CN101503431A - Technology for extracting high purity lignin from pulping black liquor by organic carboxyl acid method - Google Patents
Technology for extracting high purity lignin from pulping black liquor by organic carboxyl acid method Download PDFInfo
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- CN101503431A CN101503431A CNA2008100453684A CN200810045368A CN101503431A CN 101503431 A CN101503431 A CN 101503431A CN A2008100453684 A CNA2008100453684 A CN A2008100453684A CN 200810045368 A CN200810045368 A CN 200810045368A CN 101503431 A CN101503431 A CN 101503431A
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- acid
- black liquor
- lignin
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- purity lignin
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Abstract
The invention relates to a technology for extracting high-purity lignin from pulping black liquor through an organic carboxylic acid method. The technology sequentially comprises the following steps: separating pulping slurry and extracting black liquor; condensing the black liquor till above Baume 20 degrees; adding carboxylic acid at a temperature of 30-90 DEG C to adjust the pH of the condensed black liquor to be below 4, and carrying out settlement separation for 2-16h; adding 3-10 percent of organic solvent in the settlement separation matter containing lignin, stirring for 1-3h for the sake of reaction, dissolving and separating organic impurities, filtering and washing till neutrality is reached; drying and crushing a washed filter cake to obtain high-purity lignin; and condensing residual components after the separation till above Baume 25 degrees so as to begin heat energy and alkali recovery. The invention has low cost and no secondary pollution; the separated high-purity lignin has even molecular weight distribution, can not be dissolved in water, and is thermoplastic and degradable; and conditions are created for large-scale application of the high-purity lignin in the aspects such as thermoplastic stuffing materials, co-mixing, copolymerization, biomass energy materials, etc.
Description
(1) technical field
The present invention relates to a kind of organic carboxyl acid method extracts high purity lignin from black liquor of pulp making technology.
(2) background technology
Xylogen (abbreviation lignin) is the main component that constitutes the plant skeleton with Mierocrystalline cellulose and hemicellulose, is a kind of natural organic high-molecular material of plant materials secondary metabolism synthetic.Estimate that the annual whole world can produce 1,500 hundred million tons of lignins by plant-growth.Lignin is the monomeric amorphous high polymer of phenylpropyl alcohol alkane.But industrial lignin is a kind of thermoplasticity natural macromolecular material of wide molecular weight distribution, no stable second-order transition temperature.Lignin is owing to its complex structure, and the biological degradation difficulty is the main organic pollutant of paper industry, if do not made full use of, will cause a large amount of wastings of resources and serious environmental to pollute.Condensation or degraded owing to taken place in industrial lignin, and complicated component, relative molecular mass distribute from hundreds of to several ten thousand; Viscosity is low, and the dispersity height is water-soluble, and poor processability does not almost have thermoplastic property, these characteristic limitations the industrial lignin Products Development utilize.At present at China's lignocellulose processing industry papermaking wastewater about more than 1,000 ten thousand tons only with regard to callable lignin, major part direct burn processing when alkali reclaims, remainder is produced industrial lignin product (mainly being Sulfite lignin) annual production less than 500,000 tons through the Acid precipitation drying.Industry alkaline process, the isolating lignin of imido method is characterized in that lignin content is low because condensation or degraded have taken place, only 40%～60%, and complicated component, relative molecular mass distribute from hundreds of to several ten thousand; Viscosity is low, dispersity height, poor processability; And it is residual, water-soluble to contain pulping chemical (high sulphite, high sodium content etc.), does not almost have thermoplastic property, except that part directly is used as water reducer, the dispersion agent, and a large amount of valuable lignin resource research and development poor effect.Because the restriction of various technical qualification up to now, does not also have a kind of lignin is extracted in industrialization from black liquor of pulp making method that all can satisfy technically, economically.The complex art method of extracting lignin from black liquor of pulp making of patent disclosure generally is to adopt to add mineral acid, SO in black liquor of pulp making at present
2And CO
2Deng acidic cpd, make black liquor PH reduce to 6～8, then the separation and Extraction lignin; Or in black liquor of pulp making separately or mix organic polymer ionogen separation and Extraction lignins such as adding positively charged ion, negatively charged ion, nonionic polypropylene phthalein amine.The present accessible purity of the undeclared the whole bag of tricks isolated lignin of content of patent disclosure, and high purity lignin kind surplus to be high-tech product that raw material can be researched and developed have 400.What is more important, mineral acid, SO
2And CO
2The secondary pollution that forms Deng the residuum behind the acidic cpd neutralization precipitation lignin is still insurmountable problem.Current, International Paper had realized less contamination, the leap of oligosaprobic technology already.Along with pulping technique, papermaking wastewater recycling technology, lignin separates and the progress of modification technology, but purity height, molecular weight lignin Industrial products big, that be insoluble in the processing of water thermoplastic will enter the research and development field in a large number.High purity lignin can be widely because process for processing fields such as chemical industry, mulch film, electromechanics, material of construction, packing and environmental protection.To drive the development of industry aspects such as papermaking, chemical industry, chemical fertilizer, plastic sheeting for farm use, electromechanics, material, packing and environmental protection simultaneously, help realizing ecological benefits, social benefit and economic benefit three's unification, Sustainable development has important application prospects and meaning to economy and society.
(3) summary of the invention
1, goal of the invention the objective of the invention is to cause deterioration of the ecological environment problem for a large amount of lignin wastes in the solution pulping and paper-making processing and utilization, providing a kind of is raw material with black liquor of pulp making etc., adopt the organic carboxyl acid partition method, the production even molecular weight distribution, water insoluble, but thermoplastic, the extractive technique of degradable high purity lignin.Development and use service for energy-saving and emission-reduction and renewable xylogen resource.
2, technical scheme technical scheme of the present invention is: the slurrying slurries separate, and extract black liquor; Black liquor is concentrated into Baume more than 20 °; At 30～90 ℃ of pH that add carboxylic acid adjusting concentrated black liquor is below 4, carries out settlement separate 2～16 hours; The settlement separate thing that contains lignin adds 3～10% organic solvents, and stirring reaction 1～3 hour with the organic impurity separated and dissolved, filters, washs to neutral; Filtration cakes torrefaction after the washing, pulverizing are obtained high purity lignin; Remaining component behind the separation high purity lignin is concentrated into Baume and enters heat energy and alkali recovery more than 25 °; Except that extracting high purity lignin, be below 7 at 30～90 ℃ of pH that add acid adjusting concentrated black liquor, can directly obtain general thick lignin products by spraying drying.
Carboxylic acid is that general formula is compound and its derivative of R-COOH, select formic acid, acetate, propionic acid, butyric acid, pyruvic acid and other monocarboxylic acid for use, oxalic acid, oxysuccinic acid, succsinic acid, toxilic acid, oxaloacetic acid, fumaric acid and other di-carboxylic acid, citric acid, equisetic acid and other tribasic carboxylic acid, the arbitrary combination of one or more in Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), diacetyl oxide, maleic anhydride and other carboxylic acid derivative.
Organic solvent is selected one or more the arbitrary combination in ethanol, acetone, butanone, ethyl acetate and other alcohol, ketone, the ester for use.
3, beneficial effect
Beneficial effect of the present invention mainly shows:
(1) be raw material with black liquor of pulp making etc., adopt the carboxylic acid partition method, the production even molecular weight distribution, water insoluble, but thermoplastic, degradable high purity lignin.Comprehensive cost of the present invention is low, and non-secondary pollution discharging will become and solve that a large amount of lignin wastes cause one of major technique approach of deterioration of the ecological environment problem and energy-saving and emission-reduction in the pulping and paper-making processing and utilization.
(2) carboxylate salt that forms in the high purity lignin separation and Extraction of carboxylic acid and carboxylic acid derivative at high temperature can be decomposed to form CO
2, water and metal oxide, do not have the residual of secondary pollutant and handle.
(3) appurtenant work that can be directly reclaims as alkali of the present invention, remaining component behind the separation high purity lignin is concentrated into Baume and enters heat energy and alkali recovery more than 25 °, has fundamentally solved the influence of compounds such as the remaining acid of general lignin acidizing separation technology, muriate, vitriol to heat energy and alkali recovery.
(4) except that extracting high purity lignin, be below 7 at 30～90 ℃ of pH that add acid adjusting concentrated black liquor, can directly obtain general thick lignin products by spraying drying.
(4) embodiment
1, the slurrying slurries separate, extract black liquor, black liquor is concentrated into 20 ° of Baumes, is 4 at 30 ℃ of pH that add oxalic acid adjusting concentrated black liquor, carries out settlement separate 16 hours, the settlement separate thing that contains lignin adds 3% ethanol, stirring reaction 3 hours with the organic impurity separated and dissolved, filters, washs to neutral, filtration cakes torrefaction after the washing, pulverizing are obtained high purity lignin, and the remaining component behind the separation high purity lignin is concentrated into 25 ° of Baumes and enters heat energy and alkali recovery.
2, the slurrying slurries separate, and extract black liquor; Black liquor is concentrated into 25 ° of Baumes, and the pH that regulates concentrated black liquor at 60 ℃ of adding citric acids is 2, carries out settlement separate 6 hours; The settlement separate thing that contains lignin adds 5% acetone, stirring reaction 2 hours with the organic impurity separated and dissolved, filters, washs to neutral, filtration cakes torrefaction after the washing, pulverizing are obtained high purity lignin, and the remaining component behind the separation high purity lignin is concentrated into 30 ° of Baumes and enters heat energy and alkali recovery.
3, the slurrying slurries separate, and extract black liquor; Black liquor is concentrated into 30 ° of Baumes, at 70 ℃ of pH that add trichoroacetic acid(TCA) adjusting concentrated black liquor is 1, carried out settlement separate 4 hours, the settlement separate thing that contains lignin adds 10% ethyl acetate, stirring reaction 1 hour with the organic impurity separated and dissolved, filters, washs to neutral, filtration cakes torrefaction after the washing, pulverizing are obtained high purity lignin, and the remaining component behind the separation high purity lignin is concentrated into 32 ° of Baumes and enters heat energy and alkali recovery.
4, the slurrying slurries separate, and extract black liquor; Black liquor is concentrated into 28 ° of Baumes, at 80 ℃ of pH that add diacetyl oxide adjusting concentrated black liquor is 3, carried out settlement separate 2 hours, the settlement separate thing that contains lignin adds 5% ethanol and acetone 1:1 mixing solutions, stirring reaction 3 hours with the organic impurity separated and dissolved, filters, washs to neutral, filtration cakes torrefaction after the washing, pulverizing are obtained high purity lignin, and the remaining component behind the separation high purity lignin is concentrated into 30 ° of Baumes and enters heat energy and alkali recovery.
5, the slurrying slurries separate, extract black liquor, black liquor is concentrated into 30 ° of Baumes, at 90 ℃ of pH that add the mixing solutions adjusting concentrated black liquor of propionic acid and oxalic acid 1:1 is 2, carried out settlement separate 6 hours, the settlement separate thing that contains lignin adds 8% the ethanol and the mixed solution of ethyl acetate, stirring reaction 2 hours, with the organic impurity separated and dissolved, filter, wash to neutral, filtration cakes torrefaction after the washing, pulverizing are obtained high purity lignin, and the remaining component behind the separation high purity lignin is concentrated into 28 ° of Baumes and enters heat energy and alkali recovery.
6, the slurrying slurries separate, and extract black liquor; Black liquor is concentrated into 27 ° of Baumes, is 7 at 90 ℃ of pH that add oxalic acid adjusting concentrated black liquor, directly obtains general thick lignin products by spraying drying.
Claims (3)
1, a kind of organic carboxyl acid method extracts the technology of high purity lignin from black liquor of pulp making, and its main process comprises: the slurrying slurries separate, and extract black liquor; Black liquor is concentrated into Baume more than 20 °; At 30～90 ℃ of pH that add carboxylic acid adjusting concentrated black liquor is below 4, carries out settlement separate 2～16 hours; The settlement separate thing that contains lignin adds 3～10% organic solvents, and stirring reaction 1～3 hour with the organic impurity separated and dissolved, filters, washs to neutral; Filtration cakes torrefaction after the washing, pulverizing are obtained high purity lignin; Remaining component behind the separation high purity lignin is concentrated into Baume and enters heat energy and alkali recovery more than 25 °; Except that extracting high purity lignin, be below 7 at 30～90 ℃ of pH that add acid adjusting concentrated black liquor, can directly obtain general thick lignin products by spraying drying.
2, organic carboxyl acid method according to claim 1 extracts the technology of high purity lignin from black liquor of pulp making, it is characterized in that, described carboxylic acid is that general formula is compound and its derivative of R-COOH, selects formic acid, acetate, propionic acid, butyric acid, pyruvic acid and other monocarboxylic acid for use; Oxalic acid, oxysuccinic acid, succsinic acid, toxilic acid, oxaloacetic acid, fumaric acid and other di-carboxylic acid; Citric acid, equisetic acid and other tribasic carboxylic acid; The arbitrary combination of one or more in Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), diacetyl oxide, maleic anhydride and other carboxylic acid derivative.
3, organic carboxyl acid method according to claim 1 extracts the technology of high purity lignin from black liquor of pulp making, it is characterized in that described organic solvent is selected one or more the arbitrary combination in ethanol, acetone, butanone, ethyl acetate and other alcohol, ketone, the ester for use.
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| CN 200810045368 CN101503431B (en) | 2008-02-04 | 2008-02-04 | Technology for extracting high purity lignin from pulping black liquor by organic carboxyl acid method |
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| CN101503431B CN101503431B (en) | 2011-05-25 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337138A (en) * | 2011-05-27 | 2012-02-01 | 刘长福 | Biodegradable liquid mulch film produced from papermaking waste liquid, and production method thereof |
| CN102733230A (en) * | 2012-07-05 | 2012-10-17 | 东北林业大学 | Process for producing high-purity ammonium lignin by taking papermaking black liquid as material |
| CN102924728A (en) * | 2012-11-16 | 2013-02-13 | 湖南鸿鹰生物科技有限公司 | Method for preparing modified xylogen and applications thereof in wastewater treatment |
| CN103435082A (en) * | 2013-08-21 | 2013-12-11 | 浙江理工大学 | Method for regulating growth of calcium carbonate crystal grains by using pulping black liquor lignin |
| CN106468032A (en) * | 2015-08-18 | 2017-03-01 | 海南金海浆纸业有限公司 | The method and device of lignin is extracted a kind of black liquor from sulfate pulping |
| WO2018004427A1 (en) * | 2016-06-22 | 2018-01-04 | Valmet Ab | Method of producing lignin with reduced amount of odorous substances |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358811C (en) * | 2003-08-26 | 2008-01-02 | 山东泉林纸业有限责任公司 | Process for extracting lignin by acid separation |
-
2008
- 2008-02-04 CN CN 200810045368 patent/CN101503431B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337138A (en) * | 2011-05-27 | 2012-02-01 | 刘长福 | Biodegradable liquid mulch film produced from papermaking waste liquid, and production method thereof |
| CN102733230A (en) * | 2012-07-05 | 2012-10-17 | 东北林业大学 | Process for producing high-purity ammonium lignin by taking papermaking black liquid as material |
| CN102924728A (en) * | 2012-11-16 | 2013-02-13 | 湖南鸿鹰生物科技有限公司 | Method for preparing modified xylogen and applications thereof in wastewater treatment |
| CN103435082A (en) * | 2013-08-21 | 2013-12-11 | 浙江理工大学 | Method for regulating growth of calcium carbonate crystal grains by using pulping black liquor lignin |
| CN103435082B (en) * | 2013-08-21 | 2015-10-28 | 浙江理工大学 | A kind of method utilizing lignin from pulping black liquor to regulate and control calcium carbonate crystal particle growth |
| CN106468032A (en) * | 2015-08-18 | 2017-03-01 | 海南金海浆纸业有限公司 | The method and device of lignin is extracted a kind of black liquor from sulfate pulping |
| CN106468032B (en) * | 2015-08-18 | 2019-08-02 | 海南金海浆纸业有限公司 | A kind of method and device for extracting lignin from sulfate pulping black liquor |
| WO2018004427A1 (en) * | 2016-06-22 | 2018-01-04 | Valmet Ab | Method of producing lignin with reduced amount of odorous substances |
| US10882879B2 (en) | 2016-06-22 | 2021-01-05 | Valmet Ab | Method of producing lignin with reduced amount of odorous substances |
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