrolysis product is not condensed through condenser is rich in low-carbon alkene, this gas not being condensed obtains alkane product under catalyzer and hydrogen effect after olefin catalytic oligomerisation hydrogenator, wherein hydrogen is supplied with by hydrogen gas compressor suction hydrogen-holder, after described alkane product product is separated with liquid alkane by catalyzer via gas-liquid-solid three-phase separator, catalyzer enters catalyst regeneration reactor and regenerates, send into again catalyzer storage tank, then add olefin catalytic oligomerisation hydrogenator to continue on for oligomerisation and hydrogenation reaction, realize whole catalyst recirculation,
The aromatic hydrocarbon that the alkane that gas-liquid-solid mixing tank triphase separator is separated and aromatic hydrocarbon part flow arrangement obtain passes into stirring mixer, prepares after sufficiently mixing Aviation Fuel.
Beneficial effect: the present invention utilizes the feature of biomass by selective pyrolysis, prepare aromatic liquid hydrocarbon, incondensable gas is collected and further transformed simultaneously, olefin oligomerization hydroisomerizing in incondensable gas is generated to the alkane of certain carbon chain lengths, by changing the percentage composition of aromatic hydrocarbon and alkane, obtain dissimilar Aviation Fuel, the step of having realized biomass transforms.Step method for transformation of the present invention combines the oligomerisation hydrogenation reaction of the selectivity pyrolysis of biomass and alkene, has improved the utilization ratio of biomass.In the present invention, biomass by selective pyrolysis is prepared aromatic hydrocarbon and low-carbon alkene carries out under normal pressure and cheap zeolite catalyst effect, have advantages of with short production cycle, technique is simple, floor space is little and less investment, and low-carbon alkene oligomerisation hydrogenation carries out in a reactor, single stage method is prepared alkane, can obtain total composition Aviation Fuel.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that biomass by selective pyrolysis of the present invention-step transforms the method nuclear machinery of preparing Aviation Fuel;
Wherein have: biomass by selective pyrolysis system I, low-carbon alkene oligomerisation hydrogenation system II and aromatic hydrocarbon and alkane mixing system III;
Selectivity pyrolysis reactor 1, cyclonic separator 2, catalyst regeneration reactor 3, product condenser 4, water-and-oil separator 5, aromatic hydrocarbon splitter 6, olefin catalytic oligomerisation hydrogenator 7, gas-liquid-solid three-phase separator 8, catalyst regeneration reactor 9, catalyzer storage tank 10, hydrogen-holder 11, hydrogen gas compressor 12, stirring mixer 13.
Embodiment
Say that the present invention will be described with reference to accompanying drawing below.
Embodiment 1
As shown in Figure 1, the invention provides a kind of biomass by selective pyrolysis-step and transform the device of preparing Aviation Fuel, this device comprises three system biological matter selectivity pyrolysis system I, low-carbon alkene oligomerisation hydrogenation system II and aromatic hydrocarbon and alkane mixing system III.
Biomass by selective pyrolysis system I for being prepared by catalytic pyrolysis of biomass to aromatic hydrocarbon and low-carbon alkene, realizes the regeneration of catalyzer and the supply of pyrolysis heat simultaneously;
Low-carbon alkene oligomerisation hydrogenation system II, the low-carbon alkene oligomerisation Hydrogenation that is used for biomass by selective pyrolysis system I to produce, for alkane fuel, is realized the regeneration of oligomerisation hydrogenation catalyst simultaneously;
Aromatic hydrocarbon and alkane mixing system III, for proportionally, fully mixed arenes and alkane, make oil for aviation;
The import of described biomass by selective pyrolysis system I is the biomass inlet of this device, gaseous phase outlet is connected with the olefin catalytic oligomerisation hydrogenator entrance in low-carbon alkene oligomerisation hydrogenation system II, and the entrance of the oil phase outlet of biomass by selective pyrolysis system I and aromatic hydrocarbon and aromatic hydrocarbon splitter in alkane mixing system III is connected; The entrance of the alkane liquid exit in low-carbon alkene oligomerisation hydrogenation system II and aromatic hydrocarbon and stirring mixer in alkane mixing system III is connected; The liquid exit of described aromatic hydrocarbon and alkane mixing system III is aromatic hydrocarbon and the Aviation Fuel outlet of this device.
Described biomass by selective pyrolysis system I comprises selectivity pyrolysis reactor 1, cyclonic separator 2, catalyst regeneration reactor 3, product condenser 4 and water-and-oil separator 5, the wherein import of selectivity pyrolysis reactor 1 import of matter selective pyrolysis system I of making a living, the outlet of selectivity pyrolysis reactor 1 is connected with the entrance of cyclonic separator 2, the upper outlet of cyclonic separator 2 is connected with the entrance of product condenser 4, the liquid-phase outlet of product condenser 4 is connected with the entrance of water-and-oil separator 5, the lower outlet of cyclonic separator 2 is connected with the entrance of catalyst regeneration reactor 3, the outlet of catalyst regeneration reactor 3 is connected with the catalyst inlet of selectivity pyrolysis reactor 1, the make a living gaseous phase outlet of matter selective pyrolysis system I of the gaseous phase outlet of product condenser 4, the oil phase of water-and-oil separator 5 exports the oil phase outlet of the matter selective pyrolysis system I that makes a living.In selectivity pyrolysis reactor, there is catalyse pyrolysis and generate aromatic hydrocarbon and low-carbon alkene in biomass material, product arrives product condenser after cyclonic separator is separated with coke by the catalyzer of inactivation, in product condenser, the water of aromatic hydrocarbon and generation is condensed, then through water-and-oil separator, realize the separated of aromatic hydrocarbon and water, low-carbon alkene is stayed in incondensable gas, the catalyzer of inactivation is regenerated in catalyst regenerator, then return to selectivity pyrolysis reactor, complete whole biomass by selective pyrolysis circulation.
Described low-carbon alkene oligomerisation hydrogenation system II comprises olefin catalytic oligomerisation hydrogenator 7, gas-liquid-solid three-phase separator 8, catalyst regeneration reactor 9, catalyzer storage tank 10, hydrogen-holder 11 and hydrogen gas compressor 12, wherein 7 imports of olefin catalytic oligomerisation hydrogenator are the gas phase import of low-carbon alkene oligomerisation hydrogenation system II, the import of hydrogen gas compressor 12 connects hydrogen-holder 11, outlet connects the import of olefin catalytic oligomerisation hydrogenator 7, the outlet of olefin catalytic oligomerisation hydrogenator 7 connects the import of gas-liquid-solid three-phase separator 8, the liquid-phase outlet of gas-liquid-solid three-phase separator 8 is the liquid-phase outlet of low-carbon alkene oligomerisation hydrogenation system II, the gaseous phase outlet of gas-liquid-solid three-phase separator 8 is the mixed gas outlet of low-carbon alkene oligomerisation hydrogenation system II, the solid phase outlet of gas-liquid-solid three-phase separator 8 connects the import of catalyst regeneration reactor 9, and the outlet of catalyst regeneration reactor 9 connects the entrance of catalyzer storage tank 10, and the outlet of catalyzer storage tank 10 connects olefin catalytic oligomerisation hydrogenator 7 catalyst inlets.In olefin catalytic oligomerisation hydrogenator, there is oligomerisation hydrogenation reaction in low-carbon alkene, product enters gas-liquid-solid three-phase separator and carries out separation after product condenser condenses, the hydrogen supply of the needed hydrogen of hydrogenation in hydrogen gas compressor suction hydrogen-holder, the catalyzer of oligomerisation hydrogenation inactivation enters catalyst regeneration reactor and regenerates, catalyzer after regeneration enters catalyzer storage tank, and then enter olefin catalytic oligomerisation hydrogenator, complete whole low-carbon alkene oligomerisation hydrogenation system circulation.
Aromatic hydrocarbon and alkane mixing system III comprise aromatic hydrocarbon splitter 6 and stirring mixer 13, the import of aromatic hydrocarbon splitter 6 is the aromatic hydrocarbon entrance of aromatic hydrocarbon and alkane mixing system III, the alkane import of the outlet of aromatic hydrocarbon splitter 6 and aromatic hydrocarbon and alkane mixing system III connects stirring mixer 13 and mixes, by stirring mixer 13 output Aviation Fuels.Aromatic hydrocarbon prepared by catalytic pyrolysis of biomass is shunted in aromatic hydrocarbon splitter, and the alkane standby with low-carbon alkene oligomerisation Hydrogenation fully mixes at stirring mixer according to a certain percentage, makes Aviation Fuel.
In selectivity pyrolysis reactor 1 in described biomass by selective pyrolysis system I, adopt zeolite micropore class catalyzer, described zeolite micropore class catalyzer is HZSM-5, SAPO-34, Fe/HZSM-5, Cu/HZSM-5 or Ga/HZSM-5, pressure is normal pressure, temperature, between 500-650 ℃, can change ratio and the selectivity of aromatic hydrocarbon and low-carbon alkene by different catalyzer and condition.
In olefin catalytic oligomerisation hydrogenator 7 in described low-carbon alkene oligomerisation hydrogenation system II, adopt Fe, Cu, Ni as active element, HZSM-5 and MCM-41 or HZSM-5 and Al
2o
3be made into combined multi-stage duct carrier, be prepared into Fe/HZSM-5/MCM-41, Cu/HZSM-5/MCM-41, Ni/HZSM-5/MCM-41 or Cu/HZSM-5/Al
2o
3catalyzer is as the catalyzer of native system, and working pressure is 2-5MPa, and temperature, between 150-300 ℃, can change the length of gained alkane productive rate and carbochain by different catalyzer and condition.
The device that the present invention also provides the conversion of a kind of biomass by selective pyrolysis-step to prepare Aviation Fuel is prepared the method for Aviation Fuel, the method comprises the steps: first to be prepared by catalytic pyrolysis of biomass aromatic hydrocarbon and low-carbon alkene, then aromatic hydrocarbon is separated with low-carbon alkene, low-carbon alkene is completed to oligomerisation Hydrogenation for alkane process in a reactor, then aromatic hydrocarbon and alkene are hybridly prepared into Aviation Fuel according to aviation by oil ratio example.
The device of described the method based on being formed by biomass by selective pyrolysis system I, low-carbon alkene oligomerisation hydrogenation system II and aromatic hydrocarbon and alkane mixing system III, biomass by selective pyrolysis system I comprises selectivity pyrolysis reactor 1, cyclonic separator 2, catalyst regeneration reactor 3, product condenser 4 and water-and-oil separator 5; Low-carbon alkene oligomerisation hydrogenation system II comprises olefin catalytic oligomerisation hydrogenator 7, gas-liquid-solid three-phase separator 8, catalyst regeneration reactor 9, catalyzer storage tank 10, hydrogen-holder 11 and hydrogen gas compressor 12; Aromatic hydrocarbon and alkane mixing system III comprise aromatic hydrocarbon splitter 6 and stirring mixer 13, and the method concrete steps are as follows: first biomass are added to selectivity pyrolysis under normal pressure, normal temperature and catalyzer from pyrolysis reactor 1 bottom; Biomass pyrolysis reactor 1 outlet product enters cyclonic separator 2, the separated catalyst regeneration reactor 3 that enters of catalyzer wherein and coke solid matter, this reactor passes into air, the coke heatable catalyst that burning generates on the one hand, burn off catalyst surface coking on the other hand, make its regeneration, come back in pyrolysis reactor 1, realization recycles;
Cyclonic separator 2 gas is out through condenser 4 condensations, water and aromatic product are wherein condensed, through water-and-oil separator 5, isolate aromatic hydrocarbon, aromatic hydrocarbon is through aromatic hydrocarbon part flow arrangement 6, alkane prepared by part aromatic hydrocarbon and low-carbon alkene oligomerisation hydrogenation system II is hybridly prepared into Aviation Fuel, and remaining aromatic hydrocarbon is as chemical products;
The gas that cyclonic separator 2 biomass by selective pyrolysis product is not out condensed through condenser 4 is rich in low-carbon alkene, this gas not being condensed obtains alkane product under catalyzer and hydrogen effect after olefin catalytic oligomerisation hydrogenator 7, wherein hydrogen is supplied with by hydrogen gas compressor 12 suction hydrogen-holders 11, after described alkane product is separated with liquid alkane by catalyzer via gas-liquid-solid three-phase separator 8, catalyzer enters catalyst regeneration reactor 9 and regenerates, send into again catalyzer storage tank 10, then add olefin catalytic oligomerisation hydrogenator 7 to continue on for oligomerisation and hydrogenation reaction, realize whole catalyst recirculation,
The aromatic hydrocarbon that the alkane of finally gas-liquid-solid mixing tank triphase separator 8 being separated and aromatic hydrocarbon part flow arrangement 6 obtain passes into stirring mixer 13, prepares after sufficiently mixing Aviation Fuel.
Embodiment 2
In this example, biomass material is the rice straw particle that is less than 5mm, selectivity pyrolysis catalyzer selects zeolites HZSM-5 catalyzer to expect as bed, first stalk particle is added from selectivity pyrolysis reactor 1 bottom, in pyrolysis bed in selectivity pyrolysis reactor 1 double bed, be heated to 600 ℃ pyrolysis occurs, pyrolysis steam enters the catalyzed conversion in catalyzer duct, generate the products such as aromatic hydrocarbon and low-carbon alkene, enter cyclonic separator 2, the HZSM-5 of inactivation and coke by the separated catalyst regeneration reactor 3 that enters of cyclonic separator 2 to the burning bed in double bed, burning bed passes into air, coke heats to catalyzer in the interior burning of catalyst regeneration reactor 3, catalyzer is regenerated simultaneously, HZSM-5 catalyzer after regeneration returns in the pyrolysis bed in selectivity pyrolysis reactor 1, complete whole pyrolysis circulation, cyclonic separator 2 gas is out through 4 condensations of product condenser, wherein water and aromatic product (benzene, toluene and dimethylbenzene etc.) be condensed and isolate aromatic hydrocarbon by water-and-oil separator 5, the gas that biomass by selective pyrolysis product is not condensed in condenser 4 is rich in low-carbon alkene.
What the pyrolysis of stalk particle selectivity was produced is rich in low-carbon alkene class incondensable gas, by oligomerisation method of hydrotreating, prepares alkane.Reaction conditions is as follows: use Ni/HZSM-5/MCM-41 catalyzer, pressure is 3MPa, and temperature is 200 ℃.The gas not being condensed in condenser 4 enters olefin catalytic oligomerisation hydrogenator 7, low-carbon alkene is wherein generated C10-C16 alkane by oligomerisation hydrogenation, wherein hydrogen is supplied with by hydrogen gas compressor 12 suction hydrogen-holders 11, after product is separated with liquid alkane by catalyzer via gas-liquid-solid three-phase separator 8, Ni/HZSM-5/MCM-41 catalyzer enters catalyst regeneration reactor 9 and regenerates, enter again catalyzer storage tank, then enter olefin catalytic oligomerisation hydrogenator 7 and continue on for oligomerisation and hydrogenation reaction, realize whole catalyst recirculation.
The aromatic hydrocarbon that the C10-C16 alkane that gas-liquid-solid three-phase separator 8 is separated and aromatic hydrocarbon splitter 6 obtain passes into stirring mixer 13 in aromatic hydrocarbon 30% ratio, prepares after sufficiently mixing Aviation Fuel.
The foregoing is only better embodiment of the present invention; protection scope of the present invention is not limited with above-mentioned embodiment; in every case the equivalence that those of ordinary skills do according to disclosed content is modified or is changed, and all should include in the protection domain of recording in claims.
Claims (9)
1. biomass by selective pyrolysis-step transforms a device of preparing Aviation Fuel, it is characterized in that: this device comprises:
Biomass by selective pyrolysis system (I) for being prepared by catalytic pyrolysis of biomass to aromatic hydrocarbon and low-carbon alkene, realizes the regeneration of catalyzer and the supply of pyrolysis heat simultaneously;
Low-carbon alkene oligomerisation hydrogenation system (II), the low-carbon alkene oligomerisation Hydrogenation that is used for biomass by selective pyrolysis system (I) to produce, for alkane fuel, is realized the regeneration of oligomerisation hydrogenation catalyst simultaneously;
Aromatic hydrocarbon and alkane mixing system (III), for proportionally, fully mixed arenes and alkane, make oil for aviation;
The import of described biomass by selective pyrolysis system (I) is the biomass inlet of this device, gaseous phase outlet is connected with the olefin catalytic oligomerisation hydrogenator entrance in low-carbon alkene oligomerisation hydrogenation system (II), and the entrance of the oil phase outlet of biomass by selective pyrolysis system (I) and aromatic hydrocarbon and aromatic hydrocarbon splitter in alkane mixing system (III) is connected; The entrance of the alkane liquid exit in low-carbon alkene oligomerisation hydrogenation system (II) and aromatic hydrocarbon and stirring mixer in alkane mixing system (III) is connected; The liquid exit of described aromatic hydrocarbon and alkane mixing system (III) is aromatic hydrocarbon and the Aviation Fuel outlet of this device.
2. a kind of biomass by selective pyrolysis according to claim 1-step transforms the device of preparing Aviation Fuel, it is characterized in that: biomass by selective pyrolysis system (I) comprises selectivity pyrolysis reactor (1), cyclonic separator (2), catalyst regeneration reactor (3), product condenser (4) and water-and-oil separator (5), the wherein import of selectivity pyrolysis reactor (1) import of matter selective pyrolysis system (I) of making a living, the outlet of selectivity pyrolysis reactor (1) is connected with the entrance of cyclonic separator (2), the upper outlet of cyclonic separator (2) is connected with the entrance of product condenser (4), the liquid-phase outlet of product condenser (4) is connected with the entrance of water-and-oil separator (5), the lower outlet of cyclonic separator (2) is connected with the entrance of catalyst regeneration reactor (3), the outlet of catalyst regeneration reactor (3) is connected with the catalyst inlet of selectivity pyrolysis reactor (1), the make a living gaseous phase outlet of matter selective pyrolysis system (I) of the gaseous phase outlet of product condenser (4), the oil phase of water-and-oil separator (5) exports the oil phase outlet of the matter selective pyrolysis system (I) of making a living.
3. a kind of biomass by selective pyrolysis according to claim 1-step transforms the device of preparing Aviation Fuel, it is characterized in that: low-carbon alkene oligomerisation hydrogenation system (II) comprises olefin catalytic oligomerisation hydrogenator (7), gas-liquid-solid three-phase separator (8), catalyst regeneration reactor (9), catalyzer storage tank (10), hydrogen-holder (11) and hydrogen gas compressor (12), wherein olefin catalytic oligomerisation hydrogenator (7) import is the gas phase import of low-carbon alkene oligomerisation hydrogenation system (II), the import of hydrogen gas compressor (12) connects hydrogen-holder (11), outlet connects the import of olefin catalytic oligomerisation hydrogenator (7), the outlet of olefin catalytic oligomerisation hydrogenator (7) connects the import of gas-liquid-solid three-phase separator (8), the liquid-phase outlet of gas-liquid-solid three-phase separator (8) is the liquid-phase outlet of low-carbon alkene oligomerisation hydrogenation system (II), the gaseous phase outlet of gas-liquid-solid three-phase separator (8) is the mixed gas outlet of low-carbon alkene oligomerisation hydrogenation system (II), the solid phase outlet of gas-liquid-solid three-phase separator (8) connects the import of catalyst regeneration reactor (9), the outlet of catalyst regeneration reactor (9) connects the entrance of catalyzer storage tank (10), and the outlet of catalyzer storage tank (10) connects olefin catalytic oligomerisation hydrogenator (7) catalyst inlet.
4. a kind of biomass by selective pyrolysis according to claim 1-step transforms the device of preparing Aviation Fuel, it is characterized in that: aromatic hydrocarbon and alkane mixing system (III) comprise aromatic hydrocarbon splitter (6) and stirring mixer (13), the import of aromatic hydrocarbon splitter (6) is the aromatic hydrocarbon entrance of aromatic hydrocarbon and alkane mixing system (III), the alkane import of the outlet of aromatic hydrocarbon splitter (6) and aromatic hydrocarbon and alkane mixing system (III) connects stirring mixer (13) and mixes, by stirring mixer (13) output Aviation Fuel.
5. a kind of biomass by selective pyrolysis according to claim 2-step transforms the device of preparing Aviation Fuel, it is characterized in that: in biomass by selective pyrolysis system (I), adopt zeolite micropore class catalyzer, pressure is normal pressure, and temperature is between 500-650 ℃.
6. a kind of biomass by selective pyrolysis according to claim 5-step transforms the device of preparing Aviation Fuel, it is characterized in that: described zeolite micropore class catalyzer is HZSM-5, SAPO-34, Fe/HZSM-5, Cu/HZSM-5 or Ga/HZSM-5.
7. a kind of biomass by selective pyrolysis according to claim 3-step transforms the device of preparing Aviation Fuel, it is characterized in that: in low-carbon alkene oligomerisation hydrogenation system (II), adopt Fe, Cu, Ni as active element, HZSM-5 and MCM-41 or HZSM-5 and Al
2o
3be made into combined multi-stage duct carrier, be prepared into Fe/HZSM-5/MCM-41, Cu/HZSM-5/MCM-41, Ni/HZSM-5/MCM-41 or Cu/HZSM-5/Al
2o
3catalyzer is as the catalyzer of native system, and working pressure is 2-5MPa, and temperature is between 150-300 ℃.
8. a biomass by selective pyrolysis as claimed in claim 1-step transforms the method that the device of preparing Aviation Fuel is prepared Aviation Fuel, it is characterized in that, the method comprises the steps: first to be prepared by catalytic pyrolysis of biomass aromatic hydrocarbon and low-carbon alkene, then aromatic hydrocarbon is separated with low-carbon alkene, low-carbon alkene is completed to oligomerisation Hydrogenation for alkane process in a reactor, then aromatic hydrocarbon and alkene are hybridly prepared into Aviation Fuel according to aviation by oil ratio example.
9. biomass by selective pyrolysis according to claim 8-step transforms the method that the device of preparing Aviation Fuel is prepared Aviation Fuel, it is characterized in that, the device of the method based on being formed by biomass by selective pyrolysis system (I), low-carbon alkene oligomerisation hydrogenation system (II) and aromatic hydrocarbon and alkane mixing system (III), biomass by selective pyrolysis system (I) comprises selectivity pyrolysis reactor (1), cyclonic separator (2), catalyst regeneration reactor (3), product condenser (4) and water-and-oil separator (5); Low-carbon alkene oligomerisation hydrogenation system (II) comprises olefin catalytic oligomerisation hydrogenator (7), gas-liquid-solid three-phase separator (8), catalyst regeneration reactor (9), catalyzer storage tank (10), hydrogen-holder (11) and hydrogen gas compressor (12); Aromatic hydrocarbon and alkane mixing system (III) comprise aromatic hydrocarbon splitter (6) and stirring mixer (13), and concrete steps are as follows:
First biomass are added to selectivity pyrolysis under normal pressure, normal temperature and catalyzer from pyrolysis reactor (1) bottom; Biomass pyrolysis reactor (1) outlet product enters cyclonic separator (2), the separated catalyst regeneration reactor (3) that enters of catalyzer wherein and coke solid matter, this reactor passes into air, the coke heatable catalyst that burning generates on the one hand, burn off catalyst surface coking on the other hand, make its regeneration, come back in pyrolysis reactor (1), realization recycles;
Cyclonic separator (2) gas is out through condenser (4) condensation, water and aromatic product are wherein condensed, through water-and-oil separator (5), isolate aromatic hydrocarbon, aromatic hydrocarbon is through aromatic hydrocarbon part flow arrangement (6), alkane prepared by part aromatic hydrocarbon and low-carbon alkene oligomerisation hydrogenation system (II) is hybridly prepared into Aviation Fuel, and remaining aromatic hydrocarbon is as chemical products;
The gas that biomass by selective pyrolysis product is not condensed through condenser (4) is rich in low-carbon alkene, this gas not being condensed obtains alkane product under catalyzer and hydrogen effect after olefin catalytic oligomerisation hydrogenator (7), wherein hydrogen is supplied with by hydrogen gas compressor (12) suction hydrogen-holder (11), after described alkane product is separated with liquid alkane by catalyzer via gas-liquid-solid three-phase separator (8), catalyzer enters catalyst regeneration reactor (9) and regenerates, send into again catalyzer storage tank (10), then add olefin catalytic oligomerisation hydrogenator (7) to continue on for oligomerisation and hydrogenation reaction, realize whole catalyst recirculation,
The aromatic hydrocarbon that the alkane that gas-liquid-solid mixing tank triphase separator (8) is separated and aromatic hydrocarbon part flow arrangement (6) obtain passes into stirring mixer (13), prepares after sufficiently mixing Aviation Fuel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410287728.7A CN104059682B (en) | 2014-06-24 | 2014-06-24 | Biomass by selective pyrolysis-step transforms device and the method for preparing Aviation Fuel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410287728.7A CN104059682B (en) | 2014-06-24 | 2014-06-24 | Biomass by selective pyrolysis-step transforms device and the method for preparing Aviation Fuel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104059682A true CN104059682A (en) | 2014-09-24 |
| CN104059682B CN104059682B (en) | 2016-06-08 |
Family
ID=51547619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410287728.7A Active CN104059682B (en) | 2014-06-24 | 2014-06-24 | Biomass by selective pyrolysis-step transforms device and the method for preparing Aviation Fuel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104059682B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623702A (en) * | 2014-10-28 | 2016-06-01 | 中国科学技术大学 | Method for synthesizing aviation kerosene cycloparaffin and aroma components by utilization of wood chips |
| CN105176605B (en) * | 2015-09-01 | 2018-04-20 | 天津大学 | A kind of Aviation Fuel process units and production method |
| CN108238283A (en) * | 2017-12-26 | 2018-07-03 | 彩虹无人机科技有限公司 | A kind of aircraft fuel system upper air performance system and method |
| CN108893128A (en) * | 2018-08-02 | 2018-11-27 | 北京中富瑞科环保科技有限公司 | A kind of carbonizing treatment method of biomass |
| CN110721734A (en) * | 2019-11-12 | 2020-01-24 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing aviation oil and co-producing gasoline by olefin oligomerization, preparation method and application |
| WO2022063994A1 (en) * | 2020-09-25 | 2022-03-31 | Haldor Topsøe A/S | Methanol to jet fuel (mtj) process |
| WO2022063992A1 (en) * | 2020-09-25 | 2022-03-31 | Haldor Topsøe A/S | Methanol to olefin (mto) process |
| WO2022063995A1 (en) * | 2020-09-25 | 2022-03-31 | Haldor Topsøe A/S | Methanol to olefin (mto) process |
| WO2022063993A1 (en) * | 2020-09-25 | 2022-03-31 | Haldor Topsøe A/S | Alternative methanol to olefin (mto) process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101755038A (en) * | 2007-06-29 | 2010-06-23 | 能源与环境研究中心基金会 | Aviation-grade kerosene from the independent mixture of producing |
| CN102015969A (en) * | 2008-03-04 | 2011-04-13 | 马萨诸塞大学 | Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds |
| CN102666796A (en) * | 2009-09-09 | 2012-09-12 | 马萨诸塞大学 | Systems and processes for catalytic pyrolysis of biomass and hydrocarbonaceous materials for production of aromatics with optional olefin recycle, and catalysts having selected particle size for catalytic pyrolysis |
| US20140107306A1 (en) * | 2012-10-17 | 2014-04-17 | Annellotech, Inc. | Chemical intermediates by catalytic fast pyrolysis process |
-
2014
- 2014-06-24 CN CN201410287728.7A patent/CN104059682B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101755038A (en) * | 2007-06-29 | 2010-06-23 | 能源与环境研究中心基金会 | Aviation-grade kerosene from the independent mixture of producing |
| CN102015969A (en) * | 2008-03-04 | 2011-04-13 | 马萨诸塞大学 | Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds |
| CN102666796A (en) * | 2009-09-09 | 2012-09-12 | 马萨诸塞大学 | Systems and processes for catalytic pyrolysis of biomass and hydrocarbonaceous materials for production of aromatics with optional olefin recycle, and catalysts having selected particle size for catalytic pyrolysis |
| US20140107306A1 (en) * | 2012-10-17 | 2014-04-17 | Annellotech, Inc. | Chemical intermediates by catalytic fast pyrolysis process |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623702A (en) * | 2014-10-28 | 2016-06-01 | 中国科学技术大学 | Method for synthesizing aviation kerosene cycloparaffin and aroma components by utilization of wood chips |
| CN105623702B (en) * | 2014-10-28 | 2018-04-10 | 中国科学技术大学 | A kind of method that aviation kerosine cycloalkane and aromatised fraction are synthesized using wood chip |
| CN105176605B (en) * | 2015-09-01 | 2018-04-20 | 天津大学 | A kind of Aviation Fuel process units and production method |
| CN108238283A (en) * | 2017-12-26 | 2018-07-03 | 彩虹无人机科技有限公司 | A kind of aircraft fuel system upper air performance system and method |
| CN108893128A (en) * | 2018-08-02 | 2018-11-27 | 北京中富瑞科环保科技有限公司 | A kind of carbonizing treatment method of biomass |
| CN108893128B (en) * | 2018-08-02 | 2021-03-02 | 北京中富瑞科环保科技有限公司 | Carbonization treatment method of biomass |
| CN110721734A (en) * | 2019-11-12 | 2020-01-24 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing aviation oil and co-producing gasoline by olefin oligomerization, preparation method and application |
| WO2022063994A1 (en) * | 2020-09-25 | 2022-03-31 | Haldor Topsøe A/S | Methanol to jet fuel (mtj) process |
| WO2022063992A1 (en) * | 2020-09-25 | 2022-03-31 | Haldor Topsøe A/S | Methanol to olefin (mto) process |
| WO2022063995A1 (en) * | 2020-09-25 | 2022-03-31 | Haldor Topsøe A/S | Methanol to olefin (mto) process |
| WO2022063993A1 (en) * | 2020-09-25 | 2022-03-31 | Haldor Topsøe A/S | Alternative methanol to olefin (mto) process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104059682B (en) | 2016-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104059682B (en) | Biomass by selective pyrolysis-step transforms device and the method for preparing Aviation Fuel | |
| Santillan‐Jimenez et al. | Catalytic deoxygenation of fatty acids and their derivatives to hydrocarbon fuels via decarboxylation/decarbonylation | |
| Gao et al. | Green carbon science: Keeping the pace in practice | |
| Bielansky et al. | Catalytic conversion of vegetable oils in a continuous FCC pilot plant | |
| JP6752399B2 (en) | Method and apparatus for producing aromatic hydrocarbons and olefins by coupling of catalytic hydrogenation and catalytic cracking of biological oils | |
| CN102653691B (en) | Device and method for preparing oxygen-containing liquid fuel by catalytically converting biological oil | |
| CN103289740B (en) | Method for preparing clean fuel oil from coal tar | |
| CN103130602B (en) | A kind of method utilizing animal-plant oil and abendoned oil thereof to produce low-carbon alkene | |
| Wang et al. | Conversion of microalgae to jet fuel: Process design and simulation | |
| Kuo et al. | Catalytic aromatization of ethylene in syngas from biomass to enhance economic sustainability of gas production | |
| Gujar et al. | A review on catalytic conversion of biodiesel derivative glycerol to bio-olefins | |
| CN102531816A (en) | Method for preparing low carbon olefin by catalytic pyrolysis of microalgae | |
| González-Arias et al. | Hydrogen production by catalytic aqueous-phase reforming of waste biomass: a review | |
| CN103864564B (en) | Technique for processing methanol-to-propylene by-products | |
| CN103130600B (en) | A kind of method utilizing animal-plant oil and abendoned oil thereof to produce low-carbon alkene | |
| CN105602612B (en) | Method for hydrofinishing biological crude oil by using high temperature gas cooled reactor | |
| KR101167110B1 (en) | Continuous method and device for preparing hydrocarbon from biological origins using hydrotalcites as catalyst | |
| Street et al. | Production of high-value products including gasoline hydrocarbons from the thermochemical conversion of syngas | |
| CN202543163U (en) | Device for preparing oxygen-containing liquid fuel by performing catalytic conversion on bio oil | |
| CN102070386A (en) | Two-step method for preparing olefin and aromatic hydrocarbon by catalyzing and upgrading bio-oil | |
| CN103130599B (en) | A kind of method utilizing animal-plant oil and abendoned oil thereof to produce low-carbon alkene | |
| CN104557362A (en) | System and method for preparing aromatic hydrocarbons and co-producing ethylene and propylene by transforming methanol and/or dimethyl ether | |
| CN203976663U (en) | A kind of fixed-bed reactor of methanol-to-olefins | |
| CN104557366B (en) | System and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether | |
| CN105251524A (en) | Catalytic cracking deoxidation catalyst for biomass liquefaction oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |