CN102173980A - Method for preparing phenolic chemicals through thermo-chemical conversion of industrial lignin - Google Patents
Method for preparing phenolic chemicals through thermo-chemical conversion of industrial lignin Download PDFInfo
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Abstract
The invention provides a method for preparing phenolic chemicals through the thermo-chemical conversion of industrial lignin. The method is as follows: under the common functions of solid acid catalyst and hydrogen supply solvent, industrial lignin performs atmospheric thermo-chemical conversion in high boiling point organic reaction medium to prepare homogeneous low molecular weight organic matter with rich phenolic compounds such as phenol, methoxyphenol, dimethoxyphenol and 2-methoxy-4-methylphenol, and the organic reaction medium is recycled through the technologies such as vacuum distillation. The method has simple process, good stability and low production cost; and the yield of the prepared phenolic compounds is more than 54%. The method plays an important role in the high-valued comprehensive utilization of the renewable resource, namely ndustrial lignin; and the converted phenolic chemicals can be used to synthesize phenolic resin, prepare high efficiency cement water-reducing agent and further separate, purify and prepare bio-chemicals. Particularly, by adopting the method, the lignin in papermaking black liquid and preparation residue of biological fuel ethanol prepared from cellulose can be converted to phenolic chemicals; and the method has wide application prospect.
Description
Technical field
The present invention relates to the method that xylogen prepares the phenols chemical, be specifically related to the industrial lignin thermochemistry and transform the method for preparing the phenols chemical.
Background technology
Xylogen is one of plant fiber material moiety, and its content is only second to Mierocrystalline cellulose, and formula has the natural aromatic polymer of three-dimensional net structure.Exist hydroxyl, carbonyl, aromatic base, methoxyl group, conjugated double bond isoreactivity group in the lignin molecule, can realize the number of chemical reaction.But the utilization to xylogen also is not very abundant at present.
The method that the xylogen thermochemistry is converted into the phenols chemical is a kind of under normal pressure, catalyst action, can realize that the xylogen thermochemistry transforms the technology of preparation industrial chemicals.It has need not pressure-resistant equipment, relatively low, the phenols chemical yield advantages of higher of energy consumption.Thermal transition medium commonly used mainly contains polyhydroxy-alcohol and phenol two big classes.Selecting which type of catalyzer and liquefaction medium is the core technology of this method for transformation.The kind of tradition method for transformation used medium is a lot, has: mineral acid (vitriol oil, concentrated hydrochloric acid), organic acid, alkalimetal oxide etc.; Solvent is based on phenol or polyvalent alcohol.
Existing discovering, with appropriate catalyst, in appropriate solvent, the thermochemistry that can carry out xylogen under the relatively mild condition that compares transforms.Hui P., Todd F., people such as Shupe [Polymer Science, 2007,105 (7): 3739-3746] make solvent with phenol, oxalic acid is made catalyzer, and when finding that xylogen liquefies in shedding motion, the liquefaction of temperature rising xylogen is very fast, but in the liquefying plant of sealing condition, same xylogen and solvent burden ratio, when liquefaction temperature raise, content of lignin increased in the residue after the liquefaction.Illustrate that sealing condition is unfavorable for the liquefaction of xylogen.Dietrich M., Ronald A., people [Bioresource Technology, 1992,40:171-177] such as Oskar F. use Pa/C, Raney Ni, Fe respectively
2O
3, and NiO etc. make the hydrogenation liquefaction catalyzer, kind, catalyst levels, hydrogen pressure, temperature, liquefying time and the different sources xylogen of catalyzer have been discussed, and the various liquefaction conditions in the liquefaction of hydrogenation high temperature are to the influence of liquefied product yield and product quality.Though experimental result proves the xylogen liquefaction productive rate difference that different liquifying methods obtain, but the yield and the chemical constitution of the phenols chemical that obtains are constant substantially, this studies show that the highest yield 38% of initial pressure 10MPa, 400 ℃ of phenols chemical of temperature, but this method is very high to equipment requirements, and energy consumption is big.
Summary of the invention
For overcoming deficiency of the prior art, the object of the present invention is to provide a kind of industrial lignin thermochemistry to transform the method for preparing the phenols chemical, be with industrial lignin under the acting in conjunction of solid acid catalyst, an amount of hydrogen supply dissolvent, in high boiling point organic reaction medium, make by the conversion of normal pressure thermochemistry.In reaction process, lignin depolymerization is the homogeneous phase low molecule organic matter of phenol-rich, methoxyphenol, syringol, 2-methoxyl group-phenolic compounds such as 4-methylphenol.Organic reaction medium in the reaction process can reclaim further utilization through technology such as underpressure distillation.
Industrial lignin thermochemistry of the present invention transforms the method for preparing the phenols chemical, and its raw materials by weight portion meter is composed as follows:
The A component:
100 parts of industrial lignins
2～7 parts of solid acid catalysts
3～10 parts of hydrogen supply dissolvents
The B component:
300～700 parts in organic reaction medium
Concrete reactions steps is: the liquefaction of (1) xylogen: reactor is dried and placed to the industrial lignin of above-mentioned weight part, add described catalyzer, hydrogen supply dissolvent and organic reaction medium then, 180 ℃～240 ℃ next time stream carry out thermal conversion reaction, react after 0.3 hour～2 hours and obtain the thermal transition liquefied product; Described solid acid catalyst is phospho-wolframic acid, silicon phosphoric acid or silicoaluminate; Described hydrogen supply dissolvent is tetraline or phenol; Described organic reaction medium is glycerol or ethylene glycol;
(2) separation and Extraction of phenols chemical: the dioxane of 60～120 parts of volume ratio 1:3～1:10 and the mixed solution of water are poured in the above-mentioned thermal transition liquefied product, the back centrifugation that stirs, standing demix obtains upper strata liquid and subnatant; Described subnatant is the organic reaction medium of thermal conversion reaction, recyclable utilization after underpressure distillation; Described upper strata liquid is the mixed solution of phenolic product, dioxane and water, and dioxane and water in the described mixed solution of rotary evaporation promptly obtain the phenols chemical.
Industrial lignin among the present invention is that the Acid precipitation xylogen, the alkali lignin in the paper black liquor, the sulfonated lignin in the paper black liquor, wood fibre in the black liquid separates the xylogen that is rich in the xylogen that obtains or acid hydrolysis of preparation of cellulose alcohol fuel or the enzymic hydrolysis residue.
Described solid acid catalyst is preferably silicoaluminate.
Described hydrogen supply dissolvent is preferably and is tetraline.
Described organic reaction medium is preferably glycerol.
Xylogen thermochemistry of the present invention transforms the method for preparing the phenols chemical, and the optimization of its raw materials by weight portion meter consists of:
The A component:
100 parts of industrial lignins
3～4 parts of catalyzer
4～5 parts of hydrogen supply dissolvents
The B component:
400～500 parts in organic reaction medium
The phenols chemical of the present invention's preparation mainly comprises: phenol, methoxyphenol, syringol, 2-methoxyl group-4-methylphenol, total phenol yield reaches 54%.
The mensuration of its total phenol yield of phenols chemical that the present invention is prepared is pressed GC-MS uantitative analytical method, and concrete operations are:
(1) choosing of internal standard substance: selected cyclohexane give internal standard substance, mainly be because: 1. in liquor, do not contain the hexanaphthene composition; 2. its retention time is close with component to be measured, but can separate fully; 3. chemical structure is similar to component to be measured; 4. with component to be measured any chemical reaction does not take place;
(2) the GC-MS quantitative analysis of sample: during the GC-MS detection by quantitative, the quality of internal standard substance hexanaphthene is known.Can obtain the quality of phenolic product corresponding in the sample according to the peak area percentage ratio of phenols component and the ratio of the peak area percentage ratio of internal standard substance hexanaphthene.The peak area percentage ratio of correspondence is the peak area percentage ratio sum of phenolic product when calculating total phenol yield.
Method of calculation are suc as formula (1):
Wherein: A
1Be the total peak area that the product examine of phenols chemistry is surveyed, A
0Be the peak area that the internal standard substance hexanaphthene detects, M
1Be phenols chemical total mass in the product, M
0Be the internal standard substance quality.
Compare with the plain liquifying method of existing conventional wooden, the present invention has the following advantages:
(1) the present invention has tangible cost advantage with the thermochemistry method for transformation of solid acid catalyst.Especially silicoaluminate is cheap, repeatedly recycling, and recovery process is simple, convenient.Lignin conversion method cost depends primarily on the cost of solvent and catalyzer, solvent glycerol and catalyzer silicoaluminate used among the present invention all can be back to production again, and the mixed solution of the used dioxane/water of separation circuit, also the method for available evaporation reclaims, and so just greatly reduces production cost;
(2) the present invention transforms the industrial lignin thermochemistry and is prepared into the phenols chemical, can make full use of reproducible plant resources, makes full use of the surrogate of plant refuse as petroleum products.Present most of industrial chemicals all is the derived product of petroleum industry, and the energy situation of China is very severe, shortage of resources, and consumption structure is single, the import interdependency height of oil.The China's oil reserves only account for 2% of world's total amount, and consumption but is a second in the world, and demand grows continuously and fast.China in 2010 is with 2.5 hundred million tons of Imported oils, and the import interdependency will be above 50%, and energy security is troubling.And industrial lignin is a kind of reproducible plant resources, and is cheap, wide material sources;
(3) the present invention's industrial lignin is a raw material, compares the advantage with oneself as raw material with utilizing other plant biomass.No matter the alkaline process technology that paper industry extensively adopts be raw material with woody or nonwood plant, all produces a large amount of black liquor of pulp making.Main organism is based on industrial lignin in the black liquor, and the lignin molecule amount that extracts from pulping waste liquor to millions of, and has significant polymolecularity at hundreds of, water insoluble, have good physics, chemical property, as fire-retardant, solvent resistance, good thermal stability.Industrial lignin generally exists with the alkali lignin form, at present and alkali lignin has mainly only utilized its heat energy in the black-liquor combustion process, it is waste to this important chemical material resource, the present invention can realize the higher value application of xylogen, minimizing is to the dependence of fossil resources such as oil, can turn waste into wealth, have tangible economic benefit.
Description of drawings
Fig. 1 is the GC-MS detection figure that embodiment 2 xylogen thermochemistrys transform the phenols chemical component for preparing;
Fig. 2 is the GC-MS detection figure that embodiment 3 xylogen thermochemistrys transform the phenols chemical component for preparing.
Embodiment
For a better understanding of the present invention, be described further, but the invention is not restricted to this below in conjunction with specific embodiment.
The silicoaluminate that is adopted among the present invention, phospho-wolframic acid, silicon phosphoric acid, tetraline, phenol, glycerol, ethylene glycol etc. are industrial goods, can be in buying on the market.
Embodiment 1
The A component:
Acid precipitation xylogen 100 grams in the black liquid
Silicoaluminate 5 grams
Tetraline 7 grams
The B component:
Glycerol 300 grams
With the Acid precipitation xylogen in the black liquid in baking oven 60 ℃ down oven dry removed residual moisture in 8 hours, mix in reactor with other component and the B component of above-mentioned A component again, 230 ℃ of following back flow reaction 1 hour, obtain the thermal transition liquefied product.
The 60 parts of volume ratios dioxane that is 1:3 and the mixed solution of water are poured in the above-mentioned Thermochemical Liquefaction product.Centrifugation (5000 rev/mins) after stirring obtains upper strata liquid and subnatant behind the standing demix; Subnatant is the glycerol solvent, recycles after underpressure distillation; Upper strata liquid is the mixed solution of phenols chemical and dioxane/water, removes dioxane/water through rotary evaporation, obtains the phenols chemical.
Recording described phenols chemical yield by GC-MS uantitative analytical method, is 54.17%.
Embodiment 2
The A component:
Alkali lignin 100 grams in the black liquid
Silicoaluminate 4 grams
Phenol 3 grams
The B component:
Glycerol 450 grams
With the alkali lignin in the black liquid of above-mentioned weight part in baking oven 80 ℃ down oven dry removed behind the residual moisture in 8 hours and go up other component and mix in reactor, 200 ℃ of reactions 0.5 hour down, obtain the thermal transition liquefied product.
The 80 parts of volume ratios dioxane that is 1:6 and the mixed solution of water are poured in the above-mentioned Thermochemical Liquefaction product.Centrifugation (5000 rev/mins) after stirring obtains upper strata liquid and subnatant behind the standing demix; Subnatant is the glycerol solvent, recycles after underpressure distillation; Upper strata liquid is the mixed solution of phenols chemical and dioxane/water, removes dioxane/water through rotary evaporation, obtains the phenols chemical.
Recording described phenols chemical yield by GC-MS uantitative analytical method is 56.25%.
Embodiment 3
The A component:
Sulfonated lignin 100 grams in the black liquid
Silicon phosphoric acid 3 grams
Phenol 5 grams
The B component:
Glycerol 400 grams
With the sulfonated lignin in the black liquid in baking oven 60 ℃ down oven dry removed residual moisture in 8 hours, again with the A component in other component and B component mix in reactor, 230 ℃ of reactions 1 hour down, obtain the thermal transition liquefied product.
The 100 parts of volume ratios dioxane that is 1:10 and the mixed solution of water are poured in the above-mentioned Thermochemical Liquefaction product.Centrifugation (5000 rev/mins) after stirring obtains upper strata liquid and subnatant behind the standing demix; Subnatant is the glycerol solvent, recycles after underpressure distillation; Upper strata liquid is the mixed solution of phenols chemical and dioxane/water, removes dioxane/water through rotary evaporation, obtains the phenols chemical.
Recording described phenols chemical yield by GC-MS uantitative analytical method is 57.36%.
Embodiment 4
The A component:
Xylogen 100 grams after wood fibre separates
Phospho-wolframic acid 7 grams
Tetraline 8 grams
The B component:
Ethylene glycol 600 grams
The 100 ℃ of following oven dry in baking oven of above-mentioned xylogen were removed residual moisture in 6 hours, mix in reactor with other component and the B component of A component again, reacted 0.3 hour down, obtain the thermal transition liquefied product at 200 ℃.
The 120 parts of volume ratios dioxane that is 1:8 and the mixed solution of water are poured in the above-mentioned Thermochemical Liquefaction product.Centrifugation (5000 rev/mins) after stirring obtains upper strata liquid and subnatant behind the standing demix; Subnatant is an ethylene glycol solvent, recycles after underpressure distillation; Upper strata liquid is the mixed solution of phenols chemical, dioxane/water, removes dioxane/water through rotary evaporation, obtains the phenols chemical.
Recording described phenols chemical yield by GC-MS uantitative analytical method is 54.22%.
Embodiment 5
The A component:
Xylogen 100 grams in the preparation of cellulose alcohol fuel acid hydrolysis residue
Silicoaluminate 2 grams
Tetraline 10 grams
The B component:
Ethylene glycol 700 grams
The 100 ℃ of following oven dry in baking oven of above-mentioned xylogen were removed residual moisture in 6 hours, mix in reactor with other component and the B component of A component again, reacted 0.5 hour down, obtain the thermal transition liquefied product at 240 ℃.
The 90 parts of volume ratios dioxane that is 1:7 and the mixed solution of water are poured in the above-mentioned Thermochemical Liquefaction product.Centrifugation (5000 rev/mins) after stirring obtains upper strata liquid and subnatant behind the standing demix; Subnatant is an ethylene glycol solvent, recycles after underpressure distillation; Upper strata liquid is the mixed solution of phenols chemical, dioxane/water, removes dioxane/water through rotary evaporation, obtains the phenols chemical.
Recording described phenols chemical yield by GC-MS uantitative analytical method is 54.22%.
Embodiment 6
The A component:
Xylogen 100 grams after wood fibre separates
Silicoaluminate 3.5 grams
Phenol 3.5 grams
The B component:
Glycerol 600 grams
The 100 ℃ of following oven dry in baking oven of above-mentioned xylogen were removed residual moisture in 6 hours, mix in reactor with other component and the B component of A component again, reacted 0.5 hour down, obtain the thermal transition liquefied product at 240 ℃.
The 100 parts of volume ratios dioxane that is 1:6 and the mixed solution of water are poured in the above-mentioned Thermochemical Liquefaction product.Centrifugation (5000 rev/mins) after stirring obtains upper strata liquid and subnatant behind the standing demix; Subnatant is an ethylene glycol solvent, recycles after underpressure distillation; Upper strata liquid is the mixed solution of phenols chemical, dioxane/water, removes dioxane/water through rotary evaporation, obtains the phenols chemical.
Recording described phenols chemical yield by GC-MS uantitative analytical method is 53.79%.
Table 1 is the GC-MS analytical results of the prepared phenols chemical component of embodiment 2; Table 2 is the GC-MS analytical results of the prepared phenols chemical component of embodiment 3.
By table 1 and Fig. 1 as can be known, similarity is in the existence that can confirm this material more than 85%.Retention time
RT=14.7813 is the 2-methoxyphenol,
RT=16.301 is phenol,
RT=18.739 is 2,6-syringol, the main phenolic product of liquefaction reaction when above-mentioned three kinds of phenols chemical are pure aluminium silicate catalysis.By table 2 and Fig. 2 as can be known, the liquefied product basically identical of sulfonated lignin liquefaction after product and alkali lignin illustrates that the rule of two kinds of lignin molecule structural changess is basic identical.
Table 1
| Retention time/min | Peak area/% | Component | Similarity |
| 3.2305 | 1.7392 | Dimethyl diketone | 72 |
| 5.1852 | 2.0724 | Ally alcohol | 78 |
| 7.415 | 20.7741 | Hexanaphthene | 88 |
| 10.292 | 0.8499 | 4,4-dimethyl-2-cyclopentanone | 86 |
| 12.2448 | 1.6914 | 2-ethyl-1,3-dioxolane-4-methyl alcohol | 90 |
| 14.7813 | 7.5672 | The 2-methoxyphenol | 97 |
| 16.301 | 8.2916 | Phenol | 91 |
| 17.9228 | 1.0799 | The 4-ethylphenol | 95 |
| 18.3225 | 2.1562 | 2-methoxyl group-4-methylphenol | 94 |
| 18.739 | 8.8264 | 2, the 6-syringol | 97 |
| 19.1741 | 2.0696 | 3-three silyl phenol | 80 |
| 19.3297 | 43.6905 | Glycerol | 83 |
| 20.5863 | 0.5479 | 4-propyl group-1,1'-biphenyl | 72 |
Table 2
| Retention time/min | Peak area/% | Component | Similarity/% |
| 3.2307 | 2.4458 | Dimethyl diketone | 85 |
| 5.1852 | 5.0417 | Ally alcohol | 90 |
| 7.4152 | 19.5773 | Hexanaphthene | 91 |
| 9.9269 | 4.1569 | Acetate | 86 |
| 10.292 | 4.3741 | 4,4-dimethyl-2-cyclopentanone | 93 |
| 12.2449 | 2.1413 | 2-ethyl-1,3-dioxolane-4-methyl alcohol | 86 |
| 14.782 | 7.6625 | The 2-methoxyphenol | 88 |
| 16.301 | 7.7348 | Phenol | 90 |
| 17.9228 | 1.9892 | The 4-ethylphenol | 91 |
| 18.7391 | 9.6541 | 2, the 6-syringol | 87 |
| 19.1748 | 1.1075 | 3-three silyl phenol | 90 |
| 19.3297 | 36.5583 | Glycerol | 94 |
Claims (6)
1. the industrial lignin thermochemistry transforms the method for preparing the phenols chemical, it is characterized in that its raw materials by weight portion meter is composed as follows:
The A component:
100 parts of industrial lignins
2～7 parts of solid acid catalysts
3～10 parts of hydrogen supply dissolvents
The B component:
300～700 parts in organic reaction medium
Concrete reactions steps is: the liquefaction of (1) xylogen: reactor is dried and placed to the industrial lignin of above-mentioned weight part, add described catalyzer, hydrogen supply dissolvent and organic reaction medium then, 180 ℃～240 ℃ next time stream carry out thermal conversion reaction, react after 0.3 hour～2 hours and obtain the thermal transition liquefied product; Described solid acid catalyst is phospho-wolframic acid, silicon phosphoric acid or silicoaluminate; Described hydrogen supply dissolvent is tetraline or phenol; Described organic reaction medium is glycerol, ethylene glycol;
(2) separation and Extraction of phenols chemical: the dioxane of 60～120 parts of volume ratio 1:3～1:10 and the mixed solution of water are poured in the above-mentioned thermal transition liquefied product, the back centrifugation that stirs, standing demix obtains upper strata liquid and subnatant; Described subnatant is the organic reaction medium of thermal conversion reaction, recycles after underpressure distillation; Described upper strata liquid is the mixed solution of phenolic product, dioxane and water, and dioxane and water in the described mixed solution of rotary evaporation promptly obtain the phenols chemical.
2. industrial lignin thermochemistry according to claim 1 transforms the method that prepare the phenols chemical, it is characterized in that described industrial lignin is the xylogen that is rich in the acid hydrolysis of the Acid precipitation xylogen, the sulfonated lignin in the black liquid, the alkali lignin in the black liquid in the black liquid, xylogen that the wood fibre separation obtains or preparation of cellulose alcohol fuel or the enzymic hydrolysis residue.
3. industrial lignin thermochemistry according to claim 1 transforms the method for preparing the phenols chemical, it is characterized in that described solid acid catalyst is a silicoaluminate.
4. industrial lignin thermochemistry according to claim 1 transforms the method for preparing the phenols chemical, it is characterized in that described hydrogen supply dissolvent is a tetraline.
5. industrial lignin thermochemistry according to claim 1 transforms the method for preparing the phenols chemical, it is characterized in that described organic reaction medium is a glycerol.
6. industrial lignin thermochemistry according to claim 1 transforms the method for preparing the phenols chemical, it is characterized in that described raw materials by weight portion meter is composed as follows:
The A component:
100 parts of industrial lignins
3～4 parts of catalyzer
4～5 parts of hydrogen supply dissolvents
The B component:
400～500 parts in organic reaction medium.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4731491A (en) * | 1986-01-22 | 1988-03-15 | Uop Inc. | Process for liquefaction of lignin |
| CN1528824A (en) * | 2003-09-26 | 2004-09-15 | 中国科学院广州化学研究所 | Vegetable fiber liquefied matter, and preparing method and use thereof |
| CN1931456A (en) * | 2006-06-08 | 2007-03-21 | 南昌大学 | Method of catalytically liquefying biomass with nanometer catalyst |
| CN101245566A (en) * | 2008-03-28 | 2008-08-20 | 中国科学院过程工程研究所 | Method for selective liquefaction of lignocellulose with phynol |
| CN101597469A (en) * | 2009-06-29 | 2009-12-09 | 北京林业大学 | A kind of waste preservative timber synthetic synvaren and preparation method thereof that utilizes |
| CN101638442A (en) * | 2009-08-28 | 2010-02-03 | 中国科学院西双版纳热带植物园 | Method for hydrolyzing lignocellulose |
| CN101298744B (en) * | 2008-06-04 | 2010-09-15 | 大连工业大学 | Method for stalk liquefaction preprocessing to prepare fuel ethyl hydrate raw material |
-
2011
- 2011-03-18 CN CN2011100652463A patent/CN102173980B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4731491A (en) * | 1986-01-22 | 1988-03-15 | Uop Inc. | Process for liquefaction of lignin |
| CN1528824A (en) * | 2003-09-26 | 2004-09-15 | 中国科学院广州化学研究所 | Vegetable fiber liquefied matter, and preparing method and use thereof |
| CN1931456A (en) * | 2006-06-08 | 2007-03-21 | 南昌大学 | Method of catalytically liquefying biomass with nanometer catalyst |
| CN101245566A (en) * | 2008-03-28 | 2008-08-20 | 中国科学院过程工程研究所 | Method for selective liquefaction of lignocellulose with phynol |
| CN101298744B (en) * | 2008-06-04 | 2010-09-15 | 大连工业大学 | Method for stalk liquefaction preprocessing to prepare fuel ethyl hydrate raw material |
| CN101597469A (en) * | 2009-06-29 | 2009-12-09 | 北京林业大学 | A kind of waste preservative timber synthetic synvaren and preparation method thereof that utilizes |
| CN101638442A (en) * | 2009-08-28 | 2010-02-03 | 中国科学院西双版纳热带植物园 | Method for hydrolyzing lignocellulose |
Non-Patent Citations (5)
| Title |
|---|
| 冯国东等: "木质素液化技术研究进展", 《生物质化学工程》 * |
| 吕晓静，杨军等: "木质素的高附加值应用新进展", 《化工进展 专论与综述》 * |
| 徐俊明等: "生物质热解油精制改性用固体酸催化剂研究进展", 《化工进展》 * |
| 牟莉等: "常规加热条件下四种不同强度酸对玉米秸秆降解的影响", 《长春大学学报》 * |
| 郭贵全，王红娟，谌凡更: "植物纤维在供氢溶剂中的液化反应", 《纤维素科学与技术》 * |
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