CN114105739A - Green alkali lignin micromolecule separation method and product - Google Patents
Green alkali lignin micromolecule separation method and product Download PDFInfo
- Publication number
- CN114105739A CN114105739A CN202111329450.1A CN202111329450A CN114105739A CN 114105739 A CN114105739 A CN 114105739A CN 202111329450 A CN202111329450 A CN 202111329450A CN 114105739 A CN114105739 A CN 114105739A
- Authority
- CN
- China
- Prior art keywords
- separation method
- small molecule
- alkali lignin
- green
- lignin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 63
- 239000003513 alkali Substances 0.000 title claims abstract description 35
- 238000000926 separation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 238000004537 pulping Methods 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 238000010790 dilution Methods 0.000 claims abstract description 10
- 239000012895 dilution Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 150000003384 small molecules Chemical class 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000010411 cooking Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000000413 hydrolysate Substances 0.000 abstract description 7
- 238000001816 cooling Methods 0.000 abstract description 6
- 108010009736 Protein Hydrolysates Proteins 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000284 extract Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 241000219927 Eucalyptus Species 0.000 description 25
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 229920005611 kraft lignin Polymers 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The invention discloses a green alkali lignin micromolecule separation method and a product; adding water or ethanol/water into black liquor for dilution, performing centrifugal treatment, and performing self-hydrolysis reaction on supernate to obtain hydrolysate; and cooling the hydrolysate, acidifying, standing and centrifuging, extracting the obtained filtrate by using a green organic solvent, and drying to obtain a soluble micromolecule fraction, namely the alkali lignin micromolecules. The method extracts and utilizes the lignin in the alkaline pulping black liquor of an alkaline method, a sulfate method and the like, and has the characteristics of waste utilization, environmental protection, high economic benefit and the like; the method can obtain lignin fractions with different molecular weights, and the polydispersity of each fraction is reduced, and small molecular fractions can be selectively dissolved out; the separation method is environment-friendly, the solvent is non-toxic, the content of the small molecular fraction is rich, the whole process is environment-friendly, and the method has a good industrial production prospect.
Description
Technical Field
The invention relates to the technical field of lignin pretreatment and the technical field of lignin recycling, in particular to a green alkali lignin micromolecule separation method and a product.
Background
The industrial alkali lignin is an important industrial raw material, has good flame retardance, oxidation resistance, thermal stability and the like, and has good application potential in the fields of high polymer materials, carbon materials, adhesives, water reducing agents and the like due to the fact that molecules contain various active functional groups. Currently, industrial alkali lignin is mainly extracted from black liquor generated in the cooking process of the pulping and papermaking industry, and a large amount of lignin micromolecule degradation products are contained in the industrial alkali lignin. Research reports that the methylene dichloride is adopted to classify the crude lignin extracted from the black liquor, so that high-yield lignin small molecular fractions can be obtained, and the small molecular fractions contain a large amount of monomers, dimers and the like, so that the method has important significance for developing and utilizing new materials and chemicals. Although dichloromethane is more selective for small molecule fractions, it is more toxic and unfavorable for subsequent production (C.ZHao, Z.Hu, L.Shi, C.Wang, F.Yue, S.Li, H.Zhang, F.Lu, Green Chem 2020,22, 7366-.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to realize the fractional separation of lignin micromolecule fraction with considerable content from black liquor by adopting a green and efficient self-hydrolysis grading method and combining a green solvent system, so as to replace the traditional solvent system with high selectivity and high toxicity and realize the efficient utilization of lignin.
A large amount of alkali liquor can be remained in the pulping black liquor of an alkaline method and a sulfate method, so that the residual alkali liquor can be utilized to perform self-hydrolysis reaction at high temperature to realize classification, in the process, the bonds which are not completely broken in the lignin are further broken to form fragment products with low molecular weight, and then the lignin micromolecule fraction with relatively high yield is obtained by green organic solvent extraction. The whole process is green and nontoxic, is expected to replace dichloromethane with high toxicity, directly extracts lignin micromolecule fractions from black liquor, realizes effective utilization of lignin, and has important significance from the environmental protection perspective and the economic perspective.
In order to achieve the purpose, the invention adopts the following technical scheme:
a green alkali lignin micromolecule separation method and a product thereof comprise the following steps:
(1) self-hydrolysis reaction: adding water or ethanol/water into the black liquor for dilution, performing centrifugal treatment, and performing self-hydrolysis reaction on supernatant to obtain hydrolysate;
(2) alkali lignin micromolecule separation: and (2) cooling the hydrolysate obtained in the step (1), acidifying, standing and centrifuging, extracting the obtained filtrate with a green organic solvent, and drying to obtain a soluble micromolecule fraction, namely the alkali lignin micromolecules.
Further, the black liquor in the step (1) is black liquor generated in a cooking stage in an alkaline pulping process.
Further preferably, the alkaline pulping process is an alkaline pulping process or a sulfate pulping process.
Further, the dilution quality of the step (1) is 5-15 times of that of the black liquor.
Further, the volume ratio of ethanol to water in the ethanol/water in the step (1) is 0-5: 1 and is not 0; further preferably, the volume ratio of ethanol to water in the ethanol/water in the step (1) is 1:5, 1:1, 5: 1.
Further, the reaction in the step (1) is carried out in a high-pressure reaction kettle.
Further, the temperature of the reaction in the step (1) is 90-140 ℃.
Further, the reaction time of the step (1) is 1-4 h.
Further, the acidification in the step (2) uses hydrochloric acid with the acid concentration of 0.1-6 mol/L; the acidification is to pH < 3.
Further, the standing time in the step (2) is 4-16 h. Further preferably, the standing time is 12 hours.
Further, the organic solvent in the step (2) is ethyl acetate.
Further, the extraction times in the step (2) are 1-5 times.
Further, the solvent removing condition in the step (2) is that the solvent is evaporated to dryness under reduced pressure at the temperature of 30-60 ℃.
The alkali lignin micromolecules obtained by the green alkali lignin micromolecule separation method are separated.
Compared with the prior art, the invention has the following advantages:
(1) the method utilizes the characteristic that a large amount of alkali liquor is remained in alkaline pulping black liquor such as an alkaline method and a sulfate method, and adopts a simple, green and low-cost self-hydrolysis method combined with a green organic solvent extraction method to reduce lignin heterogeneity, thereby improving the utilization rate of lignin wastes with rich content.
(2) The invention utilizes the autohydrolysis reaction to further break the connecting bond in the lignin, form fragments with lower molecular weight and improve the yield of small molecular fraction.
(3) The solvent selected by the method is green and nontoxic, is expected to replace the traditional toxic solvent with high selectivity on small molecule level, and is an economic and sustainable method.
Drawings
FIG. 1 is a GC-MS graph of the small molecular fraction of eucalyptus kraft lignin from example 1.
FIG. 2 is a GC-MS graph of the small molecular fraction of eucalyptus kraft lignin from example 2.
FIG. 3 is a GC-MS graph of the small molecular fraction of eucalyptus kraft lignin from example 3.
FIG. 4 is a GC-MS graph of the small molecular fraction of eucalyptus kraft lignin from example 4.
FIG. 5 is a GC-MS graph of the eucalyptus sulphate lignin small molecule fraction of example 5 (blank).
FIG. 6 is a structural view of each substance in each example.
Detailed Description
The present invention will be described in further detail below with reference to examples for better understanding of technical features of the present invention, but the scope of the present invention as claimed is not limited thereto.
Example 1
A green alkali lignin small molecule separation method comprises the following steps:
(1) taking 10g of black liquor sample generated in the cooking stage in the eucalyptus kraft pulping process, adding 60mL of distilled water for dilution, carrying out centrifugal treatment (8000r/min, 15min), and carrying out self-hydrolysis reaction on the supernatant in a reaction kettle at the temperature of 120 ℃ for 3h to obtain hydrolysate;
(2) cooling the hydrolysate, acidifying with 1mol/L hydrochloric acid until pH is less than 3, standing for 12h, centrifuging (8000r/min, 15min), separating the residue from the filtrate, and washing the residue with deionized water for 2 times;
(3) combining the filtrates obtained in step (2), extracting with ethyl acetate for 3 times, evaporating the organic phase at 40 deg.C under reduced pressure to remove ethyl acetate, and vacuum drying at 40 deg.C (overnight) to obtain soluble fraction (eucalyptus sulfate lignin small molecule fraction); the filter residue was dried under vacuum (overnight) at 40 ℃ to give an insoluble fraction.
The GC-MS diagram of the obtained eucalyptus sulfate lignin small molecular fraction is shown in figure 1.
The yield of the obtained small molecular fraction of the eucalyptus sulfate lignin is 20.7%.
Example 2
A green alkali lignin small molecule separation method comprises the following steps:
(1) taking 10g of black liquor sample generated in the cooking stage in the eucalyptus sulfate pulping process, adding 50mL of distilled water and 10mL of ethanol for dilution, carrying out centrifugal treatment (8000r/min, 15min), and carrying out self-hydrolysis reaction on the supernatant in a reaction kettle at the temperature of 120 ℃ for 3h to obtain hydrolysate;
(2) cooling the hydrolysate, acidifying with 1mol/L hydrochloric acid until pH is less than 3, standing for 12h, centrifuging (8000r/min, 15min), separating the residue from the filtrate, and washing the residue with deionized water for 2 times;
(3) combining the filtrates obtained in step (2), extracting with ethyl acetate for 3 times, evaporating the organic phase at 40 deg.C under reduced pressure to remove ethyl acetate, and vacuum drying at 40 deg.C (overnight) to obtain soluble fraction (eucalyptus sulfate lignin small molecule fraction); the filter residue was dried under vacuum (overnight) at 40 ℃ to give an insoluble fraction.
The GC-MS chart of the obtained eucalyptus sulfate lignin small molecular fraction is shown in figure 2.
The yield of the obtained small molecular fraction of the eucalyptus sulfate lignin is 29.8%.
Example 3
A green alkali lignin small molecule separation method comprises the following steps:
(1) taking 10g of black liquor sample generated in the cooking stage in the eucalyptus sulfate pulping process, adding 30mL of distilled water and 30mL of ethanol for dilution, carrying out centrifugal treatment (8000r/min, 15min), and carrying out self-hydrolysis reaction on the supernatant in a reaction kettle at the temperature of 120 ℃ for 3h to obtain hydrolysate;
(2) cooling the hydrolysate, acidifying with 1mol/L hydrochloric acid until pH is less than 3, standing for 12h, centrifuging (8000r/min, 15min), separating the residue from the filtrate, and washing the residue with deionized water for 2 times;
(3) combining the filtrates obtained in step (2), extracting with ethyl acetate for 3 times, evaporating the organic phase at 40 deg.C under reduced pressure to remove ethyl acetate, and vacuum drying at 40 deg.C (overnight) to obtain soluble fraction (eucalyptus sulfate lignin small molecule fraction); the filter residue was dried under vacuum (overnight) at 40 ℃ to give an insoluble fraction.
The GC-MS chart of the obtained eucalyptus sulfate lignin small molecular fraction is shown in figure 3.
The yield of the obtained small molecular fraction of the eucalyptus sulfate lignin is 41.1%.
Example 4
A green alkali lignin small molecule separation method comprises the following steps:
(1) taking 10g of black liquor sample generated in the cooking stage in the eucalyptus sulfate pulping process, adding 10mL of distilled water and 50mL of ethanol for dilution, carrying out centrifugal treatment (8000r/min, 15min), and carrying out self-hydrolysis reaction on the supernatant in a reaction kettle at the temperature of 120 ℃ for 3h to obtain hydrolysate;
(2) cooling the hydrolysate, acidifying with 1mol/L hydrochloric acid until pH is less than 3, standing for 12h, centrifuging (8000r/min, 15min), separating the residue from the filtrate, and washing the residue with deionized water for 2 times;
(3) combining the filtrates obtained in step (2), extracting with ethyl acetate for 3 times, evaporating the organic phase at 40 deg.C under reduced pressure to remove ethyl acetate, and vacuum drying at 40 deg.C (overnight) to obtain soluble fraction (eucalyptus sulfate lignin small molecule fraction); the filter residue was dried under vacuum (overnight) at 40 ℃ to give an insoluble fraction.
The GC-MS chart of the obtained eucalyptus sulfate lignin small molecular fraction is shown in figure 4.
The yield of the obtained eucalyptus kraft lignin micromolecule fraction is 52.5%.
Example 5
A green alkali lignin small molecule separation method comprises the following steps:
(1) taking 10g of black liquor sample generated in the cooking stage in the eucalyptus kraft pulping process, adding 60mL of distilled water for dilution, carrying out centrifugal treatment (8000r/min, 15min), acidifying the supernatant by 1mol/L hydrochloric acid until the pH value is less than 3, standing for 12h, centrifuging (8000r/min, 15min), separating filter residue from filtrate, and washing the filter residue by deionized water for 2 times;
(2) combining the filtrates obtained in step (1), extracting with ethyl acetate for 3 times, evaporating the organic phase at 40 deg.C under reduced pressure to remove ethyl acetate, and vacuum drying at 40 deg.C (overnight) to obtain soluble fraction (eucalyptus sulfate lignin small molecule fraction); the filter residue was dried under vacuum (overnight) at 40 ℃ to give an insoluble fraction.
The GC-MS chart of the obtained eucalyptus sulfate lignin small molecular fraction is shown in figure 5.
The yield of the obtained small molecular fraction of the eucalyptus sulfate lignin is 14.6%.
The structural diagrams of the substances are shown in fig. 6, and the substances have important roles in developing new materials and chemicals and have important guiding significance for identifying the structure of industrial lignin.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111329450.1A CN114105739B (en) | 2021-11-10 | 2021-11-10 | Green alkali lignin micromolecule separation method and product |
| PCT/CN2022/128478 WO2023083029A1 (en) | 2021-11-10 | 2022-10-31 | Green alkali lignin micromolecule separation method and product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111329450.1A CN114105739B (en) | 2021-11-10 | 2021-11-10 | Green alkali lignin micromolecule separation method and product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114105739A true CN114105739A (en) | 2022-03-01 |
| CN114105739B CN114105739B (en) | 2022-09-20 |
Family
ID=80378297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111329450.1A Active CN114105739B (en) | 2021-11-10 | 2021-11-10 | Green alkali lignin micromolecule separation method and product |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114105739B (en) |
| WO (1) | WO2023083029A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023083029A1 (en) * | 2021-11-10 | 2023-05-19 | 华南理工大学 | Green alkali lignin micromolecule separation method and product |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562792A (en) * | 2004-04-16 | 2005-01-12 | 黄德丰 | New technique of no pollution discharge for treating black liquor from papermaking |
| CN102776797A (en) * | 2011-05-12 | 2012-11-14 | 秦才东 | Neutralizing treatment method of pulping black liquor and synchronous acidic water solution |
| CN103275331A (en) * | 2013-05-23 | 2013-09-04 | 广西大学 | Method for preparing lignin nanoparticles by taking papermaking black liquid as raw material |
| CN106866382A (en) * | 2017-01-24 | 2017-06-20 | 中国科学院广州能源研究所 | The extracting method of aldehydes matter in a kind of catalytic lignin depolymerization product liquid |
| CN106906685A (en) * | 2017-02-28 | 2017-06-30 | 齐鲁工业大学 | A kind of method that high added value phenol products are prepared by black liquor of pulp making |
| CN109179845A (en) * | 2018-11-16 | 2019-01-11 | 河南省科学院化学研究所有限公司 | A kind of disposal of resources method of sulfate method pulp black liquor |
| CN109851814A (en) * | 2014-07-09 | 2019-06-07 | 威尔迪亚公司 | For the method and combinations thereof of lignin to be separated and refined from black liquor |
| CN109970991A (en) * | 2019-03-20 | 2019-07-05 | 华南理工大学 | A Comprehensive Utilization Method for Demethoxylation of Small Fractions of Fractionated Lignin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014116150A1 (en) * | 2013-01-24 | 2014-07-31 | Valmet Power Ab | Method for producing high purity lignin |
| CN114105739B (en) * | 2021-11-10 | 2022-09-20 | 华南理工大学 | Green alkali lignin micromolecule separation method and product |
-
2021
- 2021-11-10 CN CN202111329450.1A patent/CN114105739B/en active Active
-
2022
- 2022-10-31 WO PCT/CN2022/128478 patent/WO2023083029A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562792A (en) * | 2004-04-16 | 2005-01-12 | 黄德丰 | New technique of no pollution discharge for treating black liquor from papermaking |
| CN102776797A (en) * | 2011-05-12 | 2012-11-14 | 秦才东 | Neutralizing treatment method of pulping black liquor and synchronous acidic water solution |
| CN103275331A (en) * | 2013-05-23 | 2013-09-04 | 广西大学 | Method for preparing lignin nanoparticles by taking papermaking black liquid as raw material |
| CN109851814A (en) * | 2014-07-09 | 2019-06-07 | 威尔迪亚公司 | For the method and combinations thereof of lignin to be separated and refined from black liquor |
| CN106866382A (en) * | 2017-01-24 | 2017-06-20 | 中国科学院广州能源研究所 | The extracting method of aldehydes matter in a kind of catalytic lignin depolymerization product liquid |
| CN106906685A (en) * | 2017-02-28 | 2017-06-30 | 齐鲁工业大学 | A kind of method that high added value phenol products are prepared by black liquor of pulp making |
| CN109179845A (en) * | 2018-11-16 | 2019-01-11 | 河南省科学院化学研究所有限公司 | A kind of disposal of resources method of sulfate method pulp black liquor |
| CN109970991A (en) * | 2019-03-20 | 2019-07-05 | 华南理工大学 | A Comprehensive Utilization Method for Demethoxylation of Small Fractions of Fractionated Lignin |
Non-Patent Citations (3)
| Title |
|---|
| 康世民: "木质素水热转化及其产物基础应用研究", 《中国优秀博硕士学位论文全文数据库(博士)农业科技辑》 * |
| 王敏姣等: "低温水热法降解桉木和绵竹硫酸盐木素的研究", 《化工科技》 * |
| 罗小林等: "尾叶桉KP法制浆黑液中小分子酚类化合物的分离与GC-MS分析", 《林产化学与工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023083029A1 (en) * | 2021-11-10 | 2023-05-19 | 华南理工大学 | Green alkali lignin micromolecule separation method and product |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023083029A1 (en) | 2023-05-19 |
| CN114105739B (en) | 2022-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110540508B (en) | Eutectic solvent and application thereof in extracting lignin | |
| CN110804893B (en) | Method for separating holocellulose in wood fibers by using choline eutectic solvent | |
| CN105860090B (en) | The method of high activity lignin and its obtained lignin are extracted from biomass | |
| US8585863B2 (en) | Separation of lignin from hydrolyzate | |
| CN110241644B (en) | Method for separating and comprehensively utilizing all components of crop straws | |
| CN109232909B (en) | A method for separating highly active lignin from agricultural and forestry biomass | |
| WO2014142289A1 (en) | Method for manufacturing lignin degradation product | |
| Duan et al. | A novel ternary deep eutectic solvent pretreatment for the efficient separation and conversion of high-quality gutta-percha, value-added lignin and monosaccharide from Eucommia ulmoides seed shells | |
| CN108822304A (en) | A kind of method of gamma-valerolactone/aqueous systems classification lignin | |
| CN114105739A (en) | Green alkali lignin micromolecule separation method and product | |
| CN110054783A (en) | The method for being separated from wood fibre pre-hydrolyzed solution, extracting lignin-carbohydrate complexes | |
| CN112321652B (en) | A method for efficient separation of high-quality lignin from biomass | |
| CN114108350A (en) | A kind of method for rapid separation of main components of woody biomass by deep eutectic solvent | |
| CN113698625A (en) | Pretreatment method of lignocellulose raw material | |
| CN105672016B (en) | A kind of washing of organic solvent method paper pulp and method for recovering solvents | |
| Yaakob et al. | The Extraction of Lignin from Empty Fruit Bunch Fiber via Microwave-Assisted Deep-Eutectic Solvent Heating: Extraction of Lignin from Empty Fruit Bunch Fiber via Microwave-Assisted Deep-Eutectic Solvent Heating | |
| CN113372572B (en) | A method for recycling solid organic acid to separate lignin | |
| JP6274478B2 (en) | Method for producing lignin degradation product | |
| CN113831372B (en) | A method for rapid extraction of waste biomass lignin and resource utilization by microwave method | |
| Feng et al. | Research progress on the fractionation and structural properties of lignin based on deep eutectic solvents | |
| CN1255367C (en) | Preparing method for phenol series substances | |
| CN116043591A (en) | A kind of method adopting phenolic deep eutectic solvent to separate lignocellulose | |
| CN103266145B (en) | Method for preparing fermentable sugar and lignosulfonate from furfural residues | |
| CN110550797B (en) | Method for efficiently classifying and separating organic matters in pulping yellow liquor | |
| CN105167174A (en) | Leaching liquor capable of effectively reducing lignin content in tobacco waste as well as preparation method and application of leaching liquor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |