CN103408671A - Method for preparing carboxymethylcellulose and sodium lignin sulfonate from crop straws - Google Patents
Method for preparing carboxymethylcellulose and sodium lignin sulfonate from crop straws Download PDFInfo
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- CN103408671A CN103408671A CN2013103723811A CN201310372381A CN103408671A CN 103408671 A CN103408671 A CN 103408671A CN 2013103723811 A CN2013103723811 A CN 2013103723811A CN 201310372381 A CN201310372381 A CN 201310372381A CN 103408671 A CN103408671 A CN 103408671A
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- crop straw
- mierocrystalline cellulose
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Abstract
The invention provides a method for preparing carboxymethylcellulose and sodium lignin sulfonate from crop straws. The method comprises the following steps of: washing, drying and crushing crop straws, preparing sodium lignin sulfonate through a one-bath process, bleaching remained cellulose, crushing again and etherifying so as to obtain carboxymethylcellulose. According to the method, sodium lignin sulfonate and carboxymethylcellulose can be prepared simultaneously; the utilization rate of resources is increased; simultaneously, emission of pollutants is reduced; and the method is beneficial to environmental protection.
Description
Technical field
The present invention relates to the comprehensive utilization of farm crop, relate in particular to a kind of method of utilizing agricultural crop straw to produce carboxymethyl cellulose and sodium lignosulfonate.
Background technology
In recent years, how " digestion " agricultural crop straw has become the large problem of Agricultural management department.Agricultural crop straw becomes need " refuse " to be processed from the wealth of farmers', the field burning in succession occurred, contaminate environment, and danger side of body aircraft landing, affect Vehicle Driving Cycle.As everyone knows, stalk, with regard to its material property, is to belong to well to utilize material, from ancient times to the present, is widely used, and can be summarized as " five material ", i.e. fuel, feed, fertilizer, base-material, starting material.Agricultural crop straw, as the Main By product of agricultural-food, mainly contains following purposes in present stage: 1, straw-returning; 2, the feed of animal; 3, the rural area part is as fuel.Yet in a lot of Rural areass, some stalk is even directly burnt, very large environmental pollution and the wasting of resources have been caused.Therefore, recycling research to agricultural crop straw has become a current important research topic, the invention provides a kind of from agricultural crop straw, producing the method for carboxymethyl cellulose, because carboxymethyl cellulose (CMC) is one of important cellulose ethers, it has valuable colloid chemistry character, so in weaving, oil, toothpaste, medicine, building, pottery, the industries such as papermaking have a wide range of applications, therefore, how agricultural crop straw being carried out to producing of carboxymethyl cellulose is a research that has very much application prospect, can realize the recycle value of agricultural crop straw.
Summary of the invention
The new way that provides a kind of agricultural crop straw to utilize is provided technical problem solved by the invention, low cost fabrication carboxymethyl cellulose and sodium lignosulfonate, and the utilization ratio of raising stalk, reduce the discharge of pollutent simultaneously.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: a kind of method of utilizing agricultural crop straw to produce carboxymethyl cellulose and sodium lignosulfonate comprises the steps:
The first step: by the washing of agricultural crop straw, oven dry, then be ground into the fine particle of 2-10mm;
Second step: the agricultural crop straw after pulverizing carries out etherification reaction, obtains mixing solutions;
The 3rd step: described mixing solutions is carried out to centrifugation, obtain filtrate and Mierocrystalline cellulose filter residue, and described filtrate is concentrated and spraying drying, make sodium lignosulfonate;
The 4th step: by the isolated Mierocrystalline cellulose filter residue of previous step, carry out hydrogen peroxide bleaching;
The 5th step: the Mierocrystalline cellulose filter residue after bleaching is washed, dries and pulverizes, then to the Mierocrystalline cellulose filter residue after pulverizing alkalize successively, etherificate;
The 6th step: carry out again sour neutralization, washing with alcohol, oven dry, pulverization process, obtain carboxymethyl cellulose.
Further improvement as the technical program, in described second step, the technique of sulfonation reaction is: the agricultural crop straw after pulverizing is placed in the mixing solutions of sodium hydroxide and S-WAT, and described agricultural crop straw: sodium hydroxide: the proportioning of S-WAT is 1:0.1-0.3:0.3-0.7.
As the further improvement of the technical program, in described second step, during sulfonation reaction, bath raio is 1:4-7, and temperature is controlled at 100-107 ℃, and the reaction times is 3-7 hour.
As the further improvement of the technical program, the hydrogen peroxide bleaching process in described the 4th step is: by the Mierocrystalline cellulose filter residue: the proportioning of the hydrogen peroxide of concentration 30% is made as 1:1-3, and reaction medium is the sodium hydroxide solution of 1-3g/L.
As the further improvement of the technical program, in described the 4th step, the bath raio of hydrogen peroxide bleaching process is 1:10-20, and bleaching temperature is 90-100 ℃, and bleaching time is 20-30 minute.
As the further improvement of the technical program, while in described the 5th step, the Mierocrystalline cellulose filter residue being alkalized, by Mierocrystalline cellulose: sodium hydroxide: the proportioning of the ethanol of concentration 75% is made as 1:0.5-1.0:5-10, alkalization 1-2 hour under 20-40 ℃.
Further improvement as the technical program, after in described the 5th step, the Mierocrystalline cellulose filter residue being alkalized, again in Mierocrystalline cellulose: chloroacetic proportioning is that the ratio of 1:0.7-1.5 adds Mono Chloro Acetic Acid, controls temperature of reaction and carries out etherificate at 75-80 ℃, and the etherificate time is 1-3 hour.
Compared with prior art, the invention solves the recycling problem of agricultural crop straw, when producing carboxymethyl cellulose, can also make sodium lignosulfonate, not only improve the utilization ratio of resource, reduced simultaneously the discharge of pollutent, be beneficial to environmental protection, pollutant emission is dropped to minimum, make environmental benefit and maximization of economic benefit.
Embodiment
The invention provides a kind of method of utilizing agricultural crop straw to produce carboxymethyl cellulose and sodium lignosulfonate, comprise the steps:
The first step: by the washing of agricultural crop straw, oven dry, then be ground into the fine particle of 2-10mm.
Second step: the agricultural crop straw after pulverizing carries out the etherification reaction of xylogen, obtains mixing solutions.Concrete technology is: the agricultural crop straw after pulverizing is placed in the mixing solutions of sodium hydroxide and S-WAT, wherein, described agricultural crop straw: sodium hydroxide: the proportioning of S-WAT is 1:0.1-0.3:0.3-0.7; bath raio is 1:4-7; temperature is controlled at 100-107 ℃, and the reaction times is 3-7 hour.
The 3rd step: described mixing solutions is carried out to centrifugation, and the filtrate obtained and filter residue, it is worth mentioning that, in this step, spraying drying after also described filtrate being concentrated, can make sodium lignosulfonate.
The 4th step: by the isolated filter residue of previous step (being Mierocrystalline cellulose), carry out hydrogen peroxide bleaching.Its technique is: by Mierocrystalline cellulose: hydrogen peroxide (concentration 30%)=1:1-3, and reaction medium is the sodium hydroxide solution of 1-3g/L, and bath raio 1:10-20, bleaching temperature are 90-100 ℃, and bleaching time is 20-30 minute.
The 5th step: to the Mierocrystalline cellulose filter residue after bleaching through washing, dry and pulverize, then to the Mierocrystalline cellulose filter residue after pulverizing alkalize successively, etherificate two steps.Specifically, at first, in Mierocrystalline cellulose: sodium hydroxide: the ratio of 75 ethanol (being that concentration is 75% ethanol)=1:0.5-1.0:5-10, alkalization 1-2 hour under 20-40 ℃; Alkalized rear directly in Mierocrystalline cellulose: the ratio of Mono Chloro Acetic Acid=1:0.7-1.5 adds Mono Chloro Acetic Acid, controls temperature of reaction and carries out etherificate at 75-80 ℃, and the etherificate time is 1-3 hour.
The 6th step: through peracid neutralization, 75 washing with alcohol, oven dry, pulverize and sieve, finally make carboxymethyl cellulose.
Below briefly introduce two specific embodiments that utilize the inventive method to produce carboxymethyl cellulose and sodium lignosulfonate.
Embodiment 1
The maize straw of take is raw material, first maize straw is washed, dry, be ground into the particle of 4-10mm, then press maize straw: sodium hydroxide: S-WAT=1:0.15-0.2:0.3-0.7, bath raio is 1:5-7, reaction times is 4-5 hour, then centrifugation, the filtrate acid neutralization, adjust pH is to 7-8, concentrated, spraying is dried into sodium lignosulfonate, filter residue exists: hydrogen peroxide (30%)=1:1-3, reaction medium is the sodium hydroxide solution of 2-3g/L, bath raio 1:10-20, temperature is under 90-100 ℃, bleaching 20-30 minute, Mierocrystalline cellulose after bleaching, then in Mierocrystalline cellulose: sodium hydroxide: the ratio of 75 ethanol=1:0.5-1.0:5-10, temperature is 20-40 ℃, alkalized 1 hour, then in Mierocrystalline cellulose: the ratio of Mono Chloro Acetic Acid=1:0.7-1.5 adds Mono Chloro Acetic Acid, under 75-80 ℃, etherificate 1.5-2 hour.The etherificate after product is used 75 washing with alcohol after the acid neutralization, through centrifugation, dry, and pulverizes, and sieves, and finished product is carboxymethyl cellulose.
Embodiment 2
The maize straw of take is raw material, first maize straw is washed, dry, be ground into the particle of 2-5mm, then press maize straw: sodium hydroxide: S-WAT=1:0.15-0.2:0.3-0.7, bath raio is 1:4-7, reaction times is 5-7 hour, then centrifugation, the filtrate acid neutralization, adjust pH is to 7-8, concentrated, spraying is dried into sodium lignosulfonate, filter residue exists: hydrogen peroxide (30%)=1:1-3, reaction medium is the sodium hydroxide solution of 2-3g/L, bath raio 1:10-20, temperature is under 90-100 ℃, bleaching 20-30 minute, Mierocrystalline cellulose after bleaching, then in Mierocrystalline cellulose: sodium hydroxide: the ratio of 75 ethanol=1:0.5-1.0:5-10, temperature is 20-40 ℃, alkalization 1-2 hour, then in Mierocrystalline cellulose: the ratio of Mono Chloro Acetic Acid=1:0.7-1.5 adds Mono Chloro Acetic Acid, under 75-80 ℃, etherificate 2-3 hour.The etherificate after product is used 75 washing with alcohol after the acid neutralization, through centrifugation, dry, and pulverizes, and sieves, and finished product is carboxymethyl cellulose.
Because carboxymethyl cellulose is that cellulosic carboxymethyl is rolled into a ball substitution product; it can form full-bodied colloid, solution, adhesion is arranged, thickening, flow, emulsion dispersion, figuration, water conservation, protective colloid, film forming, acidproof, salt tolerant, the characteristic such as be suspended; and physiology is harmless, therefore in producing, the fields such as food, medicine, daily use chemicals, oil, papermaking, weaving, building are used widely.
In sum, the invention provides a kind of new way of utilizing agricultural crop straw, mainly solved the recycling problem of agricultural crop straw, and not only improved the utilization ratio of stalk, pollutant emission is dropped to minimum, make environmental benefit and maximization of economic benefit, and the present invention is when making carboxymethyl cellulose, also can make sodium lignosulfonate, improve the utilization ratio of agricultural crop straw.And in prior art, the production of traditional carboxymethyl cellulose is all to take linters to be raw material, there is lack of raw materials for it, and cost is higher.
The above; it is only most preferred embodiment of the present invention; not the present invention is done to any pro forma restriction; any those of ordinary skill in the art; do not breaking away from technical solution of the present invention scope situation; utilize the method content of above-mentioned announcement to make many possible changes and modification to technical solution of the present invention, all belong to the scope of claims protection.
Claims (7)
1. a method of utilizing agricultural crop straw to produce carboxymethyl cellulose and sodium lignosulfonate, is characterized in that: comprise the steps:
The first step: by the washing of agricultural crop straw, oven dry, then be ground into the fine particle of 2-10mm;
Second step: the agricultural crop straw after pulverizing carries out sulfonation reaction, obtains mixing solutions;
The 3rd step: described mixing solutions is carried out to centrifugation, obtain filtrate and Mierocrystalline cellulose filter residue, and described filtrate is concentrated and spraying drying, make sodium lignosulfonate;
The 4th step: by the isolated Mierocrystalline cellulose filter residue of previous step, carry out hydrogen peroxide bleaching;
The 5th step: the Mierocrystalline cellulose filter residue after bleaching is washed, dries and pulverizes, then to the Mierocrystalline cellulose filter residue after pulverizing alkalize successively, etherificate;
The 6th step: carry out again sour neutralization, washing with alcohol, oven dry, pulverization process, obtain carboxymethyl cellulose.
2. the method for utilizing agricultural crop straw to produce carboxymethyl cellulose and sodium lignosulfonate according to claim 1, it is characterized in that: in described second step, the technique of etherification reaction is: the agricultural crop straw after pulverizing is placed in the mixing solutions of sodium hydroxide and S-WAT, and described agricultural crop straw: sodium hydroxide: the proportioning of S-WAT is 1:0.1-0.3:0.3-0.7.
3. the method for utilizing agricultural crop straw to produce carboxymethyl cellulose and sodium lignosulfonate according to claim 2 is characterized in that: in described second step, during sulfonation reaction, bath raio is 1:4-7, and temperature is controlled at 100-107 ℃, and the reaction times is 3-7 hour.
4. the method for utilizing agricultural crop straw to produce carboxymethyl cellulose and sodium lignosulfonate according to claim 3, it is characterized in that: the hydrogen peroxide bleaching process in described the 4th step is: by the Mierocrystalline cellulose filter residue: the proportioning of the hydrogen peroxide of concentration 30% is made as 1:1-3, and reaction medium is the sodium hydroxide solution of 1-3g/L.
5. the method for utilizing agricultural crop straw to produce carboxymethyl cellulose and sodium lignosulfonate according to claim 4, it is characterized in that: in described the 4th step, the bath raio of hydrogen peroxide bleaching process is 1:10-20, bleaching temperature is 90-100 ℃, and bleaching time is 20-30 minute.
6. the method for utilizing agricultural crop straw to produce carboxymethyl cellulose and sodium lignosulfonate according to claim 5, it is characterized in that: while in described the 5th step, the Mierocrystalline cellulose filter residue being alkalized, by Mierocrystalline cellulose: sodium hydroxide: the proportioning of the ethanol of concentration 75% is made as 1:0.5-1.0:5-10, alkalization 1-2 hour under 20-40 ℃.
7. the method for utilizing agricultural crop straw to produce carboxymethyl cellulose and sodium lignosulfonate according to claim 6, it is characterized in that: after in described the 5th step, the Mierocrystalline cellulose filter residue being alkalized, again in Mierocrystalline cellulose: chloroacetic proportioning is that the ratio of 1:0.7-1.5 adds Mono Chloro Acetic Acid, control temperature of reaction and carry out etherificate at 75-80 ℃, the etherificate time is 1-3 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937840A (en) * | 2014-04-11 | 2014-07-23 | 浙江清华长三角研究院 | Wood fiber raw material pretreatment method for producing fuel ethanol |
| CN104388203A (en) * | 2014-10-24 | 2015-03-04 | 中国石油天然气股份有限公司 | Petroleum mud-sand cleaning agent and preparation method of xylogen-polyethylenepolyamine |
| CN105885058A (en) * | 2014-11-03 | 2016-08-24 | 吴迪 | Method utilizing crop straws to prepare sodium lignosulfonate |
| CN107827548A (en) * | 2017-11-03 | 2018-03-23 | 金正大生态工程集团股份有限公司 | A kind of Controlled Release Fertilizer and preparation method and application |
-
2013
- 2013-08-24 CN CN2013103723811A patent/CN103408671A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937840A (en) * | 2014-04-11 | 2014-07-23 | 浙江清华长三角研究院 | Wood fiber raw material pretreatment method for producing fuel ethanol |
| CN104388203A (en) * | 2014-10-24 | 2015-03-04 | 中国石油天然气股份有限公司 | Petroleum mud-sand cleaning agent and preparation method of xylogen-polyethylenepolyamine |
| CN104388203B (en) * | 2014-10-24 | 2018-03-09 | 中国石油天然气股份有限公司 | A kind of preparation method of oil silt particle cleaning agent and lignin polyamines polyene |
| CN105885058A (en) * | 2014-11-03 | 2016-08-24 | 吴迪 | Method utilizing crop straws to prepare sodium lignosulfonate |
| CN107827548A (en) * | 2017-11-03 | 2018-03-23 | 金正大生态工程集团股份有限公司 | A kind of Controlled Release Fertilizer and preparation method and application |
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Application publication date: 20131127 |