CN110550797B - Method for efficiently classifying and separating organic matters in pulping yellow liquor - Google Patents
Method for efficiently classifying and separating organic matters in pulping yellow liquor Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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Abstract
本发明提供了一种制浆黄液中有机物高效分级分离的方法，包括步骤：1)纤维植物经固体碱活性氧制浆方法蒸煮后，得到浆料和制浆黄液；2)将步骤1)中的制浆黄液加入有机溶剂中，析出白色沉淀I；3)步骤2)中白色沉淀I通过过滤方式回收，滤液中有机溶剂通过精馏方式回收，馏出的有机溶剂回收反复利用；4)向步骤3)中釜液中加入酸类调节pH值至2.0及以下，析出淡黄色沉淀II；5)步骤2)中白色沉淀I用有机溶剂洗涤，用于进一步分离精制，步骤4)中淡黄色沉淀II用水洗涤，作为高纯木质素作后续使用。应用本技术方案可实现对制浆黄液进行分级沉淀，达到良好的沉淀回收效果。
The present invention provides a method for efficient fractionation and separation of organic matter in pulping yellow liquor, comprising the steps of: 1) after fibrous plants are cooked by a solid alkali active oxygen pulping method, pulp and pulping yellow liquor are obtained; 2) step 1 ) in the pulping yellow liquor is added in the organic solvent, and separates out the white precipitation I; 3) in the step 2), the white precipitation I is recovered by the filtration mode, the organic solvent in the filtrate is recovered by the rectification mode, and the distilled organic solvent is recycled and reused; 4) Add acid to the kettle liquid in step 3) to adjust the pH value to 2.0 and below, and separate out light yellow precipitate II; 5) In step 2), the white precipitate I is washed with an organic solvent for further separation and purification, step 4) The medium pale yellow precipitate II was washed with water and used as high-purity lignin for subsequent use. The application of the technical solution can realize the classification and precipitation of the pulping yellow liquor, and achieve a good precipitation recovery effect.
Description
Technical Field
The invention relates to the field of pulping waste liquid treatment, in particular to a method for efficiently classifying and separating organic matters in pulping yellow liquid.
Background
With the increasing environmental protection requirements of the chemical industry in China, the wastewater treatment of the paper pulp and paper industry draws wide attention. The treatment of pulp waste liquor is still a large cost item in the paper and pulp industry at present. Extensive waste liquid treatment technical methods, such as concentration incineration and the like, are gradually replaced by more elaborate and intensive technologies in future industrial technologies due to poor economic and environmental benefits. Patent CN105332310A discloses a method for separating organic components from diethanolamine pulping waste liquor by membrane filtration methods such as ultrafiltration, etc., and feeding the rest liquid for cyclic cooking, which mechanically separates macromolecular organic matters. Patent CN1995280A discloses a method for modifying sand-fixing material by lignin from pulp and paper making waste liquor, which is to supplement urea and aldehyde compounds into yellow liquor to form lignin urea-formaldehyde resin for utilization. However, the two methods do not realize the all-component specific classification utilization of the waste liquid components.
Disclosure of Invention
The invention aims to provide a method for efficiently separating organic matters in yellow pulping liquor by stages, which realizes the stage precipitation of the yellow pulping liquor and achieves a good precipitation recovery effect.
In order to solve the technical problem, the invention provides a method for efficiently classifying and separating organic matters in pulping yellow liquor, which comprises the following steps:
1) after the fiber plant is cooked by a solid alkali active oxygen pulping method, the reaction product is filtered and separated to obtain pulp and yellow pulping liquid;
2) adding the yellow pulping liquid obtained in the step 1) into an organic solvent to separate out a white precipitate I, wherein the white precipitate I is a macromolecular aliphatic organic matter and a micromolecular organic acid salt;
3) recovering the white precipitate I in the step 2) in a filtering mode, recovering the organic solvent in the filtrate in a rectifying mode, recovering and recycling the distilled organic solvent, and collecting the kettle liquid;
4) adding acids into the kettle liquid in the step 3) to adjust the pH value to be 2.0 or below, and separating out a light yellow precipitate II which is a macromolecular aromatic organic matter, namely lignin which is separated from the biomass raw material and is not degraded or has low degradation degree;
5) washing the white precipitate I in the step 2) with an organic solvent for further separation and refining, and washing the light yellow precipitate II in the step 4) with water for subsequent use as high-purity lignin.
In a preferred embodiment, the organic solvent used in step 2) is a water-miscible organic solvent.
In a preferred embodiment, in step 2), the volume ratio of the yellow liquid to the organic solvent is greater than 2: 1.
In a preferred embodiment, in step 2), if complete separation of macromolecular fatty substances and micromolecular organic acid substances is to be achieved, the addition volume ratio of the yellow liquid to the organic solvent is greater than 1: 5.
In a preferred embodiment, in step 4), the acid-like substance added includes inorganic acid and organic acid.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention provides a method for efficiently grading and separating organic matters in yellow pulping liquor, which lays a good foundation for full component utilization of the yellow pulping liquor and refined utilization of lignin and realizes separation and recovery of the organic matters in the yellow pulping liquor by a simple chemical precipitation mode according to different property types of components in waste liquor, such as molecular weight, chemical structure and the like based on the component composition and properties of the yellow pulping liquor. The organic solvent and different acids are used as the precipitating agent to carry out fractional precipitation on the yellow pulping liquor, so that a good precipitation recovery effect is achieved, the full-component fractional separation of the yellow liquor is realized, and the full-component utilization of the yellow liquor and the biomass raw material is possible. The method effectively overcomes the defects that the traditional pulping waste liquid treatment process is complex, the treatment cost is high, yellow liquid organic matters are difficult to effectively utilize and the like, realizes the high-efficiency classification and separation of fat organic matters and aromatic organic matters in the yellow liquid by a simple chemical precipitation mode, has simple and convenient process and lower cost, provides possibility for the classification and separation utilization of the yellow liquid organic matters, and realizes the environment-friendly industrial concept of zero emission.
Drawings
FIG. 1 is a 2D HSQC NMR spectrum of a yellow liquor fatty organic precipitate according to a preferred embodiment of the present invention;
FIG. 2 is a comparison of the 2D HSQC NMR spectra of the yellow liquor acid precipitation lignin according to the preferred embodiment of the present invention;
FIG. 3 is a comparison of the 2D HSQC NMR spectra of groundwood lignin in a preferred embodiment of the invention.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
A method for efficiently classifying and separating organic matters in yellow pulping liquid comprises the following steps:
1) after the fiber plant is cooked by a solid alkali active oxygen pulping method, the reaction product is filtered and separated to obtain pulp and yellow pulping liquid.
2) Adding the yellow pulping liquid obtained in the step 1) into an organic solvent to separate out a white precipitate I, wherein the white precipitate I is a macromolecular aliphatic organic matter and a micromolecular organic acid salt; the organic solvent is water-miscible organic solvent, such as alcohols (methanol), ketones (acetone), aldehydes (acetaldehyde), and ethers (tetrahydrofuran).
3) Recovering the white precipitate I in the step 2) in a filtering mode, recovering the organic solvent in the filtrate in a rectifying mode, recovering and recycling the distilled organic solvent, and collecting the kettle liquid;
4) adding acids into the kettle liquid in the step 3) to adjust the pH value to be 2.0 or below, and separating out a light yellow precipitate II which is a macromolecular aromatic organic matter, namely lignin which is separated from the biomass raw material and is not degraded or has low degradation degree; in step 4), the added acid substances comprise inorganic acids such as hydrochloric acid and sulfuric acid and organic acids such as formic acid and acetic acid.
5) Washing the white precipitate I in the step 2) with an organic solvent for further separation and refining, and washing the light yellow precipitate II in the step 4) with water for subsequent use as high-purity lignin.
Specifically, in the step 2), the adding volume ratio of the yellow liquid to the organic solvent is more than 2: 1. If the complete separation of macromolecular fat and micromolecular organic acid substances is to be achieved, the adding volume ratio of the yellow liquid to the organic solvent is more than 1: 5.
Example 1
Weighing 1kg (dry weight) of fiber plant raw material, cooking by a solid alkali active oxygen method for pulping, and collecting yellow liquid. The dry weight of the yellow liquid was measured by sampling to be about 6.15% of the total weight of the liquid. Adding the yellow liquid into a methanol solvent with the volume ratio of 5 times, uniformly mixing, separating out white precipitate which is macromolecular aliphatic organic matter and micromolecular organic acid salt, filtering, washing with methanol, drying, and weighing the white precipitate to account for 81.3 percent of the total dry weight of the liquid. Rectifying the mixed solution, recovering the solvent methanol at the tower top, wherein the methanol can be recycled, and collecting the residual aqueous solution at the tower bottom. And (3) adding a hydrochloric acid solution into the kettle liquid to adjust the pH value to 1.02, separating out a light yellow precipitate which is a macromolecular aromatic organic matter, namely lignin which is removed from the biomass raw material and is not degraded or has low degradation degree, filtering and washing the part of precipitate, drying, and weighing the precipitate to account for 9.1% of the total dry weight of the liquid.
Example 2
Weighing 1kg (dry weight) of fiber plant raw material, cooking by a solid alkali active oxygen method for pulping, and collecting yellow liquid. The dry weight of the yellow liquid was measured by sampling to be about 6.15% of the total weight of the liquid. Adding the yellow liquid into a tetrahydrofuran solvent with the volume ratio of 8 times, uniformly mixing, separating out white precipitate which is macromolecular aliphatic organic matter and micromolecular organic acid salt, filtering, washing with tetrahydrofuran, drying, and weighing the white precipitate to be 81.4 percent of the total dry weight of the liquid. Rectifying the mixed solution, recovering solvent tetrahydrofuran at the tower top, wherein the tetrahydrofuran can be repeatedly used, and collecting residual aqueous solution at the tower bottom. Adding sulfuric acid solution into the kettle liquid to adjust the pH value to 0.72, separating out light yellow precipitate which is macromolecular aromatic organic matter, namely lignin which is removed from the biomass raw material and is not degraded or has low degradation degree, filtering the precipitate, washing with water, drying, and weighing the precipitate to account for 9.1 percent of the total dry weight of the liquid.
Example 3
Weighing 1kg (dry weight) of fiber plant raw material, cooking by a solid alkali active oxygen method for pulping, and collecting yellow liquid. The dry weight of the yellow liquid was measured by sampling to be about 6.15% of the total weight of the liquid. Adding the yellow liquid into an acetaldehyde solvent with the volume ratio of 2 times, uniformly mixing, separating out white precipitate which is macromolecular aliphatic organic matter and micromolecular organic acid salt, filtering, washing with acetaldehyde, drying, and weighing the white precipitate to account for 68.5 percent of the total dry weight of the liquid. Rectifying the mixed solution, recovering acetaldehyde from the tower top, and collecting residual water solution from the tower bottom. Adding formic acid solution into the kettle liquid to adjust the pH value to 1.94, separating out light yellow precipitate which is macromolecular aromatic organic matter, namely lignin which is removed from the biomass raw material and is not degraded or has low degradation degree, filtering the precipitate, washing with water, drying, and weighing the precipitate to account for 15.4% of the total dry weight of the liquid.
Example 4
Weighing 1kg (dry weight) of fiber plant raw material, cooking by a solid alkali active oxygen method for pulping, and collecting yellow liquid. The dry weight of the yellow liquid was measured by sampling to be about 6.15% of the total weight of the liquid. Adding the yellow liquid into an acetone solvent with the volume ratio of 0.8 time, uniformly mixing, separating out white precipitate which is macromolecular aliphatic organic matter and micromolecular organic acid salt, filtering, washing with acetone, drying, and weighing the white precipitate to be 13.2 percent of the total dry weight of the liquid. Rectifying the mixed solution, recovering acetone as solvent from the tower top, reusing acetone, and collecting residual water solution in the tower bottom. Adding acetic acid solution into the residue to adjust pH to 1.27, precipitating yellowish precipitate which is macromolecular aromatic organic matter, i.e. lignin which is removed from biomass raw material and is not degraded or has low degradation degree, filtering the precipitate, washing with water, drying, and weighing the precipitate to account for 18.0% of the total dry weight of the liquid.
The invention provides a method for efficiently grading and separating organic matters in yellow pulping liquor, which lays a good foundation for full component utilization of the yellow pulping liquor and refined utilization of lignin and realizes separation and recovery of the organic matters in the yellow pulping liquor by a simple chemical precipitation mode according to different property types of components in waste liquor, such as molecular weight, chemical structure and the like based on the component composition and properties of the yellow pulping liquor. The organic solvent and different acids are used as the precipitating agent to carry out fractional precipitation on the yellow pulping liquor, so that a good precipitation recovery effect is achieved, the full-component fractional separation of the yellow liquor is realized, and the full-component utilization of the yellow liquor and the biomass raw material is possible. The method effectively overcomes the defects that the traditional pulping waste liquid treatment process is complex, the treatment cost is high, yellow liquid organic matters are difficult to effectively utilize and the like, realizes the high-efficiency classification and separation of fat organic matters and aromatic organic matters in the yellow liquid by a simple chemical precipitation mode, has simple and convenient process and lower cost, provides possibility for the classification and separation utilization of the yellow liquid organic matters, and realizes the environment-friendly industrial concept of zero emission.
The above description is only a preferred embodiment of the present invention, but the design concept of the present invention is not limited thereto, and any person skilled in the art can make insubstantial changes in the technical scope of the present invention within the technical scope of the present invention, and the actions infringe the protection scope of the present invention are included in the present invention.
Claims (5)
1. A method for efficiently separating organic matters in pulping yellow liquid is characterized by comprising the following steps:
1) after the fiber plant is cooked by a solid alkali active oxygen pulping method, the reaction product is filtered and separated to obtain pulp and yellow pulping liquid;
2) adding the yellow pulping liquid obtained in the step 1) into an organic solvent to separate out a white precipitate I, wherein the white precipitate I is a macromolecular aliphatic organic matter and a micromolecular organic acid salt;
3) recovering the white precipitate I in the step 2) in a filtering mode, recovering the organic solvent in the filtrate in a rectifying mode, recovering and recycling the distilled organic solvent, and collecting the kettle liquid;
4) adding acids into the kettle liquid in the step 3) to adjust the pH value to be 2.0 or below, and separating out a light yellow precipitate II which is a macromolecular aromatic organic matter, namely lignin which is separated from the biomass raw material and is not degraded or has low degradation degree;
5) washing the white precipitate I in the step 2) with an organic solvent for further separation and refining, and washing the light yellow precipitate II in the step 4) with water for subsequent use as high-purity lignin.
2. The method for efficiently fractionating organic matter in yellow pulping liquor according to claim 1, wherein the organic solvent used in step 2) is a water-miscible organic solvent.
3. The method for efficiently separating organic matters in pulping yellow liquor according to claim 1, wherein in the step 2), the adding volume ratio of the yellow liquor to the organic solvent is more than 2: 1.
4. The method for efficiently classifying and separating organic matters in yellow pulping liquor according to claim 1, wherein in the step 2), if complete separation of macromolecular fats and micromolecular organic acids is achieved, the addition volume ratio of the yellow liquor to the organic solvent is more than 1: 5.
5. The method for efficiently classifying organic matters in yellow pulping liquor according to claim 1, wherein in the step 4), the added acid substances comprise inorganic acids and organic acids.
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