CN106118706A - A kind of method utilizing abandoned biomass to prepare composite biodiesel - Google Patents
A kind of method utilizing abandoned biomass to prepare composite biodiesel Download PDFInfo
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- CN106118706A CN106118706A CN201610638633.4A CN201610638633A CN106118706A CN 106118706 A CN106118706 A CN 106118706A CN 201610638633 A CN201610638633 A CN 201610638633A CN 106118706 A CN106118706 A CN 106118706A
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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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
- 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
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a kind of method utilizing abandoned biomass to prepare composite biodiesel, comprise the following steps: first regulate the water content of abandoned biomass, it is carried out pyrohydrolysis, filter, obtain bio-crude oil and aqueous phase；Then bio-crude oil carries out the organic facies that upgrading refine obtains mix with diesel oil, emulsion adjuvant, pour-point depressant, prepare composite biodiesel；Finally the aqueous phase obtained is carried out anaerobic fermentation technology process or supercritical water gasification processes, reclaimed the most of nutrient substance in aqueous phase and nutrient substance, decreased pollution on the environment.The present invention utilizes abandoned biomass to prepare composite biodiesel, turns waste into wealth, it is achieved that effective utilization of carbon resource, decreases atmospheric pollution.
Description
Technical field:
The present invention relates to biological engineering and energy technology field, be specifically related to one and utilize abandoned biomass preparation compound
The method of type biodiesel.
Background technology:
Bio-oil is a kind of mixture that the various degradation products of cellulose, hemicellulose and lignin are formed.Biological
Matter mainly includes firewood forests, economic forest, Timber stands, agricultural crop straw and the sweetest slag of agriculture and forestry product residual processing thing, wood flour etc..Raw
Material oil is as being uniquely converted into a kind of regenerative resource of liquid fuel, and biomass are huge with its yield, can store up
Deposit and cause the extensive concern in the whole world with the advantage such as Carbon cycle.Reproducible biomass resource is converted into the high-grade liquid of cleaning
Fuel meat petroleum replacing, not only can make us break away from the undue dependence to limited petroleum resources, and can be greatly reduced
Pollutant and the discharge of greenhouse gases, improve environment, protecting ecology.
The key technique of bio-oil is that this technical know-how is set forth in 20 how by abandoned biomass fast pyrogenation
Century 70 end, will quickly heat up to spend 500 by agricultural crop straw after crushed more, promotes it by macromole pyrolysis fission
Formed for little molecule oily from steam, then rapid condensation generates bio-oil.But the aqueous phase after pyrohydrolysis contains abundant seeking containing N
Support material, the eutrophication of water body, and its COD content overproof can be caused, not directly discharge.
Summary of the invention:
It is an object of the invention to provide a kind of method utilizing abandoned biomass to prepare composite biodiesel, the party's legal system
Standby composite diesel good stability, burning consumption is little, and preparation technology is simple, and the aqueous phase after pyrohydrolysis processes, favorably
In environmental conservation.
For achieving the above object, the present invention is by the following technical solutions:
A kind of method utilizing abandoned biomass to prepare composite biodiesel, comprises the following steps:
(1) water content of regulation abandoned biomass is 60-80%, is then transferred in reactor, stirs under 500-1000rpm
Mix 30-60min, then reactor is warming up to 300-500 DEG C, carry out pyrohydrolysis reaction；
(2) after pyrohydrolysis reaction terminates, reactor is cooled to room temperature, first collects the gas in reactor, then open
Reactor, collects remaining mixture in reactor, filters, obtains bio-crude oil and aqueous phase；
(3) bio-crude oil step (2) prepared and the mixing of ruthenium C catalyst, be placed in hermetic container, at 160-180
DEG C, Hydrogen Vapor Pressure is to carry out under 3.5-5.0MPa reacting 2-3h, obtains primary hydrogenated products；
(4) primary hydrogenated products step (3) prepared and the mixing of perrhenic acid sodium, be placed in hermetic container, at 220-260
DEG C, Hydrogen Vapor Pressure is to react under 5.0MPa, obtains degree of depth hydrogenated products, it is mixed with silicon dioxide carried iridium tungsten catalyst
It is placed in hermetic container and carries out condensation reaction, obtain the organic facies containing long chain alkane rich in Hydrocarbon；
(6) respectively by the organic facies containing long chain alkane rich in Hydrocarbon that mass percent is 10-30wt%,
The diesel oil of 55-80wt%, the emulsion adjuvant of 1-5wt%, the pour-point depressant mixing and stirring of 5-10wt%, then heat to 30-
40 DEG C, continue stirring mixing 20-30min, ultrasonic 1-2h under the power of last 800-1000W, then stand 5-10h, obtain on
Layer composite biodiesel, lower floor is the biological oil reservoir rich in pyrolysis lignin；
(7) aqueous phase obtained step (2) uses anaerobic fermentation technology to process further, obtains methane, reclaims in aqueous phase
Organic substance and nutrient substance；Or use supercritical water gasification technology that the aqueous phase obtained is processed further, obtain hydrogen and first
Alkane；
(8) aqueous phase after being processed by anaerobic fermentation or the aqueous phase after supercritical water gasification, for waste gas biomass water content
Regulation, recycle.
Preferred as technique scheme, in step (1), the time of described pyrohydrolysis reaction is 50-180min.
Preferred as technique scheme, in step (2), described gas is carbon dioxide, can be fertile as plant gas
Material.
Preferred as technique scheme, in step (3), described bio-crude oil with the mass ratio of ruthenium C catalyst is
15-20:1。
Preferred as technique scheme, in step (4), described primary hydrogenated products with the mass ratio of perrhenic acid sodium is
10-17:1。
Preferred as technique scheme, in step (4), the consumption of described silicon dioxide carried iridium tungsten catalyst is
The 8-12% of degree of depth hydrogenated products quality.
Preferred as technique scheme, in step (6), described emulsion adjuvant is the mixture of span80, span85,
The two mass ratio is 1.5-2:1.
Preferred as technique scheme, in step (6), described pour-point depressant is isodecyl methacrylate, acetyl second
Acetoacetic ester, the mixture of 2-Propenoic acid, 2-methyl-, isooctyl ester, its volume ratio is 1:(0.5-1): (0.2-0.6).
Preferred as technique scheme, in step (7), the temperature of described anaerobic fermentation technology is 30-50 DEG C, described
The temperature of supercritical water gasification technology is 400-800 DEG C.
Preferred as technique scheme, in step (7), the reactor that described anaerobic fermentation technology uses is up flow type
Sludge reaction bed, packed bed reactor, CGSB, anaerobic combined reactor, internal circulating anaerobic react
In device, external circular anaerobic processes, up-flow anaerobic solids reactor, anaerobic baffled reactor, anaerobic fluidized bed reactor
One or more.
The method have the advantages that
(1) present invention uses pyrohydrolysis technology, anaerobic fermentation technology or supercritical water gasification technology to enter abandoned biomass
Row processes, and no waste discharge in processing procedure decreases atmospheric pollution, beneficially environmental conservation；
(2) bio-crude oil that the present invention obtains after reacting pyrohydrolysis carries out upgrading refine, and conservative control refining process
The kind of middle catalyst and consumption, thus realize effective utilization of carbon resource；
(3) organic facies after bio-crude oil refine is mixed by the present invention with diesel oil, and compounding with emulsion adjuvant and pour-point depressant,
The composite biodiesel good stability prepared, burning consumption is low, low cost.
Detailed description of the invention:
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
Release the present invention, the present invention will not be constituted any restriction.
Embodiment 1
A kind of method utilizing abandoned biomass to prepare composite biodiesel, comprises the following steps:
(1) water content of regulation abandoned biomass is 60%, is then transferred in reactor, stirs 60min under 500rpm,
Then reactor is warming up to 300 DEG C, carries out pyrohydrolysis reaction 180min；
(2) after pyrohydrolysis reaction terminates, reactor is cooled to room temperature, first collects the gas in reactor, then open
Reactor, collects remaining mixture in reactor, filters, obtains bio-crude oil and aqueous phase；
(3) bio-crude oil step (2) prepared and the mixing of ruthenium C catalyst, be placed in hermetic container, at 160 DEG C, and hydrogen
Atmospheric pressure is to carry out under 3.5MPa reacting 3h, obtains primary hydrogenated products, wherein, bio-crude oil and the mass ratio of ruthenium C catalyst
For 15:1；
(4) primary hydrogenated products step (3) prepared and the mixing of perrhenic acid sodium, be placed in hermetic container, at 220 DEG C,
Hydrogen Vapor Pressure is to react under 5.0MPa, obtains degree of depth hydrogenated products, it is mixed with silicon dioxide carried iridium tungsten catalyst and put
In hermetic container, carry out condensation reaction, obtain the organic facies containing long chain alkane rich in Hydrocarbon, wherein, primary hydrogen
The mass ratio changing product and perrhenic acid sodium is 10:1, and the consumption of silicon dioxide carried iridium tungsten catalyst is degree of depth hydrogenated products matter
The 8% of amount；
(6) respectively by the organic facies containing long chain alkane rich in Hydrocarbon that mass percent is 10wt%,
The diesel oil of 80wt%, the emulsion adjuvant of 5wt%, the pour-point depressant mixing and stirring of 5wt%, then heat to 30-40 DEG C, continues
Stirring mixing 20-30min, ultrasonic 2h under the power of last 800W, then stand 5h, obtain upper strata composite biodiesel, under
Layer is the biological oil reservoir rich in pyrolysis lignin, and wherein, emulsion adjuvant is the mixture of span80, span85, the two mass ratio
For 1.5:1, pour-point depressant is the mixture of isodecyl methacrylate, ethyl acetoacetate, 2-Propenoic acid, 2-methyl-, isooctyl ester, its volume
Ratio is 1:0.5:0.2；
(7) aqueous phase obtained step (2) uses anaerobic fermentation technology to process further at 30 DEG C, obtains methane, returns
Receive the Organic substance in aqueous phase and nutrient substance；Or use the supercritical water gasification technology aqueous phase to obtaining further at 800 DEG C
Process, obtain hydrogen and methane；
(8) aqueous phase after being processed by anaerobic fermentation or the aqueous phase after supercritical water gasification, for waste gas biomass water content
Regulation, recycle.
Embodiment 2
A kind of method utilizing abandoned biomass to prepare composite biodiesel, comprises the following steps:
(1) water content of regulation abandoned biomass is 80%, is then transferred in reactor, stirs under 1000rpm
30min, is then warming up to 500 DEG C by reactor, carries out pyrohydrolysis reaction 50min；
(2) after pyrohydrolysis reaction terminates, reactor is cooled to room temperature, first collects the gas in reactor, then open
Reactor, collects remaining mixture in reactor, filters, obtains bio-crude oil and aqueous phase；
(3) bio-crude oil step (2) prepared and the mixing of ruthenium C catalyst, be placed in hermetic container, at 180 DEG C, and hydrogen
Atmospheric pressure is to carry out under 5.0MPa reacting 2h, obtains primary hydrogenated products, wherein, bio-crude oil and the mass ratio of ruthenium C catalyst
For 20:1；
(4) primary hydrogenated products step (3) prepared and the mixing of perrhenic acid sodium, be placed in hermetic container, at 260 DEG C,
Hydrogen Vapor Pressure is to react under 5.0MPa, obtains degree of depth hydrogenated products, it is mixed with silicon dioxide carried iridium tungsten catalyst and put
In hermetic container, carry out condensation reaction, obtain the organic facies containing long chain alkane rich in Hydrocarbon, wherein, primary hydrogen
The mass ratio changing product and perrhenic acid sodium is 17:1, and the consumption of silicon dioxide carried iridium tungsten catalyst is degree of depth hydrogenated products matter
The 12% of amount；
(6) respectively by the organic facies containing long chain alkane rich in Hydrocarbon that mass percent is 30wt%,
The diesel oil of 55wt%, the emulsion adjuvant of 5wt%, the pour-point depressant mixing and stirring of 10wt%, then heat to 30-40 DEG C, continue
Continuous stirring mixing 20-30min, ultrasonic 1h under the power of last 1000W, then stand 10h, obtain upper strata complex biological bavin
Oil, lower floor is the biological oil reservoir rich in pyrolysis lignin, and wherein, emulsion adjuvant is the mixture of span80, span85, the two matter
Amount ratio is 2:1, and pour-point depressant is the mixture of isodecyl methacrylate, ethyl acetoacetate, 2-Propenoic acid, 2-methyl-, isooctyl ester, its body
Long-pending ratio is 1:1:0.6；
(7) aqueous phase obtained step (2) uses anaerobic fermentation technology to process further at 50 DEG C, obtains methane, returns
Receive the Organic substance in aqueous phase and nutrient substance；Or use the supercritical water gasification technology aqueous phase to obtaining further at 400 DEG C
Process, obtain hydrogen and methane；
(8) aqueous phase after being processed by anaerobic fermentation or the aqueous phase after supercritical water gasification, for waste gas biomass water content
Regulation, recycle.
Embodiment 3
A kind of method utilizing abandoned biomass to prepare composite biodiesel, comprises the following steps:
(1) water content of regulation abandoned biomass is 65%, is then transferred in reactor, stirs 55min under 900rpm,
Then reactor is warming up to 350 DEG C, carries out pyrohydrolysis reaction 160min；
(2) after pyrohydrolysis reaction terminates, reactor is cooled to room temperature, first collects the gas in reactor, then open
Reactor, collects remaining mixture in reactor, filters, obtains bio-crude oil and aqueous phase；
(3) bio-crude oil step (2) prepared and the mixing of ruthenium C catalyst, be placed in hermetic container, at 165 DEG C, and hydrogen
Atmospheric pressure is to carry out under 4.5MPa reacting 2.8h, obtains primary hydrogenated products, wherein, bio-crude oil and the quality of ruthenium C catalyst
Ratio is 16:1；
(4) primary hydrogenated products step (3) prepared and the mixing of perrhenic acid sodium, be placed in hermetic container, at 230 DEG C,
Hydrogen Vapor Pressure is to react under 5.0MPa, obtains degree of depth hydrogenated products, it is mixed with silicon dioxide carried iridium tungsten catalyst and put
In hermetic container, carry out condensation reaction, obtain the organic facies containing long chain alkane rich in Hydrocarbon, wherein, primary hydrogen
The mass ratio changing product and perrhenic acid sodium is 12:1, and the consumption of silicon dioxide carried iridium tungsten catalyst is degree of depth hydrogenated products matter
The 9% of amount；
(6) respectively by the organic facies containing long chain alkane rich in Hydrocarbon that mass percent is 15wt%,
The diesel oil of 75wt%, the emulsion adjuvant of 5wt%, the pour-point depressant mixing and stirring of 5wt%, then heat to 30-40 DEG C, continues
Stirring mixing 20-30min, ultrasonic 1.8h under the power of last 850W, then stand 6h, obtain upper strata composite biodiesel,
Lower floor is the biological oil reservoir rich in pyrolysis lignin, and wherein, emulsion adjuvant is the mixture of span80, span85, the two quality
Ratio is 1.6:1, and pour-point depressant is the mixture of isodecyl methacrylate, ethyl acetoacetate, 2-Propenoic acid, 2-methyl-, isooctyl ester, its body
Long-pending ratio is 1:0.6:0.3；
(7) aqueous phase obtained step (2) uses anaerobic fermentation technology to process further at 35 DEG C, obtains methane, returns
Receive the Organic substance in aqueous phase and nutrient substance；Or use the supercritical water gasification technology aqueous phase to obtaining further at 700 DEG C
Process, obtain hydrogen and methane；
(8) aqueous phase after being processed by anaerobic fermentation or the aqueous phase after supercritical water gasification, for waste gas biomass water content
Regulation, recycle.
Embodiment 4
A kind of method utilizing abandoned biomass to prepare composite biodiesel, comprises the following steps:
(1) water content of regulation abandoned biomass is 70%, is then transferred in reactor, stirs 50min under 800rpm,
Then reactor is warming up to 400 DEG C, carries out pyrohydrolysis reaction 120min；
(2) after pyrohydrolysis reaction terminates, reactor is cooled to room temperature, first collects the gas in reactor, then open
Reactor, collects remaining mixture in reactor, filters, obtains bio-crude oil and aqueous phase；
(3) bio-crude oil step (2) prepared and the mixing of ruthenium C catalyst, be placed in hermetic container, at 170 DEG C, and hydrogen
Atmospheric pressure is to carry out under 4MPa reacting 2.6h, obtains primary hydrogenated products, wherein, bio-crude oil and the mass ratio of ruthenium C catalyst
For 17:1；
(4) primary hydrogenated products step (3) prepared and the mixing of perrhenic acid sodium, be placed in hermetic container, at 240 DEG C,
Hydrogen Vapor Pressure is to react under 5.0MPa, obtains degree of depth hydrogenated products, it is mixed with silicon dioxide carried iridium tungsten catalyst and put
In hermetic container, carry out condensation reaction, obtain the organic facies containing long chain alkane rich in Hydrocarbon, wherein, primary hydrogen
The mass ratio changing product and perrhenic acid sodium is 14:1, and the consumption of silicon dioxide carried iridium tungsten catalyst is degree of depth hydrogenated products matter
The 10% of amount；
(6) respectively by the organic facies containing long chain alkane rich in Hydrocarbon that mass percent is 20wt%,
The diesel oil of 68wt%, the emulsion adjuvant of 5wt%, the pour-point depressant mixing and stirring of 7wt%, then heat to 30-40 DEG C, continues
Stirring mixing 20-30min, ultrasonic 1.6h under the power of last 900W, then stand 7h, obtain upper strata composite biodiesel,
Lower floor is the biological oil reservoir rich in pyrolysis lignin, and wherein, emulsion adjuvant is the mixture of span80, span85, the two quality
Ratio is 1.7:1, and pour-point depressant is the mixture of isodecyl methacrylate, ethyl acetoacetate, 2-Propenoic acid, 2-methyl-, isooctyl ester, its body
Long-pending ratio is 1:0.7:0.4；
(7) aqueous phase obtained step (2) uses anaerobic fermentation technology to process further at 40 DEG C, obtains methane, returns
Receive the Organic substance in aqueous phase and nutrient substance；Or use the supercritical water gasification technology aqueous phase to obtaining further at 600 DEG C
Process, obtain hydrogen and methane；
(8) aqueous phase after being processed by anaerobic fermentation or the aqueous phase after supercritical water gasification, for waste gas biomass water content
Regulation, recycle.
Embodiment 5
A kind of method utilizing abandoned biomass to prepare composite biodiesel, comprises the following steps:
(1) water content of regulation abandoned biomass is 75%, is then transferred in reactor, stirs 35min under 800rpm,
Then reactor is warming up to 450 DEG C, carries out pyrohydrolysis reaction 80min；
(2) after pyrohydrolysis reaction terminates, reactor is cooled to room temperature, first collects the gas in reactor, then open
Reactor, collects remaining mixture in reactor, filters, obtains bio-crude oil and aqueous phase；
(3) bio-crude oil step (2) prepared and the mixing of ruthenium C catalyst, be placed in hermetic container, at 175 DEG C, and hydrogen
Atmospheric pressure is to carry out under 3.5MPa reacting 2.6h, obtains primary hydrogenated products, wherein, bio-crude oil and the quality of ruthenium C catalyst
Ratio is 18:1；
(4) primary hydrogenated products step (3) prepared and the mixing of perrhenic acid sodium, be placed in hermetic container, at 250 DEG C,
Hydrogen Vapor Pressure is to react under 5.0MPa, obtains degree of depth hydrogenated products, it is mixed with silicon dioxide carried iridium tungsten catalyst and put
In hermetic container, carry out condensation reaction, obtain the organic facies containing long chain alkane rich in Hydrocarbon, wherein, primary hydrogen
The mass ratio changing product and perrhenic acid sodium is 15:1, and the consumption of silicon dioxide carried iridium tungsten catalyst is degree of depth hydrogenated products matter
The 11% of amount；
(6) respectively by the organic facies containing long chain alkane rich in Hydrocarbon that mass percent is 24wt%,
The diesel oil of 65wt%, the emulsion adjuvant of 1wt%, the pour-point depressant mixing and stirring of 10wt%, then heat to 30-40 DEG C, continue
Continuous stirring mixing 20-30min, ultrasonic 1.2h under the power of last 950W, then stand 9h, obtain upper strata complex biological bavin
Oil, lower floor is the biological oil reservoir rich in pyrolysis lignin, and wherein, emulsion adjuvant is the mixture of span80, span85, the two matter
Amount ratio is 1.8:1, and pour-point depressant is the mixture of isodecyl methacrylate, ethyl acetoacetate, 2-Propenoic acid, 2-methyl-, isooctyl ester, its
Volume ratio is 1:0.9:0.5；
(7) aqueous phase obtained step (2) uses anaerobic fermentation technology to process further at 45 DEG C, obtains methane, returns
Receive the Organic substance in aqueous phase and nutrient substance；Or use the supercritical water gasification technology aqueous phase to obtaining further at 700 DEG C
Process, obtain hydrogen and methane；
(8) aqueous phase after being processed by anaerobic fermentation or the aqueous phase after supercritical water gasification, for waste gas biomass water content
Regulation, recycle.
Claims (10)
1. one kind utilizes the method that abandoned biomass prepares composite biodiesel, it is characterised in that comprise the following steps:
(1) water content of regulation abandoned biomass is 60-80%, is then transferred in reactor, stirs under 500-1000rpm
30-60min, is then warming up to 300-500 DEG C by reactor, carries out pyrohydrolysis reaction；
(2) after pyrohydrolysis reaction terminates, reactor is cooled to room temperature, first collects the gas in reactor, then open reaction
Still, collects remaining mixture in reactor, filters, obtains bio-crude oil and aqueous phase；
(3) bio-crude oil step (2) prepared and the mixing of ruthenium C catalyst, be placed in hermetic container, at 160-180 DEG C, and hydrogen
Atmospheric pressure is to carry out under 3.5-5.0MPa reacting 2-3h, obtains primary hydrogenated products；
(4) primary hydrogenated products step (3) prepared and the mixing of perrhenic acid sodium, be placed in hermetic container, at 220-260 DEG C,
Hydrogen Vapor Pressure is to react under 5.0MPa, obtains degree of depth hydrogenated products, it is mixed with silicon dioxide carried iridium tungsten catalyst and put
In hermetic container, carry out condensation reaction, obtain the organic facies containing long chain alkane rich in Hydrocarbon；
(6) it is the organic facies containing long chain alkane rich in Hydrocarbon of 10-30wt%, 55-by mass percent respectively
The diesel oil of 80wt%, the emulsion adjuvant of 1-5wt%, the pour-point depressant mixing and stirring of 5-10wt%, then heat to 30-40
DEG C, continue stirring mixing 20-30min, finally ultrasonic 1-2h under the power of 800-1000W, then stands 5-10h, obtain on
Layer composite biodiesel, lower floor is the biological oil reservoir rich in pyrolysis lignin；
(7) aqueous phase obtained step (2) uses anaerobic fermentation technology to process further, obtains methane, reclaims having in aqueous phase
Machine thing and nutrient substance；Or use supercritical water gasification technology that the aqueous phase obtained is processed further, obtain hydrogen and methane；
(8) aqueous phase after being processed by anaerobic fermentation or the aqueous phase after supercritical water gasification, for the tune of waste gas biomass water content
Joint, recycles.
A kind of method utilizing abandoned biomass to prepare composite biodiesel, it is characterised in that:
In step (1), the time of described pyrohydrolysis reaction is 50-180min.
A kind of method utilizing abandoned biomass to prepare composite biodiesel, it is characterised in that:
In step (2), described gas is carbon dioxide, can be as plant gaseous fertilizer.
A kind of method utilizing abandoned biomass to prepare composite biodiesel, it is characterised in that:
In step (3), described bio-crude oil is 15-20:1 with the mass ratio of ruthenium C catalyst.
A kind of method utilizing abandoned biomass to prepare composite biodiesel, it is characterised in that:
In step (4), described primary hydrogenated products is 10-17:1 with the mass ratio of perrhenic acid sodium.
A kind of method utilizing abandoned biomass to prepare composite biodiesel, it is characterised in that:
In step (4), the 8-12% that consumption is degree of depth hydrogenated products quality of described silicon dioxide carried iridium tungsten catalyst.
A kind of method utilizing abandoned biomass to prepare composite biodiesel, it is characterised in that:
In step (6), described emulsion adjuvant is the mixture of span80, span85, and the two mass ratio is 1.5-2:1.
A kind of method utilizing abandoned biomass to prepare composite biodiesel, it is characterised in that:
In step (6), described pour-point depressant is the mixture of isodecyl methacrylate, ethyl acetoacetate, 2-Propenoic acid, 2-methyl-, isooctyl ester,
Its volume ratio is 1:(0.5-1): (0.2-0.6).
A kind of method utilizing abandoned biomass to prepare composite biodiesel, it is characterised in that:
In step (7), the temperature of described anaerobic fermentation technology is 30-50 DEG C, and the temperature of described supercritical water gasification technology is 400-800
℃。
A kind of method utilizing abandoned biomass to prepare composite biodiesel, its feature exists
In: in step (7), the reactor that described anaerobic fermentation technology uses is up flow type sludge reaction bed, packed bed reactor, expansion
Granular sludge bed reactor, anaerobic combined reactor, internal-circulation anaerobic reactor, external circular anaerobic processes, up-flow are detested
One or more in oxygen solid reactor, anaerobic baffled reactor, anaerobic fluidized bed reactor.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108905962A (en) * | 2018-06-26 | 2018-11-30 | 江苏新亿源环保科技有限公司 | A kind of preparation method of biomass carbon adsorbent material |
| CN110551767A (en) * | 2019-09-20 | 2019-12-10 | 农业农村部规划设计研究院 | Method for co-producing biological crude oil and methane by using waste biomass |
| CN112877084A (en) * | 2021-01-20 | 2021-06-01 | 西北大学 | Method for preparing oil-electricity-gas-heat from self-circulation oil-electricity balance domestic garbage |
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| CN103421543A (en) * | 2012-05-16 | 2013-12-04 | 中国科学院化学研究所 | Catalytic refining method of biomass pyrolysis oil |
| CN104357101A (en) * | 2014-11-06 | 2015-02-18 | 金景达(北京)环保动力科技有限公司 | High-efficiency stable composite biodiesel fuel |
| CN105219453A (en) * | 2015-10-20 | 2016-01-06 | 上海应用技术学院 | A kind of biofuel used for buses and preparation method thereof |
| CN105733641A (en) * | 2016-05-06 | 2016-07-06 | 中国农业大学 | Harmless treatment method of waste biomass |
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| CN103421543A (en) * | 2012-05-16 | 2013-12-04 | 中国科学院化学研究所 | Catalytic refining method of biomass pyrolysis oil |
| CN104357101A (en) * | 2014-11-06 | 2015-02-18 | 金景达(北京)环保动力科技有限公司 | High-efficiency stable composite biodiesel fuel |
| CN105219453A (en) * | 2015-10-20 | 2016-01-06 | 上海应用技术学院 | A kind of biofuel used for buses and preparation method thereof |
| CN105733641A (en) * | 2016-05-06 | 2016-07-06 | 中国农业大学 | Harmless treatment method of waste biomass |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108905962A (en) * | 2018-06-26 | 2018-11-30 | 江苏新亿源环保科技有限公司 | A kind of preparation method of biomass carbon adsorbent material |
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| CN112877084A (en) * | 2021-01-20 | 2021-06-01 | 西北大学 | Method for preparing oil-electricity-gas-heat from self-circulation oil-electricity balance domestic garbage |
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