CN102877348A - Method for recycling lignin from low-boiling alcohol method pulping waste liquor - Google Patents
Method for recycling lignin from low-boiling alcohol method pulping waste liquor Download PDFInfo
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- CN102877348A CN102877348A CN2012104112670A CN201210411267A CN102877348A CN 102877348 A CN102877348 A CN 102877348A CN 2012104112670 A CN2012104112670 A CN 2012104112670A CN 201210411267 A CN201210411267 A CN 201210411267A CN 102877348 A CN102877348 A CN 102877348A
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Abstract
The invention relates to a method for recycling lignin from low-boiling alcohol method pulping waste liquor, which relates to the technical field of pulping papermaking engineering. The method for recycling the lignin from the low-boiling alcohol method pulping waste liquor is applicable to the waste liquor which is obtained by boiling reagent of plant raw materials with low-boiling alcohols, the waste liquor is processed in steps such as flash evaporation, diluting, cooling, precipitation, filtering, separating, drying and the like to obtain lignin, calcium hydroxide is added in filter liquor, and the precipitate is filtered, separated and dried again to obtain low-molecule lignin. The method has characteristics of high recycling rate, less investment, no pollution and low energy consumption.
Description
Technical field
The present invention relates to a kind of method that from the low pure method pulping waste liquor that boils, reclaims lignin, relate to the Pulp and Paper Engineering technical field.
Background technology
Along with the rapid development of economy, China increases sharply to the demand of pulp and paper.Yet well-known, China still adopts traditional pulping process in a lot of pulp mills, and waste liquid recovery energy consumption is high, investment is large, still can produce secondary pollution, brings very large pressure for environment and the energy.Therefore, China classifies the clearer production technology of greatly developing paper pulp processed as key content in " pulping and paper-making ' 11th Five-Year ' planning ".Given this, seek and a kind ofly new can effectively reclaim the utility such as lignin, the pulping process of protection of the environment preferably again, having become paper industry needs the urgent problem that solves.
The Organosolv Pulping that grew up in the last few years can provide better delignification method, leaves more response function group in the lignin of degraded, the hemicellulose, and can easierly reclaim from solvent medium, purify.Organosolv pulping is a kind of pulping technique to the environment friendliness, under certain condition, the lignin of organic solvent in can degrade plant material, thus reach lignin, cellulose, the efficient purpose of separating of hemicellulose.Because what adopt in the whole process is organic solvent separation, hydrolysis or dissolved lignin, and organic solvent can be by Distillation recovery and by repeatedly recycle and reuse, without waste water or only have a small amount of discharge of wastewater, can really solve the pollution problem the pulping process from the source, be the effective technical way of realizing pollution-free or low pollution " environmental protection " slurrying.
The low pure method slurrying of boiling is one of the most typical pulping process in the organic solvent pulping, the studied low pure method pulping technique that boils that acid catalysis, base catalysis, peroxide catalyzed and self-catalysis are arranged, this patent belong to the low pure legal system pulp waste that boils and reclaim and the comprehensive utilization category.Reclaiming lignin from the low pure method pulping waste liquor that boils, is the important component part of the low pure legal system pulp waste recovery technology of boiling, and is equivalent to the important component that refining goes out from plant fiber material----lignin.
Summary of the invention
The purpose of this invention is to provide a kind of method that from the low pure method pulping waste liquor that boils, reclaims lignin, it is the waste liquid that obtains after master's the reagent boiling that this recovery method is applicable to the low alcohol that boils of plant material employing, waste liquid is through processes such as flash distillation, dilution, cooling, precipitating, isolated by filtration and dryings, obtain lignin, filtrate is added calcium hydroxide, the gained precipitation is carried out isolated by filtration, drying again, obtains low molecule lignin.
A kind of method that reclaims lignin from the low pure method pulping waste liquor that boils comprises the step that flash distillation dilution, filtration drying, filtrate are processed, and comprises following processing step:
1. flash distillation dilution: the waste liquid that will utilize the low pure legal system slurry that boils to produce carries out flash distillation to be processed, the concentration of hanging down the alcohol that boils in the waste liquid after the flash distillation is down to 15% ~ 50%(V/V), and temperature is down to 95 ℃ ~ 100 ℃, with above-mentioned waste liquid dilution, make the concentration to 5% of the low alcohol that boils ~ 35%(V/V), after be cooled to 5 ~ 40 ℃;
2. filtration drying: with step 1. the gained waste liquid filter, solid carries out drying, gets lignin;
3. filtrate is processed: to step 2. gained filtrate add calcium hydroxide, precipitating filters, dryly must hang down the molecule lignin.
The waste liquid that the low pure legal system slurry that boils produces in the method for recovery lignin of the present invention is main mixture by low boil alcohol, water, lignin, degraded sugar, organic acid, furfural and ash composition, wherein, boiling 100g fibrous raw material, lignin content is generally 6 ~ 30g in the waste liquid.
The low pure legal system slurry that boils described in the method for recovery lignin of the present invention refers to be preferably methyl alcohol or ethanol among the present invention take the low alcohol that boils as the pulping process of boiling main agents.
The low employed raw material of the pure method slurrying papermaking plant fiber material that can be used for slurrying known to those skilled in the art that boils described in the method for recovery lignin of the present invention, the present invention is preferably wood type, grass or bast class papermaking plant fiber material, more preferably poplar, reed, wheat straw, bagasse.
The catalysis method that is used for slurrying known to those skilled in the art of the low pure method pulping process that boils described in the method for recovery lignin of the present invention, preferred salt catalysis method of the present invention, autocatalytic method, peroxide catalyzed method or base catalysis method.
Principle of the present invention be lignin in the plant fiber material under the catalysis of acid (or alkali, salt, peroxide), high temperature degradation also is dissolved in the low alcohol-water solution of boiling, delignification, carbohydrate Partial digestion, fiber dispersion pulping.The gained waste liquid reclaims the accessory substances such as lignin, degraded sugar, furfural, organic acid, but the low alcohol-water solution reuse boiling of boiling.
In the method for recovery lignin of the present invention preferred described step 1. in after the dilution in the waste liquid the low determining alcohol that boils be 15% ~ 30%(V/V), after be cooled to 15 ~ 25 ℃.
The temperature of the waste liquid that the preferred described low pure legal system slurry that boils produces in the method for recovery lignin of the present invention is 160 ~ 220 ℃, and the low determining alcohol that boils is 40% ~ 65%(V/V), and the temperature of preferred waste liquid is 170 ~ 210 ℃, the low determining alcohol 45% ~ 60%(V/V) that boils.
To be used for the solvent of waste liquid dilution in 1. be water to preferred described step in the method for recovery lignin of the present invention.
In the method for recovery lignin of the present invention preferred described step 3. the addition of calcium hydroxide be 2 ~ 10g/L, more preferably 3 ~ 6g/L.
Utilize the method for recovery lignin of the present invention to carry out the lignin recovery, 100g plant fiber material lignin yield 5 ~ 25g, low molecule lignin yield 0.1 ~ 3g.
The invention has the beneficial effects as follows:
(1) recyclable high added value lignin.
(2) reduced investment.Owing to using common apparatus, can reduce investment outlay.
(3) accessory substance purity is high.After reclaiming lignin, waste liquid colourity reduces, solid content descends, destroyed the complicated azeotrope system that higher boil organic acid participates in the system, created conditions for from waste liquid, reclaiming the accessory substances such as the low alcohol that boils, water and degraded sugar, furfural, formic acid, acetic acid, and can improve the purity that reclaims accessory substance.
(4) pollution-free.Reclaim in the lignin process and produce, discharge without any pollutant.
(5) energy consumption is low.Waste liquid has reduced the concentration of low boil alcohol, higher boil organic acid by flash distillation, the ability of dissolved lignin reduces, and is beneficial to lignin and separates out, and reduces the consumption of follow-up dilution water, and system amount of residual heat will after taking full advantage of simultaneously boiling and finishing effectively reduces waste liquid and reclaims energy consumption.
The specific embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Test method described in the following embodiment if no special instructions, is conventional method; Described reagent and material if no special instructions, all can obtain from commercial channels, or can the conventional method preparation.
Embodiment 1
A kind of method that from the low pure method pulping waste liquor that boils, reclaims lignin, pulping waste liquor is from reed by ethanol-water-hydrogen peroxide adverse current slurrying, and the lignin recycling step is as follows:
1. flash distillation dilution: 170 ℃ of dense waste liquid temperatures, concentration of alcohol are 45%, and after the flash tank flash distillation, temperature is reduced to 95 ℃, and concentration of alcohol is reduced to 30%, and being diluted to concentration of alcohol with the normal temperature water for industrial use is 18%, is cooled to 20 ℃ through heat exchanger;
2. filtration drying: the lignin of precipitating is through filtering, after the drying, obtaining lignin, 100g reed raw material results lignin 12g;
3. filtrate is processed: add calcium hydroxide in filtrate, addition is 4g/L, and precipitating is filtered, drying obtains low molecule lignin, the low molecule lignin 0.4g of 100g reed raw material results.
Embodiment 2
A kind of method that from the low pure method pulping waste liquor that boils, reclaims lignin, pulping waste liquor is from the slurrying of base catalysis poplar methanol-water, and the lignin recycling step is as follows:
1. flash distillation dilution: 200 ℃ of dense waste liquid temperatures, methanol concentration are 50%, and after the flash tank flash distillation, temperature is reduced to 98 ℃, and methanol concentration is reduced to 30%, and being diluted to methanol concentration with the normal temperature water for industrial use is 20%, is cooled to 25 ℃ through heat exchanger;
2. filtration drying: the lignin of precipitating is through filtering, after the drying, obtaining lignin, 100g poplar raw material results lignin 14g;
3. filtrate is processed: add calcium hydroxide in filtrate, addition is 3g/L, and precipitating is filtered, drying obtains low molecule lignin, the low molecule lignin 0.6g of 100g poplar raw material results.
Embodiment 3
A kind of method that from the low pure method pulping waste liquor that boils, reclaims lignin, pulping waste liquor is from the slurrying of self-catalysis poplar alcohol-water, and the lignin recycling step is as follows:
1. flash distillation dilution: 205 ℃ of concentrated black liquid temperature, concentration of alcohol are 55%, and after the flash tank flash distillation, temperature is reduced to 96 ℃, and concentration of alcohol is reduced to 35%, and it is 15% that the Recycled ethanol aqueous solution with 5% is diluted to concentration of alcohol, are cooled to 25 ℃ through heat exchanger;
2. filtration drying: the lignin of precipitating is through filtering, after the drying, obtaining lignin, 100g poplar raw material results lignin 13g;
3. filtrate is processed: add calcium hydroxide in filtrate, addition is 4g/L, and precipitating is filtered, drying obtains low molecule lignin, the low molecule lignin 0.7g of 100g poplar raw material results.
Claims (8)
1. a method that reclaims lignin from the low pure method pulping waste liquor that boils comprises the step that flash distillation dilution, filtration drying, filtrate are processed, and comprises following processing step:
1. flash distillation dilution: the waste liquid that will utilize the low pure legal system slurry that boils to produce carries out flash distillation to be processed, after the flash distillation in the waste liquid low concentration of boiling alcohol be down to 15% ~ 50%, with above-mentioned waste liquid dilution, make low pure concentration to 5% ~ 35% that boils, after be cooled to 5 ~ 40 ℃;
2. filtration drying: with step 1. the gained waste liquid filter, solid carries out drying, gets lignin;
3. filtrate is processed: to step 2. gained filtrate add calcium hydroxide, precipitating filters, dryly must hang down the molecule lignin.
2. method according to claim 1, it is characterized in that: the described step 3. addition of calcium hydroxide is 2 ~ 10g/L.
3. method according to claim 1 is characterized in that: described step 1. in after the dilution in the waste liquid the low determining alcohol that boils be 15% ~ 30%, after be cooled to 15 ~ 25 ℃.
4. method according to claim 1 is characterized in that: the temperature of the waste liquid that the described low pure legal system slurry that boils produces is 160 ~ 220 ℃, and the low determining alcohol that boils is 40% ~ 65%.
5. method according to claim 1 is characterized in that: described low boil pure be methyl alcohol or ethanol.
6. method according to claim 1 is characterized in that: raw materials usedly in the described low pure method slurrying of boiling be wood type, grass or bast class papermaking plant fiber material.
7. method according to claim 1 is characterized in that: the described low pure method slurrying of boiling is the low pure method slurrying of boiling of salt catalysis method, autocatalytic method, peroxide catalyzed method or base catalysis method.
8. method according to claim 1 is characterized in that: the waste liquid that the low pure legal system slurry that boils of described utilization produces contains low boil alcohol, water, lignin, degraded sugar, organic acid, furfural and ash content.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103321075A (en) * | 2013-05-22 | 2013-09-25 | 大连工业大学 | Method for recovering low-boiling-point alcohol process pulping waste liquid components |
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| CN101864683A (en) * | 2010-03-25 | 2010-10-20 | 清华大学 | Pretreatment method of wood fiber raw materials |
| CN102561082A (en) * | 2012-03-01 | 2012-07-11 | 北京林业大学 | Method of extracting hemicellulose, cellulose and lignin from wood fiber raw materials |
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| US5788812A (en) * | 1985-11-05 | 1998-08-04 | Agar; Richard C. | Method of recovering furfural from organic pulping liquor |
| WO1992013849A1 (en) * | 1991-02-01 | 1992-08-20 | Alcell Technologies Inc. | Pulping of lignocellulosic materials and recovery of resultant by-products |
| CN101143881A (en) * | 2007-10-11 | 2008-03-19 | 孔延华 | Method for synchronously extracting hemicellulose, cellulose and lignin and reclaiming phenolic acid compounds |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103321075A (en) * | 2013-05-22 | 2013-09-25 | 大连工业大学 | Method for recovering low-boiling-point alcohol process pulping waste liquid components |
| CN103321075B (en) * | 2013-05-22 | 2016-04-06 | 大连工业大学 | A kind of method reclaiming low alcohol legal system pulp waste component of boiling |
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Application publication date: 20130116 Assignee: Liaoning Chang Ying straw comprehensive utilization Co., Ltd. Assignor: Dalian Polytechnic University Contract record no.: 2018210000021 Denomination of invention: Method for recycling lignin from low-boiling alcohol method pulping waste liquor Granted publication date: 20150513 License type: Common License Record date: 20180925 |
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Application publication date: 20130116 Assignee: Guangdong Yunhai Agroforestry Development Co., Ltd. Assignor: Dalian Polytechnic University Contract record no.: 2019210000003 Denomination of invention: Method for recycling lignin from low-boiling alcohol method pulping waste liquor Granted publication date: 20150513 License type: Common License Record date: 20190320 |