CN111592906A - Preparation of C from biomass6~C18Method for powering fuel - Google Patents

Preparation of C from biomass6~C18Method for powering fuel Download PDF

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CN111592906A
CN111592906A CN202010314301.7A CN202010314301A CN111592906A CN 111592906 A CN111592906 A CN 111592906A CN 202010314301 A CN202010314301 A CN 202010314301A CN 111592906 A CN111592906 A CN 111592906A
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catalyst
supported
biomass
oxygen
reactor
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邵珊珊
项贤亮
刘成跃
李小华
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Jiangsu University
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Jiangsu University
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

The invention relates to a method for preparing C by using biomass6～C18The fuel power method mainly comprises the following steps: 1) in a two-section pyrolysis reactor, biomass is subjected to catalytic pyrolysis under the action of a metal oxide catalyst to prepare an oxygen-containing small molecular compound; 2) in a fixed bed continuous reactor, the oxygen-containing small molecular compound realizes one-step C-C coupling hydrogenation to form C6‑C18Alkanes and aromatics within the range; 3) in a reflux condenser, C6‑C18The alkane and the aromatic hydrocarbon in the range are condensed in stages according to the carbon number distribution of gasoline, kerosene and diesel oil. The method has the advantages that the steps are continuously carried out, the separation of the catalyst and the rectification of the product are not needed, the cost is greatly saved, and the reaction time is effectively reduced. Renewable biomass is used as a raw material, and power fuels such as gasoline, kerosene, diesel oil and the like are simultaneously prepared and separated, so that the renewable biomass can partially replace the traditional petroleum sourceThe refining technology of (1).

Description

Preparation of C from biomass6～C18Method for powering fuel
Technical Field
The invention belongs to the field of preparing liquid fuel and chemical products by catalytic conversion of biomass, and particularly relates to a method for preparing C from biomass6～C18A method of powering a fuel.
Background
In the world, people are urgently required to find a sustainable alternative energy source against various problems of fossil fuel depletion and environmental protection. The currently used fuel sources are mainly coal, petroleum and natural gas, but the sources are all non-renewable resources, and the power fuel prepared by using fossil fuel can discharge a large amount of carbon dioxide to the atmosphere in the use process, thereby causing greenhouse effect and being extremely not beneficial to environmental protection. Biomass resources, as an inexhaustible energy source, gradually enter the human vision, can be converted into various forms of energy sources and high-value chemicals, and have renewability and low emission. Therefore, the rapid development of biomass energy sources has very important significance for the progress of the human society and the maintenance of civilized forms.
At present, the utilization of biomass in the prior art at home and abroad comprises the preparation of bio-oil by catalytic pyrolysis of the biomass, but the quality problem of the bio-oil is still not ideal. The organic matter components in the bio-oil prepared by direct pyrolysis are very complex, and more than 300 substances can be detected at present. In addition, the biological oil has the problems of high oxygen content, high moisture content, high solid content, high acidity, low heat value, poor thermal stability and the like. In order to realize the effective utilization of the bio-oil, the bio-oil must be further upgraded by hydrofining, catalytic cracking, catalytic reforming, esterification, emulsification and the like.
In recent years, researchers have conducted experimental studies on various production methods in the field of producing power fuels from biomass. The method comprises a grease hydrogenation-deoxidation technology, a Fischer-Tropsch synthesis-hydrogenation quality improvement technology, a biomass hydrolysis-water phase catalytic hydrogenation synthesis technology, an olefin oligomerization technology, a biological pyrolysis oil catalytic quality improvement technology and the like.
For example, in patent CN 107304367 a, a method for preparing branched alkane with carbon number in the range of gasoline, aviation fuel, kerosene and diesel oil by using acetone in biomass pyrolysis product as raw material is proposed. However, the yield of acetone in the biomass pyrolysis product is very low, and even if ketones are prepared by catalytic pyrolysis of biomass, the yield is also low, and the high-efficiency utilization of biomass energy is not met, so that the utilization rate of the biomass pyrolysis product needs to be improved, namely, the full-component utilization of biomass pyrolysis gas is realized.
In patent CN109054875A, a method for converting biomass into liquid fuel with high efficiency is proposed, even if heat is provided by coke generated in the process of catalytic cracking of petroleum, so as to realize conversion of biomass into liquid fuel. However, the liquid fuel directly prepared from biomass has poor quality, the carbon number of the product is difficult to control even if a catalyst is used, and the oil product is acidic and difficult to directly utilize.
From the above, the biomass catalytic pyrolysis is mainly a one-step method for directly preparing the bio-oil at present, and the component analysis of the prepared bio-oil can find that the yield of alkane and aromatic hydrocarbon is below 45%, and the bio-oil contains a large amount of acetic acid, macromolecular compounds and the like, even if the optimized products are extracted by a plurality of subsequent methods, the whole process from the raw material to the target product is independent and separate, discontinuous, low in yield, high in requirement on the raw material, high in cost and difficult to industrially produce.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for selectively obtaining alkanes and aromatics in the range of gasoline, kerosene and diesel oil, and oxygen-containing small molecular compounds, alkanes and aromatics with high carbon yield by directly using biomass as a raw material, and provides a green route for preparing an excellent liquid energy substitute by using biomass as a raw material. To achieve the above object, the present invention first performs catalytic pyrolysis of biomass by controlling the matching of pyrolysis temperature and catalytic temperatureThe relationship and the reasonable selection of the catalyst are that the carbon number of the catalyst is C as much as possible8The oxygen-containing small molecular compounds are converted, and then alkane and aromatic hydrocarbon with carbon number in the range of gasoline, kerosene and diesel oil can be directly generated through one-step C-C coupling hydrodeoxygenation reaction. The specific scheme is as follows:
preparation of C from biomass6～C18A method of powering a fuel, the method comprising the steps of:
(1) performing catalytic pyrolysis in a two-section pyrolysis reactor, wherein biomass is pyrolyzed at the temperature of 300-460 ℃ in a first-section reactor, pyrolysis gas enters a second-section reactor, and an oxygen-containing micromolecule compound is generated at the temperature of 300-460 ℃ through catalysis of a metal oxide catalyst;
(2) carrying out one-step C-C coupling hydrogenation reaction on the oxygen-containing micromolecule compound in a fixed bed continuous reactor to obtain C6～C18The power fuel of (1), wherein the pressure in the reactor is 5-7 MPa, the temperature is 300-375 ℃, the catalyst is a supported metal dual-function A/X type catalyst, the hydrogen flow rate is 100-300 mL/min, and the reaction time is 20-60 min;
(3)C6～C18the power fuel is subjected to fractional condensation in a reflux condenser to realize product separation.
The metal oxide catalyst in the step (1) is one or more of cerium dioxide, manganese dioxide, zirconium dioxide or titanium dioxide.
The bifunctional catalyst in the step (2) is a supported metal bifunctional A/X type catalyst, and the carrier X is an active carbon, silicon oxide and silicon-aluminum composite carrier SiO2-Al2Any one of O3 or red mud; the active component A is one or more of copper, nickel, platinum, cobalt or iron, and the mass fraction of the active component A is 5-50%.
Preferably, the biomass in the step (1) is pyrolyzed at 380 ℃, the pyrolysis gas enters a second-stage reactor, and the oxygen-containing small molecular compounds are generated at 420 ℃ through catalysis of a metal oxide catalyst.
Preferably, the pressure in the reactor in the step (2) is 6.2MPa, the temperature is 350 ℃, the catalyst is a bifunctional catalyst, the hydrogen flow rate is 200mL/min, and the reaction time is 30 min.
The temperature of the reflux condenser in the step (3) is respectively 10-20 ℃, 10-0 ℃ and-30 to-10 ℃.
The supported metal bifunctional A/X catalyst is a copper-supported red mud catalyst, a copper-supported activated carbon catalyst, a copper-supported silicon oxide catalyst, a copper-supported silicon-aluminum composite carrier SiO2-Al2O3Any one of a catalyst, a nickel-supported red mud catalyst, an iron-supported red mud catalyst, or a cobalt-supported red mud catalyst.
Preferably, the silicon-aluminum composite carrier SiO2-Al2O3The silicon-aluminum ratio is 40-60: 1.
preferably, the mass fraction of the active component A is 20%.
The supported metal bifunctional catalyst is prepared by adopting an isometric impregnation method or a coprecipitation method.
The oxygen-containing small molecule compound comprises acetone, butanone, pentanone, hexanone, heptanone, 2-cyclopentanone, acetaldehyde, butyraldehyde, octanal, furfural, phenol and the like, and the carbon number is kept below C8.
The power fuel of C6-C18 passes through a reflux condenser and is subjected to fractional condensation to obtain alkane and aromatic hydrocarbon in the range of C6-C18 such as gasoline, kerosene and diesel oil.
The invention has the beneficial effects that:
1. solves the problem that the single product aldol condensation reaction is difficult to realize multiple condensation to meet the required carbon chain length.
2. The length of the hydrocarbon carbon chain is determined by the coupling condition of catalytic pyrolysis oxygen-containing micromolecules, and the reasonable control of the carbon chain can be realized by regulating and controlling the components of pyrolysis gas.
3. Compared with the conventional method for generating the power mixed fuel by the aldol condensation-hydrogenation reaction, the reaction time of the one-step C-C coupling hydrogenation reaction can be controlled to be 20-60min, and the conventional method for generating the power mixed fuel is about 12 hours, so that the reaction time is greatly shortened.
4. The whole experiment is continuous and uninterrupted, the separation of the catalyst and the rectification of the product are not needed, the cost is greatly saved, and the method can directly realize that the alkane and the aromatic hydrocarbon in the ranges of gasoline, kerosene and diesel oil are selectively obtained by taking the biomass as the raw material.
5. The method can directly realize that the biomass is used as the raw material to selectively obtain alkane and aromatic hydrocarbon in the range of gasoline, kerosene and diesel, the carbon yield of oxygen-containing small molecular compounds is above 80 percent at most, and the carbon yield of alkane and aromatic hydrocarbon is above 65 percent at most, compared with the traditional method for preparing bio-oil by pyrolyzing the biomass, the method has the advantage that the hydrocarbon yield is improved by 40-60 percent, and the method is a green route for preparing excellent liquid energy substitutes by using the biomass as the raw material.
Drawings
FIG. 1 is a flow chart of an implementation method;
FIG. 2 analysis of results of different biomass sources for producing power fuels;
FIG. 3 analysis of the effect of metal oxide catalyst species on the yield of small molecular oxygen-containing compounds;
FIG. 4 analysis of the effect of bifunctional catalyst species on hydrocarbon yield.
FIG. 5 analysis of influence of pyrolysis temperature on yield of small molecular compounds containing oxygen;
FIG. 6 analysis of influence of catalytic temperature on yield of oxygen-containing small molecule compound
FIG. 7 analysis of the effect of reactor pressure on hydrocarbon yield;
FIG. 8 is a graph showing the effect of the temperature of the C-C coupled hydrogenation reaction on the yield of hydrocarbon compounds;
FIG. 9 analysis of the effect of bifunctional catalyst support species on hydrocarbon compound yield.
Detailed Description
The present invention will be further explained with reference to the following examples and the accompanying drawings, which are only illustrative and not intended to limit the scope of the present invention.
As shown in figure 1, the invention provides a method for preparing C through biomass catalytic pyrolysis and C-C coupling hydrogenation grading6～C18A method of powering a fuel in a fuel cell,the method comprises the following steps:
the biomass is subjected to catalytic pyrolysis in a two-section pyrolysis reactor, and pyrolysis gas is catalyzed by a metal oxide catalyst at the temperature of 300-460 ℃ to generate an oxygen-containing micromolecule compound; carrying out one-step C-C coupling hydrogenation reaction on the oxygen-containing small molecule mixed gas in a fixed bed continuous reactor to generate alkane and aromatic hydrocarbon, wherein the pressure in the reactor is 5-7 MPa, the temperature is 300-375 ℃, the catalyst is a supported metal dual-function catalyst, the hydrogen flow rate is 100-300 mL/min, and the reaction time is 20-60 min; and (3) carrying out fractional condensation on the final product in a reflux condenser, wherein the temperature of the reflux condenser is respectively 10-20 ℃, 10-0 ℃ and-30-10 ℃, and finally separating the final product into gasoline, kerosene and diesel oil.
Wherein the supported metal bifunctional catalyst is prepared by an isometric impregnation method or a coprecipitation method.
The process of the isometric impregnation method is as follows: firstly, adding soluble salt solution of A into a preformed carrier X according to a metering ratio, soaking in a medium volume, standing for 12 hours, then placing into a drying oven, drying for 24 hours at 110 ℃, and then calcining for 4 hours at 550 ℃ to obtain the catalyst meeting the requirements.
The coprecipitation process is as follows: firstly, adding soluble salt solution A into suspension of preformed carrier X according to a metering ratio, magnetically stirring for 3h at 180 ℃, taking out the obtained precipitate by using a centrifugal machine, drying for 24h at 110 ℃ in a drying box, and calcining for 4h at 550 ℃ to prepare the catalyst meeting the requirement.
Preferably, the calcined material is reduced at 450 ℃ using a reducing gas (10% H)2And 90% N2) The reduction was carried out for 6h at a flow rate of 20mL/min to obtain a catalyst which could be used directly.
Example 1
In a two-section pyrolysis reactor, straws are quickly pyrolyzed at 380 ℃, pyrolysis gas is directionally converted into oxygen-containing micromolecule compounds under the action of a cerium dioxide catalyst at 420 ℃, and the pyrolysis reaction time is 30min so as to ensure that all raw materials are pyrolyzed fully.
In a fixed bed continuous reactor, the oxygen-containing small molecular compound generated by biomass pyrolysis is loaded at 20% of copperUnder the action of the red mud catalyst (prepared by an isometric impregnation method), the pressure in a reactor is 6.2MPa, the reaction temperature is 350 ℃, and the hydrogen flow rate is 100mL/min, and a one-step C-C coupling hydrogenation reaction is carried out to obtain C6～C18The reaction time of the power fuel is 20 min.
Wherein, the oxygen-containing small molecule compound is detected by gas chromatography-mass spectrometry, and according to the gas chromatography-mass spectrometry detection result, the carbon yield of the oxygen-containing small molecule is 81.26, and the oxygen-containing small molecule compound specifically comprises substances, as shown in table 1:
TABLE 1 composition of matter of oxygen-containing small molecule compounds
Figure BDA0002457872290000051
Figure BDA0002457872290000061
BDLaIs below the detection limit
C6～C18By power fuel is meant paraffins, naphthenes and aromatics and their isomers having carbon numbers in the range. The detection is also carried out by adopting a gas chromatography-mass spectrometry combined method, and the detection is carried out on the C6～C18The power fuel comprises n-hexane body, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, toluene, o-xylene, m-xylene, p-xylene, hexamethylbenzene, ethylbenzene, n-propylbenzene, isopropylbenzene, diphenylmethane, styrene, phenylacetylene, naphthalene, tetrahydronaphthalene, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, methylcycloheptane, cyclooctane. The overall carbon yield was 65.8%.
In a reflux condenser, C6～C18The power fuel is fractionated and condensed to realize product separation, and the temperature of the shunt condenser is respectively set to 10 ℃, 10 ℃ below zero and 20 ℃ below zero. Detecting the condensed substances by gas chromatography-mass spectrometry (GC-MS), wherein the hydrocarbons with carbon atoms between 5 and 12 are collected at 10 ℃ and are in the range of gasoline carbon atomsThe inside of the enclosure; -hydrocarbons with carbon atoms between 10 and 22, collected at 10 ℃, in the carbon atom range of diesel; hydrocarbons with carbon atoms between 11 and 17, in the kerosene carbon atom range, were collected at-20 ℃.
Example 2
In a two-stage pyrolysis reactor, straws are quickly pyrolyzed at 380 ℃, pyrolysis gas is directionally converted into oxygen-containing small molecular compounds under the action of a cerium dioxide catalyst (prepared by an isometric impregnation method) at 420 ℃, and the pyrolysis reaction time is 30min to ensure that all raw materials are pyrolyzed fully.
In a fixed bed continuous reactor, the content of oxygen-containing small molecular compounds generated by biomass pyrolysis is about, under the action of a 20% copper-loaded red mud catalyst, the pressure in the reactor is 6.2MPa, the reaction temperature is 350 ℃, the hydrogen flow rate is 150mL/min, and a one-step C-C coupling hydrogenation reaction is carried out to obtain C6～C18The reaction time of the power fuel is 40 min.
In a reflux condenser, C6～C18The power fuel is fractionated and condensed to realize product separation, and the temperature of the shunt condenser is respectively set to be 15 ℃, 5 ℃ and 15 ℃.
Wherein, the oxygen-containing small molecule compound is detected by gas chromatography-mass spectrometry, the total carbon content yield is 81.81, and the oxygen-containing small molecule compound comprises substances shown in table 2:
Figure BDA0002457872290000071
TABLE 2 composition of oxygen-containing Small molecule Compounds
BDLaIs below the detection limit
C6～C18By power fuel is meant paraffins, naphthenes and aromatics and their isomers having carbon numbers in the range. The detection is also carried out by adopting a gas chromatography-mass spectrometry combined method, and the detection is carried out on the C6～C18The power fuel comprises n-hexane body, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecanePentadecane, n-hexadecane, toluene, o-xylene, m-xylene, p-xylene, hexamethylbenzene, ethylbenzene, n-propylbenzene, isopropylbenzene, diphenylmethane, styrene, phenylacetylene, naphthalene, tetrahydronaphthalene, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, methylcycloheptane, cyclooctane. The overall carbon yield was 65.3%.
The product separation is carried out according to hydrocarbon substances with different carbon numbers and different condensation points, and the hydrocarbon substances with the carbon numbers in the gasoline range (hydrocarbons with the carbon atoms between 5 and 12), the diesel range (with the carbon atoms between 10 and 22) and the kerosene range (with the carbon atoms between 11 and 17) are formed through fractional condensation.
Example 3
In a two-stage pyrolysis reactor, cypress is rapidly pyrolyzed at 380 ℃, pyrolysis gas is directionally converted into oxygen-containing small molecular compounds under the action of a cerium dioxide catalyst at 420 ℃, and the pyrolysis reaction time is 30min to ensure that all raw materials are pyrolyzed fully.
In a fixed bed continuous reactor, oxygen-containing small molecular compounds generated by biomass pyrolysis are subjected to one-step C-C coupling hydrogenation reaction under the action of a 20% copper-loaded red mud catalyst (prepared by a coprecipitation method) at the pressure of 6.2MPa, the reaction temperature of 350 ℃ and the hydrogen flow rate of 200mL/min to obtain C6～C18The reaction time of the power fuel is 60 min. Wherein the carbon yield of the oxygen-containing small molecular compound is 78.93, and the carbon yield of the power fuel is 62.4.
In a reflux condenser, C6～C18The power fuel is fractionated and condensed to realize product separation, the temperatures of the shunt condenser are respectively set to be 20 ℃, 10 ℃ and 25 ℃ below zero, and hydrocarbons in the ranges of gasoline, diesel oil and kerosene are respectively obtained.
Example 4
In a two-stage pyrolysis reactor, bagasse is subjected to fast pyrolysis at 380 ℃, pyrolysis gas is subjected to directional conversion to oxygen-containing small molecular compounds under the action of a cerium dioxide catalyst at 420 ℃, and the pyrolysis reaction time is 30min to ensure that all raw materials are pyrolyzed fully.
In a fixed bedIn the reactor, under the action of a 20% copper-loaded red mud catalyst (prepared by a coprecipitation method), the pressure in the reactor is 6.2MPa, the reaction temperature is 350 ℃, the hydrogen flow rate is 200mL/min, and a one-step C-C coupling hydrogenation reaction is carried out to obtain C6～C18The reaction time of the power fuel is 30 min. Wherein the carbon yield of the oxygen-containing small molecular compound is 87.96, and the yield of the power fuel, namely the hydrocarbon compound is 67.2.
In a reflux condenser, C6～C18The power fuel is fractionated and condensed to realize product separation, the temperatures of the shunt condenser are respectively set to be 10 ℃, 10 ℃ below zero and 20 ℃ below zero, and hydrocarbons in the ranges of gasoline, diesel oil and kerosene are respectively obtained. By analyzing the results of the products of examples 1-4, the experimental results are shown in fig. 2, and the biomass feedstock with the highest yield of oxygen-containing small molecule compounds and hydrocarbon compounds is found to be bagasse. The yield of the oxygen-containing small molecular compound is 87.96%, and the yield of the hydrocarbon compound is 67.2%. Compared with the traditional one-step method for preparing the bio-oil, the yield of the hydrocarbon compound is obviously improved. On the basis, the influence of the catalyst on the test is analyzed.
Examples 5 to 7
The test methods of examples 5-7 are the same as example 4 except that the metal oxide catalysts are manganese dioxide, zirconium dioxide, titanium dioxide; the temperatures of the split condenser were set to 10 ℃, -10 ℃ and-30 ℃ respectively.
The results of the experiment are shown in FIG. 3.
Examples 8 to 10
The test methods of examples 8-10 are the same as in example 4, except that the bifunctional supported catalysts are a 20% nickel-supported red mud catalyst (prepared by an isometric impregnation method), a 20% iron-supported red mud catalyst (prepared by a coprecipitation method), and a 20% cobalt-supported red mud catalyst (prepared by an isometric impregnation method), respectively. The results of the experiment are shown in FIG. 4.
Examples 11 to 14
Examples 11-14 were conducted in the same manner as in example 1 except that the pyrolysis temperatures were 300 deg.C, 340 deg.C, 420 deg.C and 460 deg.C, respectively. The results of the experiment are shown in FIG. 5.
Examples 15 to 18
Examples 15-18 were conducted in the same manner as in example 1 except that the catalytic temperature was changed from 420 ℃ in example 1 to 300 ℃, 340 ℃, 380 ℃ and 460 ℃, respectively. The results of the experiment are shown in FIG. 6.
Examples 19 to 23
Examples 19 to 23 were conducted in the same manner as in example 1 except that the pressure in the reactor was set to 5.0MPa, 5.4MPa, 5.8MPa, 6.6MPa and 7.0MPa, respectively. The results of the experiment are shown in FIG. 7.
Examples 24 to 26
Examples 24 to 26 were conducted in the same manner as in example 1 except that the temperature in the reactor was set to 300 deg.C, 325 deg.C and 375 deg.C, and the temperature in the bypass condenser was set to 30 deg.C, 10 deg.C and-10 deg.C, respectively. The results of the experiment are shown in FIG. 8.
Examples 27 to 29
Examples 27-29 differ from example 1 in that the dual-function catalysts used in the fixed bed continuous reactor were 20% copper-supported activated carbon catalyst, 20% copper-supported silica catalyst, and 20% copper-supported silica-alumina composite supported catalyst, respectively. The results of the experiment are shown in FIG. 9.

Claims (9)

1. Preparation of C from biomass6～C18A method of powering a fuel, comprising the steps of:
(1) the biomass is catalytically pyrolyzed into oxygen-containing small molecular compounds in a two-section pyrolysis reactor, wherein the pyrolysis temperature is 300-460 ℃, the catalysis temperature is 300-460 ℃, and the catalyst is a metal oxide catalyst;
(2) carrying out C-C coupling hydrogenation reaction on the oxygen-containing micromolecule compound in a fixed bed continuous reactor to obtain C6～C18The power fuel of (1), wherein the pressure in the reactor is 5-7 MPa, the temperature is 300-375 ℃, the catalyst is a supported metal dual-function A/X type catalyst, the hydrogen flow rate is 100-300 mL/min, and the reaction time is 20-60 min;
(3)C6～C18the power fuel is subjected to fractional condensation in a reflux condenser.
2. The method of claim 1, wherein the metal oxide catalyst in step (1) is one or more of ceria, manganese dioxide, zirconia or titania.
3. The method as claimed in claim 1, wherein the supported metal bifunctional A/X catalyst in step (2) is prepared by using activated carbon, silicon oxide and silicon-aluminum composite carrier SiO as carrier X2-Al2O3Or any of red mud; the active component A is one or more of copper, nickel, platinum, cobalt or iron, and the mass fraction of the active component A is 5-50%.
4. The method according to any one of claims 1 to 3, wherein the pyrolysis temperature in the step (1) is 380 ℃ and the catalytic temperature is 420 ℃.
5. The method according to any one of claims 1 to 3, wherein the pressure in the reactor in the step (2) is 6.2MPa, the temperature is 350 ℃, the flow rate of hydrogen is 200mL/min, and the reaction time is 30 min.
6. The method as set forth in any one of claims 1 to 3, wherein the temperatures of said reflux condenser in said step (3) are set to 10 to 20 ℃, to 10 to 0 ℃ and to-30 to-10 ℃, respectively.
7. The method according to claim 3, wherein the supported metal bifunctional A/X type catalyst is a copper-supported red mud catalyst, a copper-supported activated carbon catalyst, a copper-supported silicon oxide catalyst, a copper-supported silicon-aluminum composite carrier SiO2-Al2O3Any one of a catalyst, a nickel-supported red mud catalyst, an iron-supported red mud catalyst, or a cobalt-supported red mud catalyst.
8. The method of claim 3 or 7, wherein the SiO is supported on a silicon-aluminum composite carrier2-Al2O3The silicon-aluminum ratio is 40-60: 1.
9. the method according to claim 8, wherein the mass fraction of the active component A is 20%.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112280579A (en) * 2020-10-21 2021-01-29 戴丹妮 Process method for preparing bio-oil by pyrolyzing straw-office waste paper
CN113262789A (en) * 2021-05-28 2021-08-17 厦门大学 Ni/RM hydrodeoxygenation catalyst and preparation method and application thereof
CN114874794A (en) * 2022-05-05 2022-08-09 阚世坤 Intelligent production system for flame-gathering gas fuel
CN116622399A (en) * 2023-05-23 2023-08-22 河南大学 Method and device for preparing hydrocarbon-rich biological oil by biomass classification and upgrading

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104560091A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Preparation method for light-aromatic-rich bio-oil
CN105647582A (en) * 2014-12-02 2016-06-08 中国科学技术大学 Method for synthesis of aviation kerosene cycloalkane and aromatic hydrocarbon components from bio-oil
CN107022369A (en) * 2017-06-16 2017-08-08 江苏大学 A kind of apparatus and method that biological Aviation Fuel is prepared based on ketone platform chemicals
CN107304367A (en) * 2016-04-21 2017-10-31 中国科学院大连化学物理研究所 A kind of preparation method of branched paraffin in gasoline, aviation kerosine or diesel range

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104560091A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Preparation method for light-aromatic-rich bio-oil
CN105647582A (en) * 2014-12-02 2016-06-08 中国科学技术大学 Method for synthesis of aviation kerosene cycloalkane and aromatic hydrocarbon components from bio-oil
CN107304367A (en) * 2016-04-21 2017-10-31 中国科学院大连化学物理研究所 A kind of preparation method of branched paraffin in gasoline, aviation kerosine or diesel range
CN107022369A (en) * 2017-06-16 2017-08-08 江苏大学 A kind of apparatus and method that biological Aviation Fuel is prepared based on ketone platform chemicals

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王燕: "《赤泥基瓦斯抑爆粉体材料》", 31 August 2017 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112280579A (en) * 2020-10-21 2021-01-29 戴丹妮 Process method for preparing bio-oil by pyrolyzing straw-office waste paper
CN113262789A (en) * 2021-05-28 2021-08-17 厦门大学 Ni/RM hydrodeoxygenation catalyst and preparation method and application thereof
CN114874794A (en) * 2022-05-05 2022-08-09 阚世坤 Intelligent production system for flame-gathering gas fuel
CN116622399A (en) * 2023-05-23 2023-08-22 河南大学 Method and device for preparing hydrocarbon-rich biological oil by biomass classification and upgrading

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