CN103555353A - Method for catalyzing liquefaction of plant raw material by supercutical fluid - Google Patents
Method for catalyzing liquefaction of plant raw material by supercutical fluid Download PDFInfo
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- CN103555353A CN103555353A CN201310374307.3A CN201310374307A CN103555353A CN 103555353 A CN103555353 A CN 103555353A CN 201310374307 A CN201310374307 A CN 201310374307A CN 103555353 A CN103555353 A CN 103555353A
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Abstract
The invention discloses a method for catalyzing the liquefaction of a plant raw material by a supercutical fluid. The method comprises the following steps: 1, crushing the plant raw material, sieving by a 40-60 mesh sieve, and drying; and 2, adding the plant raw material and an alcoholic solvent into an autoclave, reacting in a supercritical state for 10-50min with a solid heteropoly acid as a catalyst, eluting the obtained liquefied product with anhydrous ethanol, carrying out pumping filtration, and carrying out rotary evaporation to obtain biomass oil. The method substantially improves the liquefaction rate of the plant raw material; the method adopting the solid heteropoly acid as a catalyst to substitute a traditional liquid strong acid catalyst, such as H2SO4, HCl and HNO3, has the advantages of small environmental pollution, no corrosion to an apparatus, easy separation and the like; and the obtained biomass oil has a high content of esters, has a highest levulinate content reaching 20.82%, can be directly used as a gasoline additive and biological liquid fuel oil, has the advantages of non-toxicity, high lubricity, high gross calorific value and the like, and is clean energy.
Description
technical field
The invention belongs to green chemical industry field, be specifically related to a kind of method that supercutical fluid catalytic liquefaction plant material obtains high-quality biological matter oil.
Background technology
Along with traditional fossil resource being depended on unduly use, cause that energy security and problem of environmental pollution become increasingly conspicuous, utilize the alternative traditional fossil resource of renewable biomass to be subject to people and more and more pay close attention to.In annual China agroforestry process of manufacture, can produce the plant material waste of enormous amount, people adopt traditional direct combustion method to process conventionally, and this method not only resource utilization is low, and easily causes environmental pollution.Therefore, by thermochemistry method for transformation, realize the efficient liquefaction of plant material, obtain fuel or chemical has application prospect.Supercutical fluid refers to that temperature and pressure is all close to or higher than the fluid of its critical temperature and emergent pressure, has high diffusibility and high resolution, can realize the liquefaction of plant material using it as solvent.But plant material liquefied fraction is conventionally lower under catalyst-free existence condition.Result of study shows that traditional strong acid catalysts such as sulfuric acid, hydrochloric acid can promote the liquefaction of plant material in supercutical fluid, but they have the shortcomings such as strong oxidizing property, severe corrosive, are unfavorable for suitability for industrialized production.Solid heteropoly acid, as a kind of efficient, eco-friendly catalyzer, can substitute the traditional liquid strong acid such as sulfuric acid, hydrochloric acid, meets green chemical industry development trend, can realize the efficient liquefaction of plant material.
Summary of the invention
The object of the present invention is to provide a kind of method of supercutical fluid catalytic liquefaction plant material, take alcohol as solvent, solid heteropoly acid is catalyzer, under super critical condition, realize the liquefaction of biomass, in gained liquefaction oil product, Ester content is high, as clean energy, can directly be used as gasoline dope, biomass liquid fuel etc.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method of supercutical fluid catalytic liquefaction plant material comprises the following steps:
(1) plant material is pulverized and is crossed 40 ~ 60 mesh sieves, oven dry;
(2) in autoclave, add plant material and alcoholic solvent, take solid heteropoly acid as catalyzer, under supercritical state, react after 10-50min, liquefied product is washed out with dehydrated alcohol, pass through suction filtration, revolve and steam acquisition bio-oil.
Described alcoholic solvent is methyl alcohol, ethanol or Virahol.
Described solid heteropoly acid is phospho-wolframic acid, phospho-molybdic acid or zirconium phosphate.
Described plant material comprises timber, stalk, crudefiber crop.
Remarkable advantage of the present invention is:
(1) can improve widely the liquefied fraction of plant material.
(2) take solid heteropoly acid as catalyzer, substitute traditional liquid strong acid catalyst as H
2sO
4, HCl, HNO
3deng, there is environmental pollution little, not etching apparatus, the advantage such as easily separated.
(3) in the bio-oil obtaining, Ester content is high, and particularly levulinic acid ester content, up to 20.82%, can directly be used as gasoline dope, bio liquid fuel, has the advantages such as nontoxic, high lubricity, high heating value, is a kind of clean energy.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the liquefied residue (b) of cedar sawdust (a) and embodiment 4.
Embodiment
A kind of concrete steps of method of supercutical fluid catalytic liquefaction plant material are:
(1) take 150 g dehydrated alcohols, 1 g cedar sawdust adds in autoclave, adds 0.5 g phosphotungstic acid catalyst.
(2) reactor is heated to 260 ℃, reaction times 30 min, liquefied fraction is 95.35%.
embodiment 2
A kind of concrete steps of method of supercutical fluid catalytic liquefaction plant material are:
(1) take 120 g methyl alcohol, 1 g maize straw adds in autoclave, adds 0.5 g phospho-molybdic acid catalyzer.
(2) reactor is heated to 280 ℃, reaction times 10 min, liquefied fraction is 90.34%.
embodiment 3
A kind of concrete steps of method of supercutical fluid catalytic liquefaction plant material are:
(1) take 120 g Virahols, 1 g flax adds in autoclave, adds 0.4 g zirconium phosphate catalyzer.
(2) reactor is heated to 250 ℃, reaction times 30 min, liquefied fraction is 91.53%.
embodiment 4
?a kind of concrete steps of method of supercutical fluid catalytic liquefaction plant material are:
(1) take 150 g dehydrated alcohols, 1 g cedar sawdust adds in autoclave, adds 0.4 g phosphotungstic acid catalyst.
(2) reactor is heated to 260 ℃, reaction times 30 min, liquefied fraction is 92.68%.
embodiment 5
A kind of concrete steps of method of supercutical fluid catalytic liquefaction plant material are:
(1) take 120 g methyl alcohol, 1 g cedar sawdust adds in autoclave, adds 0.5 g phosphotungstic acid catalyst.
(2) reactor is heated to 280 ℃, reaction times 30 min, liquefied fraction is 93.41%.
embodiment 6
A kind of concrete steps of method of supercutical fluid catalytic liquefaction plant material are:
(1) take 120g Virahol, 1 g maize straw adds in autoclave, adds 0.5 g phosphotungstic acid catalyst.
(2) reactor is heated to 250 ℃, reaction times 50 min, liquefied fraction is 92.31%.
embodiment 7
Adopt the U.S. Thermo electro Nicolet of company 380 type Fourier transformation infrared spectrometers (FT-IR) to carry out FT-IR sign to plant material, embodiment 4 liquefied residues: by sample mill powdered, in the abundant mixed grinding of 1:150 ratio, compressing tablet, wave number useful range is 4000 ~ 400 cm with KBr
-1, scanning times is 32 s
-1, resolving power is 4 cm
-1.Result as shown in Figure 1.Comparing with its raw material, there is obvious variation in the FT-IR collection of illustrative plates of liquefied residue.In liquefied residue infrared spectrum at 1079 cm
-1, 984 cm
-1, 892 cm
-1with 811 cm
-1there is the strong absorption peak of feature of keggin structure phospho-wolframic acid in place, belongs to respectively tetrahedron oxygen P-O
avibration, end oxygen W=O
dvibration, bridging oxygen W-O
b-W vibration, bridging oxygen W-Oc-W vibration, consistent with the standard FT-IR collection of illustrative plates of phospho-wolframic acid, illustrate that liquefied residue contains more phosphotungstic acid catalyst.3392 cm
-1, 2915 cm
-1place's absorption peak weakens, 1732 cm
-1place's absorption peak has disappeared, and illustrates that hemicellulose liquefies completely, can see at 2860 cm
-1there are the charateristic avsorption band of an xylogen methoxyl group, 1700 cm in place
-1place's absorption peak belongs to the C=O stretching vibration with aromatic proton conjugation, and 1600,1420cm
-1still there is belonging to phenyl ring skeletal vibration absorption peak, but 1510 cm
-1place's absorption peak has disappeared, and this explanation has material enrichment in residue of benzene ring structure, and different from lignin structure in raw material, is mainly liquefying lignin derivative.
embodiment 8
Normal hexane is added to embodiment 4 liquefaction oil products, by extraction, centrifugal, get supernatant liquor, be defined as light oil.Adopt the U.S. 7890A/5975C of Agilent company gas chromatograph-mass spectrometer (GC-MS) to characterize light oil: chromatographic column is mm * 0.25, Semi-polarity DB-17m(30 m * 0.25 μ m), 280 ℃ of injector temperatures; Heating schedule, starting temperature: 50 ℃, keep 3 min, with 5 ℃ of min
-1rise to 280 ℃, keep 10 min, carrier gas (He) flow velocity 20 mLmin
-1.Sample introduction 1 μ L, splitting ratio 15:1; 150 ℃ of quadrupole temperature, 230 ℃ of ion source temperatures, 280 ℃ of satellite interface temperature; Retrieval spectrum storehouse is NIST 2011.The composition of known liquefaction oil product is complicated, and GC-MS is also difficult to all components completely separated, illustrates that wood chip liquefaction is a very complicated reaction process.By peak area normalization method, estimate the relative content of these compositions.Liquefaction oil product contains compared with polyester class and aromatic compound, ethyl levulinate content is up to 20.82%, is secondly 4-hydroxyl 3-methoxyphenylacetic acid methyl esters 5.18%, hydroxyanisole 3.78%, vanillic acid ethyl ester 3.31%, also has the materials such as 2-methoxyl group-4-propylphenol, 2-methoxyl group-4-methylphenol, 2-methoxyl group-4-ethylphenol in addition.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (4)
1. a method for supercutical fluid catalytic liquefaction plant material, is characterized in that: comprise the following steps:
(1) plant material is pulverized and is crossed 40 ~ 60 mesh sieves, oven dry;
(2) in autoclave, add plant material and alcoholic solvent, take solid heteropoly acid as catalyzer, under supercritical state, react after 10-50min, liquefied product is washed out with dehydrated alcohol, pass through suction filtration, revolve and steam acquisition bio-oil.
2. the method for supercutical fluid catalytic liquefaction plant material according to claim 1, is characterized in that: described alcoholic solvent is methyl alcohol, ethanol or Virahol.
3. the method for supercutical fluid catalytic liquefaction plant material according to claim 1, is characterized in that: described solid heteropoly acid is phospho-wolframic acid, phospho-molybdic acid or zirconium phosphate.
4. the method for supercutical fluid catalytic liquefaction plant material according to claim 1, is characterized in that: described plant material comprises timber, stalk, crudefiber crop.
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Cited By (2)
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| 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 |
| CN105860428A (en) * | 2016-05-30 | 2016-08-17 | 四川国能高科生物树脂有限公司 | Biomass oil suitable for modifying thermosetting resin and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107090303B (en) * | 2017-05-22 | 2018-08-07 | 华南农业大学 | Prepared by overcritical mixed solvent liquefaction lignin is rich in aromatic compound bio oil method |
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| 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 |
| CN105860428A (en) * | 2016-05-30 | 2016-08-17 | 四川国能高科生物树脂有限公司 | Biomass oil suitable for modifying thermosetting resin and preparation method thereof |
| CN105860428B (en) * | 2016-05-30 | 2018-07-27 | 四川国能高科生物树脂有限公司 | A kind of bio-oil and preparation method thereof being modified suitable for thermosetting resin |
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