CN105441107B - With ionic liquid and supercritical CO2For the biomass electrochemistry liquifying method and device of medium - Google Patents

With ionic liquid and supercritical CO2For the biomass electrochemistry liquifying method and device of medium Download PDF

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CN105441107B
CN105441107B CN201610001904.5A CN201610001904A CN105441107B CN 105441107 B CN105441107 B CN 105441107B CN 201610001904 A CN201610001904 A CN 201610001904A CN 105441107 B CN105441107 B CN 105441107B
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ionic liquid
electrode
biomass
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medium
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CN105441107A (en
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瞿广飞
赵茜
李军燕
宁平
谷俊杰
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Kunming University of Science and Technology
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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
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • 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)
  • Processing Of Solid Wastes (AREA)

Abstract

The present invention relates to one kind with ionic liquid and supercritical CO2For the biomass electrochemistry liquifying method and device of medium, the inventive method is with supercritical CO2For medium, biomass is handled in the presence of catalyst, ionic liquid, water, by electrolysis water hydrogen supply, promotes the biological oily product of biomass cracking generation；Biomass is heated evenly in method, lignocellulosic chemical bond rupture, generates ion pair intermediate, and by electrical field stimulation, accelerates heating rate, and efficiency high, process is easily controllable, improves the utilization rate of biomass；Offer free hydrogen is constantly provided by water, free radical chain reactionses are blocked in time, liquid fuel yield is effectively increased and improves its quality；Supercritical CO2Preferably it is dissolved in ionic liquid, hence it is evident that reduce the viscosity of ionic liquid, improves its electrical conductivity, effectively facilitate biomass cracking.

Description

With ionic liquid and supercritical CO2Biomass electrochemistry liquifying method for medium and Device
Technical field
The present invention relates to biomass regeneration and its technical field of energy, specifically a kind of electrolysis water hydrogen supply and with Ionic liquid-supercritical CO2The method and its device of bio oil are prepared for the biomass electrochemistry liquefaction of medium.
Background technology
Current oil resource increasingly heaviness in poor quality, heavy inferior oil mainly passes through coking, catalytic cracking or hydrogenation Cracking is oily to produce light fraction, and processing cost is higher caused by material quality difference.Biomass is widely distributed, yield is huge, sulphur Nitrogen content is low, cleanliness without any pollution, and is unique renewable resource that can be used for preparing vapour, diesel oil containing carbon, protium, with The fossil energies such as coal, oil, natural gas, which are compared, has the advantages that protrusion.
Biomass preparing liquid fuel is used, pyrolysis liquefaction technology is mainly taken.Biomass pyrolysis liquefaction process is related to life Material is crushed, dried, heat carrier is heated, heat carrier is conveyed, biomass is converted in anaerobic closed reactor high speed endothermic pyrolysis Into bio-fuel-oil gas and carbon residue, bio-fuel-oil gas and carbon residue, the gas solid separation of heat carrier, the condensation liquefaction of bio-fuel-oil gas, change Heat and can not coagulate combustion gas processing etc. series of process link.Biomass pyrolysis liquefaction product include bio-fuel-oil, carbon residue carbon dust and Combustion gas can not be coagulated.Bio-fuel-oil is not only used directly for the burning of the equipment such as existing boiler and combustion gas turbine, and can pass through It is processed further being modified as bavin Water Oil Or Gas and as power fuel, being alternatively arranged as industrial chemicals.Patent 200510057216.2 " process and its apparatus system of a kind of biomass pyrolysis liquefaction " describes high temperature fluidized gas and thermophore and biomass powder Pyrolysis gas, by gas solid separations such as pyrolysis gas and carbon residues, is then condensed into biology by material mixing to carry out thermal cracking to biomass Oil.Although this method slightly increases thermal cracking speed, and device is also relatively simple, but temperature is high needed for reaction, gas-liquid product composition More complicated, calorific value is low.
Supercritical CO2There is fluid asepsis environment-protecting, viscosity to be bordering on gas, and density is bordering on liquid, and diffusion coefficient is high, and dissolving is oozed The advantages of ability is big thoroughly, has extremely important purposes in fields such as pharmaceutical extraction, foaming, sewage disposals.In supercritical CO2With In the two-phase system of ionic liquid composition, carbon dioxide is soluble in ionic liquid, and solubility is very high.Ionic liquid It is almost insoluble in supercritical carbon dioxide, extraction is more cleaned, do not result in cross pollution, and carbon dioxide is in condition of high voltage Under can be very good to be dissolved in ionic liquid, hence it is evident that reduce viscosity of il, have rush to the mass transfer in ionic liquid Enter effect.Patent 201410251337.X " CO2Supercritical fluid, which carries ionic liquid, improves the method for cellulose dissolution " carry Go out and used supercritical CO2Be swelled and osmosis, make ionic liquid enter cellulose surface and inside so that ionic liquid With the hydroxyl formation hydrogen bond on cellulose, and make between cellulosic molecule or the hydrogen bond action of intramolecular weakens, be more beneficial for fiber The dissolving of element, but it does not form the biomass pyrolysis method of system.
The content of the invention
It is an object of the invention to provide one kind with electrolysis water hydrogen supply and with ionic liquid-supercritical CO2For the biology of medium The method that the liquefaction of matter electrochemistry prepares bio oil, this method is with supercritical CO2For medium, deposited in catalyst, ionic liquid, water Biomass is handled lower, by electrolysis water hydrogen supply, promotes biomass cracking to generate the bio oil of high heating value.
Biomass is handled in the presence of ionic liquid, biomass is cracked in ionic liquid by electrochemical stimulation Reaction；It is passed through CO2Supercriticality is reached by adjusting pressure and temperature, ionic liquid-supercritical carbon dioxide is formed Two-phase system, reduces viscosity of il, promotes the effect of mass transmitting of ionic liquid；By electrolysis water hydrogen supply, biomass is promoted to split Solution generation high heating value bio oil, effectively increases biomass pyrolytic efficiency.
The cation of the ionic liquid is [Bmim]+、[Emim]+、[Amim]+In one kind, anion is [PF6]-、 [BF4]-、[NTf2]-、Cl-、Br-、CH3COO-、OTf-Middle one kind.
The catalyst is Al2O3、K2CO3、KCl、NaCl、NaOH、Na2CO3、NiCl3、NiO、ZnCl3、FeSO4、 CuSO4、CaCO3, one kind in CaO, the addition of catalyst makes a living the 1.5-8% of material mass.
The decomposition voltage is 0.1-60V.
The supercritical CO2Temperature is 120-260 DEG C, absolute pressure is 8-15MPa.
Concrete technical scheme of the present invention is：
（1）Biomass material is crushed, dried, raw material is well mixed with catalyst after drying；
（2）Water and ionic liquid are passed through in cracking reactor, heated up, temperature control is at 120-260 DEG C, then by step （1）In mixture feeding cracking reactor, CO is passed through2, pressure is reached 8-15MPa, voltage 0.1- be passed through to reactor electrodes 60V, is kept for 0.1-2 hours in this case, and the volatile matter of reaction generation is condensed to obtain liquid bio oil, wherein ionic liquid Body addition is made a living the 200%-500% of material mass, and catalyst loading is made a living the 1.5-8% of material mass.
During the biomass can be maize straw, sawdust, tobacco leaf, straw, bamboo, pine, shell, sugarcane, plastics etc. One kind or any several mixture, be the lignocellulosic containing polymer such as cellulose, hemicellulose and lignin Class raw material.
The preferred 20-70 mesh of biological particles degree scope.
According to the method for the present invention, supercritical carbon dioxide and ionic liquid form two-phase system, and carbon dioxide can be with It is dissolved in ionic liquid, and solubility is very high, hence it is evident that the viscosity of ionic liquid is reduced, there is rush to the mass transfer of ionic liquid Enter effect.
According to the method for the present invention, if there is substantial amounts of free hydrogen in biomass through pyrolysis reaction system（-H）, these Free hydrogen can be combined preferentially with free radical, and the chain reaction of free radical is blocked in time, make originally unstable intermediate product rapid Settle out, greatly reduce the generation of coke and low molecular weight gas product；Meanwhile, the structure that free hydrogen also can be original with biomass Oxygen reacts to form water, effectively the oxygen content in reduction product.
Another object of the present invention is to provide a kind of realize with ionic liquid and supercritical CO2For the biomass electrochemistry of medium The device of liquifying method, it includes blender 1, CO2Gas tank 2, cracking reactor 3, solid-liquid separator 4, ionic liquid storage tank 5, Solid collector 6, condenser 7, liquid header 8, gas collector 9, delivery pump 10, blender 1 by cracking reactor 3 with Condenser 7 is connected, and condenser 7 is connected with liquid header 8, gas collector 9 respectively, the bottom of cracking reactor 3 and solid-liquid point Connected from device 4, solid-liquid separator 4 is connected by ionic liquid storage tank 5 with delivery pump 10, delivery pump 10 is communicated to cracking reactor 3 form loop, CO2Gas tank 2 is connected with cracking reactor 3, and solid-liquid separator 4 is connected with solid collector 6；Cracking reactor 3 Be provided with anode 11, negative electrode 12 in cylinder, cylinder upper end is provided with charging aperture, gas outlet, cylinder bottom be provided with discharging opening, from Be provided with outside sub- liquid inlet and air inlet, cylinder in chuck, chuck be provided with electrical heating wire or chuck deep fat entrance and Outlet（Logical deep fat heating）, charging aperture is connected with blender 1, and gas outlet is connected with condenser 7, air inlet and CO2Gas tank 2 connects Connect, ionic liquid entrance is connected with delivery pump 10, discharging opening is connected with solid-liquid separator 4.
The cracking reactor middle-jiao yang, function of the spleen and stomach extremely activated carbon electrodes, graphite electrode, carbon fiber electrode, metal electrode, aeroge Electrode etc., wherein metal electrode are platinum electrode, gold electrode, Ti electrode, aluminium electrode or palladium electrode；Electrode shape be wire, tabular, Spiral form, netted, bar-shaped, tubular etc.；Porous support type battery lead plate, such as activated carbon also may be selected outside negative electrode divided by upper electrode material Electrode, graphite electrode, carbon fiber electrode, metal electrode, silica aerogel electrode, ferrous alloy hydrogen-precipitating electrode, nickel-base alloy liberation of hydrogen electricity Pole, Modified by Rare Earth Elements hydrogen-precipitating electrode etc., wherein metal electrode are platinum electrode, gold electrode, Ti electrode, aluminium electrode or palladium electrode； Ferrous alloy hydrogen-precipitating electrode is Fe-P, Fe-P-Pt, Fe-Mo, Fe-Mo-Pt alloy hydrogen-precipitating electrode；Nickel-base alloy hydrogen-precipitating electrode is Ni-Mo, Ni-Co, Ni-Sn, Ni-Co-Sn alloy hydrogen-precipitating electrode；Modified by Rare Earth Elements hydrogen-precipitating electrode is Pt-Ce, Pt-Sm, Pt- Ho alloy hydrogen-precipitating electrodes；Electrode size and die opening can be adjusted according to cracking reactor size.Single electrode length is accounted for instead The 65%-85% of device height is answered, the Different electrodes width according to electrode shape is the 0.5%-45% of reactor width.
The present apparatus in use, will dry after raw material be well mixed with catalyst in blender 1, water and ionic liquid are led to Enter in cracking reactor 3, heat up, then temperature control is sent into mixture in cracking reactor 3, by CO at 120-260 DEG C2 Gas tank 2 is passed through CO2, pressure is reached 8-15MPa, voltage 0.1-60V is passed through to reactor electrodes, react 0.1-2 hours, reaction The volatile matter of generation enters condenser 7 by gas outlet, is collected into after a part of volatile matter condensation in liquid header 8, through drying Remove wherein moisture and obtain bio oil, the volatile matter not being condensed is collected into gas collector 9, remaining residue and ion Liquid is entered in solid-liquid separator 4 by discharging opening to be separated, and ionic liquid is flowed into ionic liquid storage tank 5, can be by the pump of delivery pump 10 Enter and recycled in cracking reactor 3, it is residual that residue finally gives solid-state into solid collector 6 through dry removing wherein moisture Slag, it can be used as fuel or industrial chemicals.
The pressuring method of electrode is one kind in anode pressurization, negative electrode pressurization, anode and cathode pressurization in the cracking reactor, Voltage can be provided by direct current or AC power.
During the biomass cracking of the present invention, offer free hydrogen is constantly electrolysed by water, blocks free radical chain anti-in time Should, it is effectively increased liquid fuel yield and improves its quality, supercritical CO2Preferably it is dissolved in ionic liquid, hence it is evident that reduction The viscosity of ionic liquid, improves its electrical conductivity, effectively facilitates biomass cracking.Biomass is heated evenly, lignocellulosic Key fracture is learned, ion pair intermediate is generated, by electrical field stimulation after voltage is passed through, ion pair stability and density are by shadow Ring, pyrolysis product is carried out towards the direction of high added value product, accelerate biomass cracking speed, efficiency high, process is easy to Control, improves the utilization rate of biomass and adds the calorific value of generation product.
Brief description of the drawings
Fig. 1 is apparatus of the present invention structural representation；
In figure, 1- blenders；2-CO2Gas tank；3- cracking reactors；4- solid-liquid separators；5- ionic liquid storage tanks；6- consolidates Body collector；7- condensers；8- liquid headers；9- gas collectors；10- delivery pumps；11- anodes；12- negative electrodes.
Embodiment
The present invention is described in further detail below by drawings and examples, but the scope of the present invention is not limited to The content.
Embodiment 1：With [Bmim] Cl- supercritical COs2It is reaction for medium, perforated plate-like Fe-Mo alloy hydrogen-precipitating electrodes Device negative electrode, carbon fiber electrically extremely anode, Al2O3It is as follows for the pine liquefaction bio oil preparation method of catalyst：
As shown in figure 1, the device that the present embodiment is used includes blender 1, CO2Gas tank 2, cracking reactor 3, separation of solid and liquid Device 4, ionic liquid storage tank 5, solid collector 6, condenser 7, liquid header 8, gas collector 9, delivery pump 10, blender 1 is connected by cracking reactor 3 with condenser 7, and condenser 7 is connected with liquid header 8, gas collector 9 respectively, and cracking is anti- The bottom of device 3 is answered to be connected with solid-liquid separator 4, solid-liquid separator 4 is connected by ionic liquid storage tank 5 with delivery pump 10, delivery pump 10 are communicated to the formation of cracking reactor 3 loop, CO2Gas tank 2 is connected with cracking reactor 3, solid-liquid separator 4 and solid collector 6 connections；Anode 11, negative electrode 12 are provided with the cylinder of cracking reactor 3, cylinder upper end is provided with charging aperture, gas outlet, cylinder Portion, which is provided with to be provided with chuck, chuck outside discharging opening, ionic liquid entrance and air inlet, cylinder, is provided with heating electrical heating Silk or logical deep fat, charging aperture are connected with blender 1, and gas outlet is connected with condenser 7, air inlet and CO2Gas tank 2 is connected, ion Liquid inlet is connected with delivery pump 10, and discharging opening is connected with solid-liquid separator 4.
By 15kg through pine powder and 1kg catalyst Al of the dry and granularity for 20 mesh2O3It is mixed in blender 1, stirs Valve is turned on after uniform, feeds the mixture into cracking reactor 3, adds 150L water and 37kg ionic liquids [Bmim] Cl, Close valve；By CO2By CO2Gas tank 2 is passed through in cracking reactor 3, and sealing is warming up to 140 DEG C, 9MPa is boosted to, to reactor Negative electrode is passed through 15V DC voltage, and automatic exhaust steam valve is vented constant pressure automatically when biomass pyrolytic starts aerogenesis superpressure, in the state It is lower to be kept for 0.8 hour；The volatile matter for reacting generation enters condenser 7 by gas outlet, and liquid is collected into after a part of volatile matter condensation In body collector 8, bio oil is obtained through drying removing wherein moisture, the volatile matter not being condensed is collected into gas collector 9 In, remaining residue is entered with ionic liquid by discharging opening to be separated in solid-liquid separator 4, and ionic liquid flows into ionic liquid storage tank It is pumped into cracking reactor 3 and is recycled by delivery pump 10 in 5, residue enters solid collector 6 and removes wherein moisture through drying Solid residue is finally given, it can be used as fuel or industrial chemicals；Its biological oily yield is 74wt%, and oxygen content is 9%, and calorific value is 36.71MJ/Kg, dried residue reaches 3.14wt%.
Note：The preparation method bibliography of Fe-Mo alloy hydrogen-precipitating electrodes《 Electro-chemicalsynthesis of Fe-Mo and Fe-Mo-Pt alloys and their electrocatalytic activity for methanol oxidation》Middle method.
Embodiment 2：With [Amim] Br- supercritical COs2Be reactor negative electrode for medium, tabular activated carbon electrodes, it is netted The tobacco leaf liquefaction bio oil that Ti electrode is anode, NaCl is catalyst prepares as follows：
The apparatus structure be the same as Example 1 that the present embodiment is used；
23kg is mixed in blender through dry and granularity for the tobacco leaf powder of 35 mesh with 1.15kg catalyst ns aCl, stirred Valve is turned on after mixing uniformly, feeds the mixture into cracking reactor, adds 345L water and 57.5kg ionic liquids [Amim] Br, closes valve, by CO2It is passed through in cracking reactor, sealing is warming up to 180 DEG C, boosts to 11MPa, it is logical to reactor anode Enter 45V alternating voltage, automatic exhaust steam valve is vented constant pressure automatically when biomass pyrolytic starts aerogenesis superpressure, keeps in this condition 0.7 hour；The volatile matter for reacting generation enters condenser 7 by gas outlet, and liquid collection is collected into after a part of volatile matter condensation In device 7, bio oil is obtained through drying removing wherein moisture, the volatile matter not being condensed is collected into gas collector 9, remaining Residue and ionic liquid entered by discharging opening and separated in solid-liquid separator 4, ionic liquid is flowed into ionic liquid storage tank 5 and circulated Utilize；Its biological oily yield is 71wt%, and oxygen content is 8%, and calorific value is 37.82MJ/Kg, and dried residue reaches 4.51wt%.
Embodiment 3：With [Emim] OTf- supercritical COs2It is reaction for medium, perforated plate-like Pt-Ce alloy hydrogen-precipitating electrodes Device negative electrode, bar-shaped aluminium electrode are anode, NiCl3It is as follows for the maize straw liquefaction bio oil preparation of catalyst：
The apparatus structure be the same as Example 1 that the present embodiment is used；
By 18kg through corn stalk powder and 0.9kg catalyst n iCl of the dry and granularity for 48 mesh3It is mixed in blender In, valve is turned on after stirring, is fed the mixture into cracking reactor, 270L water and 54kg ionic liquids is added [EMIM] OTf, closes valve；By CO2It is passed through in cracking reactor, sealing is warming up to 210 DEG C, 9.5MPa is boosted to, to reaction Device negative electrode and anode are passed through 0.8V alternating voltage, and automatic exhaust steam valve is vented perseverance automatically when biomass pyrolytic starts aerogenesis superpressure Pressure, is kept for 1.2 hours in this condition；The volatile matter for reacting generation enters condenser 7, a part of volatile matter condensation by gas outlet After be collected into liquid header 8, through dry remove wherein moisture obtain bio oil, the volatile matter not being condensed is collected into gas In body collector 9, remaining residue and ionic liquid are entered by discharging opening to be separated in solid-liquid separator 4, ionic liquid flow into from Recycled in sub- wet tank 5.Its biological oily yield is 72wt%, and oxygen content is 6%, and calorific value is 39.26MJ/Kg, after drying Residue reach 3.58wt%.
Note：The preparation method bibliography of Pt-Ce alloy hydrogen-precipitating electrodes《Platinumerare earth electrodes for hydrogene volution in alkaline water electrolysis》Middle method.
Embodiment 4：With [Bmim] Ac- supercritical COs2It is reactor negative electrode, bar-shaped gold for medium, spiral form platinum electrode Electrode is anode, CuSO4It is as follows for the sawdust liquefaction bio oil preparation of catalyst：
By 900kg through sawdust powder and 54kg catalyst CuSO of the dry and granularity for 55 mesh4It is mixed in blender, stirs Valve is turned on after mixing uniformly, feeds the mixture into cracking reactor, adds 18000L water and 3600kg ionic liquids [Bmim] Ac, closes valve；By CO2It is passed through in cracking reactor, sealing is warming up to 150 DEG C, 11MPa is boosted to, to reactor Negative electrode is passed through 14V DC voltage, and automatic exhaust steam valve is vented constant pressure automatically when biomass pyrolytic starts aerogenesis superpressure, in the state It is lower to be kept for 1.5 hours.The volatile matter for reacting generation enters condenser 7 by gas outlet, and liquid is collected into after a part of volatile matter condensation In body collector 8, bio oil is obtained through drying removing wherein moisture, the volatile matter not being condensed is collected into gas collector 9 In, remaining residue is entered with ionic liquid by discharging opening to be separated in solid-liquid separator 4, and ionic liquid flows into ionic liquid storage tank Recycled in 5.Its biological oily yield is 69wt%, and oxygen content is 7%, and calorific value is 38.56MJ/Kg, and dried residue reaches 5.26wt%。

Claims (10)

1. one kind is with ionic liquid and supercritical CO2For the biomass electrochemistry liquifying method of medium, it is characterised in that：Faced with super Boundary CO2For medium, biomass is handled in the presence of catalyst, ionic liquid, water, by electrolysis water hydrogen supply, promoted Biomass cracking generates bio oil.
2. it is according to claim 1 with ionic liquid and supercritical CO2For the biomass electrochemistry liquifying method of medium, its It is characterised by：The cation of ionic liquid is [Bmim]+、[Emim]+、[Amim]+In one kind, anion is [PF6]-、 [BF4]-、[NTf2]-、Cl-、Br-、CH3COO-、OTf-Middle one kind.
3. it is according to claim 1 with ionic liquid and supercritical CO2For the biomass electrochemistry liquifying method of medium, its It is characterised by：Catalyst is Al2O3、K2CO3、KCl、NaCl、NaOH、Na2CO3、NiCl3、NiO、ZnCl3、FeSO4、CuSO4、 CaCO3, one kind in CaO, the addition of catalyst makes a living the 1.5-8% of material mass.
4. it is according to claim 1 with ionic liquid and supercritical CO2For the biomass electrochemistry liquifying method of medium, its It is characterised by：Decomposition voltage is 0.1-60V.
5. complete described in claim 1 with ionic liquid and supercritical CO2For the dress of the biomass electrochemistry liquifying method of medium Put, it is characterised in that including blender（1）、CO2Gas tank（2）, cracking reactor（3）, solid-liquid separator（4）, ionic liquid for storing Tank（5）, solid collector（6）, condenser（7）, liquid header（8）, gas collector（9）, delivery pump（10）, blender （1）Pass through cracking reactor（3）With condenser（7）Connection, condenser（7）Respectively with liquid header（8）, gas collector （9）Connection, cracking reactor（3）Bottom and solid-liquid separator（4）Connection, solid-liquid separator（4）Pass through ionic liquid storage tank（5） With delivery pump（10）Connection, delivery pump（10）It is communicated to cracking reactor（3）Form loop, CO2Gas tank（2）With cracking reactor （3）Connection, solid-liquid separator（4）With solid collector（6）Connection；Cracking reactor（3）Anode is provided with cylinder（11）, it is cloudy Pole（12）, cylinder upper end is provided with charging aperture, gas outlet, and cylinder bottom is provided with discharging opening, ionic liquid entrance and air inlet, It is provided with outside cylinder in chuck, chuck and is provided with deep fat entrance and outlet on electrical heating wire or chuck, charging aperture and blender （1）Connection, gas outlet and condenser（7）Connection, air inlet and CO2Gas tank（2）Connection, ionic liquid entrance and delivery pump（10） Connection, discharging opening and solid-liquid separator（4）Connection.
6. it is according to claim 5 with ionic liquid and supercritical CO2For the biomass electrochemistry liquefying plant of medium, its It is characterised by：Reactor middle-jiao yang, function of the spleen and stomach extremely activated carbon electrodes, graphite electrode, carbon fiber electrode, metal electrode or silica aerogel electrode, its Middle metal electrode is platinum electrode, gold electrode, Ti electrode, aluminium electrode or palladium electrode.
7. it is according to claim 5 with ionic liquid and supercritical CO2For the biomass electrochemistry liquefying plant of medium, its It is characterised by：Negative electrode is activated carbon electrodes, graphite electrode, carbon fiber electrode, metal electrode, silica aerogel electrode, iron in reactor Based alloy hydrogen-precipitating electrode, nickel-base alloy hydrogen-precipitating electrode or Modified by Rare Earth Elements hydrogen-precipitating electrode.
8. it is according to claim 7 with ionic liquid and supercritical CO2For the biomass electrochemistry liquefying plant of medium, its It is characterised by：Ferrous alloy hydrogen-precipitating electrode is one kind in Fe-P, Fe-P-Pt, Fe-Mo, Fe-Mo-Pt alloy hydrogen-precipitating electrode.
9. it is according to claim 7 with ionic liquid and supercritical CO2For the biomass electrochemistry liquefying plant of medium, its It is characterised by：Nickel-base alloy hydrogen-precipitating electrode is one kind in Ni-Mo, Ni-Co, Ni-Sn, Ni-Co-Sn alloy hydrogen-precipitating electrode.
10. it is according to claim 7 with ionic liquid and supercritical CO2For the biomass electrochemistry liquefying plant of medium, its It is characterised by：Modified by Rare Earth Elements hydrogen-precipitating electrode is one kind in Pt-Ce, Pt-Sm, Pt-Ho alloy hydrogen-precipitating electrode.
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CN110791595B (en) * 2019-11-11 2020-10-09 西南科技大学 Method for realizing regeneration and utilization of waste biomass by adopting acidic electrolyzed water
CN110791596B (en) * 2019-11-11 2020-10-30 西南科技大学 Method for realizing regeneration and utilization of waste biomass by adopting alkaline electrolyzed water
CN111378986B (en) * 2020-04-02 2022-11-08 上海大学 Preparation method of porous lead composite nickel-iron alloy catalytic electrode and application of porous lead composite nickel-iron alloy catalytic electrode in coal electrolysis liquefaction
CN111662738B (en) * 2020-04-23 2022-05-10 廖益强 Subcritical water liquefaction method for Chinese fir powder and biomass oil thereof
CN113115977A (en) * 2021-04-02 2021-07-16 河南中烟工业有限责任公司 Green preparation method of tobacco lysate
CN113862015A (en) * 2021-11-22 2021-12-31 华南农业大学 Method for promoting quality of pyrolysis oil to be improved by seawater electrochemical pretreatment of biomass and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992488A (en) * 2014-06-09 2014-08-20 东华大学 Method for improving cellulose solubility by use of CO2 supercritical fluid together with ionic liquid
CN105038835A (en) * 2015-08-12 2015-11-11 昆明理工大学 Method and device for performing electrochemical strengthening liquid phase catalysis and low-temperature splitting decomposition on biomass
CN205501198U (en) * 2016-01-06 2016-08-24 昆明理工大学 Use ionic liquid and overcritical CO2 living beings electrochemistry liquefying plant as medium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992488A (en) * 2014-06-09 2014-08-20 东华大学 Method for improving cellulose solubility by use of CO2 supercritical fluid together with ionic liquid
CN105038835A (en) * 2015-08-12 2015-11-11 昆明理工大学 Method and device for performing electrochemical strengthening liquid phase catalysis and low-temperature splitting decomposition on biomass
CN205501198U (en) * 2016-01-06 2016-08-24 昆明理工大学 Use ionic liquid and overcritical CO2 living beings electrochemistry liquefying plant as medium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
离子液体-超临界二氧化碳两相体系研究进展;王晓刚等;《现代化工》;20080531;第28卷(第5期);第30-38页 *

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