CN108165290A - The method of producing fuel oil by biomass hydrothermal liquefaction - Google Patents
The method of producing fuel oil by biomass hydrothermal liquefaction Download PDFInfo
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- CN108165290A CN108165290A CN201611116383.4A CN201611116383A CN108165290A CN 108165290 A CN108165290 A CN 108165290A CN 201611116383 A CN201611116383 A CN 201611116383A CN 108165290 A CN108165290 A CN 108165290A
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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
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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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
-
- 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
-
- 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
- C10G2300/70—Catalyst aspects
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- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of methods of biomass liquefying made fuel oil.It is characterized in that biomass material and aqueous solvent (or plus aqueous catalyst solution) are sufficiently mixed into slurries.Catalyst is 1: 10 to 1: 50 with material quality ratio, raw material and water quality ratio ranging from 1: 2 to 1: 8, are reacted under reducing atmosphere in paste state bed reactor, and liquefaction reaction temperature is controlled at 300 450 DEG C, 5 30MPa of reaction pressure, reaction time are 5 40min.Separation is carried out to product after reaction and can obtain fuel oil, solid residue, water and gas etc..Biomass conversion of the present invention is complete, oil product yield is high, and gained oil product calorific value is suitable with standard oil, can alleviate the dependence to fossil energy, and conducive to environmental protection, production cost is low, has good society and economic benefit.
Description
Technical field
Method more particularly to a kind of biology under reducing atmosphere the present invention relates to a kind of biomass liquefying made fuel oil
The method that matter hydrothermal liquefaction produces fuel oil, belongs to energy conversion field.
Background technology
Biomass is reproducible resource, while is also the green energy resource that can realize carbon dioxide " zero-emission ".In recent years,
Particularly developed countries become increasingly active to the research of biomass utilization technologies in the world.China is large agricultural country, is had abundant
Biomass resource, but at present based on traditional burning, the thermal efficiency is low, it is most of not to be reasonably utilized.Exploitation biology
Matter liquefaction technology can not only make up the deficiency of China's fossil energy, but also be conducive to environmental protection.Current biomass liquefying skill
Based on rapidly pyrolysing and liquefying, which is simple and convenient to operate for the research of art, but the higher (＞ 500 of the process required temperature
DEG C), cause energy consumption larger, and generally gained oil product oxygen content higher (＞ 20%), calorific value are relatively low (＜ 25MJ/kg), it is impossible to straight
It connects and is used instead of oil.
Biomass high-pressure liquefaction be using liquid flux as medium, biomass relatively low temperature (200-500 DEG C), compared with
Reaction generates a large amount of fluid products and the process of a small amount of gas and solid residue under high pressure (＞ 5MPa).With pyrolysis liquefaction phase
Than, high-pressure liquefaction process condition is relatively mild, and gained oil product oxygen content relatively low (＜ 18%), calorific value are higher (＞ 30MJ/kg), after
Continuous processing procedure is relatively easy.It is concerned due to the process is in the superiority in terms of liquiefied product quality in recent years.Solvent
Selection is most important for high-pressure liquefaction process, and the solvent that people have studied at present includes water, hydro carbons (such as hexamethylene), rudimentary
Alcohols (such as methanol, ethyl alcohol, isopropanol, butanol), polyalcohols (such as ethylene glycol, glycerine), phenols (such as phenol), organic acid
(such as acetic acid, lactic acid), organic base (such as ethanol amine), ethers (such as Propylene Glycol ether), ketone (such as acetone, cyclohexanone).With
Organic solvent is compared, and water has good development prospect as a kind of green solvent, and the most water content of biomass is high, using water as
Solvent can remove drying process from, reduce energy consumption.Research shows that water can remove part in biomass by converting reforming reaction
Oxygen so as to improve oil product calorific value, has the potentiality of commercial Application.
Have some patented technologies about biomass by hydro-thermal liquefaction process at present both at home and abroad, such as the HTU skills of Shell Co. Ltd
Art (United States Patent (USP)：4,670,613), Japanese lignocellulosic liquefaction technology (United States Patent (USP)：4,935,567) and China is learned
Biomass catalyzing and liquefying technology (the Chinese patent of person's application：200510109176.1) etc..Pass through optimization in above-mentioned existing patent
The measures such as process conditions, addition basic catalyst have obtained liquefaction oil product more preferable than fast pyrogenation quality, but still remain
Not exclusively (＜ 95%), liquefaction oily yield not high (＜ 35%), oxygen content higher (12-18%), calorific value are relatively low for biomass conversion
, still there is certain gap in the problems such as (30-35MJ/kg) compared with standard oil calorific value (41.8MJ/kg), and it is still necessary to further upgrading processing
Oil substitute could be used as to be used.In short, hydrothermal liquefaction technology in biomass conversion aspect there are unique advantage, but mesh
Preceding technical merit still has certain defect, needs further to optimize the technology, can promote the process of commercial Application.
Invention content
The defects of it is an object of the invention to overcome the above method, and its advantage is combined, a kind of biomass is provided and has been converted
Entirely, the technology that oil product yield is high, calorific value is high.
It is idea of the invention is that such：The quality of oil quality and the height of yield and life during biomass liquefying
The selection of the feature, the property of solvent, process conditions and catalyst of substance in itself has relationship.
Organic matter is mainly made of cellulose, hemicellulose and lignin in biomass, and wherein the above two polymerize for carbohydrate
Object easily decomposes；The latter is aromatic structure, it is more difficult to point conversion.Comparatively, agricultural crop straw contains less than forestry timber
Lignin is easy to convert under similarity condition, and obtained oil product contains more aliphatic compound.Simultaneously in agricultural crop straw ash content
Contain more alkali metal, the particularly necessary potassium element of crops growth.The experimental results show that alkali metal turns biomass
Change process has good catalytic action.Therefore biomass material tends to select but is not limited to stalk biology in the present invention
Matter.
Water has various advantages as a kind of green solvent applied to biomass high-pressure liquefaction process.First, in life
During preprocessing substance, drying process can be removed from by solvent of water.General fresh biomass moisture content is 20-60%, even if
The still moisture containing 5-20% after exposure in sunshine.Fast pyrogenation and using organic compound as the high-pressure liquefaction process of solvent
In, dry or advance dehydration is needed, industrially usually to consume the energy of 20-30%；Without dry during hydrothermal liquefaction
Dry and dehydration (only need to suitably add water), this part energy consumption can be saved, so as to reduce production cost.Secondly, in biomass
In liquefaction process, water not only participated in reaction as solvent but also as reactant.Relative to the water under usual state, high-temperature high pressure water is special
It is not under near critical and overcritical (critical point of water is 374 DEG C, 22.1MPa) state, density (slightly becomes smaller, but far above gas
Body), dielectric constant (substantially reduce), ionic product (first become larger, then become smaller), viscosity (becoming smaller), the properties such as diffusion coefficient (becoming larger)
It will change, the solvability of water will be similar with organic solvent at this time, can be completely dissolved most of organic matter and nearly all
Gas, so as to break through resistance to mass tranfer, the reaction for gas and organic matter provides good location, and effectively prevent heterogeneous catalysis
The coking on surface and carbon deposit；For the inorganic matter that normality water can dissolve, particularly oxide and salt, near critical and supercritical water
It declines to a great extent to its solvability, so as to effectively prevent the loss of catalyst metal ion.Water is directly joined as reactant
Hydrolysis and reforming reaction with biomass and secondary organic matter effectively improve biomass cracking rate, improve products obtained therefrom quality.
Again, using organic matter as the high-pressure liquefaction of solvent during, oil product and solvent are a phase, and the processes such as rectifying and extraction will expend phase
As big energy (30-50% that gross energy would generally be accounted for)；And during using water as solvent, water after cooling and part oil product are (particularly
Hydrocarbon compound) layering, convenient for separation, the burden subsequently handled water phase can be mitigated, so as to save separation costs；Finally, from
Application of engineering project says, high pressure (pressure is consistently higher than the saturated vapor pressure of water under relevant temperature) water is not without evaporation process, therefore not
Evaporation latent heat (evaporation latent heat of water is typically larger than the sensible heat that heats up) can be consumed, this part energy consumption can be saved.It is reacted using leaving
The high-temperature water of device is heated into the cold water before reactor, and group can be optimized to hydrothermal liquefaction process in a manner that energy integrates
It closes, cooling water and additional heat can be saved.
Reducing atmosphere seldom was used for the liquefied research of biomass by hydro-thermal in the past, causes oxygen atom in biomass cannot
Effectively removing.It is considered that the addition of the reducibility gas such as hydrogen can accelerate the subtractive process of biomass cracking and oxygen atom, from
And improve biomass conversion ratio and oil product calorific value.Under specified conditions of the water for solvent, carbon monoxide can react generation with water and live
Hydrogen atom (research shows that this reactive hydrogen atom activity is higher than hydrogen) is sprinkled, therefore using carbon monoxide as reducing atmosphere, in biology
Unique effect will be played during matter hydrothermal liquefaction.And be expected to replace using synthesis gas in commercial Application expensive pure hydrogen or
Pure carbon monoxide gas, so as to cost-effective.
The selection of catalyst is particularly important to biomass by hydro-thermal liquefaction process, and previous researcher mostly studies alkali and its metal
The catalytic process of salt (hydroxide or carbonate of such as sodium, potassium), other catalyst are seldom related to.We by transition metal (such as
Iron, cobalt, nickel, platinum, palladium etc.) and its oxide, salt for biomass by hydro-thermal liquefaction process, can also go well as catalyst
Effect.Slag, sulfur-bearing dirty coal cheap simultaneously etc. can also play catalytic action.
The present invention is achieved by the following technical solutions：
A kind of method of producing fuel oil by biomass hydrothermal liquefaction, which is characterized in that the method is：
1) biomass material is crushed and screened to grain size and is less than 80 mesh；
2) biomass material of step 1) and aqueous solvent are sufficiently mixed into the uniform slurries of ingredient, biomass material and water quality
Than being 1: 2 to 1: 8；
3) mixed solution of step 2) is reacted under reducing atmosphere in paste state bed reactor, the control of liquefaction reaction temperature
At 300-450 DEG C, reaction pressure 3-30MPa, the reaction time (is the residence time for flow reactor, batch reactor is dimension
Hold the time of predetermined reaction condition) it is 5-40min；Isolated fuel oil is carried out to product after reaction.
Wherein, the biomass material is wooden or straw biomass；
The reducing atmosphere is hydrogen or carbon monoxide；
The paste state bed reactor is anti-for stirred autoclave, micro-vibration reaction unit or continuous, semicontinuous tubular type or pot type
Answer one kind in device；
Scheme is advanced optimized the present invention also provides above-mentioned technical proposal：
The step 2) of above-mentioned technical proposal is：The biomass material of step 1) and aqueous solvent and catalyst are sufficiently mixed into ingredient
Uniform slurries, biomass material are 1: 2 to 1: 8 with water quality ratio, and catalyst is 1: 10 to 1 with biomass material mass ratio:
50；
Above-mentioned catalyst is one kind in homogeneous catalyst, heterogeneous catalysis or iron ore, and homogeneous catalyst is configured to water-soluble
Liquid, heterogeneous catalysis, iron ore powder are broken to grain size less than 160 mesh；
Above-mentioned homogeneous catalyst can be one kind in alkali, alkali metal, alkali salt, and heterogeneous catalysis is dipping or coprecipitated
Transition-metals and their oxides prepared by shallow lake method, iron ore are more than 1% iron ore for sulfur content.
It is above-mentioned to can obtain gas phase, liquid phase and solid product after reaction.Gas is collected, and isolates hydrogen, an oxygen
Change the also Primordial Qi such as carbon to recycle, carbon dioxide, methane and low molecular hydrocarbon etc. can be disposed properly；Solid phase can utilize the side such as extracting
Formula collects remaining oil product, and remaining ash content can be used as catalyst, fertilizer or construction material etc. to be used；Liquid phase be divided into organic phase and
Water phase, oil product can utilize the modes such as extraction, rectifying detach in water phase, and remaining water can be recycled.
Advantageous effect
This method is compared with other methods, biomass high conversion rate, is close to 100%, biological oily yield is up to 40-60%, oxygen
Content can be down to 5-12%, and calorific value with standard oil calorific value (41.8MJ/kg) quite, has commercial Application up to 35-45MJ/kg
Potentiality.
Specific embodiment
Below by embodiment, the present invention is further elaborated, the purpose is to be conducive to be best understood from the content of present invention and simultaneously
Unrestricted protection scope of the present invention.
Embodiment one：By 2.0g cornstalk powders, 10.0mL water adds in miniature the shaking that volume is 30ml (20 × 100mm of Φ)
Dynamic reactor displaces with hydrogen the air in reactor, and maintains hydrogen first pressing as 4.0MPa after sealing, by sand-bath in 5min
400 DEG C (system pressure rises to about 25.0MPa at this time) are heated to, 35min is kept in this state, rapidly withdraws heating source,
And with ice-water bath by microreactor Quench to room temperature.Product is isolated to fuel oil, and organic matter total conversion is 96.3%,
Fuel oil yield is 41.2%, and oxygen content is down to 11.4%, calorific value 36.5MJ/kg.
Embodiment two：By 2.0g wheat-straw powder, 8.0mL water adds in miniature the shaking that volume is 30ml (20 × 100mm of Φ)
Dynamic reactor displaces with carbon monoxide the air in reactor, and maintains first pressing as 4.0MPa after sealing, by sand-bath in 5min
390 DEG C (system pressure rises to about 23.0MPa at this time) are heated to, 30min is kept in this state, rapidly withdraws heating source,
And with ice-water bath by microreactor Quench to room temperature.Product is isolated to fuel oil, and organic matter total conversion is 97.9%,
Fuel oil yield is 42.7%, and oxygen content is down to 10.6%, calorific value 37.2MJ/kg.
Embodiment three：By 3.0g wheat-straw powder, 14.0mL water adds in miniature the shaking that volume is 30ml (20 × 100mm of Φ)
Dynamic reactor displaces with carbon monoxide the air in reactor, and maintains first pressing as 4.0MPa after sealing, by sand-bath in 5min
420 DEG C (system pressure rises to about 24.0MPa at this time) are heated to, 25min is kept in this state, rapidly withdraws heating source,
And with ice-water bath by microreactor Quench to room temperature.Product is isolated to fuel oil, and organic matter total conversion is 98.5%,
Fuel oil yield is 40.3%, and oxygen content is down to 11.8%, calorific value 35.9MJ/kg.
Example IV：By 20.0g saw dusts, it is 500ml's that aqueous solutions of the 100.0mL containing 2% sodium hydroxide, which adds in volume,
The air in reactor is displaced with carbon monoxide in high-pressure stirring reaction kettle, after sealing, and maintains hydrogen first pressing as 3.0MPa,
378 DEG C (system pressure rises to about 27.0MPa at this time) are warming up to, keep 30min in this state, it will by cooling coil in kettle
Material is down to room temperature.Product is isolated to fuel oil, and organic matter total conversion is 99.7%, fuel oil yield 44.4%,
Oxygen content is down to 9.3%, calorific value 39.8MJ/kg.
Embodiment five：By 2.0g transformation catalysts (commercially available product, purchased from Jiangsu Qingjian River catalyst head factory), 20.0g cornstalks
Powder, 100.0mL water are added in the high-pressure stirring reaction kettle that volume is 500ml, and reactor is displaced with carbon monoxide after sealing
Interior air, and first pressing is maintained to be warming up to 375 DEG C (system pressure rises to about 27.0MPa at this time), in this state for 3.0MPa
20min is kept, material is down to by room temperature by cooling coil in kettle.Product is isolated to fuel oil, organic matter total conversion
It is 99.9%, fuel oil yield 52.6%, oxygen content is down to 8.5%, calorific value 41.5MJ/kg.
Embodiment six：Nickel, molybdenum catalyst (the main item that 2.0g is prepared using ammonium hydroxide and nitrate by coprecipitation method
Part is that Ni: Mo atomic ratio is 1: 1, the ammonium hydroxide amount of skipping over, 500 DEG C of roasting 4h) transformation catalyst, 18.0g wheat-straw powder,
100.0mL water is added in the high-pressure stirring reaction kettle that volume is 500ml, and the air in reactor is changed with hydrogen after sealing, and
Maintenance first pressing is 5.0MPa, is warming up to 375 DEG C (system pressure rises to about 27.0MPa at this time), keeps 20min in this state,
Material is down to by room temperature by cooling coil in kettle.Product is isolated to fuel oil, and organic matter substantially completely converts, fuel oil
Yield is 56.1%, and oxygen content is down to 5.9%, calorific value 43.8MJ/kg.
Embodiment seven：By 2.0g Hubei troilite, 20.0g cornstalk powders, it is 500ml's that 100.0mL water, which adds in volume,
The air in reactor is changed with hydrogen in high-pressure stirring reaction kettle, after sealing, and first pressing is maintained to be warming up to 381 for 5.0MPa
DEG C (system pressure rises to about 27.0MPa at this time), keeps 30min, is down to material by cooling coil in kettle in this state
Room temperature.Product is isolated to fuel oil, and organic matter total conversion is 99.9%, fuel oil yield 49.8%, oxygen content drop
To 6.2%, calorific value 42.5MJ/kg.
Embodiment eight：By 20.0g saw dusts, it is 500ml that aqueous solutions of the 100.0mL containing 1.5% ferrous sulfate, which adds in volume,
High-pressure stirring reaction kettle in, the air in reactor is displaced with carbon monoxide after sealing, and maintain the hydrogen first pressing to be
4.0MPa is warming up to 380 DEG C (system pressure rises to about 27.0MPa at this time), keeps 30min in this state, by cold in kettle
But material is down to room temperature by coil pipe.Product is isolated to fuel oil, and organic matter total conversion is 99.2%, and fuel oil yield is
46.3%, oxygen content is down to 7.4%, calorific value 40.3MJ/kg.
Embodiment nine：By 5.0g Huainan lignite, 20.0g Cotton Stalk powder, it is 500ml that 110.0mL aqueous solutions, which add in volume,
High-pressure stirring reaction kettle in, the air in reactor is displaced with carbon monoxide after sealing, and maintain the hydrogen first pressing to be
4.0MPa is warming up to 360 DEG C (system pressure rises to about 26.0MPa at this time), keeps 30min in this state, by cold in kettle
But material is down to room temperature by coil pipe.Product is isolated to fuel oil (not deducting coal liquefaction products obtained therefrom in calculating process), has
Machine matter total conversion is 98.3%, and fuel oil yield 57.8%, oxygen content is down to 7.7%, calorific value 39.5MJ/kg.
Embodiment ten：By 0.5gPt/Al2O3Catalyst (commercially available product, purchased from Shanghai Chemical Research Inst), 5.0g Cotton Stalk powder
End is uniformly mixed and is fitted into the semicontinuous reaction tube that volume is 20mL, with high-pressure hydraulic pump and gas booster pump in proportion by water and
CO gas is passed through preheater, subsequently enters reactor.It is 25.0MPa by back pressure valve control system pressure, utilizes electricity
It is 400 DEG C (system pressure rises to about 26.0MPa at this time) that stove, which maintains reactor temperature, keeps 30min in this state, passes through
Material is cooled to room temperature by reactor aftercooler.Product is isolated to fuel oil, organic matter total conversion close to 100%,
Fuel oil yield is 59.2%, and oxygen content is down to 5.5%, calorific value 44.6MJ/kg.
Claims (5)
- A kind of 1. method of producing fuel oil by biomass hydrothermal liquefaction, which is characterized in that the method includes the following steps：1) biomass material is crushed and screened to grain size and is less than 80 mesh；2) biomass material of step 1) and aqueous solvent are sufficiently mixed into the uniform slurries of ingredient, biomass material and water quality Than being 1：2 to 1：8；3) mixed solution of step 2) is reacted under reducing atmosphere in paste state bed reactor, the control of liquefaction reaction temperature At 300-450 DEG C, reaction pressure 3-30MPa, reaction time 5-40min；Isolated combustion is carried out to product after reaction Material oil；Wherein, the biomass material is wooden or straw biomass；The reducing atmosphere is hydrogen or carbon monoxide；The reaction time is the residence time for flow reactor, for batch reactor to maintain predetermined reaction condition Time.
- 2. the method for producing fuel oil by biomass hydrothermal liquefaction as described in claim 1, which is characterized in that the slurry bed system Reactor is one kind in stirred autoclave, micro-vibration reaction unit, continuous, semicontinuous tubular type or tank reactor.
- A kind of 3. method of producing fuel oil by biomass hydrothermal liquefaction, which is characterized in that the method includes the following steps：1) biomass material is crushed and screened to grain size and is less than 80 mesh；2) biomass material of step 1) and water and catalyst are sufficiently mixed into the uniform slurries of ingredient, biomass material and water Mass ratio be 1：2 to 1：8, the mass ratio of catalyst and biomass material is 1：10 to 1：50；3) mixed solution of step 2) is reacted under reducing atmosphere in paste state bed reactor, the control of liquefaction reaction temperature At 300-450 DEG C, reaction pressure 3-30MPa, reaction time 5-40min；Isolated combustion is carried out to product after reaction Material oil；Wherein, the biomass material is wooden or straw biomass；The reducing atmosphere is hydrogen or carbon monoxide；The reaction time is the residence time for flow reactor, for batch reactor to maintain predetermined reaction condition Time；The paste state bed reactor is selected from stirred autoclave, micro-vibration reaction unit, continuous, semicontinuous tubular type or pot type One kind in reactor.
- 4. the method for producing fuel oil by biomass hydrothermal liquefaction as claimed in claim 3, which is characterized in that the catalyst is One kind in homogeneous catalyst, heterogeneous catalysis or iron ore, homogeneous catalyst are configured to aqueous solution, heterogeneous catalysis, Iron ore powder is broken to grain size less than 160 mesh.
- 5. the method for producing fuel oil by biomass hydrothermal liquefaction as claimed in claim 4, which is characterized in that described homogeneously urges Agent is one kind in alkali, alkali metal, alkali salt, and heterogeneous catalysis is mistake prepared by dipping or coprecipitation method One kind in the oxide of metal or transition metal is crossed, iron ore is one kind in iron ore of the sulfur content more than 1%.
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| CN109536197A (en) * | 2018-11-30 | 2019-03-29 | 北京三聚环保新材料股份有限公司 | A kind of biomass liquefying process |
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| WO2019205682A1 (en) * | 2018-04-28 | 2019-10-31 | 北京三聚环保新材料股份有限公司 | Conversion process for organic matter |
| CN110408420A (en) * | 2018-04-28 | 2019-11-05 | 北京三聚环保新材料股份有限公司 | A kind of organic matter transformation technique |
| US11492563B2 (en) | 2018-04-28 | 2022-11-08 | Beijing Sanju Environmental Protection & New Materials Co., Ltd | Conversion process for an inferior oil |
| US11198820B2 (en) | 2018-04-28 | 2021-12-14 | Beijing Sanju Environmental Protection & New Materials Co., Ltd | Conversion process for an organic material |
| CN110408420B (en) * | 2018-04-28 | 2021-07-30 | 北京三聚环保新材料股份有限公司 | Organic matter conversion process |
| CN109536195A (en) * | 2018-11-30 | 2019-03-29 | 北京三聚环保新材料股份有限公司 | A kind of conversion process of biomass and coal |
| CN109536193A (en) * | 2018-11-30 | 2019-03-29 | 北京三聚环保新材料股份有限公司 | A kind of biomass two-stage conversion process for refining |
| CN109536197A (en) * | 2018-11-30 | 2019-03-29 | 北京三聚环保新材料股份有限公司 | A kind of biomass liquefying process |
| CN109536195B (en) * | 2018-11-30 | 2020-12-08 | 北京三聚环保新材料股份有限公司 | Biomass and coal conversion process |
| CN110747001B (en) * | 2018-12-04 | 2021-11-09 | 北京三聚环保新材料股份有限公司 | Secondary biomass conversion process |
| CN110747001A (en) * | 2018-12-04 | 2020-02-04 | 北京三聚环保新材料股份有限公司 | Secondary biomass conversion process |
| CN111253966A (en) * | 2020-03-19 | 2020-06-09 | 浙江昌丽家居有限公司 | Environment-friendly wood leftover material recycling and harmless treatment method |
| CN114907890A (en) * | 2021-02-07 | 2022-08-16 | 中国石油天然气股份有限公司 | Method for preparing bio-oil and bio-oil obtained by method |
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