CN101130793A - Novel method for producing fuel alcohol by rice hull and comprehensive utilization of resource - Google Patents

Novel method for producing fuel alcohol by rice hull and comprehensive utilization of resource Download PDF

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CN101130793A
CN101130793A CNA200710055974XA CN200710055974A CN101130793A CN 101130793 A CN101130793 A CN 101130793A CN A200710055974X A CNA200710055974X A CN A200710055974XA CN 200710055974 A CN200710055974 A CN 200710055974A CN 101130793 A CN101130793 A CN 101130793A
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rice husk
alcohol
waste residue
straw
cellulose
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王子忱
任素霞
赵旭
刘艳华
郭玉鹏
周兵
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Jilin University
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Jilin University
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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

Abstract

The invention discloses a new method for producing an alcohol fuel with a rice husk and resource comprehensive utilization, which solves the prior technique problem that the low hydrolytic decomposition ratio of cellulose in the alcohol fuel production with straw (includes rice husk). The method comprises the following steps: hydrolyzing hemicellulose in the rice husk; alcoholysising lignin in the rice husk in order to remove fixing function of cellulose for lignin, breaking crystalline state of cellulose and making the hydrolytic decomposition ratio of cellulose accesses 100%; producing furfural with hemicellulose in the rice husk, producing surface activator with cellulose in the rice husk and producing high-purity nanometer silica dioxide with rice husk in order to make the utilization ratio of the rice husk resource more than 90% and make the fuel alcohol economy production more rational. The invention can extend and utilize maize ear, rice straw and other straw fuel alcohol production and the resource comprehensive utilization, which pushes the application of the alcohol production with hydrocellulose in the straw in the industry production, and provides a new method for renewable resources with farm and side line product straw.

Description

The novel method of a kind of producing fuel alcohol by rice hull and comprehensive utilization of resources
Technical field
The present invention relates to the novel method of a kind of producing fuel alcohol by rice hull and comprehensive utilization of resources.
Background technology
At present, world energy sources and crisis of resource make the development and utilization of renewable resources become a focus.Plant/farm crop base renewable resources is the trend of research of present domestic and international particularly developed country and utilization, and it will become replenishing and substituent of following nonrenewable resource, changes current to the dependence of the nonrenewable resource of minimizing day by day.Renewable energy source enters energy market, has become the important component part of countries in the world energy strategy.
USDOE (DOE) is planned the year two thousand twenty will account for 10% from the basic chemical structure material of plant renewable resources, will reach 50% to the year two thousand fifty.According to European Union's regulation, the ratio of the renewable energy source of its member states in primary energy source will reach 12% in 2010, and the year two thousand twenty reaches 20%.Sweden proposes, and the alcohol fuel replacing whole oil fuel that utilizes Mierocrystalline cellulose to produce after the year two thousand twenty is thoroughly broken away from the dependence to oil.
China will face the threat that petroleum resources are petered out as a developing large agricultural country after 70 years, and research, the development and utilization of paying attention to renewable plant resources are very urgent.National Development and Reform Committee makes the overall arrangement in 3 stages with regard to China's biofuel industry development: Eleventh Five-Year Plan is realized technology industrialization, and " 12 " realize industrial scale, realizes later on developing on a large scale in 2015.Expect the year two thousand twenty, China's biofuel consumption will account for about 15% of whole traffic fuel, set up the biofuel industry with international competitiveness.
Be raw material production ethanol at present with the corn, 1 ton of ethanol of about 3.3 tons of Maize Production, and the corn market value is about about 1400 yuan per ton, only raw materials cost just reaches 4620 yuan/ton.And about 4700 yuan per ton of the price of selling PetroChina Company Limited., China Petrochemical Industry is added human cost, electric cost etc., and loss is difficult to avoid.Country has formulated " breakeven and meagre profit " policy in order to encourage the popularization of ethanol petrol to ethanol enterprise, is as the criterion with the profit of alcohol fuel 1% per ton, calculates to give grain distillery's subsidy, and subsidizing at present is 1300-1600 per ton unit.And raw spirit is 6000 yuan/ton in the market, and enterprise produces ethanol and is actually and sustains losses in business.The problem that the alcohol fuel development is subjected to the starting material restriction shows especially day by day.
The more important thing is that grain security is the bottleneck problem that processing enterprise faces.National Development and Reform Committee clearly represents no longer to utilize the raw materials for production of grain as biomass energy, and what replace grain will be cash crop.In the high-rise forum of Chinese first biological economy that holds in July, 2006 in this year, brainstrust is thought, exploitation substitutes grain resource, as with the agricultural crop straw being all kinds of wood fiber biomass of representative, and corresponding fuel ethanol production technology, be to solve fuel ethyl hydrate raw material cost height, the limited basic outlet of raw material.
Up to now, to have had tens cover cellulose raw materials to become the pilot production line or the lab scale production line of monose, major part through cellulase hydrolysis be to be final major product with ethanol in the whole world.These tests or trial production mechanism comprise United States Army Natick researchdevelopment center, the Lao Lunsi of California, USA university Berkeley laboratory, U.S. University of Arkansas biomass research centre, Univ Pennsylvania USA, Canada Iogen company, Canada Forintek company, Canada SunOpta company, IFP, Japan petroleum substitute developmental research association, Sweden Forest products research laboratory, Lund, Sweden university, Graz, Austria university, Technical Research Centre of Finland, the India Institute of Technology etc.Abroad, with the cellulosic be the stage that raw material production alcohol just progressively moves towards a technology maturation.
China has some scientific research institutions, university and enterprise also to begin R﹠D work in this respect at present, has obtained some progress.Units such as sky, Henan hat group, the rich former group in Anhui, derived energy chemical system of Shanghai East China University of Science, State Key Laboratory for Microbial Technology of Shandong University, food science and technology institute of Agricultural University Of Hebei, Southern Yangtze University's bioengineering dept, Jilin light industry design and research institute produce the alcoholic acid research and development at stalk and have all obtained certain progress, indicate that China has ranked among world's ranks in the Biomass Energy Utilization research field.
The scientific research institution of countries in the world research and utilization lignocellulose fermentative production of ethanol all tackles key problems round these several big key problem in technology at present.The one, pretreatment technology promptly by the whole bag of tricks, as the combination of gas explosion method, wet oxidation, diluted acid method or several method, destroys the structure of Mierocrystalline cellulose, hemicellulose and xylogen in the stalk, makes it loose, also can make hydrolysis of hemicellulose; The 2nd, hydrolysis process promptly becomes hexose and five-carbon sugar to the Mierocrystalline cellulose in the above-mentioned substance, hydrolysis of hemicellulose by enzyme process or acid system; The 3rd, zymotechnique selects for use special common yeast-like fungi kind that above-mentioned hexose and five-carbon sugar are fermented, and produces alcohol.
But also there is not a tame technical scale to utilize cellulose raw material to produce the enterprise of alcohol fuel at present in the world.Its major obstacle is: 1. the enzymolysis cost is too high; 2. lack economically viable five-carbon sugar fermentation technique.Therefore, the useless poor problems such as comprehensive utilization of problem that cost reduces in the optimum combination problem of technological line, the production process and ethanol are worth us conscientiously deeply to inquire into, study, solve.
The domestic patent CN1880416 of relevant alcohol fuel (method of preparing fuel ethanol by using straw fiber materials) has announced a kind of stalk fibrid raw material production alcoholic acid method, this method pre-treatment is adopted the method for the solid-state cultivation degradation of rice straw of white-rot fungi to carry out lignin degradation and is handled, can improve alcohol yied, reduce cost.Patent CN1880415 (technology of preparing fuel ethanol by using straw fiber materials) discloses a kind of technology of preparing fuel ethanol by using straw fiber materials, this technology and first difference are that pretreated method is different, its result also can improve alcohol yied, reduces cost.Foreign patent DE3277699D has introduced a kind of method of producing alcohol fuel from vegetable fibre: at first same SO 2And H 2O reacts under High Temperature High Pressure, and the xylogen with the alkali lye solubilizing reaction separates xylogen with Mierocrystalline cellulose, make cellulose hydrolysis and the hydrolysate that ferments, and this method is a kind of method of effectively producing alcohol fuel from plant refuse.Patent JP59048090 has introduced the method that adopts different enzymes to produce alcohol fuel from potato, wood, straw cheaply, main research be the effect of enzyme.Patent DE3107950 has introduced fiber substance such as wood, the process of hydrolysis and saccharification such as agricultural wastes such as straw and device, at first utilize diluted acid under certain pressure and temperature, to make it hydrolysis, the carbohydrate of hydrolysis under the various conditions is collected the preparation liquid glucose, then with liquid glucose fermentative preparation alcohol fuel.Problems such as these patents exist that percent hydrolysis is low, how seriously polluted not comprehensive utilization, slag and effluent be can't realize industrialization, therefore, also do not have the production line of a fuel ethanol produced by straw in the world.
Illustrated among other patent such as the CN 1680413A a kind ofly to prepare the method for high-boiling alcohol lignin with plant refuse, and with residuum all as the slow-releasing compound manure, be not very economical like this.Patent CN 1410451A provides a kind of and has produced the method for Walocel MT 20.000PV and xylogen from straw, though this method has been utilized Mierocrystalline cellulose and the hemicellulose in the straw, fails to utilize wherein xylogen and silicon-dioxide.In addition some patent is such as patent CN 1792789A, some patents of the early 1990s such as CN1063087, and these all are only to utilize rice husk to prepare single component silicon-dioxide, and other compositions are not utilized, this can't but be a waste greatly of resource.
At the problems referred to above, the present invention is a raw material with the rice husk in the stalk family, utilize the plain alcohol fuel of producing of rice hull cellulose, utilize hemicellulose to produce furfural simultaneously, extract xylogen, utilize residue to produce nano silicon, make useful element utilization ratio in the rice husk greater than 90%.The cost that makes Mierocrystalline cellulose produce alcohol fuel reduces significantly, thoroughly captures stalk and produces alcoholic acid technology, economic bottleneck.
Summary of the invention
The objective of the invention is to solve present stalk (comprising rice husk) and produce alcohol fuel, the technological difficulties that the cellulose hydrolysis rate is low, adopt first hydrolyzed hemicellulose, the xylogen in the alcoholysis rice husk again, get rid of xylogen to cellulosic fixed action, destroy cellulosic crystalline state, thereby make cellulosic percent hydrolysis near 100% novel method; Utilize the hemicellulose in the rice husk to produce furfural, produced tensio-active agent, produced high-purity nm silicon-dioxide by rice husk silicon by the rice husk xylogen simultaneously, the utilization ratio that makes the rice husk resource is greater than 90%.
The present invention includes following four steps: (1) hydrolyzed hemicellulose, preparation furfural: the rice husk and the diluted mineral acid aqueous solution are added hydrolysis kettle by a certain percentage, be back hydrolysis 3 hours under 100 ℃ the condition in temperature, filter, separate the waste residue (I) and the wood sugar aqueous solution.Added oxide compound or composite oxides synthesis under normal pressure 1～3 hour in the acid wood sugar aqueous solution, and be prepared into composite catalyst, the rising system temperature is 100～200 ℃, reacts 1～6 hour, collects furfural steam, and smart gold-plating is purified, preparation furfural product;
(2) alcoholysis xylogen, preparation high-boiling alcohol lignin: in the waste residue (I) of moisture 50% behind the rice husk hydrolysis of hemicellulose: the boil ratio of alcohol=1: 4～10 of height adds reactor, react 4～8h down at 160～200 ℃, filter waste residue (II) and the height alcoholic solution that boils, filtrate adds the water of 2～6 times of volumes, is settled out xylogen;
(3) hydrocellulose, preparation ethanol: the rice husk waste residue (II) that height is boiled and obtains after alcohol is handled, add 6～10 times the sulfuric acid of 2mol/L or phosphoric acid, hydrochloric acid, acetum, at 130～180 ℃ of reaction 6～10h, filter waste residue (III) and D/W.Filtrate with in the ammoniacal liquor and after, fermentative production of ethanol;
(4) pyrolysis residue, produce nanometer grade silica:
1. waste residue (III) is cleaned oven dry, in 600～850 ℃ of following high temperature pyrolysis, pulverizing is broken up and can be prepared nano silicon, and its granularity is 30～90nm, and whiteness reaches about 99%;
2. waste residue (III) is cleaned, quantitatively after, add the HNO of 4～6 times 2mol/L 3Solution or hydrogen peroxide solution, at 120～180 ℃ of following reaction 2～5h, it is 30～90nm, purity greater than 99.9% that washing and filtering obtains granularity, whiteness is greater than 99% nano silicon.
Advance of the present invention is: adopt the hemicellulose and the method for alcoholysis xylogen again in the first hydrolysis rice husk, get rid of xylogen to cellulosic fixed action, destroy cellulosic crystalline state, thereby make cellulosic percent hydrolysis reach 90～100%, improved the productive rate of alcohol fuel.Utilize the hemicellulose in the rice husk to produce furfural, produced tensio-active agent, produced high-purity nm silicon-dioxide by rice husk silicon by the rice husk xylogen simultaneously, the utilization ratio that makes the rice husk resource is greater than 90% (seeing Table 1).The present invention has not only made full use of the rice husk resource, and has reduced the production of fuel ethanol cost significantly, the economic benefit highly significant.
See Table 1 rice husk resource utilization comparative analysis
The rice husk main component Hemicellulose 19.9% Mierocrystalline cellulose 38.7% Xylogen 20.1% Silica 1 8.52% Other are 2.78% years old Add up to 100%
Actual product Wood sugar Glucose The HBS xylogen Nano silicon Add up to
Yield 18.97 36.8％ 19.8％ 18.33％ 94.04％
* annotate: rice husk is because the place of production slightly changes different the composition: 16～22% hemicellulose, 35.5～45% Mierocrystalline cellulose, 16～21% xylogen, rice husk silicon 17～19%
Embodiment
At first the rice husk and the diluted mineral acid aqueous solution being added hydrolysis kettle by a certain percentage, is back hydrolysis 3 hours under 100 ℃ the condition in temperature, filters, and the waste residue (I) and the wood sugar aqueous solution of hemicellulose is isolated in preparation.Added oxide compound, composite oxides synthesis under normal pressure 1～3 hour in the acid wood sugar aqueous solution, and be prepared into composite catalyst, the rising system temperature is 100～200 ℃, reacts 1～6 hour, collects furfural steam, and smart gold-plating is purified, preparation furfural product.Wherein used oxide compound is ZrO 2, Al 2O 3, TiO 2, SiO 2, Fe 3O 4, transition metal oxides such as ZnO, CuO; Composite oxides are combinations of above-mentioned oxide compound, as: ZrO 2/ Al 2O 3, CuO/SiO 2Deng.Acid solution reaction after oxide compound or composite oxides and the hydrolysis generates corresponding super acids as solid catalyst.
Secondly, waste residue (I) in moisture 50% behind the rice husk hydrolysis of hemicellulose: the boil ratio of alcohol=1: 4～10 of height adds reactor, at 160～200 ℃ of reaction 4～8h down, filter waste residue (II) and the height alcoholic solution that boils, filtrate adds the water of 2～6 times of volumes, is settled out xylogen.
The rice husk waste residue (II) that then height is boiled and obtain after alcohol is handled adds 6～10 times the sulfuric acid of 2mol/L or hydrochloric acid, phosphoric acid, acetum, reacts 6～10h at 130～180 ℃, filter waste residue (III) and D/W.Filtrate adopt in the ammoniacal liquor and after, fermentative production of ethanol.
At last waste residue (III) is cleaned oven dry, in 600～1000 ℃ of following high temperature pyrolysis, pulverizing is broken up and can be obtained nano silicon, and its granularity is 30-90nm, and whiteness reaches about 99%.Or waste residue (III) cleaned, quantitatively after, add the HNO of 4～6 times 2mol/L 3Solution (or hydrogen peroxide solution), at 120～180 ℃ of following reaction 2～5h, it is 30～90nm, purity greater than 99.99% nano silicon that washing and filtering obtains granularity, whiteness is greater than 99%.
Further set forth the present invention below in conjunction with specific examples.
Embodiment one:
With 3Kg rice husk and concentration 0.5% H 2SO 4The aqueous solution adds hydrolysis kettle in 1: 10 ratio, hydrolysis 6h under 100 ℃ the condition, filter waste residue (I) 2.35Kg and contain the 0.565Kg wood sugar and get the aqueous solution.In the acid wood sugar aqueous solution, add CuO/Al 2O 3Composite catalyst, rising system temperature to 160 ℃, compressive reaction 3h collects furfural steam, and rectification and purification obtains furfural 0.34Kg.
Embodiment two:
With 3Kg rice husk and concentration 1% H 2SO 4The aqueous solution adds hydrolysis kettle in 1: 10 ratio, hydrolysis 6h under 100 ℃ the condition, filter residue (I) 2.36Kg and contain the aqueous solution of 0.569Kg wood sugar.In the acid wood sugar aqueous solution, add ZrO 2/ CuO composite catalyst, rising system temperature to 160 ℃, compressive reaction 3h collects furfural steam, and rectification and purification obtains furfural 0.38Kg.
Embodiment three:
With 3Kg rice husk and concentration 1% H 2SO 4The aqueous solution adds hydrolysis kettle in 1: 10 ratio, hydrolysis 6h under 100 ℃ the condition, filter filter residue (I) 2.36Kg and contain the aqueous solution of wood sugar 0.569Kg.In the acid wood sugar aqueous solution, add TiO 2/ SiO 2Composite catalyst, rising system temperature to 160 ℃, compressive reaction 3h collects furfural steam, and rectification and purification obtains furfural 0.396Kg.
Embodiment four:
Filter residue (I) 3.54Kg and ethylene glycol are added reactor according to 1: 6 ratio, 200 ℃ of reaction 6h, filter filter residue (II) 1.71Kg and filtrate.Filtrate gets high-boiling alcohol lignin 0.588Kg with the cold water precipitation of 4 times of volumes.
Embodiment five:
Filter residue (I) 3.54Kg and ethylene glycol solution are added reactor according to 1: 10 ratio, 200 ℃ of reaction 4h, filter filter residue (II) 1.67Kg and filtrate, filtrate is precipitated with the cold water of 3 times of volumes, obtains high-boiling alcohol lignin 0.594Kg.
Embodiment six
Filter residue (I) 3.54Kg and ethylene glycol solution are added reactor according to 1: 10 ratio, 180 ℃ of reaction 4h, filter filter residue (II) 1.68Kg and filtrate.Filtrate gets high-boiling alcohol lignin 0.588Kg with the cold water precipitation of 3 times of volumes.
Embodiment seven
The sulphuric acid soln of filter residue (II) 1.67Kg and 2mol/L is added reactor according to 1: 6 ratio, 130 ℃ of reaction 6h down, filter filter residue (III) 0.61Kg and contain the aqueous solution of glucose 1.104Kg.The aqueous solution with in the ammoniacal liquor and after, ethanol 0.519Kg is produced in fermentation.
Embodiment eight
The phosphoric acid solution of waste residue (II) 1.67Kg and 2mol/L is added reactor in 1: 6 ratio, 150 ℃ of reaction 6h down, filter waste residue (III) 0.66Kg and contain the aqueous solution of glucose 1.056Kg.The aqueous solution is with in the ammoniacal liquor and after the allotment, and ethanol 0.497Kg is produced in fermentation.
Embodiment nine
The acetum of waste residue (II) 1.67Kg and 2mol/L is added reactor in 1: 6 ratio, 150 ℃ of following reaction 6h, filter waste residue (III) 0.68Kg and contain the aqueous solution of glucose 1.038Kg, the aqueous solution is with in the ammoniacal liquor and after the allotment, ethanol 0.488Kg is produced in fermentation.
Embodiment 11:
Waste residue (III) 0.61Kg is cleaned oven dry, and with 700 ℃ of following high temperature pyrolysis, pulverizing is broken up and is obtained nano silicon 0.553Kg, and its granularity is 52nm, whiteness 99%.
Embodiment 12:
Waste residue (III) is cleaned oven dry, and with 800 ℃ of following high temperature pyrolysis, pulverizing is broken up and can be obtained nano silicon 0.55Kg, and its granularity is 56nm, whiteness 99.2%.
Embodiment 13:
Get waste residue (III) 0.61Kg, add the HNO of 2mol/L in 1: 6 ratio 3Solution reacts 2h down at 130 ℃, and washing and filtering obtains nano silicon 0.552Kg, and granularity is 38nm, and purity is 99.99%, and whiteness is 99.5%.
Embodiment 14:
Get waste residue (III) 0.61Kg, the hydrogen peroxide solution in 1: 8 ratio adding 2mol/L reacts 2h down at 130 ℃, and washing and filtering obtains nano silicon 0.549Kg, and granularity is 42nm, and purity is 99.99%, and whiteness is 99.8%.

Claims (2)

1. the method for producing fuel alcohol by rice hull and comprehensive utilization of resources comprises following four steps:
(1) hydrolyzed hemicellulose, the preparation furfural: rice husk and the diluted mineral acid aqueous solution are added hydrolysis kettle by a certain percentage, are back hydrolysis 3 hours under 100 ℃ the condition in temperature, filter the separation waste residue (I) and the wood sugar aqueous solution.Added oxide compound or composite oxides synthesis under normal pressure 1～3 hour in the acid wood sugar aqueous solution, and be prepared into composite catalyst, the rising system temperature is 100～200 ℃, reacts 1～6 hour, collects furfural steam, and smart gold-plating is purified, preparation furfural product;
(2) alcoholysis xylogen, preparation high-boiling alcohol lignin: in the waste residue (I) of moisture 50% behind the rice husk hydrolysis of hemicellulose: the boil ratio of alcohol=1: 4～10 of height adds reactor, react 4～8h down at 160～200 ℃, filter waste residue (II) and the height alcoholic solution that boils, filtrate adds the water of 2～6 times of volumes, is settled out xylogen;
(3) hydrocellulose, preparation ethanol: the rice husk waste residue (II) that height is boiled and obtains after alcohol is handled, add 6～10 times the sulfuric acid of 2mol/L or phosphoric acid, hydrochloric acid, acetum, at 130～180 ℃ of reaction 6～10h, filter waste residue (III) and D/W.Filtrate with in the ammoniacal liquor and after, fermentative production of ethanol;
(4) pyrolysis residue, produce nanometer grade silica:
1. waste residue (III) is cleaned oven dry, in 600～850 ℃ of following high temperature pyrolysis, pulverizing is broken up and can be prepared nano silicon, and its granularity is 30～90nm, and whiteness reaches about 99%;
2. waste residue (III) is cleaned, quantitatively after, add the HNO of 4～6 times 2mol/L 3Solution or hydrogen peroxide solution, at 120～180 ℃ of following reaction 2～5h, it is 30～90nm, purity greater than 99.9% that washing and filtering obtains granularity, whiteness is greater than 99% nano silicon.
2. according to the method for described producing fuel alcohol by rice hull of claim 1 and comprehensive utilization of resources, it is characterized in that. the oxide compound that adds in the acid wood sugar aqueous solution in the step of preparation furfural is ZrO 2, Al 2O 3, TiO 2, SiO 2, Fe 3O 4, ZnO or CuO; Composite oxides are combinations of above-mentioned oxide compound, as: ZrO 2/ Al 2O 3, CuO/SiO 2, TiO 2/ SiO 2Deng, the acid solution reaction after oxide compound or composite oxides and the hydrolysis generates corresponding super acids as solid catalyst.
CNA200710055974XA 2007-08-20 2007-08-20 Novel method for producing fuel alcohol by rice hull and comprehensive utilization of resource Pending CN101130793A (en)

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Cited By (14)

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CN102336728A (en) * 2011-10-28 2012-02-01 南京林业大学 Method for preparing furfural from fiber pentosan hydrolysate by using composite solid acid as catalyst
CN102382310A (en) * 2011-08-31 2012-03-21 广州优锐生物科技有限公司 Lignin co-production method by comprehensively utilizing lignocellulose resources
CN101358214B (en) * 2008-09-23 2012-03-28 王建设 Method for producing furfural coupled cogeneration of propanone and butanol using stalk
CN102433358A (en) * 2011-10-20 2012-05-02 清华大学 Method for coproduction of xylose, lignin and ethanol from corncobs
CN102516209A (en) * 2011-10-20 2012-06-27 清华大学 Method for coproducing furfural, ethanol and lignin from corncob
CN101413016B (en) * 2008-12-03 2012-06-27 北京林业大学 Method for preparing microcrystalline cellulose and cellulose fuel ethanol by separating furfural residue
CN101696152B (en) * 2009-09-30 2012-11-07 郑州大学生化工程中心 Method and device for separating cellulosic ethanol
CN103724632A (en) * 2014-01-03 2014-04-16 东北林业大学 Catalytic activation method of alkali lignin in black liquor by virtue of CuO/SO42-/ZrO2
CN103819688A (en) * 2008-03-14 2014-05-28 弗吉尼亚暨州立大学知识产权公司 Method and apparatus for lignocellulose pretreatment by using super-cellulose-solvent and highly volatile solvents
CN110407214A (en) * 2018-04-27 2019-11-05 中国科学院大连化学物理研究所 A kind of process preparing silica by lignocellulosic hydrolysis residue
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WO2021032195A1 (en) * 2019-08-22 2021-02-25 济南圣泉唐和唐生物科技有限公司 Method for separating xylose and lignin from mixed sugar solution

Cited By (18)

* Cited by examiner, † Cited by third party
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CN103819688A (en) * 2008-03-14 2014-05-28 弗吉尼亚暨州立大学知识产权公司 Method and apparatus for lignocellulose pretreatment by using super-cellulose-solvent and highly volatile solvents
CN101358214B (en) * 2008-09-23 2012-03-28 王建设 Method for producing furfural coupled cogeneration of propanone and butanol using stalk
CN101413016B (en) * 2008-12-03 2012-06-27 北京林业大学 Method for preparing microcrystalline cellulose and cellulose fuel ethanol by separating furfural residue
CN101696152B (en) * 2009-09-30 2012-11-07 郑州大学生化工程中心 Method and device for separating cellulosic ethanol
CN102382310A (en) * 2011-08-31 2012-03-21 广州优锐生物科技有限公司 Lignin co-production method by comprehensively utilizing lignocellulose resources
CN102382310B (en) * 2011-08-31 2013-08-14 广州优锐生物科技有限公司 Lignin co-production method by comprehensively utilizing lignocellulose resources
CN102433358A (en) * 2011-10-20 2012-05-02 清华大学 Method for coproduction of xylose, lignin and ethanol from corncobs
CN102516209A (en) * 2011-10-20 2012-06-27 清华大学 Method for coproducing furfural, ethanol and lignin from corncob
CN102336728A (en) * 2011-10-28 2012-02-01 南京林业大学 Method for preparing furfural from fiber pentosan hydrolysate by using composite solid acid as catalyst
CN103724632A (en) * 2014-01-03 2014-04-16 东北林业大学 Catalytic activation method of alkali lignin in black liquor by virtue of CuO/SO42-/ZrO2
CN103724632B (en) * 2014-01-03 2016-04-13 东北林业大学 CuO/SO 42-/ ZrO 2the method of alkali lignin in catalytic activation black liquid
CN110407214A (en) * 2018-04-27 2019-11-05 中国科学院大连化学物理研究所 A kind of process preparing silica by lignocellulosic hydrolysis residue
CN110429264A (en) * 2019-08-13 2019-11-08 吉林大学 A method of preparing rice husk base negative electrode material
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CN110950706A (en) * 2019-12-18 2020-04-03 上海永通生态工程股份有限公司 Silicon-rich fertilizer special for ginger and preparation method thereof
CN110950706B (en) * 2019-12-18 2022-03-08 上海永通生态工程股份有限公司 Silicon-rich fertilizer special for ginger and preparation method thereof
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