CN103613689A - Carboxymethylation modification method and applications of semi-cellulose in waste liquor from viscose fiber production - Google Patents
Carboxymethylation modification method and applications of semi-cellulose in waste liquor from viscose fiber production Download PDFInfo
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- CN103613689A CN103613689A CN201310594737.6A CN201310594737A CN103613689A CN 103613689 A CN103613689 A CN 103613689A CN 201310594737 A CN201310594737 A CN 201310594737A CN 103613689 A CN103613689 A CN 103613689A
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Abstract
The invention relates to a carboxymethylation modification method and applications of semi-cellulose in waste liquor from viscose fiber production. The modification method comprises the steps of: adding monochloroacetic acid in a raw material which is alkaliferous semi-cellulose extracted from the waste liquor from viscose fiber production, reacting for 120-180min at 70-90DEG C, cooling, standing, washing supernated liquor with 90% ethanol, precipitating, and performing suction filtration to obtain a crude product; dissolving the crude product into water, and performing centrifugal separation; washing supernated liquor with 90% ethanol, precipitating, filtering, performing vacuum drying for 24h to obtain a carboxymethyl semi-cellulose product. After being applied to dispersing agents of coating, printing and dyeing, industrial water treatment and the like, the modified carboxymethyl semi-cellulose product has good adsorportion property, is low in usage amount and good in dispersity. The alkaliferous semi-cellulose extracted from the waste viscose fiber production liquor is subjected to carboxymethylation modification, the carboxymethylation modification method is simple in technology, easy to operate and low in production cost, the hydrophilicity of the modified semi-cellulose is greatly improved, the application performance is good, and the waste liquor pollution and the semi-cellulose plant resource reutilization problems can be reasonably solved.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of viscose fiber and produce hemicellulose carboxymethyl-modification method and application in waste liquid.
Background technology
Hemicellulose is a kind of inexhaustible, nexhaustible reproducibility plant resources.Enter after 21st century, along with the sharply minimizing of the World Forests area and the raising of timber price, hemicellulose is as degradable natural macromolecular material, as infant industry's product exploitation, list in state key program for tackling key problems in science and technology, become the important research direction of renewable resources aspect green chemical industry.
In viscose fiber is produced, produce a large amount of waste liquids containing hemicellulose, can utility value high, but owing to containing a large amount of alkali in waste liquid simultaneously, difficulty of processing is large, and relevant its processing is a technical barrier of current viscose fiber industry.Viscose fiber is produced the exploitation of hemicellulose in waste liquid, is the important topic of the recycling of current solution waste liquor contamination and hemicellulose plant resources.
Hemicellulose has complicated chemical structure and molecular structure; as branch, amorphous, dissimilar monose and dissimilar function base; as hydroxyl, ethanoyl, carboxyl, methoxyl group etc.; these dissimilar glycan show different chemical conducts, make its application have great limitation.Being modified as of hemicellulose developed hemicellulose to greatest extent provides prerequisite, for it becomes a kind of novel degradable polymer, provides very large application space.
Carboxymethyl hemicellulose is as having the functional high molecule material of negatively charged ion on molecule chain, the biodegradable not only with hemicellulose, give the fabulous adsorptivity of material and water-soluble simultaneously, can be as the dispersion agent in the fields such as papermaking, weaving, environmental protection and oil production, thickening material, retention aid, flocculation agent etc., play the effect of thickening, softness, agglomeration resistance etc., excellent performance.
Summary of the invention
The present invention, for solving the above-mentioned problems in the prior art, provides a kind of viscose fiber to produce hemicellulose carboxymethyl-modification method and application in waste liquid.In the application of the method products obtained therefrom, there is good absorption property, show less consumption, good flowing properties, dispersing property is good, and technique is simple, and cost is low, have fabulous social benefit.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
The method that a kind of viscose fiber of the present invention is produced hemicellulose carboxymethyl-modification in waste liquid, it comprises the following steps;
It is raw material containing alkali hemicellulose that the viscose fiber of take is produced what in waste liquid, extract, adds etherifying agent, stirs, heat up, at 70-90 ℃, reaction 120-180min, cooling standing after, 90% washing with alcohol, precipitation for supernatant liquid, suction filtration obtains crude product; Its crude product is soluble in water, centrifugation, the washing with alcohol that supernatant liquid is 90% by concentration, precipitation, after suction filtration, vacuum-drying 24h obtains carboxymethyl hemicellulose product.
Described containing alkali hemicellulose, wherein alkalinity is the 10-20% of hemicellulose mass percent.
Described etherifying agent is monochloroacetic acid.
The described mole proportioning containing alkali hemicellulose and etherifying agent is 1:1.5-3.5.
Described a kind of viscose fiber is produced the method for hemicellulose carboxymethyl-modification in waste liquid, and the substitution value of described carboxymethyl hemicellulose is 0.47-1.72.
Preferably, described a kind of viscose fiber is produced the method for hemicellulose carboxymethyl-modification in waste liquid, and it comprises following concrete steps:
What in the viscose fiber of take production waste liquid, extract is raw material containing alkali hemicellulose, adds monochloroacetic acid, at 70 ℃, and reaction 180min, cooling, standing, 90% washing with alcohol, precipitation for supernatant liquid, suction filtration obtains crude product; Its crude product is soluble in water, centrifugation; 90% washing with alcohol, precipitation for supernatant liquid, filter, and vacuum-drying 24h obtains carboxymethyl hemicellulose product.
Described raw material be viscose fiber produce pulp thickening containing alkali hemicellulose, wherein alkalinity is 20% of hemicellulose mass percent.
Described material is 1:2 containing mole proportioning of alkali hemicellulose and monochloroacetic acid.
The purposes of the carboxymethyl hemicellulose that aforesaid method obtains is, described carboxymethyl hemicellulose is for the dispersion agent of coating, printing and dyeing, paint or paper making and cloth coating technical field, and its addition is 20-50kg/ ton slurry.
The present invention compared with prior art has following significant advantage:
What in the present invention, utilize viscose fiber to produce to extract in waste liquid is raw material containing alkali hemicellulose, take monochloroacetic acid as etherifying agent modification, obtains the different carboxymethyl hemicellulose of a series of substitution values.
In invention, viscose fiber is produced in waste liquid containing the utilization of alkali hemicellulose, has rationally solved waste liquor contamination and hemicellulose plant resources effectively utilizes problem.
The carboxymethylated modified technique of hemicellulose is simple, simplified adding of catalyzer in modified-reaction, easy handling, and processing cost is low.In modified-reaction, can obtain the different carboxymethyl hemicellulose of substitution value according to different technology conditions, meet different application demand.Dispersion agent with it as coating, printing and dyeing, coating, printing and dyeing, paint, paper making and cloth coating, has good adsorptivity and water-soluble, and consumption is few, and dispersing property is good.
In a word, viscose fiber is produced a large amount of application containing alkali hemicellulose and hemicellulose carboxymethyl-modification in waste liquid, not only significant to solving waste liquor contamination, gives hemicellulose plant resources high-value-use bright prospects simultaneously, has fabulous social benefit.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment mono-
What in the viscose fiber of take production waste liquid, extract is raw material containing alkali hemicellulose, adds monochloroacetic acid, at 70 ℃, and reaction 120min, cooling, standing, 90% washing with alcohol, precipitation for supernatant liquid, suction filtration obtains crude product; Its crude product is soluble in water, centrifugation; 90% washing with alcohol, precipitation for supernatant liquid, filter, and vacuum-drying 24h obtains carboxymethyl hemicellulose product.
Described raw material be viscose fiber produce pulp thickening containing alkali hemicellulose, wherein alkalinity is 10% of hemicellulose mass percent;
Described etherifying agent is monochloroacetic acid;
Described material is 1:1.5 containing mole proportioning of alkali hemicellulose and monochloroacetic acid;
Described carboxymethyl hemicellulose, its substitution value is 0.47.
Gained carboxymethyl hemicellulose dispersion agent in the present invention, is applied in titanium dioxide slurry, and addition is 50kg/ ton slurry.
According to the property indices of national standard test coating dispersant, in Table 1.
Table 1 carboxymethyl hemicellulose dispersing agent performance index
Embodiment bis-:
What in the viscose fiber of take production waste liquid, extract is raw material containing alkali hemicellulose, adds monochloroacetic acid, at 80 ℃, and reaction 150min, cooling, standing, 90% washing with alcohol, precipitation for supernatant liquid, suction filtration obtains crude product; Its crude product is soluble in water, centrifugation; 90% washing with alcohol, precipitation for supernatant liquid, filter, and vacuum-drying 24h obtains carboxymethyl hemicellulose product.
Described raw material be viscose fiber produce pulp thickening containing alkali hemicellulose, wherein alkalinity is 15% of hemicellulose mass percent;
Described etherifying agent is monochloroacetic acid;
Described material is 1:2 containing mole proportioning of alkali hemicellulose and monochloroacetic acid;
Described carboxymethyl hemicellulose, its substitution value is 0.68.
Gained carboxymethyl hemicellulose dispersion agent in the present invention, is applied in titanium dioxide slurry, and addition is 40kg/ ton slurry.
According to the property indices of national standard test coating dispersant, in Table 2.
Table 2 carboxymethyl hemicellulose dispersing agent performance index
Embodiment tri-:
What in the viscose fiber of take production waste liquid, extract is raw material containing alkali hemicellulose, adds monochloroacetic acid, at 80 ℃, and reaction 150min, cooling, standing, 90% washing with alcohol, precipitation for supernatant liquid, suction filtration obtains crude product; Its crude product is soluble in water, centrifugation; 90% washing with alcohol, precipitation for supernatant liquid, filter, and vacuum-drying 24h obtains carboxymethyl hemicellulose product.
Described raw material be viscose fiber produce pulp thickening containing alkali hemicellulose, wherein alkalinity is 20% of hemicellulose mass percent;
Described etherifying agent is monochloroacetic acid;
Described material is 1:2.5 containing mole proportioning of alkali hemicellulose and monochloroacetic acid;
Described carboxymethyl hemicellulose, its substitution value is 0.91.
Gained carboxymethyl hemicellulose dispersion agent in the present invention, is applied in titanium dioxide slurry, and addition is 30kg/ ton slurry.
According to the property indices of national standard test coating dispersant, in Table 3.
Table 3 carboxymethyl hemicellulose dispersing agent performance index
Embodiment tetra-:
What in the viscose fiber of take production waste liquid, extract is raw material containing alkali hemicellulose, adds monochloroacetic acid, at 90 ℃, and reaction 180min, cooling, standing, 90% washing with alcohol, precipitation for supernatant liquid, suction filtration obtains crude product; Its crude product is soluble in water, centrifugation; 90% washing with alcohol, precipitation for supernatant liquid, filter, and vacuum-drying 24h obtains carboxymethyl hemicellulose product.
Described raw material be viscose fiber produce pulp thickening containing alkali hemicellulose, wherein alkalinity is 20% of hemicellulose mass percent;
Described etherifying agent is monochloroacetic acid;
Described material is 1:3.5 containing mole proportioning of alkali hemicellulose and monochloroacetic acid;
Described carboxymethyl hemicellulose, its substitution value is 1.49.
Gained carboxymethyl hemicellulose dispersion agent in the present invention, is applied in titanium dioxide slurry, and addition is 30kg/ ton slurry.
According to the property indices of national standard test coating dispersant, in Table 4.
Table 4 carboxymethyl hemicellulose dispersing agent performance index
Embodiment five:
What in the viscose fiber of take production waste liquid, extract is raw material containing alkali hemicellulose, adds monochloroacetic acid, at 80 ℃, and reaction 180min, cooling, standing, 90% washing with alcohol, precipitation for supernatant liquid, suction filtration obtains crude product; Its crude product is soluble in water, centrifugation; 90% washing with alcohol, precipitation for supernatant liquid, filter, and vacuum-drying 24h obtains carboxymethyl hemicellulose product.
Described raw material be viscose fiber produce pulp thickening containing alkali hemicellulose, wherein alkalinity is 20% of hemicellulose mass percent;
Described material is 1:2.5 containing mole proportioning of alkali hemicellulose and monochloroacetic acid;
Described carboxymethyl hemicellulose, its substitution value is 1.64.
Gained carboxymethyl hemicellulose dispersion agent in the present invention, is applied in titanium dioxide slurry, and addition is 30kg/ ton slurry.
According to the property indices of national standard test coating dispersant, in Table 5.
Table 5 carboxymethyl hemicellulose dispersing agent performance index
Embodiment six:
What in the viscose fiber of take production waste liquid, extract is raw material containing alkali hemicellulose, adds monochloroacetic acid, at 70 ℃, and reaction 180min, cooling, standing, 90% washing with alcohol, precipitation for supernatant liquid, suction filtration obtains crude product; Its crude product is soluble in water, centrifugation; 90% washing with alcohol, precipitation for supernatant liquid, filter, and vacuum-drying 24h obtains carboxymethyl hemicellulose product.
Described raw material be viscose fiber produce pulp thickening containing alkali hemicellulose, wherein alkalinity is 20% of hemicellulose mass percent;
Described material is 1:2 containing mole proportioning of alkali hemicellulose and monochloroacetic acid;
Described carboxymethyl hemicellulose, its substitution value is 1.72.
Gained carboxymethyl hemicellulose dispersion agent in the present invention, is applied in titanium dioxide slurry, and addition is 20kg/ ton slurry.
According to the property indices of national standard test coating dispersant, in Table 6.
Table 6 carboxymethyl hemicellulose dispersing agent performance index
The carboxymethyl hemicellulose dispersion agent that the present invention makes, is applied in coating, has good absorption property, shows less consumption, good flowing properties, and dispersing property is good.
Claims (4)
1. viscose fiber is produced a method for hemicellulose carboxymethyl-modification in waste liquid, it is characterized in that it comprises the following steps;
It is raw material containing alkali hemicellulose that the viscose fiber of take is produced what in waste liquid, extract, adds etherifying agent, stirs, heat up, at 70-90 ℃, reaction 120-180min, cooling standing after, 90% washing with alcohol, precipitation for supernatant liquid, suction filtration obtains crude product; Its crude product is soluble in water, centrifugation, the washing with alcohol that supernatant liquid is 90% by concentration, precipitation, after suction filtration, vacuum-drying 24h obtains carboxymethyl hemicellulose product;
Described containing alkali hemicellulose, wherein alkalinity is the 10-20% of hemicellulose mass percent;
Described etherifying agent is monochloroacetic acid;
The described mole proportioning containing alkali hemicellulose and etherifying agent is 1:1.5-3.5.
2. the method that a kind of viscose fiber as claimed in claim 1 is produced hemicellulose carboxymethyl-modification in waste liquid, is characterized in that, described carboxymethyl hemicellulose, and its substitution value is 0.47-1.72.
3. the method that a kind of viscose fiber as claimed in claim 1 is produced hemicellulose carboxymethyl-modification in waste liquid, is characterized in that it comprises following concrete steps:
What in the viscose fiber of take production waste liquid, extract is raw material containing alkali hemicellulose, adds monochloroacetic acid, at 70 ℃, and reaction 180min, cooling, standing, 90% washing with alcohol, precipitation for supernatant liquid, suction filtration obtains crude product; Its crude product is soluble in water, centrifugation; 90% washing with alcohol, precipitation for supernatant liquid, filter, and vacuum-drying 24h obtains carboxymethyl hemicellulose product;
Described raw material be viscose fiber produce pulp thickening containing alkali hemicellulose, wherein alkalinity is 20% of hemicellulose mass percent;
Described material is 1:2 containing mole proportioning of alkali hemicellulose and monochloroacetic acid.
4. a purposes for the carboxymethyl hemicellulose that method obtains as claimed in claim 1, is characterized in that, described carboxymethyl hemicellulose is for the dispersion agent of coating, printing and dyeing, paint or paper making and cloth coating technical field, and its addition is 20-50kg/ ton slurry.
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| CN105368160A (en) * | 2015-12-23 | 2016-03-02 | 河北科技大学 | Water-based carbon black color paste dispersing agent and application thereof to preparation of carbon black color paste |
| CN114561169A (en) * | 2022-02-28 | 2022-05-31 | 上海昶法新材料有限公司 | Preparation method of hemicellulose coating adhesive |
| CN114773609A (en) * | 2022-05-20 | 2022-07-22 | 华南理工大学 | Camellia oleifera fruit shell semi-cellulose-based nonionic emulsifier and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105368160A (en) * | 2015-12-23 | 2016-03-02 | 河北科技大学 | Water-based carbon black color paste dispersing agent and application thereof to preparation of carbon black color paste |
| CN105368160B (en) * | 2015-12-23 | 2019-01-15 | 河北科技大学 | A kind of aqueous carbon black color paste dispersing agent and its preparing the application in carbon black color paste |
| CN114561169A (en) * | 2022-02-28 | 2022-05-31 | 上海昶法新材料有限公司 | Preparation method of hemicellulose coating adhesive |
| CN114773609A (en) * | 2022-05-20 | 2022-07-22 | 华南理工大学 | Camellia oleifera fruit shell semi-cellulose-based nonionic emulsifier and preparation method and application thereof |
| CN114773609B (en) * | 2022-05-20 | 2022-12-13 | 华南理工大学 | Camellia oleifera fruit shell semi-cellulose-based nonionic emulsifier and preparation method and application thereof |
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