CN103122034A - Method for preparing cellulose compounds by using cottonseed hull as raw material - Google Patents
Method for preparing cellulose compounds by using cottonseed hull as raw material Download PDFInfo
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- CN103122034A CN103122034A CN2012105671855A CN201210567185A CN103122034A CN 103122034 A CN103122034 A CN 103122034A CN 2012105671855 A CN2012105671855 A CN 2012105671855A CN 201210567185 A CN201210567185 A CN 201210567185A CN 103122034 A CN103122034 A CN 103122034A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a method for preparing cellulose compounds by using a cottonseed hull as a raw material, which is realized by hydrolyzing hemicellulose of cottonseed hull staple by using high-temperature and high-pressure liquid water, removing lignin through supercritical extraction, removing a small amount of impurities by using organic acid and inorganic acid and simultaneously preparing microcrystalline cellulose. The method comprises the following steps: separating a hull wrapped by cottonseed hull staple through ultrasonic treatment, and hydrolyzing hemicellulose in the cottonseed hull staple by using liquid water at high temperature and high pressure; performing supercritical CO2 extraction, and adding a right amount of assistant to remove lignin, thus obtaining coarse cellulose; and removing a small amount of impurities by using organic acid and inorganic acid, and simultaneously preparing microcrystalline cellulose, wherein the prepared cellulose can react with chloroacetic acid, sodium hydroxide, urea, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and other reagents to be prepared into carbamate cellulose, carboxymethyl cellulose, hydroxyethyl methyl cellulose and other cellulose ether compounds. The method overcomes the defect of using a large amount of acid and alkali in the existing cottonseed hull cellulose recovery, has the advantages of quick and effective hemicellulose separation, low cellulose loss, obviously shortened separation period, low energy consumption and high cellulose product purity, and has remarkable economic benefits and social benefits.
Description
Technical field
The agricultural that the present invention relates to produce in the cotton preliminary working process in agriculture cotton producing region is given up and is got a kind of method that the thing cotton seed hulls is recycled, and comprises specifically the fields such as agricultural, Cotton Industry and chemical industry.
Background technology
China is that the first in the world is produced cotton big country, and the latest data that provides according to Cotton association shows, the sowing cotton seed area in the whole nation in 2010 is 7,275 ten thousand mu, and the cotton ultimate production is 5,970,000 tons.Xinjiang is the Cotton Production base of China's maximum, and 2010 sowing cotton seed areas are 1,609 thousand hectares, account for the national cotton ultimate production 40% and Gross World Product 11%.
Unginned cotton is through cotton gin processing removal gined cotton and obtain cottonseed, and cottonseed separates through decorticator, and cotton benevolence is used for oil expression, and the shell that is left is exactly cotton seed hulls, also claims cotton skin.Different according to the type of the machinery of peeling off, the cotton seed kind different, the place of production is different, water content is different, the rear broken cotton benevolence powder of peeling off sieves, and degree is not equal, the size of the cotton seed hulls that processes, color, velveteen length, nutrition are also different.The compositions such as cotton seed hulls three major polymers: cellulose (37～48%), xylogen (29～32%), hemicellulose (22～28%).
The cotton processing industry can be produced a large amount of cotton seed hulls byproducts.Because cotton seed hulls density is little, be difficult for transportation, store, and shell is hard, therefore be regarded as waste, to be that the form of burning is processed fall major part, and this has not only wasted a large amount of resources, has also polluted environment.In the U.S., cotton seed hulls is widely used in milk cow, calf, bull and beef cattle daily ration.In China, cotton seed hulls is multiplex to be come culturing edible fungus or makees fertilizer.At present, cotton seed hulls mainly utilizes approach to have: burning, preparation silicon-containing compound, preparation material of construction, feed etc., and its economic benefit is not remarkable, and added value of product is low.
At present, to mainly concentrating on the hemicellulose of facile hydrolysis in the utilization of cotton seed hulls.Cotton seed hulls carries out hydrolysis of hemicellulose under acidity or alkalescence, the solid matter major part is abandoned processing with burning, lysate go to prepare ethanol, Zhang Laixin with cotton seed hulls levulinic acid processed, Wang Qiao with cotton seed hulls hydrolysis _ oxidation _ hydrolysis legal system oxalic acid etc., the most representative is by ethanol dilution crystallization legal system xylo-oligosaccharide or Xylitol and reducing sugar.
Summary of the invention
Goal of the invention: overcome the deficiencies in the prior art, a kind of effective method of utilizing of cotton seed hulls of energy-saving, environment-friendly and high-efficiency is provided.The water hydrolysis of High Temperature High Pressure liquid state and supercritical extraction are combined, adopt acid treatment, realized that by cotton seed hulls be the novel process that raw material prepares cellulose compound, characteristics: method is simple, separation is quick effectively, energy consumption is low, product purity is high.
The present invention can be achieved through the following technical solutions:
A kind of method for preparing cellulose compound take cotton seed hulls as raw material is characterized in that it comprises the following steps:
The first step: cotton seed hulls is cleaned removal of impurities, and drying is sent into pulverizer and pulverized, and cyclonic separation or screening obtain housing and the suede body of cotton seed hulls;
Second step: gained suede body of upper step is added the water ultrasonic sedimentation separate, suspension adds in autoclave, and heat temperature raising carries out the liquid water hydrolysis under High Temperature High Pressure, and hydrolyzed solution solution ultrasonic sedimentation, suspension filter and obtain solid suede body;
The 3rd step: second step gained suede body is carried out supercritical extraction, separate obtaining suede body and a small amount of xylogen;
The 4th step: will add nitric acid, formic acid and acetic acid in the 3rd step gained suede body, reacting by heating is filtered and is obtained the white fiber element, pulverizes and obtains Microcrystalline Cellulose;
The 5th step: the reagent such as the 4th step gained Mierocrystalline cellulose and Mono Chloro Acetic Acid, sodium hydroxide, urea, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride are prepared the ether of cellulose compounds such as carbamate cellulose, carboxymethyl cellulose, hydroxyethylmethyl-cellulose.
Further scheme of the present invention is to sieve after the first step is pulverized to separate housing and suede body, comprises cyclonic separation, screening or settlement separate, obtains suede body and housing.
Further scheme of the present invention is that ultrasonic sedimentation separates, and frequency is 5～25KHz, and temperature is 20～100 ℃.
Further scheme of the present invention is to carry out the liquid water hydrolysis under the second step High Temperature High Pressure, and pressure is 0.01～5Mpa, and temperature is 110～260 ℃.
Further scheme of the present invention is to be hydrolyzed under the second step High Temperature High Pressure, comprises adding the diluted acid of pure water or 1～10% to be hydrolyzed, and diluted acid comprises formic acid, acetic acid, sulfuric acid, hydrochloric acid, nitric acid etc.
Further scheme of the present invention is that the 3rd step supercritical extraction comprises CO
2Supercritical extraction, CO
2With organic solvent mixed solution supercritical extraction, organic solvent comprises ethanol, ethylene glycol, BDO etc.
Further scheme of the present invention is to add nitric acid, formic acid and acetic acid to react in the 4th step, the ratio 0.2～4: 0.1～2: 1 of nitric acid, formic acid and acetic acid, and temperature of reaction is 20～110 ℃.
Further scheme of the present invention is to add nitric acid, formic acid and acetic acid to react in the 4th step, and reaction reagent also comprises: the reagent such as propionic acid, sodium hydroxide, sodium sulphite, S-WAT.
The present invention compares with art methods, present method has overcome the shortcoming of using a large amount of soda acids in existing cotton seed hulls Mierocrystalline cellulose recovery, adopt the hemicellulose of high temperature and high pressure hydrolysis suede body, and utilize its xylogen of supercritical fluid extraction and fractionation, organic acid and mineral acid are removed a small amount of impurity, make simultaneously Microcrystalline Cellulose.Have following obvious advantage: 1) hemicellulose separates fast: hemicellulose is hydrolyzed under High Temperature High Pressure fast and fully, improves more than 6 times with ordinary-pressure hydrolysis speed, and hydrolysis of hemicellulose is complete; 2) energy consumption is low: whole process disengaging time is short, and treatment capacity is large; 3) environmental protection: lignin separation adopts supercritical extraction method, and organic acid and mineral acid are removed a small amount of impurity, make simultaneously Microcrystalline Cellulose, and soda acid uses and greatly reduces, and the discharging of the three wastes is low; 4) cellulose loss is few: adopt high temperature and high pressure hydrolysis hemicellulose and organic acid and mineral acid except matter, cellulosic destructiveness is poor, reduces cellulose loss.Simple at whole production process technology, separation cycle is short, has obvious economic benefit and social benefit.
Description of drawings
Fig. 1 is a kind of method process flow sheet for preparing cellulose compound take cotton seed hulls as raw material of the present invention.
Embodiment
Embodiment 1
Get Alar City, Xinjiang cotton seed hulls 200 grams, pulverize with the pulverizer that fills 40 mesh sieve, crushed material sieves with 40 orders, 60 mesh sieves, the suede body (Mierocrystalline cellulose 71.7%, hemicellulose 10.2%, xylogen 18.1%) that utilizes the present invention to process to obtain.The suede body is put into beaker, adding water puts into the supersound washing agent and shakes, frequency 20KHz, shook 15 minutes, the housing that wraps up in the suede body sinks to the bottom of beaker, and upper strata suspension is sent in autoclave, heat temperature raising, 140 ℃ of hydrolysis 3 hours, hydrolyzed solution solution ultrasonic sedimentation, suspension filtration washing obtained solid suede body; The suede body adds supercritical CO
2In abstraction instrument, add 10% ethylene glycol extraction auxiliary agent, filtering separation obtains a small amount of xylogen and suede body (crude fibre); Suede body (crude fibre) adds nitric acid, formic acid and the acetic acid solution of 1: 0.5: 1, and reacting by heating 1 hour is filtered and obtained the white fiber element, pulverizes and obtains Microcrystalline Cellulose; The reagent reacts such as gained Mierocrystalline cellulose and sodium hydroxide, urea make the carbamate cellulose compound.
Embodiment 2
Get Alar City, Xinjiang cotton seed hulls 200 grams, pulverize with the pulverizer that fills 40 mesh sieve, crushed material is with 40 orders, 60 orders, 80 purpose sieves screenings, the suede body (Mierocrystalline cellulose 68.1% that utilizes the present invention to process to obtain, hemicellulose 10.3%, xylogen 21.6%).The suede body is put into beaker, add water and put into the supersound washing agent and shake, frequency 25KHz, shook 25 minutes, upper strata suspension is sent in autoclave, heat temperature raising, 160 ℃ of hydrolysis 3 hours, hydrolyzed solution solution ultrasonic sedimentation, suspension filtration washing obtained solid suede body; The suede body adds supercritical CO
2In abstraction instrument, add 10%1,4-butyleneglycol extraction auxiliary agent, filtering separation obtains a small amount of xylogen and suede body (crude fibre); Suede body (crude fibre) adds nitric acid and the acetic acid solution of 1: 1, and reacting by heating 1.5 hours is filtered and obtained the white fiber element, pulverizes and obtains Microcrystalline Cellulose; The reagent such as gained Mierocrystalline cellulose and Mono Chloro Acetic Acid make the carboxymethyl cellulose compound.
The above is only the preferred embodiments of the invention; be noted that for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. method for preparing cellulose compound take cotton seed hulls as raw material is characterized in that it comprises the following steps:
The first step: cotton seed hulls is cleaned removal of impurities, and drying is sent into pulverizer and pulverized, and cyclonic separation or screening obtain housing and the suede body of cotton seed hulls;
Second step: gained suede body of upper step is added the water ultrasonic sedimentation separate, suspension adds in autoclave, and heat temperature raising carries out the liquid water hydrolysis under High Temperature High Pressure, and hydrolyzed solution solution ultrasonic sedimentation, suspension filter and obtain solid suede body;
The 3rd step: second step gained suede body is carried out supercritical extraction, separate obtaining suede body and a small amount of xylogen;
The 4th step: will add nitric acid, formic acid and acetic acid in the 3rd step gained suede body, reacting by heating is filtered and is obtained the white fiber element, pulverizes and obtains Microcrystalline Cellulose;
The 5th step: the reagent such as the 4th step gained Mierocrystalline cellulose and Mono Chloro Acetic Acid, sodium hydroxide, urea, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride are prepared the ether of cellulose compounds such as carbamate cellulose, carboxymethyl cellulose, hydroxyethylmethyl-cellulose.
2. a kind of method for preparing cellulose compound take cotton seed hulls as raw material according to claim 1, is characterized in that: sieve after the first step is pulverized and separate housing and suede body, comprise cyclonic separation, screening or settlement separate, obtain suede body and housing.
3. a kind of method for preparing cellulose compound take cotton seed hulls as raw material according to claim 1 is characterized in that: the second step ultrasonic sedimentation separates, and frequency is 5～25KHz, and temperature is 20～100 ℃.
4. a kind of method for preparing cellulose compound take cotton seed hulls as raw material according to claim 1 is characterized in that: carry out the liquid water hydrolysis under the second step High Temperature High Pressure, pressure is 0.01～5Mpa, and temperature is 110～260 ℃.
5. a kind of method for preparing cellulose compound take cotton seed hulls as raw material according to claim 1, it is characterized in that: be hydrolyzed under the second step High Temperature High Pressure, comprise adding the diluted acid of pure water or 1～10% to be hydrolyzed, diluted acid comprises formic acid, acetic acid, sulfuric acid, hydrochloric acid, nitric acid etc.
6. a kind of method for preparing cellulose compound take cotton seed hulls as raw material according to claim 1 is characterized in that: the 3rd step supercritical extraction comprises CO
2Supercritical extraction, CO
2With organic solvent mixed solution supercritical extraction, organic solvent comprises ethanol, ethylene glycol, BDO etc.
7. a kind of method for preparing cellulose compound take cotton seed hulls as raw material according to claim 1, it is characterized in that: the 4th step added nitric acid, formic acid and acetic acid to react, the ratio 0.2～4: 0.1～2: 1 of nitric acid, formic acid and acetic acid, temperature of reaction is 20～110 ℃.
8. a kind of method for preparing cellulose compound take cotton seed hulls as raw material according to claim 1, it is characterized in that: the 4th step added nitric acid, formic acid and acetic acid to react, and reaction reagent also comprises: the reagent such as propionic acid, sodium hydroxide, sodium sulphite, S-WAT.
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| CN2012105671855A CN103122034A (en) | 2012-12-07 | 2012-12-07 | Method for preparing cellulose compounds by using cottonseed hull as raw material |
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| CN2012105671855A CN103122034A (en) | 2012-12-07 | 2012-12-07 | Method for preparing cellulose compounds by using cottonseed hull as raw material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568744A (en) * | 2015-12-17 | 2016-05-11 | 华南理工大学 | Cornstalk nanocellulose whiskers and preparation method and application thereof |
| CN108330724A (en) * | 2018-01-17 | 2018-07-27 | 太原理工大学 | A method of using waste and old cotton for water-soluble cellulose |
| CN109234826A (en) * | 2018-09-20 | 2019-01-18 | 武汉纺织大学 | A method of Lyocell fibers are prepared by raw material of bamboo |
| CN114920606A (en) * | 2022-04-27 | 2022-08-19 | 兰州石化职业技术学院 | Preparation method of adsorption type degradable soil moisture preservation slow release fertilizer based on modified wheat straw |
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2012
- 2012-12-07 CN CN2012105671855A patent/CN103122034A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568744A (en) * | 2015-12-17 | 2016-05-11 | 华南理工大学 | Cornstalk nanocellulose whiskers and preparation method and application thereof |
| CN108330724A (en) * | 2018-01-17 | 2018-07-27 | 太原理工大学 | A method of using waste and old cotton for water-soluble cellulose |
| CN109234826A (en) * | 2018-09-20 | 2019-01-18 | 武汉纺织大学 | A method of Lyocell fibers are prepared by raw material of bamboo |
| CN114920606A (en) * | 2022-04-27 | 2022-08-19 | 兰州石化职业技术学院 | Preparation method of adsorption type degradable soil moisture preservation slow release fertilizer based on modified wheat straw |
| CN114920606B (en) * | 2022-04-27 | 2024-01-12 | 兰州石化职业技术学院 | Preparation method of adsorption type degradable soil moisture conservation slow release fertilizer based on modified wheat straw |
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Application publication date: 20130529 |