CN103555353B - A kind of method of supercritical fluid catalytic liquefaction plant material - Google Patents
A kind of method of supercritical fluid catalytic liquefaction plant material Download PDFInfo
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- CN103555353B CN103555353B CN201310374307.3A CN201310374307A CN103555353B CN 103555353 B CN103555353 B CN 103555353B CN 201310374307 A CN201310374307 A CN 201310374307A CN 103555353 B CN103555353 B CN 103555353B
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Abstract
A kind of method that the invention discloses supercritical fluid catalytic liquefaction plant material, comprises the following steps: plant material is pulverized and crosses 40 ~ 60 mesh sieves, drying by (1)；(2) in autoclave, add plant material and alcoholic solvent, with solid heteropoly acid as catalyst, after reacting 10 50min in the supercritical state, liquefaction products dehydrated alcohol is washed out, steam obtain bio-oil through sucking filtration, rotation.The present invention can greatly improve the liquefied fraction of plant material；With solid heteropoly acid as catalyst, substitute traditional liquid strong acid catalyst such as H2SO4、HCl、HNO3Deng, there is environmental pollution little, not etching apparatus, the advantage such as easily separated；In the bio-oil obtained, Ester content is high, and particularly levulic acid ester content is up to 20.82%, can be directly used as gasoline additive, bio liquid fuel, has the advantages such as nontoxic, high-lubricity, high heating value, is a kind of clean energy resource.
Description
Technical field
The invention belongs to green chemical industry field, be specifically related to a kind of method that supercritical fluid catalytic liquefaction plant material obtains high-quality biological matter oil.
Background technology
Cause energy security and problem of environmental pollution to become increasingly conspicuous along with conventional fossil resource is depended on unduly use, utilize renewable biomass to substitute conventional fossil resource and more and more paid close attention to by people.Can produce the plant material garbage of enormous amount in annual China agriculture and forestry process of manufacture, people generally use traditional direct combustion method to process, and this method not only resource utilization is low, and easily causes environmental pollution.Therefore, realized the efficient liquefaction of plant material by thermochemical study method, obtain fuel or chemicals has application prospect.Supercritical fluid refers to that temperature and pressure is all close to or higher than the fluid of its critical temperature and critical pressure, has high diffusibility and highly dissoluble, can realize the liquefaction of plant material as solvent.But, under without catalyst existence condition, plant material liquefied fraction is the most relatively low.Result of study shows that the tradition strong acid catalyst such as sulphuric acid, hydrochloric acid can promote plant material liquefaction in supercritical fluid, but they have the shortcoming such as strong oxidizing property, severe corrosive, are unfavorable for industrialized production.Solid heteropoly acid catalyst efficient as one, eco-friendly, can substitute the traditional liquid strong acid such as sulphuric acid, hydrochloric acid, meet green chemical industry development trend, it is possible to achieve the efficient liquefaction of plant material.
Summary of the invention
A kind of method that it is an object of the invention to provide supercritical fluid catalytic liquefaction plant material, with alcohol as solvent, solid heteropoly acid is catalyst, realize the liquefaction of biomass at supercritical conditions, in gained liquefaction oil product, Ester content is high, can be directly used as gasoline additive, biomass liquid fuel etc. as clean energy resource.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of method of supercritical fluid catalytic liquefaction plant material comprises the following steps:
(1) plant material pulverized and cross 40 ~ 60 mesh sieves, drying；
(2) in autoclave, add plant material and alcoholic solvent, with solid heteropoly acid as catalyst, in the supercritical state after reaction 10-50min, liquefaction products dehydrated alcohol is washed out, steam obtain bio-oil through sucking filtration, rotation.
Described alcoholic solvent is methanol, ethanol or isopropanol.
Described solid heteropoly acid is phosphotungstic acid, phosphomolybdic acid or zirconium phosphate.
Described plant material includes timber, stalk, crudefiber crop.
The remarkable advantage of the present invention is:
(1) liquefied fraction of plant material can greatly be improved.
(2) with solid heteropoly acid as catalyst, traditional liquid strong acid catalyst such as H is substituted2SO4、HCl、HNO3Deng, there is environmental pollution little, not etching apparatus, the advantage such as easily separated.
(3) in the bio-oil obtained, Ester content is high, and particularly levulic acid ester content is up to 20.82%, can be directly used as gasoline additive, bio liquid fuel, has the advantages such as nontoxic, high-lubricity, high heating value, is a kind of clean energy resource.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the liquefied residue (b) of cedar sawdust (a) and embodiment 4.
Detailed description of the invention
Embodiment
1
Concretely comprising the following steps of a kind of method of supercritical fluid catalytic liquefaction plant material:
(1) weigh 150 g dehydrated alcohol, 1 g cedar sawdust adds in autoclave, adds 0.5 g phosphotungstic acid catalyst.
(2) reactor being heated to 260 DEG C, response time 30 min, liquefied fraction is 95.35%.
Embodiment
2
Concretely comprising the following steps of a kind of method of supercritical fluid catalytic liquefaction plant material:
(1) weigh 120 g methanol, 1 g corn straw adds in autoclave, adds 0.5 g phosphomolybdic acid catalyst.
(2) reactor being heated to 280 DEG C, response time 10 min, liquefied fraction is 90.34%.
Embodiment
3
Concretely comprising the following steps of a kind of method of supercritical fluid catalytic liquefaction plant material:
(1) weigh 120 g isopropanols, 1 g Caulis et Folium Lini adds in autoclave, adds 0.4 g zirconium phosphate catalyst.
(2) reactor being heated to 250 DEG C, response time 30 min, liquefied fraction is 91.53%.
Embodiment
4
Concretely comprising the following steps of a kind of method of supercritical fluid catalytic liquefaction plant material:
(1) weigh 150 g dehydrated alcohol, 1 g cedar sawdust adds in autoclave, adds 0.4 g phosphotungstic acid catalyst.
(2) reactor being heated to 260 DEG C, response time 30 min, liquefied fraction is 92.68%.
Embodiment
5
Concretely comprising the following steps of a kind of method of supercritical fluid catalytic liquefaction plant material:
(1) weigh 120 g methanol, 1 g cedar sawdust adds in autoclave, adds 0.5 g phosphotungstic acid catalyst.
(2) reactor being heated to 280 DEG C, response time 30 min, liquefied fraction is 93.41%.
Embodiment
6
Concretely comprising the following steps of a kind of method of supercritical fluid catalytic liquefaction plant material:
(1) weigh 120g isopropanol, 1 g corn straw adds in autoclave, adds 0.5 g phosphotungstic acid catalyst.
(2) reactor being heated to 250 DEG C, response time 50 min, liquefied fraction is 92.31%.
Embodiment
7
Use U.S. Thermo electro company Nicolet 380 type Fourier transformation infrared spectrometer (FT-IR) that plant material, embodiment 4 liquefied residue are carried out FT-IR sign: to be clayed into power by sample, being sufficiently mixed grinding, tabletting with KBr in 1:150 ratio, it is 4000 ~ 400 cm that wave number measures scope-1, scanning times is 32 s-1, resolution is 4 cm-1.Result is as shown in Figure 1.Compared with its raw material, the FT-IR collection of illustrative plates of liquefied residue there occurs significantly change.At 1079 cm in liquefied residue infrared spectrum-1、984 cm-1 、892 cm-1With 811 cm-1There is the diagnostic strong absorption peak of keggin structure phosphotungstic acid in place, is respectively belonging to tetrahedron oxygen P-OaVibration, end oxygen W=OdVibration, bridging oxygen W-Ob-W vibration, bridging oxygen W-Oc-W vibration, consistent with the standard FT-IR collection of illustrative plates of phosphotungstic acid, illustrate that liquefied residue contains more phosphotungstic acid catalyst.3392 cm-1、2915 cm-1Place's absworption peak weakens, 1732 cm-1Place's absworption peak disappears, and illustrates that hemicellulose liquefies completely, it can be seen that at 2860 cm-1There are the characteristic absorption peak of a lignin methoxyl group, 1700 cm in place-1Place's absworption peak belongs to and the C=O stretching vibration of aromatic proton conjugation, and 1600,1420cm-1Still there is belonging to phenyl ring skeletal vibration absworption peak, but 1510 cm-1Place's absworption peak disappears, and the material that this explanation has benzene ring structure is enriched with in residue, and different from lignin structure in raw material, mainly liquefying lignin derivant.
Embodiment
8
Normal hexane is added embodiment 4 liquefaction oil product, by extracting, be centrifuged, taking supernatant, is defined as light oil.Use Agilent company 7890A/5975C gas chromatograph-mass spectrometer of the U.S. (GC-MS) that light oil is characterized: chromatographic column is mm × 0.25, middle polarity DB-17m(30 m × 0.25 μm), injector temperature 280 DEG C；Heating schedule, initial temperature: 50 DEG C, keep 3 min, with 5 DEG C of min-1Rise to 280 DEG C, keep 10 min, carrier gas (He) flow velocity 20 mL min-1.Sample introduction 1 μ L, split ratio 15:1；Quadrupole rod temperature 150 DEG C, ion source temperature 230 DEG C, satellite interface temperature 280 DEG C；Retrieval spectrum storehouse is NIST 2011.The composition understanding liquefaction oil product is complicated, and GC-MS also is difficult to be kept completely separate all components, illustrates that wood flour liquefaction is a sufficiently complex course of reaction.The relative amount of these compositions is estimated by peak area normalization method.Liquefaction oil product contains more esters and aromatic compound, ethyl levulinate content is up to 20.82%, next to that 4-hydroxyl 3-methoxyphenylacetic acid methyl ester 5.18%, o-methoxyphenol 3.78%, vanillic acid ethyl ester 3.31%, in addition with materials such as 2-methoxyl group-4-propylphenol, 2-methoxyl group-4-methylphenol, 2-methoxyl group-4-ethyl-phenols.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification, all should belong to the covering scope of the present invention.
Claims (1)
1. the method for a supercritical fluid catalytic liquefaction plant material, it is characterised in that: comprise the following steps:
(1) plant material pulverized and cross 40～60 mesh sieves, drying；
(2) in autoclave, add plant material and alcoholic solvent, with solid heteropoly acid as catalyst, react in the supercritical state
After 10-50min, liquefaction products dehydrated alcohol is washed out, steam obtain bio-oil through sucking filtration, rotation；
Described alcoholic solvent is methanol, ethanol or isopropanol；
Described solid heteropoly acid is phosphotungstic acid or phosphomolybdic acid；
Described plant material includes timber, stalk, crudefiber crop.
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| CN107090303A (en) * | 2017-05-22 | 2017-08-25 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104447305B (en) * | 2014-12-16 | 2017-01-11 | 华南农业大学 | Method for preparing ester compound from subcritical/supercritical ethanol liquified straw cellulose |
| 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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| CN107090303A (en) * | 2017-05-22 | 2017-08-25 | 华南农业大学 | Prepared by overcritical mixed solvent liquefaction lignin is rich in aromatic compound bio oil method |
| 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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