CN105950274A - Method for preparation of bio-oil by hydroxyl donor coordinated sub/super-critical ethanol liquefaction of straw cellulose - Google Patents
Method for preparation of bio-oil by hydroxyl donor coordinated sub/super-critical ethanol liquefaction of straw cellulose Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
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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
- C10G1/008—Controlling or regulating of liquefaction processes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/02—Pretreatment
- C11B1/04—Pretreatment of vegetable raw material
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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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Abstract
The invention discloses a method for preparation of bio-oil by hydroxyl donor coordinated sub/super-critical ethanol liquefaction of straw cellulose. The method includes: putting straw cellulose, a small molecular organic solvent under sub/super-critical condition and a hydroxyl donor in a pressure container equipped with a magnetic stirring apparatus, carrying out reaction under 240-320DEG C and 5.0-9.0Mpa for 10-130min, performing cooling to room temperature, and collecting the product to obtain bio-oil. Specifically, the dosage ratio of the straw cellulose, ethanol and hydroxyl donor is 5-20g:50-150mL:0.1-5mL. The method provided by the invention uses ethanol, salicylic acid and other hydroxyl donors as the reaction medium, can greatly enhance the concentration and activity of hydroxyl groups generated by ethanol under sub/super-critical state, the strong oxidizing property of hydroxyl groups has an obvious promoting effect on liquefaction of cellulose into bio-oil, also the method has the advantages of mild reaction conditions, low requirements for equipment and material performance, affordable price, strong practicability and generalization performance, and high bio-oil yield.
Description
Technical field
The invention belongs to derived energy chemical technical field.The method that Asia/Supercritical Ethanol liquefied straw fibrid element prepares bio oil is worked in coordination with more particularly, to a kind of hydroxyl donor.
Background technology
Along with fossil energy crisis of resource, price is surging and society is to environmental protection concern, people will seek reproducible bioenergy and substitute fossil energy.About 95,000,000,000 tons of carbon of biomass circulating that the annual photosynthesis of cosmopolitian plant produces, and the consumption of Fossil fuel is annual 6500000000 tons of carbon, far beyond resource requirement, it is seen that biomass are the preferable resource that can rely on for a long time of the mankind and the energy.Therefore; stalk cellulose biolobic material resource based on plant is a reproducible huge resource treasure-house; reproducible biomass are utilized to develop chemical products, medicine, the energy, material; many countries are the most become to dissolve crisis of resource, to realize the sustainable development strategic choice as target; and the rising industry (Miquan age etc., 2010) of 21 century will be become.Stalk fibrid element is the Renewable resource that can be converted into hydrocarbon liquid and gaseous fuel, can be converted into the platform chemicals such as esters, ketone and alcohols with direct liquefaction simultaneously.Biomass resource utilization may experience 3 stages to have research to point out: fuel production；Platform chemicals produces；All kinds of chemicals production.Compared with traditional fossil energy, stalk fibrid element biolobic material can have recyclability, environment friendly, popularity, easy firing (Peng Wencai, 2011), it is seen that exploitation stalk fibrid element resource is prepared the bio oil energy and had broad application prospects.
At present, stalk fibrid element method for transformation is broadly divided into microbial method and thermochemical method two kinds, and wherein thermochemical method mainly includes direct combustion method, be pyrolyzed, gasify and liquefy (Toor et al, 2011) etc..Utilize bioanalysis that stalk fibrid element can effectively be converted into fuel or the platform chemicals such as ethanol, methane, lactic acid, but it is high to utilize bioanalysis to utilize stalk fibrid element to there is reaction condition requirement, bacterial screening difficulty, and the shortcoming such as reaction time is longer.At present, stalk fibrid element mainly utilizes thermochemical method to be translated into useful fuel and platform chemicals, but pyrolysis and gasification technology exist the shortcomings such as tar content is high, product yield is low.
In recent years, stalk fibrid element Direct liquefaction technology, especially supercritical fluid liquefaction technology have the advantages such as liquid product yield is high, product selectivity is good and receive much attention.Therefore, supercritical liquefaction technological development stalk fibrid element resource is utilized to have vast potential for future development.Supercritical fluid, as reaction medium, has and makes reactant mixture homogeneously change, and reduces the generation of reaction temperature, beneficially free radical, overcomes interfacial tension, increases the dissolubility of reactant.Therefore shooting flow bulk properties is applied to the liquefaction of stalk fibrid element, can reach the purpose of Efficient Conversion stalk fibrid element.Study more supercritical fluid at present and have water, alcohol etc..Chinese scholars extensively study and utilizes supercritical fluid liquefaction technology process stalk fibrid plain with preparing liquid fuel and chemical products, and achieves a series of achievement in research.China carries out the research of stalk fibrid element liquefaction technology and starts late, and owing to mainly studying based on single technology, has lacked certain systematic study, has caused making slow progress, and compared with the developed country such as American-European, there is bigger gap.China is large agricultural country, stalk fibrid element aboundresources, and domestic scholars has carried out certain research to liquefaction preparing bio-oils such as corn straw, rice straw, timber, straws.Foreign scholars to palm fruit, microcrystalline Cellulose respectively in Asia/supercritical methanol, ethanol, acetone, 1,4-oxepane and water liquefy preparing bio-oil tested.Result of study shows that solvent species, reaction temperature, response time etc. are distributed considerable influence to bio oil；And under organic solvent effect, what stalk fibrid element can be more efficient is converted into bio oil.
Summary of the invention
The technical problem to be solved in the present invention is to overcome above-mentioned defect of the prior art and technical deficiency, it is provided that a kind of method of new stalk fibrid element liquefaction preparation bio oil, specifically a kind of at hydroxyl donor (H2O2, salicylic acid, the hydroxy acid such as aspirin) utilize under synergism the Small molecule organic solvents (methanol, ethanol, hexamethylene or acetone etc.) under subcritical or super critical condition to realize the stalk fibrid element method that efficiently liquefaction converts preparation bio oil.
It is an object of the invention to provide a kind of hydroxyl donor and work in coordination with the method that Asia/Supercritical Ethanol liquefied straw fibrid element prepares bio oil.
Another object of the present invention is to provide the bio oil prepared by said method.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of hydroxyl donor works in coordination with the method that Asia/Supercritical Ethanol liquefied straw fibrid element prepares bio oil, comprise the steps: to be placed in the pressure vessel with magnetic stirring apparatus the Small molecule organic solvents under stalk fibrid element, sub/super-critical condition and hydroxyl donor substance, temperature be 240～320 DEG C, pressure be to react under the conditions of 5.0～9.0Mpa, and keep 10～130min in this state, it is cooled to room temperature, collects product and obtain liquid bio oil；Wherein, the mass volume ratio of described stalk fibrid element, ethanol and hydroxyl donor substance is 5～20g:50～150mL:0.1～5mL.
Wherein it is preferred to, the mass volume ratio of described stalk fibrid element, ethanol and hydroxyl donor substance is 7～15g:100mL:0.1～4mL.
Most preferably, the mass volume ratio of described stalk fibrid element, ethanol and hydroxyl donor substance is 8g:100mL:2～3mL.
Preferably, the temperature of described reaction is 260～320 DEG C.
Preferably, the temperature of described reaction is 270～290 DEG C.
It is highly preferred that the temperature of described reaction is 280 DEG C.
Preferably, the time of described holding is 35～120min.
Preferably, described hydroxyl donor substance is hydroxy acid.
It is highly preferred that described hydroxyl donor substance is salicylic acid, aspirin or H2O2。
Preferably, the Small molecule organic solvents under described sub/super-critical condition is Asia/Supercritical Ethanol, methanol, hexamethylene or acetone etc..
It is highly preferred that described hydroxyl donor substance is salicylic acid, the Small molecule organic solvents under described sub/super-critical condition is Asia/Supercritical Ethanol.
It addition, the method for described collection product is for using washes of absolute alcohol reactor wall, collecting solid-liquid mix products, used dehydrated alcohol extraction, vacuum filtration, filtrate uses Rotary Evaporators ethanol evaporation, remaining material to be bio oil.
It addition, described stalk fibrid element is the cellulose extracted from stalk powder.
Preferably, the raw material sources of described stalk fibrid element are one or more mixture in straw, trees, herbage, rice husk, plant seed, bagasse, sawdust or wood flour.
Preferably, described raw material sources when preparing described stalk fibrid element, the grain graininess of raw material is 40～60 mesh.
Preferably, Extracting temperature during described raw material extraction cellulose it is 35～100 DEG C, extraction time 13～17h.
Further, by the described method being extracted stalk fibrid element by described raw material sources it is: described raw material (straw etc.) first removes the water-soluble substanceses such as liposoluble substance, and many sugar and starches, then delignification, finally remove hemicellulose, obtain stalk fibrid element product.
More specifically, as one preferably can embodiment, by described raw material sources extract stalk fibrid element method as follows:
S1. liposoluble substance and water-soluble substances are removed
With reference to standard GB/T/T 2677.1-93 ~ GB/T
Correlation technique in 2677.10-95, carries out pre-extracting with ethanol-benzene (volume ratio is 2:1) to stalk powder, removes liposoluble substance；With distilled water, stalk powder is stirred 2h, the water-soluble substances such as Polysaccharide removing and starch at 70～80 DEG C again；(straw, in addition to forming containing substantial amounts of cellulose, hemicellulose and lignin, possibly together with compositions such as par-tial polysaccharide, starch, liposoluble substances, therefore, first passes through the pretreatment of step S1)；
S2. delignification
S21., the sample that step S1 is removed liposoluble substance and water-soluble substances adds in distilled water；
S22. add glacial acetic acid and sodium chlorite shakes up, seal, be placed in the water bath with thermostatic control of 70～80 DEG C (preferably 75 DEG C) heating 1h；Described distilled water: glacial acetic acid: sodium chlorite=65mL:0.5mL(10 drips): 0.5g；
S23. repeating the operation 2 of step S22～4 times, until cellulose bleaches, lignin is entirely removed；
The most finally cool down, solution is filtered, arriving neutrality with distilled water wash sample pellet to washing liquid, and sample immigration 90～100 DEG C is dried to constant weight, obtain the crude fibre (cellulose and hemicellulose) being dried；
S3. hemicellulose is removed
Weigh step S2 the most delignified crude fibre sample, add 16% sodium hydroxide solution, solid-liquid ratio is 1:20, put into the constant temperature water bath vibration of 60～70 DEG C, extracting 8～9h removal hemicellulose, isolated be precipitated as cellulose, gained cellulose is dried to constant weight in 90～100 DEG C, obtains dry products and be stalk cellulose.
It addition, the bio oil prepared by said method, also within protection scope of the present invention.
The present invention uses Asia/Supercritical Ethanol and hydroxyl donor salicylic acid etc. to carry out liquefaction preparation bio oil as stalk fibrid element under reaction medium, purpose product is bio oil, it is (to there is catalyst function) with salicylic acid as initiator, prepare bio oil with Asia/Supercritical Ethanol for solvent liquefaction cellulose, it is desirable to provide as the industrialization of bioenergy for bio oil and instruct.Salicylic acid of the present invention etc. are as hydroxyl donor, hydroxyl radical free radical initiator and catalyst, in addition to himself discharges substantial amounts of hydroxyl radical free radical, also stimulate and cause Supercritical Ethanol to produce more hydroxyl radical free radical, be greatly reinforced the redox of hydroxyl radical free radical in liquefaction system.Hydroxyl radical free radical participates in the cellulolytic reaction (super critical point of ethanol, critical temperature 243.5 DEG C, critical pressure 6.34MPa), the fragment of ethanol cracking also can generate the material in some bio oil with cellulose chips reaction, the two synergism can promote cellulose more efficient change into bio oil.Due to the excitation of the hydroxyl donors such as salicylic acid, making cellulose liquefying conversion rate and reaction rate be greatly improved, liquefaction bio oil yield is also greatly improved.And, lower of same reaction conditions need to be added a small amount of hydroxyl donor materials such as () salicylic acid and cellulose Asia/Supercritical Ethanol liquefaction bio oil productivity is just greatly improved.
It addition, the present invention selects ethanol as supercritical solvent, it has relatively low critical temperature or pressure, and condition is the gentleest, and ethanol price is the most more economical；Select the materials such as salicylic acid as hydroxyl donor, it is only necessary to less addition just can be greatly improved concentration and the activity of hydroxyl radical free radical in reaction system simultaneously.Ethanol can produce the multiple free radical such as HO, H under Asia/supercriticality, and when reaction temperature raises, ethanol free radical activity strengthens, concentration increases, and Free Radical promotes the bond fission such as C-C, C-O and-OH in cellulose series biomass.Further, HO concentration and activity raise and can improve bio oil productivity, are because HO and have extremely strong oxidisability and promote the reaction between cracking and the bioactive molecule fragment of cellulose, promote cellulose and liquefy the generation of more product liquids.Therefore interpolation hydroxyl donor (H can be used2O2, the hydroxy acid such as salicylic acid, aspirin) method produce substantial amounts of hydroxyl radical free radical, thus the targetedly concentration improving HO in response system of property and activity, promote cellulolytic, reach selectively to improve the purpose of bio oil productivity.
The method of the present invention overcomes that bioanalysis utilizes that stalk fibrid element requires height, bacterial screening difficulty at reaction condition, utilization rate is low and the shortcoming such as reaction time is longer, and the shortcoming such as the tar content that the pyrolysis of stalk fibrid element and gasification are converted into useful fuel and platform compounding techniques exists is high, product yield is low, energy consumption is high and equipment requirements is high.
The method have the advantages that
The invention provides the method that Asia under a kind of hydroxyl donor synergism/supercritical medium liquefied straw fibrid element prepares bio oil, the method uses Asia/Supercritical Ethanol and hydroxyl donor to prepare bio oil as reaction medium, relatively low to equipment and materials performance requirement, transformation efficiency is high, energy consumption is relatively low, and stalk fibrid element raw material liquefaction gained bio oil yield is up to 24.7%～58.2%；And stalk fibrid element conversion ratio is up to 65.6%～90.4%.
The present invention selects ethanol as supercritical solvent (as reaction medium), it has relatively low critical temperature 240～250 DEG C and critical pressure 6～7Mpa(critical temperature about 243.5 DEG C, about critical pressure 6.34MPa), reaction condition is the gentleest, and industrial alcohol price relatively economical, practical generalization is strong.
The present invention selects hydroxyl donor (salicylic acid etc.) hydroxyl group, concentration and the activity of HO that ethanol under Asia/supercriticality produce can be substantially improved, the strong oxidizing property of HO is converted into bio oil to cellulose liquefaction and is obviously promoted effect, and hydroxyl donor addition is less, just can reach hydroxyl group concentration and the effect of activity are substantially improved, cost is relatively low, has actual application value.
Accompanying drawing explanation
Fig. 1 is the impact on bio oil yield of the salicylic acid consumption.
Fig. 2 is the reaction temperature impact on bio oil yield.
Fig. 3 is bio oil yield contrast under differential responses medium.
Detailed description of the invention
Further illustrate the present invention below in conjunction with Figure of description and specific embodiment, but the present invention is not limited in any form by embodiment.Unless stated otherwise, the present invention uses reagent, method and apparatus are the art conventional reagent, method and apparatus.
Unless stated otherwise, agents useful for same of the present invention and material are commercial.
Embodiment
1
The impact on bio oil yield of the salicylic acid consumption
1, stalk fibrid element is prepared
The method being extracted stalk fibrid element by raw materials such as straws is as follows:
The most accurately weigh 2g stalk powder, with reference to standard GB/T/T 2677.1-93 ~ GB/T
Correlation technique in 2677.10-95, extracts in advance with ethanol-benzene (volume ratio is 2:1), removes liposoluble substance；With distilled water, stalk powder is stirred 2h, the water-soluble substances such as Polysaccharide removing, starch at 70～80 DEG C again；(straw, in addition to forming containing substantial amounts of cellulose, hemicellulose and lignin, possibly together with compositions such as par-tial polysaccharide, starch, liposoluble substances, therefore, first passes through the pretreatment of step S1)；
The most then step S1 is removed in the sample addition 65mL distilled water of liposoluble substance, polysaccharide, starch, add 10 (0.5mL) glacial acetic acid and 0.5g sodium chlorite shakes up, seal, after being placed in the water bath with thermostatic control of 70～80 DEG C (preferably 75 DEG C) heating 1h；Add 10 (0.5mL) glacial acetic acid and 0.5g sodium chlorite, shake up, seal, continue to heat 1h in the water-bath of 70～80 DEG C；So repeating 2～4 times, until cellulose bleaches, now lignin is entirely removed；Finally cool down, solution is filtered, arriving neutrality with distilled water wash sample pellet to washing liquid, and sample immigration 90～100 DEG C is dried to constant weight, obtain the crude fibre (cellulose and hemicellulose) being dried；
The most then 5g step S2 the most delignified crude fibre sample is weighed, add 16% sodium hydroxide solution, solid-liquid ratio is 1:20, put into the constant temperature water bath vibration of 60～70 DEG C, extracting 8～9h removal hemicellulose, isolated be precipitated as cellulose, gained cellulose is dried to constant weight in 90～100 DEG C, obtains dry products and be stalk cellulose.
2, preparation bio oil
The 8g cellulose powder after drying produced by the corn stalk raw material that granularity is 40～60 mesh, 100mL ethanol, 0～4mL salicylic acid are added in the batch autoclave with magnetic stirring apparatus that volume is 1L, it is warming up to 280 DEG C after sealing, and keeps reaction 60 min at this temperature.It is cooled to room temperature, collects product.
Product in gaseous state is gas-phase product at normal temperatures and pressures.Using washes of absolute alcohol reactor wall, collect solid-liquid mix products, used dehydrated alcohol extraction, use vacuum pump sucking filtration, filtrate uses Rotary Evaporators ethanol evaporation, remaining material to be bio oil.Finally, the material insoluble in dehydrated alcohol is residue solid thing.Product yield is to calculate on the basis of the raw materials quality that the quality of products therefrom is later divided by removing ash.
3, stalk cellulose is carried out yield statistics in 280 DEG C, 60min, ethanol consumption 100mL, the bio oil that under salicylic acid consumption respectively 0,1,2,3 and 4mL, liquefaction is generated, by calculating, obtain the yield of bio oil.
4, result is as shown in table 1 and accompanying drawing 1.
The impact on bio oil yield of the table 1 salicylic acid consumption
As can be seen from Table 1, hydroxyl donor salicylic acid consumption creates large effect to the yield of bio oil, and when salicylic acid consumption is 0mL, bio oil yield is only 24.7%, but after salicylic acid consumption increases to 2mL, bio oil yield increases to 53.2%.Along with the increase of salicylic acid consumption, bio oil yield first increases and is reduced to 43.2% afterwards, and when salicylic acid consumption is increased to 2mL by 0mL, bio oil yield is increased to 53.2% by 24.7%.Being likely due under Asia/supercriticality, salicylic acid consumption increases, and hydroxyl radical free radical and ethanol number of free radical constantly increase, and promotes cellulose, macromolecular substances and active reaction fragment pyrolysis liquefying, promotes that bio oil generates.Add yield when bio oil yield after hydroxyl donor salicylic acid is above being not added with salicylic acid.After salicylic acid consumption is more than 2ml, part biological oil and fragment under the effect of high concentration HO, occur further polycondensation, be cyclized, cracking etc. changes into solid, gaseous product, causes bio oil yield to decrease.
Embodiment
2
The reaction temperature impact on bio oil yield when adding salicylic acid
1, method
The 8 g cellulose powders after drying produced by the corn stalk raw material that granularity is 40～60 mesh, 100 mL ethanol, 2mL salicylic acid are added in the batch autoclave with magnetic stirring apparatus that volume is 1 L, it is warming up to 240 DEG C～320 DEG C after sealing, and keeps reaction 60 min at this temperature.It is cooled to room temperature, collects product.It is cooled to room temperature, collects product.Product collection method is with embodiment 1.Product yield is to calculate on the basis of the raw materials quality that the quality of products therefrom is later divided by removing ash.
2, respectively to stalk cellulose at ethanol consumption 100mL, salicylic acid consumption 2mL, response time 60min, reaction temperature profile is 250 DEG C, 280 DEG C, liquefaction is generated at 300 DEG C and 320 DEG C bio oil carry out yield statistics, by calculating, obtain the yield of bio oil.
3, result is as shown in table 2 and accompanying drawing 2.
The reaction temperature impact on bio oil yield when table 2 adds salicylic acid
As shown in Table 2, reaction temperature has large effect to stalk fibrid element liquefaction products bio oil yield, rising along with temperature, bio oil yield occurs first rising the trend reduced afterwards, risen to 58.2% by 35.9% and drop to 41.5% again, this is increased to 280 DEG C mainly due to along with temperature, and hydroxyl radical free radical and ethanol free radical activity strengthen, and promotes that cellulose liquefaction changes into bio oil；When temperature is increased to 320 DEG C further, hydroxyl radical free radical and ethanol free radical activity are further, strengthen promote the product liquid that cellulose liquefaction generated occur to be condensed further, be cyclized, the reaction such as polymerization, be partially converted into gas and solid matter.
Comparative example
3
It is not added with the reaction temperature impact on bio oil yield during salicylic acid
1, method
The 8 g cellulose powders after drying produced by the corn stalk raw material that granularity is 40～60 mesh, 100 mL ethanol, 0mL salicylic acid are added in the batch autoclave with magnetic stirring apparatus that volume is 1 L, it is warming up to 240 DEG C～320 DEG C after sealing, and keeps reaction 60 min at this temperature.It is cooled to room temperature, collects product.It is cooled to room temperature, collects product.Product collection method is with embodiment 1.Product yield is to calculate on the basis of the raw materials quality that the quality of products therefrom is later divided by removing ash.
2, respectively to stalk cellulose at ethanol consumption 100mL, salicylic acid consumption 0mL, response time 60min, reaction temperature profile is 250 DEG C, 280 DEG C, liquefaction is generated at 300 DEG C and 320 DEG C bio oil carry out yield statistics, by calculating, obtain the yield of bio oil.
3, result is as shown in table 3.
Table 3 is not added with the reaction temperature impact on bio oil yield during salicylic acid
As shown in Table 3, reaction temperature has large effect to stalk fibrid element liquefaction products bio oil yield, rising along with temperature, there is ascendant trend in bio oil yield, 38.0% is risen to by 15.0%, this raises mainly due to along with temperature, ethanol free radical and fragment increased activity, promotes the product liquid that cellulose liquefaction is generated.But be not added with hydroxyl donor salicylic under the conditions of, bio oil yield synchronize less than add 2ml salicylic acid time bio oil yield, illustrate that salicylic acid promotes the generation of bio oil.
Comparative example
4
The reaction temperature impact on bio oil yield during simple thermal cracking
1, method
The 8 g cellulose powders after drying produced by the corn stalk raw material that granularity is 40～60 mesh, 100 mL ethanol, 0mL salicylic acid are added in the batch autoclave with magnetic stirring apparatus that volume is 1 L, it is warming up to 240 DEG C～320 DEG C after sealing, and keeps reaction 60min at this temperature.It is cooled to room temperature, collects product.It is cooled to room temperature, collects product.Product collection method is with embodiment 1.Product yield is to calculate on the basis of the raw materials quality that the quality of products therefrom is later divided by removing ash.
2, respectively to stalk cellulose at ethanol consumption 0mL, salicylic acid consumption 0mL, response time 60min, the bio oil that reaction temperature profile is 280 DEG C, liquefaction is generated at 320 DEG C carries out yield statistics, by calculating, obtains the yield of bio oil.
3, result is as shown in table 4.
Table 4 is not added with the reaction temperature impact on bio oil yield when ethanol and salicylic acid
As shown in Table 4, reaction temperature raises, and fracture, the open loop etc. such as cellulose is internal to be dehydrated, carbon-carbon bond and carbon-oxygen bond are reacted, and stalk fibrid element thermal cracking products bio oil yield is risen to 3.4% by 2.7%.When being not added with ethanol and salicylic acid, bio oil yield is the lowest, and cellulose conversion ratio is only 3% ~ 5%, and major part cellulose not yet cracks formation bio oil.This occurs cracking to need higher activation energy mainly due to the key within cellulosic molecule, cracking temperature require to reach 500 DEG C and more than.
It addition, bio oil yield contrasts as shown in Figure 3 under differential responses medium, show that the bio oil yield of the method (reaction medium is the hydroxyl donor such as ethanol and salicylic acid) of the present invention is the highest, be significantly higher than contrast groups.
Claims (10)
1. a hydroxyl donor works in coordination with the method that Asia/Supercritical Ethanol liquefied straw fibrid element prepares bio oil, it is characterized in that, comprise the steps: to be placed in the pressure vessel with magnetic stirring apparatus the Small molecule organic solvents under stalk fibrid element, sub/super-critical condition and hydroxyl donor substance, temperature be 240～320 DEG C, pressure be to react under the conditions of 5.0～9.0Mpa, and keep 10～130min in this state, it is cooled to room temperature, collects product and obtain bio oil；Wherein, the mass volume ratio of described stalk fibrid element, ethanol and hydroxyl donor substance is 5～20g:50～150mL:0.1～5mL.
Method the most according to claim 1, it is characterised in that the mass volume ratio of described stalk fibrid element, ethanol and hydroxyl donor substance is 5～20g:100mL:0.1～4mL.
Method the most according to claim 1, it is characterised in that described hydroxyl donor substance is hydroxy acid.
Method the most according to claim 1, it is characterised in that described hydroxyl donor substance is salicylic acid, aspirin or H2O2。
Method the most according to claim 1, it is characterised in that the Small molecule organic solvents under described sub/super-critical condition is Asia/Supercritical Ethanol, methanol, hexamethylene or acetone.
Method the most according to claim 1, it is characterised in that described hydroxyl donor substance is salicylic acid, the Small molecule organic solvents under described sub/super-critical condition is Asia/Supercritical Ethanol.
Method the most according to claim 1, it is characterised in that the raw material sources of described stalk fibrid element are one or more mixture in straw, trees, herbage, rice husk, plant seed, bagasse, sawdust or wood flour.
Method the most according to claim 7, it is characterized in that, described raw material sources, when preparing described stalk fibrid element, the grain graininess of raw material is 40～60 mesh, it is 35～100 DEG C by Extracting temperature during described raw material extraction cellulose, extraction time 13～17h.
Method the most according to claim 1, it is characterised in that the method for described collection product is for use washes of absolute alcohol reactor wall, collect solid-liquid mix products, used dehydrated alcohol extraction, vacuum filtration, filtrate uses Rotary Evaporators ethanol evaporation, remaining material to be bio oil.
10. the bio oil prepared according to the arbitrary described method method of claim 1～9.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107670646A (en) * | 2017-09-22 | 2018-02-09 | 中国科学院合肥物质科学研究院 | A kind of bead structure nano zero valence iron/cellulose composite material and its application |
| CN107892939A (en) * | 2017-10-20 | 2018-04-10 | 华南农业大学 | A kind of method that talan prepares bio oil with Supercritical Ethanol collective effect liquified cellulosic |
| CN108752486A (en) * | 2018-04-20 | 2018-11-06 | 华南农业大学 | One-step method sulphuric acid hydrolysis prepares cellulose II nanometer crystal method |
| CN110894513A (en) * | 2019-12-04 | 2020-03-20 | 沈阳航空航天大学 | Method for co-producing ethanol and biological oil rich in phenols by using lignocellulose biomass |
| CN112479190A (en) * | 2020-12-03 | 2021-03-12 | 天津农学院 | Method for preparing graphene-like precursor from biomass |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447305A (en) * | 2014-12-16 | 2015-03-25 | 华南农业大学 | Method for preparing ester compound from subcritical/supercritical ethanol liquified straw cellulose |
-
2016
- 2016-05-06 CN CN201610295527.0A patent/CN105950274A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447305A (en) * | 2014-12-16 | 2015-03-25 | 华南农业大学 | Method for preparing ester compound from subcritical/supercritical ethanol liquified straw cellulose |
Non-Patent Citations (2)
| Title |
|---|
| 陶红秀 等: "玉米秸秆纤维素在亚／超临界乙醇中的液化行为研究", 《西北农林科技大学学报（自然科学版）》 * |
| 黎巍等: "亚/超临界乙醇中羟基和氢自由基作用下的纤维素液化行为", 《燃料化学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107670646A (en) * | 2017-09-22 | 2018-02-09 | 中国科学院合肥物质科学研究院 | A kind of bead structure nano zero valence iron/cellulose composite material and its application |
| CN107670646B (en) * | 2017-09-22 | 2020-03-10 | 中国科学院合肥物质科学研究院 | Beaded nano zero-valent iron/cellulose composite material and application thereof |
| CN107892939A (en) * | 2017-10-20 | 2018-04-10 | 华南农业大学 | A kind of method that talan prepares bio oil with Supercritical Ethanol collective effect liquified cellulosic |
| CN108752486A (en) * | 2018-04-20 | 2018-11-06 | 华南农业大学 | One-step method sulphuric acid hydrolysis prepares cellulose II nanometer crystal method |
| CN110894513A (en) * | 2019-12-04 | 2020-03-20 | 沈阳航空航天大学 | Method for co-producing ethanol and biological oil rich in phenols by using lignocellulose biomass |
| CN110894513B (en) * | 2019-12-04 | 2023-06-13 | 沈阳航空航天大学 | Method for co-producing ethanol and phenolic bio-oil-rich biomass by lignocellulose |
| CN112479190A (en) * | 2020-12-03 | 2021-03-12 | 天津农学院 | Method for preparing graphene-like precursor from biomass |
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