CN103806318A - Method for extracting cellulose from furfural residues - Google Patents
Method for extracting cellulose from furfural residues Download PDFInfo
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- CN103806318A CN103806318A CN201410020390.9A CN201410020390A CN103806318A CN 103806318 A CN103806318 A CN 103806318A CN 201410020390 A CN201410020390 A CN 201410020390A CN 103806318 A CN103806318 A CN 103806318A
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Abstract
The invention relates to a method for extracting cellulose from furfural residues, belonging to the technical field of lignocelluloses component separation. The method comprises the steps of: by taking waste resource furfural residues as raw materials, firstly treating by adopting a formic acid and hydrogen peroxide water solution, wherein the mass percent concentration of the formic acid is 85%, and the mass percent concentration of hydrogen peroxide is 1%; then treating by adopting a sodium hydroxide and hydrogen peroxide water solution, wherein the mass percent concentration of the sodium hydroxide is 1%, and the mass percent concentration of the hydrogen peroxide is 1%-2%. The cellulose content of the extracted cellulose product can achieve 84.09%, and the crystallinity degree can achieve 69.3%. The extraction technology is carried out under the condition of being lower than 90DEG C, the solvent for use is easy to recovery, the use of concentrated alkaline is avoided, and the consumption of chemical reagents can be decreased. The method has the advantages of being simple in process, environment-friendly, easy to operate and the like, and has better application prospects.
Description
Technical field
The present invention relates to one and from furfural dregs, extract cellulosic method, belong to lignocellulose component separation technology field.
Technical background
Furfural is a kind of important industrial chemicals, produces the general agricultural byproducts leftover bits and pieces that is rich in pentosan that adopts of furfural, as corncob, bagasse etc.In furfural production process, pentosan hydrolysis stripping produces a large amount of furfural dregs waste materials simultaneously.According to estimates, 1 ton of furfural of every production approximately discharges 12～15 tons of furfural dregs.Furfural dregs is pitchy solid fragment, and its salt content is high, be acid, and furfural dregs three major polymers: cellulose and lignin composition, only contain a small amount of hemicellulose.At present, except small part furfural dregs is as fuel, mostly adopt accumulation and the method for toppling over of digging pit to process, banking process can produce and pollute soil, river.If the cellulose in furfural dregs is separated, gained cellulose can be used for preparing ethanol, functional material etc.Chinese invention patent CN101413016 adopts extraction, fermentation, acid catalysis three-step approach to prepare ethanol and microcrystalline cellulose to furfural dregs.Chinese invention patent CN103266145A adopts ethanol-sodium sulfite to prepare fermentable sugar to furfural dregs.Bibliographical information directly adopts alkaline hydrogen peroxide to process furfural dregs, and content of cellulose is only the high beautiful rosy clouds of 52.21%(etc., alkali preliminary treatment furfural dregs character and cellulase hydrolysis research thereof. living beings Chemical Engineering, 2011 (6): 24-30 page).
At present, from lignocellulosic material, extract cellulosic method and mainly contain concentrated base boiling-bleaching and steam blasting-bleaching.Highly basic boiling-bleaching process uses a large amount of NaOH and hydrogen peroxide, forms a large amount of black liquor, causes environmental pollution; Steam blasting-bleaching needs elevated pressures to carry out explosion, higher to equipment requirement.Organic solvent method separates lignocellulose and mainly utilizes dissolving and the degradation of organic solvent to lignin, is to separate cellulosic class effective ways in lignocellulose.Chinese invention patent CN103015243A adopts formic acid, acetic acid and hydrogen peroxide to carry out boiling to raw materials such as reed, straw, bamboos, adopts afterwards the processing of the multistep such as alkali treatment, chelating to prepare dissolving pulp and industrial fiber element.Chinese invention patent CN1299424, take grass as raw material and leaf wood as raw material, adopts formic acid and acetic acid mixed solution boiling to prepare paper pulp.
Summary of the invention
The object of the invention is to propose a kind of cellulosic method of extracting from furfural dregs, adopt the wide material sources such as formic acid, hydrogen peroxide, NaOH, be easy to the chemicals that obtains, under lower temperature conditions, from discarded object furfural dregs, extract cellulose, realize the high value added utilization of discarded object.
What the present invention proposed extracts cellulosic method from furfural dregs, comprises the following steps:
(1) formic acid-hydrogen peroxide treatment: the aqueous solution of preparation formic acid and hydrogen peroxide, making the wherein mass percent concentration of formic acid is 85%, the mass percent concentration of hydrogen peroxide is 1%, be designated as the first solution, by furfural dregs and the first solution by weight volume ratio be that 1:15 mixes, be warming up to 60 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, gained filter residue, the formic acid solution that is 85% with mass percent concentration washing, then water cleans, and the pH value that makes to clean waste liquid is 7, at 60 ℃, be dried 24 hours, obtain intermediate products;
(2) alkaline hydrogen peroxide processing: the aqueous solution of preparation NaOH and hydrogen peroxide, making the wherein mass percent concentration of NaOH is 1%, the mass percent concentration of hydrogen peroxide is 1%～2%, be designated as the second solution, by intermediate products and the second solution by weight volume ratio be that 1:30 mixes, be warming up to 50～80 ℃, react 1.5 hours, after reaction finishes, reactant mixture is filtered, gained filter residue water cleans, the pH value that makes to clean waste liquid is at 7,60 ℃ dry 24 hours, obtains cellulose products.
What the present invention proposed extracts cellulosic method from furfural dregs, and its advantage is:
(1) the present invention has extracted cellulose from furfural dregs, has realized the utilization of waste resource, has reduced the pollution of furfural dregs to environment; In the product obtaining, content of cellulose can reach 84.09%, and degree of crystallinity can reach 69.3%, provides raw material for preparing cellulose functional material.
(2) in the inventive method, organic solvent formic acid used easily reclaims, and hydrogen peroxide is degraded in course of reaction, not to environment.
(3) the inventive method is used dilute sodium hydroxide, has avoided use concentrated base, has reduced the consumption of chemical reagent; Course of reaction is carried out at normal pressure, and temperature, lower than 90 ℃, does not need to use pressure-resistant equipment, has reduced heating cost simultaneously.
(4) the inventive method implementation step is simple, and processing ease is easy to suitability for industrialized production.
The specific embodiment
What the inventive method proposed extracts cellulosic method from furfural dregs, comprises the following steps:
(1) formic acid-hydrogen peroxide treatment: the aqueous solution of preparation formic acid and hydrogen peroxide, making the wherein mass percent concentration of formic acid is 85%, the mass percent concentration of hydrogen peroxide is 1%, be designated as the first solution, by furfural dregs and the first solution by weight volume ratio be that 1:15 mixes, be warming up to 60 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, gained filter residue, the formic acid solution that is 85% with mass percent concentration washing, then water cleans, and the pH value that makes to clean waste liquid is 7, at 60 ℃, be dried 24 hours, obtain intermediate products;
(2) alkaline hydrogen peroxide processing: the aqueous solution of preparation NaOH and hydrogen peroxide, making the wherein mass percent concentration of NaOH is 1%, the mass percent concentration of hydrogen peroxide is 1%～2%, be designated as the second solution, by intermediate products and the second solution by weight volume ratio be that 1:30 mixes, be warming up to 50～80 ℃, react 1.5 hours, after reaction finishes, reactant mixture is filtered, gained filter residue water cleans, the pH value that makes to clean waste liquid is at 7,60 ℃ dry 24 hours, obtains cellulose products.
The present invention's furfural dregs used is taken from Hebei spring thunder furfural mill, and wherein content of cellulose is 41.90%, and degree of crystallinity is 54.8%.
Below introduce the embodiment of the inventive method:
Case study on implementation 1:
(1) formic acid-hydrogen peroxide treatment: the aqueous solution of preparation 150mL formic acid and hydrogen peroxide, wherein the mass percent concentration of formic acid is 85%, the mass percent concentration of hydrogen peroxide is 1%, is designated as the first solution, and 10g furfural dregs is mixed with the first solution, be warming up to 60 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, the formic acid solution washing that gained filter residue is 85% with mass percent concentration, then washes with water to waste liquor PH=7, at 60 ℃, be dried 24 hours, obtain intermediate products;
(2) alkaline hydrogen peroxide processing: the aqueous solution of preparation 150mL NaOH and hydrogen peroxide, wherein the mass percent concentration of NaOH is 1%, the mass percent concentration of hydrogen peroxide is 1%, be designated as the second solution, above-mentioned 5g intermediate products are mixed with the second solution, be warming up to 50 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, gained filter residue washes with water to waste liquor PH=7, at 60 ℃ dry 24 hours, obtains cellulose products.Gained cellulose products is 52.24% to the yield of furfural dregs, and its content of cellulose is 81.74%, and degree of crystallinity is 69.2%.
Case study on implementation 2:
(1) formic acid-hydrogen peroxide treatment: the aqueous solution of preparation 150mL formic acid and hydrogen peroxide, wherein the mass percent concentration of formic acid is 85%, the mass percent concentration of hydrogen peroxide is 1%, is designated as the first solution, and 10g furfural dregs is mixed with the first solution, be warming up to 60 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, the formic acid solution washing that gained filter residue is 85% with mass percent concentration, then washes with water to waste liquor PH=7, at 60 ℃, be dried 24 hours, obtain intermediate products;
(2) alkaline hydrogen peroxide processing: the aqueous solution of preparation 150mL NaOH and hydrogen peroxide, wherein the mass percent concentration of NaOH is 1%, the mass percent concentration of hydrogen peroxide is 1%, be designated as the second solution, above-mentioned 5g intermediate products are mixed with the second solution, be warming up to 60 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, gained filter residue washes with water to waste liquor PH=7, at 60 ℃ dry 24 hours, obtains cellulose products.Gained cellulose products is 50.72% to the yield of furfural dregs, and its content of cellulose is 81.89%, and degree of crystallinity is 70.0%.
Case study on implementation 3:
(1) formic acid-hydrogen peroxide treatment: the aqueous solution of preparation 150mL formic acid and hydrogen peroxide, wherein the mass percent concentration of formic acid is 85%, the mass percent concentration of hydrogen peroxide is 1%, is designated as the first solution, and 10g furfural dregs is mixed with the first solution, be warming up to 60 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, the formic acid solution washing that gained filter residue is 85% with mass percent concentration, then washes with water to waste liquor PH=7, at 60 ℃, be dried 24 hours, obtain intermediate products;
(2) alkaline hydrogen peroxide processing: the aqueous solution of preparation 150mL NaOH and hydrogen peroxide, wherein the mass percent concentration of NaOH is 1%, the mass percent concentration of hydrogen peroxide is 1%, be designated as the second solution, above-mentioned 5g intermediate products are mixed with the second solution, be warming up to 80 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, gained filter residue washes with water to waste liquor PH=7, at 60 ℃ dry 24 hours, obtains cellulose products.Gained cellulose products is 54.18% to the yield of furfural dregs, and its content of cellulose is 80.10%, and degree of crystallinity is 68.2%.
Case study on implementation 4:
(1) formic acid-hydrogen peroxide treatment: the aqueous solution of preparation 150mL formic acid and hydrogen peroxide, wherein the mass percent concentration of formic acid is 85%, the mass percent concentration of hydrogen peroxide is 1%, is designated as the first solution, and 10g furfural dregs is mixed with the first solution, be warming up to 60 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, the formic acid solution washing that gained filter residue is 85% with mass percent concentration, then washes with water to waste liquor PH=7, at 60 ℃, be dried 24 hours, obtain intermediate products;
(2) alkaline hydrogen peroxide processing: the aqueous solution of preparation 150mL NaOH and hydrogen peroxide, wherein the mass percent concentration of NaOH is 1%, the mass percent concentration of hydrogen peroxide is 2%, be designated as the second solution, above-mentioned 5g intermediate products are mixed with the second solution, be warming up to 60 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, gained filter residue washes with water to waste liquor PH=7, at 60 ℃ dry 24 hours, obtains cellulose products.Gained cellulose products is 51.70% to the yield of furfural dregs, and its content of cellulose is 84.09%, and degree of crystallinity is 69.3%.
Claims (1)
1. from furfural dregs, extract a cellulosic method, it is characterized in that the method comprises the following steps:
(1) formic acid-hydrogen peroxide treatment: the aqueous solution of preparation formic acid and hydrogen peroxide, making the wherein mass percent concentration of formic acid is 85%, the mass percent concentration of hydrogen peroxide is 1%, be designated as the first solution, by furfural dregs and the first solution by weight volume ratio be that 1:15 mixes, be warming up to 60 ℃ of reactions 1.5 hours, after reaction finishes, reactant mixture is filtered, gained filter residue, the formic acid solution that is 85% with mass percent concentration washing, then water cleans, and the pH value that makes to clean waste liquid is 7, at 60 ℃, be dried 24 hours, obtain intermediate products;
(2) alkaline hydrogen peroxide processing: the aqueous solution of preparation NaOH and hydrogen peroxide, making the wherein mass percent concentration of NaOH is 1%, the mass percent concentration of hydrogen peroxide is 1%～2%, be designated as the second solution, by intermediate products and the second solution by weight volume ratio be that 1:30 mixes, be warming up to 50～80 ℃, react 1.5 hours, after reaction finishes, reactant mixture is filtered, gained filter residue water cleans, the pH value that makes to clean waste liquid is at 7,60 ℃ dry 24 hours, obtains cellulose products.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105779525A (en) * | 2016-05-20 | 2016-07-20 | 宁夏大学 | Method for combined pretreatment on biomass by using ionic liquid and alkali liquid |
| CN110823751A (en) * | 2019-11-11 | 2020-02-21 | 安徽理工大学 | Method for determining content of catalyst sodium bisulfate in furfural residues |
| CN114874343A (en) * | 2022-05-30 | 2022-08-09 | 河南工业大学 | Spherical nanocrystalline cellulose based on furfural residues and preparation method thereof |
| CN115584653A (en) * | 2022-12-12 | 2023-01-10 | 河南禾力能源有限公司 | Method for extracting alpha-cellulose by furfural residues |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101413016A (en) * | 2008-12-03 | 2009-04-22 | 北京林业大学 | Method for preparing microcrystalline cellulose and cellulose fuel ethanol by separating furfural residue |
| US20100312006A1 (en) * | 2009-06-09 | 2010-12-09 | Meadwestvaco Corporation | Production of levulinic acid and levulinate esters from biomass |
| CN102733223A (en) * | 2012-06-18 | 2012-10-17 | 中国科学院广州能源研究所 | Pulping method by catalysis of low boiling point solvent with diluted acid generated from xylose residue and furfural residue |
| CN102887957A (en) * | 2012-10-30 | 2013-01-23 | 河南工业大学 | Method for preparing sodium carboxymethyl cellulose from furfural slag |
| CN103030815A (en) * | 2012-12-25 | 2013-04-10 | 济南圣泉集团股份有限公司 | Comprehensive utilization technology of biomass raw materials |
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2014
- 2014-01-16 CN CN201410020390.9A patent/CN103806318A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101413016A (en) * | 2008-12-03 | 2009-04-22 | 北京林业大学 | Method for preparing microcrystalline cellulose and cellulose fuel ethanol by separating furfural residue |
| US20100312006A1 (en) * | 2009-06-09 | 2010-12-09 | Meadwestvaco Corporation | Production of levulinic acid and levulinate esters from biomass |
| CN102733223A (en) * | 2012-06-18 | 2012-10-17 | 中国科学院广州能源研究所 | Pulping method by catalysis of low boiling point solvent with diluted acid generated from xylose residue and furfural residue |
| CN102887957A (en) * | 2012-10-30 | 2013-01-23 | 河南工业大学 | Method for preparing sodium carboxymethyl cellulose from furfural slag |
| CN103030815A (en) * | 2012-12-25 | 2013-04-10 | 济南圣泉集团股份有限公司 | Comprehensive utilization technology of biomass raw materials |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105779525A (en) * | 2016-05-20 | 2016-07-20 | 宁夏大学 | Method for combined pretreatment on biomass by using ionic liquid and alkali liquid |
| CN110823751A (en) * | 2019-11-11 | 2020-02-21 | 安徽理工大学 | Method for determining content of catalyst sodium bisulfate in furfural residues |
| CN110823751B (en) * | 2019-11-11 | 2021-12-24 | 安徽理工大学 | Method for determining content of catalyst sodium bisulfate in furfural residues |
| CN114874343A (en) * | 2022-05-30 | 2022-08-09 | 河南工业大学 | Spherical nanocrystalline cellulose based on furfural residues and preparation method thereof |
| CN115584653A (en) * | 2022-12-12 | 2023-01-10 | 河南禾力能源有限公司 | Method for extracting alpha-cellulose by furfural residues |
| CN115584653B (en) * | 2022-12-12 | 2023-03-10 | 河南禾力能源有限公司 | Method for extracting alpha-cellulose by furfural residues |
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Application publication date: 20140521 |