CN104910993B - The method that discharge plasma conversion stalk prepares bio-fuel - Google Patents
The method that discharge plasma conversion stalk prepares bio-fuel Download PDFInfo
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- CN104910993B CN104910993B CN201510351962.6A CN201510351962A CN104910993B CN 104910993 B CN104910993 B CN 104910993B CN 201510351962 A CN201510351962 A CN 201510351962A CN 104910993 B CN104910993 B CN 104910993B
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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
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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
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The present invention relates to the method that discharge plasma conversion stalk prepares bio-fuel, it is reaction raw materials from the renewable resource lignocellulose-like biomass stalk enriched on the earth, under the conditions of micro-streamer discharge plasma, utilize inert gas and the environment of water vapour, carry naphthane, stalk biomass is converted into bio-fuel, without using acid in this method course of reaction, the severe corrosive such as alkali chemical substance and its harmful radiation source, course of reaction is pollution-free, to human body fanout free region, it is corrosion-free to equipment, whole technical process and its product are environmentally friendly, and the conversion ratio of stalk and the quality of bio-fuel can be effectively improved in discharge environment.
Description
Technical field
The invention belongs to bio-fuel preparing technical field, specially discharge plasma conversion stalk prepares bio-fuel
Method.
Background technology
Biomass is the renewable resource enriched on the earth, is to be produced using big gas and water, soil etc. by photosynthesis
Various organisms, be all lived organic substances that can be grown, it is different from the tradition combustion such as oil, coal, nuclear energy
Material, is regenerative resource material, and bio-fuel is produced using biomass conversion, can be advantageous to environment guarantor with alleviating energy crisis
Shield.Bio-fuel refers to solid, liquid or the gaseous fuel converted by biomass, can substitute the gasoline and bavin produced by oil
Oil, it is the important directions of regenerative resource utilization.Since the 1970s, by traditional energy price, environmental protection and the whole world
The influence of climate change, the development of countries in the world pay attention to day by day bio-fuel.
Stalk is highly important one kind in biomass material, can prepare many important chemistry, industrial chemicals, wherein
It is exactly a kind of important application to prepare bio-fuel.It is at present the sound development of promotion bio-fuel industry, the weight of China's research and development
Point is concentrated mainly on the biofluid using the starchiness such as cassava, sugar grass or saccharic non-grain crop and lignocellulosic as raw material
Fuel technology.The conversion of biomass typically has two approach：One kind is chemical breakdown, and another kind is biodegradable, wherein chemistry
Conversion method is divided into directly burning and thermochemical study.Thermochemical study point is divided into gasification, pyrolysis and liquefaction.Biomass material
It is actually the liquefaction in thermochemical study to be converted into bio-fuel, is the heat chemistry mistake that Organic Ingredients is converted into product liquid
Journey.In liquefaction process, the macromolecular in biomass material is first decomposed into small molecule component in appropriate medium, meanwhile, these
The unstable small molecule of high activity regenerates bio-fuel through meeting again.
At present, people utilize the raw materials such as wood chip, rice husk, stalk under different temperature, pressure and catalyst existence condition
The bio-fuel of different component is transformed into, such as Canada, the U.S. are processed using marine alga as raw material and are adapted to what aviation used
Fuel.In technical research, scholars achieve different achievements in research, bar be present in high temperature, high pressure, water and catalyst
Under part, by it is Wood liquefied be fuel oil.With rape straw, deliming rape stalk, peanut straw, sesame stalk 500oC or so enters
Fast pyrogenation of having gone obtains bio oil U.S. renewable resource laboratory and have studied cracking technique, state using ablation Vortex reactor
Inside also there are many colleges and universities, scientific research institutions' research pyrolysis liquefaction technology, Shenyang agricultural university have studied rotation conical shell biomass through pyrolysis item
Mesh, Shandong Technology Univ, Zhejiang University, University Of Shanxi, Fudan University etc. also has made intensive studies to biomass pyrolytic technology,
The scientific research personnel that the U.S. of U.S. Losec widens just attempts the method for developing switchgrass manufacture ethanol, from the fiber of switchgrass
Sugar is refined in element, fuel then is made in sugar.But found in research, also there is certain problem in current technology, convert skill
In art, problems faced is mainly that cost is too high, and pyrolysis liquefaction thing low yield, composition are difficult to control, and are all the time
The bottleneck problem of technology.It can be seen that liquefaction technology of the prior art substantially enters under high-temperature and high-pressure conditions from being discussed above
Capable thermochemical process, convert biomass into the product liquid of high heating value.In order to obtain more bio oils, in reaction system
The catalyst such as middle addition metal carbonate, or it is filled with hydrogen, carbon monoxide.Due to the presence of high pressure, to equipment sealing requirements
Compare it is high, high temperature to the heat resistance of relevant device or accessory it is also proposed that very high requirement, flashing speed oven to heating rate requirement very
Completely cut off the further genralrlization of all influence techniques such as air in high and pyrolytic process.
Therefore, a kind of method for preparing bio-fuel to the less demanding biomass conversion such as pressure, temperature of research has
Important meaning.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art and defect, there is provided a kind of discharge plasma converts stalk
The method for preparing bio-fuel.
The raw material that the present invention selects is lignocellulose-like biomass stalk, such as maize straw, cotton stalk, rice
Stalk etc., under discharge plasma existence condition, it is converted into bio-fuel.
Discharge plasma conversion stalk of the present invention prepares bio-fuel technique and may be summarized to be：
Raw material crushing → discharge plasma conversion → product.
Discharge plasma conversion stalk is caused by electric discharge under certain condition in the presence of active particle, is directly realized by
The conversion process of straw lignocellulose.Therefore, for transformation experiment technique, according to discharge plasma process and stalk
The characteristics of biomass, is considered.Micro-streamer discharge plasma under hyperbar be under External Electrical Field electronics from electricity
Energy is obtained in, by the collision of electronics and neighboring atom, molecule, electronics gives them the energy transfer of itself, makes them
Excite, ionize and dissociate, produce electron avalanche, when the dispatch from foreign news agency field voltage on gas gap exceedes the breakdown voltage of gas, gas
Body is breakdown.
For lignocellulosic, 25 ~ 240oPhysical absorption water can be parsed during C, some glucosyl groups start to take off
Water, higher than 240oC stalks can produce low molecule amount volatile compound, therefore range of reaction temperature is 25 ~ 240oC is as reaction
The foundation of device design.In addition, stalk is readily burned, aoxidized, the volatile compound of low molecule amount, the lightweight biology of generation are produced
The products such as oil are also possible to decompose under plasma conditions, produce volatile matter, so that yield reduces.Stalk during the course of the reaction
Powder is stationary phase, and discharge gas is mobile phase, and reaction product is adsorbed on reaction mass surface, can only utilize mobile phase by product
Remove, improve mass transfer rate, powder of straw is fully contacted with discharge gas, can just effectively improve yield, therefore, in exoelectrical reaction
, it is necessary to which discharge gas fully contacts with reaction mass in device, there is provided inert gas environment, ensure certain steam rates, if
Gas handling system is counted, quickly removes reaction product.
During micro-streamer discharges stover, in addition to the appropriate reaction condition of Preliminary design, it is necessary to make stalk
Powder is as much as possible to be entered in plasma reaction section.Therefore, reactor and experimental technique meet following condition：
（1）Because ion bombardment effects weaken under hyperbar, for plasma reaction area existing for stalk, to have additional
Thermal source carry out course of reaction in aid in heating, with reach stronger under hyperbar Ions Bombardment required for temperature, in view of fiber
The characteristics of plain biolobic material, reactor temperature is not above 300oC。
（2）The volumetric efficiency of reactor is as big as possible, and the cellulose series biomass volume such as stalk is big, and density is small, raw material
Particle diameter is about 0.2 ~ 1mm.
（3）Single air supply system, there is provided inert gas environment, avoid to stalk oxidation, burning etc..
（4）System discharge voltage range is 1000V ~ 10000V, highest discharge power is 1000W.
Micro-streamer discharge plasma conversion stalk, which prepares bio-fuel device, to be included：Micro-streamer electric discharge stalk enters material list
Member, conversion reactor, reactor Drive assembly, medium gas transport unit, collection of products unit etc..
Specific requirement of the experimental technique for reaction unit is first, it is desirable to has heater, and can accurately survey
Amount temperature, and temperature is adjusted within the specific limits；Second, because reaction mass is that solid reacts in water vapour atmosphere, put
Electric electrode structure is line-cartridge type；3rd, because reaction needs inert gas environment, it is therefore desirable to reactor good seal performance, energy
Accurate measurement charge flow rate, it is resistant to certain pressure；4th, stalk under micro-streamer discharging condition, it is necessary to high-voltage discharge, because
This, reactor has good electrical insulating property, while is easy to observe electric discharge phenomena；5th, electrode spacing is adjustable, has scalable
The grounding electrode barrel mast of regulation；6th, there is product collection system.
Preparation technology is as follows：
（1）Pre- thermal reactor preheats steam generator to assigned temperature.
（2）Lignocellulose-like biomass stalk is crushed, the powder of straw being sieved is added into spiral with sieve feeds
In the funnel of device, two level feeding gas is connected；
（3）Before exoelectrical reaction, first with inert gas purge reactor, air in reactor is excluded completely, then by the gas that discharges
Body, i.e. inert gas are filled with reactor；
（4）Saturated vapor is passed through, naphthane is added with peristaltic pump in the mixed gas of inert gas and water vapour, together
It is added in plasma-converted reactor；
（5）Start micro-streamer discharge control system power switch, adjust driving voltage, start exoelectrical reaction；
（6）At the end of reaction, first turn off feeding screw, micro-streamer discharge control system power switch, stop supply, so
After turn off master switch；
（7）Reacted product is collected with condensation.
After naphthane is added to reactor with water vapour, volatilize immediately, powder of straw is suspended in naphthane with fluidized state
Water vapour and atmosphere of inert gases in, inert gas mainly has two effects：First, oxidisable gas in cleaning reactor, prevents
Only naphthane meets strong oxidizer burning；Second, as discharge gas, high energy active particle is produced.The effect of water vapour and naphthane
It is：Abundant Hydrogen Proton environment is provided, H is produced on electric discharge block media+Sheaths, water vapour is by naphthane band in a gaseous form
Enter in reactor, accelerate reaction speed.
Micro-streamer electric discharge conversion reactor is double-barrel structure, and outer barrel is the reaction tube of isolation material, and discharging structure is line-cylinder
Formula, high-field electrode are threaded metal rod, graphite rod, and inner cylinder is cylinder of quartz glass, and as block media layer, outer attached layer of metal is made
For grounding electrode.
Biofuel component prepared by discharge plasma conversion stalk is complicated, from elemental composition mainly with carbon, hydrogen,
It is the mixture of water, tar and oxygen-containing organic compound composition based on oxygen, including organic acid, ester type compound, aldehyde and contracting
Aldehyde, hemiacetal, alcohol compound, hydrocarbon compound, aromatic hydrocarbon, phenolic compound etc..Liquid product obtained by reaction passes through
Fractionation, separates water, light oil and mink cell focus, and light oil collects boiling point and is less than 100oC product, mink cell focus are collected boiling point and are higher than
200 oCProduct, obtained product is flammable, is the raw material of industry that can be made full use of after separation.
The present invention can make full use of biomass straw raw material, avoid method for pyrolysis high temperature, high pressure, it is difficult to realize very high
Heating rate requirement, without using the severe corrosive such as acid, alkali chemical substance and its harmful radiation source in course of reaction, reacted
Journey is pollution-free, corrosion-free to equipment to human body fanout free region, and whole technical process and its product are environmentally friendly.In discharge process
H is produced in stalk bisque, dielectric layer surface+Sheaths, it converts the effect in lignocellulosic under plasma conditions, can be with
In being chemically reacted applied to wider acid catalysis class, to reduce acid pollution.
The present invention, using inert gas and the environment of water vapour, carries tetrahydrochysene under the conditions of micro-streamer discharge plasma
Naphthalene, naphthane volatility in water vapour can be given full play to, can be effectively improved in discharge environment stalk conversion ratio and
The quality of bio-fuel.The method that the method for the present invention prepares bio-fuel different from traditional lignocellulosic, while will etc.
Gas ions chemical reaction has extended to solid-state reaction pattern by traditional vapor reaction pattern, for discarded lignocellulosic sources
Change to utilize and provide a New Century Planned Textbook.
Brief description of the drawings
Accompanying drawing 1 is preparation technology flow chart；Accompanying drawing 2 is conversion reactor structural representation；Fig. 3 transformation times and corn stalk
The yield graph of a relation of stalk conversion ratio, bio-fuel.
Diagram：1 stalk, 2 crushing, 3 ball millings, 4 temperature controls, 5 naphthanes, 6 peristaltic pumps, 7 mixed gas instrument, 8 plasmas turn
Change reactor, 9 media, electrode and stalk reaction residues flushing liquor, 10 inert gases, 11 steam generators, 12 pressure regulators, 13
High-frequency and high-voltage power supply, 14 products, 15 condensations, 16 high-field electrodes, 17 outer barrels, 18 inner cylinders, 19 grounding electrodes.
Embodiment
Micro-streamer electric discharge conversion reactor is double-barrel structure, and outer barrel is lucite, and discharging structure is line-cartridge type, high pressure
Electrode is stainless steel threaded bar, and diameter of thread 5mm, long 500mm, inner cylinder is cylinder of quartz glass, as block media layer, outer attached one
Layer aluminium foil is as grounding electrode.Concrete operation step is as follows：
（1）Plasma-converted reactor is first preheating to 80oC, preheat steam generator；
（2）By corn straw smashing, 0.2mm particle diameters are worn into, the powder of straw being sieved is added to feeding screw with sieve
In funnel, two level feeding gas nitrogen is connected；
（3）Before exoelectrical reaction, first with nitrogen purge 5min, air in reactor is excluded, by discharge gas nitrogen
Charge flow rate be adjusted to 5L/min；
（4）Saturated vapor is passed through, naphthane is added with peristaltic pump in the mixed gas of nitrogen and water vapour, is added together
Into plasma-converted reactor；
（5）Start micro-streamer discharge control system power switch, adjust driving voltage 5000V, exoelectrical reaction 1h；
（6）At the end of reaction, first turn off feeding screw, micro-streamer discharge control system power switch, stop supply,
It is then turned off master switch；
（7）Reacted product is collected with condensation.
The product being collected into is brownish black thick liquid, calorific value 26MJ/KJ, oxygen content 38.6%, has preferably flowing
Property, it can burn, civilian, industrial fuel can be used as, the thermal efficiency reaches 48%.
Fig. 3 is 240oUnder C and room temperature condition, transformation time and stover rate, the yield graph of a relation of bio-fuel.
The present embodiment can also select lignocellulose-like biomass raw material, the high-field electrodes such as rice straw, cotton stalk to select
Graphite rod.
Claims (2)
1. the method that discharge plasma conversion stalk prepares bio-fuel, it is characterised in that：Biomass straw is put in micro-streamer
Under the conditions of electro-plasma, using inert gas and the environment of water vapour, naphthane is carried, is converted into bio-fuel, specific step
It is rapid as follows：
（a）It is 80 DEG C to preheat conversion reactor temperature, preheats steam generator；
（b）Lignocellulose-like biomass stalk is crushed, the powder of straw being sieved is added to feeding screw with sieve
In funnel, two level feeding gas is connected；
（c）Before exoelectrical reaction, first with inert gas purge reactor, charge flow rate 5L/min, it is hollow that reactor is excluded completely
Gas, then discharge gas, i.e. inert gas are filled with reactor；
（d）Saturated vapor is passed through, naphthane is added in the mixed gas of inert gas and water vapour with peristaltic pump, is added to together
In plasma-converted reactor；
（e）Start micro-streamer discharge control system power switch, adjust driving voltage, start exoelectrical reaction；
（f）At the end of reaction, first turn off feeding screw, micro-streamer discharge control system power switch, stop supply, Ran Houguan
Fall master switch；
Reacted product is collected with condensation.
2. the method that discharge plasma conversion stalk according to claim 1 prepares bio-fuel, it is characterised in that：System
Bulk cargo put including micro-streamer electric discharge stalk feed unit, conversion reactor, reactor Drive assembly, medium gas transport unit,
Collection of products unit；
Feed unit includes feeding screw and two level feed device；
Conversion reactor is double-barrel structure, and outer barrel is the reaction tube of isolation material, and discharging structure is line-cartridge type, and high-field electrode is
Threaded metal rod or graphite rod, inner cylinder are cylinder of quartz glass or α-Al2O3Cylinder, as block media layer, outer attached layer of metal conduct
Grounding electrode；
Reactor Drive assembly includes high-frequency and high-voltage power supply and pressure regulator；
Medium gas transport unit includes two level feeding gas, discharge gas, carries out gas conveying respectively；
Collection of products unit includes condensing plant, collection of products equipment.
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| CN110527542A (en) * | 2019-09-03 | 2019-12-03 | 盐城工学院 | A kind of method of microwave radiation assist medium barrier discharge catalysis upgrading bio oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204679A (en) * | 1998-06-30 | 1999-01-13 | 丁焰 | Method and equipment for inverting biological organic matter using plasma |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204679A (en) * | 1998-06-30 | 1999-01-13 | 丁焰 | Method and equipment for inverting biological organic matter using plasma |
Non-Patent Citations (2)
| Title |
|---|
| 介质阻挡放电等离子体生物质的液化;王秋颖等;《农业工程学报》;20100228;第26卷(第2期);第290-294页 * |
| 微流注放电玉米秸秆水解制备糖类化合物;宋春莲;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20101215(第12期);第42、49-50、52、58和67页 * |
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Address after: No. 76, Heping South Street, Jiguan District, Jixi City, Heilongjiang Province 158100 Patentee after: HEILONGJIANG University OF TECHNOLOGY Address before: No. 76, Heping South Street, Jiguan District, Jixi City, Heilongjiang Province 158100 Patentee before: Jixi University |