CN101220099B - Production method for high viscosity sodium carboxymethylcellulose - Google Patents
Production method for high viscosity sodium carboxymethylcellulose Download PDFInfo
- Publication number
- CN101220099B CN101220099B CN2008100693368A CN200810069336A CN101220099B CN 101220099 B CN101220099 B CN 101220099B CN 2008100693368 A CN2008100693368 A CN 2008100693368A CN 200810069336 A CN200810069336 A CN 200810069336A CN 101220099 B CN101220099 B CN 101220099B
- Authority
- CN
- China
- Prior art keywords
- kneader
- quality
- minutes
- xylo
- mucine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a method of industrially producing sodium carboxymethyl cellulose with high viscosity by kneading method, which fills the inert gases into a kneader when the vacuum degree inside the kneader reaches to 0.002MPa after removing the air in the kneader before the alkalization process, resulting in a pressure above 0.1MPa. The whole alkalization process is carried on with the protection of the inert gases. The carboxymethyl cellulose products with high purity and high viscosity can be obtained after alkalization, etherification, washing, neutralization, centrifugation, drying and smashing. The products produced with the method are characterized by good quality, simple production technique, less equipment investment and low operation cost, etc.
Description
Technical field
The present invention relates to a kind of preparation method of Xylo-Mucine.
Background technology
Carboxymethyl cellulose is a kind of derivative with ether structure that natural cellulose obtains through chemical modification, and the carboxyl on the molecular chain can salify, and prevailing salt is sodium salt, and promptly Xylo-Mucine (Na-CMC) is called CMC traditionally, is a kind of ionic ether.
CMC is the high workability powder, and outward appearance is white in color or is faint yellow, tasteless, do not have smell, nontoxic, nonflammable, do not go mouldy, all very stable to light, heat.The CMC aqueous solution has thickening, bonding, film forming, protection glue, keeps effects such as moisture, emulsification and suspension; be widely used in multiple industry such as washing composition, food, weaving, printing and dyeing, papermaking, oil, mining, medicine, pottery, coating, makeup, be described as " monosodium glutamate " of industry.The key property of CMC is dissolved in the colloidal solution that forms certain viscosity behind the water exactly, and during above-mentioned these were used, many all was the high viscosity that has benefited from CMC.The CMC viscosity in aqueous solution mainly is subjected to strength of solution, pH value and Temperature Influence.Strength of solution is high more, and its viscosity is general also high more, the logarithmic value near linear relation of strength of solution and viscosity.In general, the 1%CMC viscosity in aqueous solution is maximum when pH value 6.5-9.0, and the most stable, and when pH＜6.0, viscosity descends rapidly, and begins to generate CMC acid, and when pH＞11.5, viscosity also begins rapid decline.The CMC viscosity in aqueous solution descends with the rising of temperature, and during cooling, viscosity can be gone up voluntarily, but when temperature is increased to a certain degree, nonvolatil viscosity will takes place reduce.In addition, the salt ion pair CMC viscosity in aqueous solution and the solvability of different valence state all have considerable influence.The CMC aqueous solution is pseudoplastic fluid, increases with shearing rate, and viscosity reduces, and is irrelevant with shear time, returns to original viscosity when shearing stops immediately.
When traditional technology is produced Xylo-Mucine; owing to do not make blanketing with inert gas; oxygen is to the Degradation of cellulosic degree of polymerization in the alkalization process; make the product substitution value greater than 0.9; when using NDJ-79 type viscometer to measure, 1% viscosity generally has only 400-500mPaS, in order to obtain full-bodied CMC; general by improving the polymerization degree of cellulosic material, perhaps adopt the method for adding linking agent.The former is subjected to the influence of Mierocrystalline cellulose quality bigger, and its limitation is also bigger; The latter can improve product viscosity to a certain extent by adding linking agent, but linking agent costs an arm and a leg mostly, so production cost is higher, and the product of handling through linking agent generally is not used in foodstuffs industry, has limited its production and use.
People's such as Bredezeck United States Patent (USP) 4,491,661 disclose a kind of method for preparing high viscosity carboxymethyl cellulose, this method is to use the ammonia activated cellulose, in the presence of ammonia with the alkalizing agent activatory Mierocrystalline cellulose that alkalizes, in the presence of alkalizing agent, from soda cellulose, remove deammoniation, in the presence of organic solvent, use etherifying reagent etherificate soda cellulose then.People's such as Edelman United States Patent (USP) 4,941,943 pull an oar into the fibre suspension of 5-15% with Mierocrystalline cellulose, be condensed into the paper pulp of 25-35%, and this paper pulp of homogenizing, after fibre suspension concentrates, this paper pulp is immersed in the alkali lye, form activated cellulose, this activated cellulose of etherificate forms Xylo-Mucine then.Chinese patent literature CN 1360651A is at first that cellulose silk is photochemical, the cellulose conversion that makes mercerization then and reclaim becomes ether of cellulose, obtain full-bodied Xylo-Mucine, by the cellulose wadding condensate that this method obtains, its loose density is greater than the Xylo-Mucine without the mercerized cellulose preparation.Chinese patent literature CN 1503807A utilizes the cellulose pulp of caustic dip and recovery to prepare full-bodied Xylo-Mucine.Above method all can improve the viscosity of carboxymethyl cellulose aqueous solution, but generally to the ingredient requirement height, reactions steps is many, and complex process is produced investment greatly, the cost height, and product yield is lower.
Summary of the invention
It is extensive to the purpose of this invention is to provide a kind of raw material sources, and technology is simple, and facility investment is few, the method for the production high-viscosity sodium carboxymethyl cellulose that running cost is low.The Xylo-Mucine that adopts this method to produce has higher viscosity, and substitution value is greater than 0.9, and when using NDJ-79 type viscometer to measure, 1% viscosity can reach more than the 700mPaS, improves 40% than traditional technology.
Technical scheme of the present invention is:
A, cotton fibre torn up after, with the aqueous sodium hydroxide solution of 30-55%, drop in the kneader together with the aqueous ethanolic solution of concentration 70-98%; Wherein, the quality ratio of cotton fibre and sodium hydroxide is generally 1: 1.6-4.2, the alcoholic acid quality normally cotton fibre 0.5-8 doubly.
After b, the end that feeds intake, get rid of the air in the kneader, make vacuum tightness reach 0.002MPa at least;
C, rare gas element is charged in the kneader, make the kneader internal pressure greater than 0.1MPa;
D, vacuumize more than repeating, the operation of filling with inert gas 2-3 time, drain the interior air of kneader as far as possible.Normally used rare gas element is meant and can not makes cellulosic degree of polymerization degraded, and the gas that does not react with raw material, as helium, argon gas etc.
E, whole alkalization process are carried out under protection of inert gas, and alkalization time is 40-120 minute, and alkalization temperature is 10-40 ℃;
After f, alkalization finish, carry out etherification reaction.The amount of substance ratio of cotton fibre and etherifying agent is generally 1: 0.8-2.0.Etherifying agent is the chloroacetic ethanolic soln of 50-80%, and etherification procedure divides two stages, the fs, in 60 minutes, equably etherifying agent is sprayed to kneader, and temperature is 30-60 ℃, subordinate phase is warming up to 75-80 ℃ gradually, continues reaction 30-90 minute.
After g, washing, neutralization, centrifugal, dry, the pulverizing, obtain the high-viscosity sodium carboxymethyl cellulose finished product through conventional.
Description of drawings
Fig. 1 is this preparation method's a FB(flow block).
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1:
Cotton fibre with 1 times of quality of tearing up, 1 times of quality 30% aqueous sodium hydroxide solution and 1.5 times of 90% ethanolic soln drop in the kneader simultaneously, get rid of air in the kneader, make vacuum tightness reach 0.002MPa, nitrogen is charged in the kneader, pressure reaches 0.1MPa, and vacuumize more than repeating, filling with inert gas operation 2-3 time, stir alkalization after 40 minutes, 0.8 times of chloroacetic ethanolic soln of cotton quality (strength of solution 50-80%) was sprayed in 60 minutes equably to kneader, and controlled temperature is warming up to 75-80 ℃ then gradually less than 60 ℃, continue reaction 30 minutes, obtain rough Xylo-Mucine, through washing, neutralization, centrifugal, dry, obtain refining Xylo-Mucine finished product after the pulverizing, substitution value is 0.72, purity is 99.5%, and 1% viscosity that NDJ-79 type viscometer is measured is 750mPaS.
Embodiment 2:
Cotton fibre with 1 times of quality of tearing up, 1.1 doubly quality 140% aqueous sodium hydroxide solution and 2 times of 93% ethanolic soln drop in the kneader simultaneously, get rid of air in the kneader, make vacuum tightness reach 0.002MPa, inert nitrogen gas is charged in the kneader, pressure reaches 0.1MPa, and vacuumize more than repeating, filling with inert gas operation 2-3 time, stir alkalization after 40 minutes, the chloroacetic ethanolic soln (strength of solution 50-80%) of 0.6 times of cotton quality was sprayed to kneader in 60 minutes equably, controlled temperature is less than 60 ℃, be warming up to 75-80 ℃ then gradually, continue reaction 90 minutes, obtain rough Xylo-Mucine, through washing, neutralization, centrifugal, dry, obtain refining Xylo-Mucine finished product after the pulverizing, substitution value is 0.73, purity is 98.5%, and 1% viscosity that NDJ-79 type viscometer is measured is 730mPaS.
Embodiment 3:
With a certain amount of 1 times of cotton fibre that quality is torn up, 1.3 doubly quality 50% aqueous sodium hydroxide solution and 2.5 times of 90% ethanolic soln drop in the kneader simultaneously, get rid of air in the kneader, make vacuum tightness reach 0.002MPa, inert nitrogen gas is charged in the kneader, pressure reaches 0.1MPa, and vacuumize more than repeating, filling with inert gas operation 2-3 time, stir alkalization after 120 minutes, the chloroacetic ethanolic soln (strength of solution 50-80%) of 0.6 times of cotton quality was sprayed to kneader in 60 minutes equably, controlled temperature is less than 60 ℃, be warming up to 75-80 ℃ then gradually, continue reaction 60 minutes, obtain rough Xylo-Mucine, through washing, neutralization, centrifugal, dry, obtain refining Xylo-Mucine finished product after the pulverizing, substitution value is 0.80, purity is 99.0%, and 1% viscosity that NDJ-79 type viscometer is measured is 720mPaS.
Embodiment 4:
Cotton fibre with 1 times of quality of tearing up, 1.5 doubly quality 55% aqueous sodium hydroxide solution and 3 times of 90% ethanolic soln drop in the kneader simultaneously, get rid of air in the kneader, make vacuum tightness reach 0.002MPa, inert nitrogen gas is charged in the kneader, pressure reaches 0.1MPa, and vacuumize more than repeating, filling with inert gas operation 2-3 time, stir alkalization after 100 minutes, 1 times of chloroacetic ethanolic soln of cotton quality (strength of solution 50-80%) was sprayed to kneader in 60 minutes equably, controlled temperature is less than 60 ℃, be warming up to 75-80 ℃ then gradually, continue reaction 90 minutes, obtain rough Xylo-Mucine, through washing, neutralization, centrifugal, dry, obtain refining Xylo-Mucine finished product after the pulverizing, substitution value is 0.92, purity is 99.0%, and 1% viscosity that NDJ-79 type viscometer is measured is 780mPaS.
Embodiment 5:
Cotton fibre with 1 times of quality of tearing up, 1.5 doubly quality 55% aqueous sodium hydroxide solution and 3 times of 90%7 alcoholic solution drop in the kneader simultaneously, get rid of air in the kneader, make vacuum tightness reach 0.002MPa, inert nitrogen gas is charged in the kneader, pressure reaches 0.1MPa, and vacuumize more than repeating, filling with inert gas operation 2-3 time, stir alkalization after 120 minutes, 0.8 times of chloroacetic ethanolic soln of cotton quality (strength of solution 50-80%) was sprayed to kneader in 60 minutes equably, controlled temperature is less than 60 ℃, be warming up to 75-80 ℃ then gradually, continue reaction 80 minutes, obtain rough Xylo-Mucine, through washing, neutralization, centrifugal, dry, obtain refining Xylo-Mucine finished product after the pulverizing, substitution value is 0.90, purity is 99.0%, and 1% viscosity that NDJ-79 type viscometer is measured is 770mPaS.
Term:
Viscosity: 1% aqueous solution, NDJ-79 type rotary viscometer detects under 25 ℃ of conditions
Substitution value (D.S): detect according to 5.5 methods among the GB 1904-2005 " foodstuff additive Xylo-Mucine ".
Purity:, obtain with minusing again according to ASTM D1439-03 standard detection sodium-chlor and sodium glycolate content.
Claims (4)
1. the preparation method of a high-viscosity sodium carboxymethyl cellulose is characterized in that:
Cotton fibre with 1 times of quality of tearing up, 1 times of quality 30% aqueous sodium hydroxide solution and 1.5 times of 90% ethanolic soln drop in the kneader simultaneously, get rid of air in the kneader, make vacuum tightness reach 0.002MPa, nitrogen is charged in the kneader, pressure reaches 0.1MPa, and vacuumize more than repeating, filling with inert gas operation 2-3 time, stir alkalization after 40 minutes, 0.8 times of chloroacetic ethanolic soln of cotton quality was sprayed to kneader in 60 minutes equably, strength of solution is 50-80%, controlled temperature is warming up to 75-80 ℃ then gradually less than 60 ℃, continues reaction 30 minutes, obtain rough Xylo-Mucine, through washing, neutralization, centrifugal, dry, obtain refining Xylo-Mucine finished product after the pulverizing.
2. the preparation method of a high-viscosity sodium carboxymethyl cellulose is characterized in that:
The cotton fibre that 1 times of quality is torn up, 1.3 doubly quality 50% aqueous sodium hydroxide solution and 2.5 times of 90% ethanolic soln drop in the kneader simultaneously, get rid of air in the kneader, make vacuum tightness reach 0.002MPa, inert nitrogen gas is charged in the kneader, pressure reaches 0.1MPa, and vacuumize more than repeating, filling with inert gas operation 2-3 time, stir alkalization after 120 minutes, the chloroacetic ethanolic soln of 0.6 times of cotton quality was sprayed to kneader in 60 minutes equably, strength of solution is 50-80%, controlled temperature is warming up to 75-80 ℃ then gradually less than 60 ℃, continues reaction 60 minutes, obtain rough Xylo-Mucine, through washing, neutralization, centrifugal, dry, obtain refining Xylo-Mucine finished product after the pulverizing.
3. the preparation method of a high-viscosity sodium carboxymethyl cellulose is characterized in that:
Cotton fibre with 1 times of quality of tearing up, 1.5 doubly quality 55% aqueous sodium hydroxide solution and 3 times of 90% ethanolic soln drop in the kneader simultaneously, get rid of air in the kneader, make vacuum tightness reach 0.002MPa, inert nitrogen gas is charged in the kneader, pressure reaches 0.1MPa, and vacuumize more than repeating, filling with inert gas operation 2-3 time, stir alkalization after 100 minutes, 1 times of chloroacetic ethanolic soln of cotton quality was sprayed to kneader in 60 minutes equably, strength of solution 50-80%, controlled temperature is warming up to 75-80 ℃ then gradually less than 60 ℃, continues reaction 90 minutes, obtain rough Xylo-Mucine, through washing, neutralization, centrifugal, dry, obtain refining Xylo-Mucine finished product after the pulverizing.
4. the preparation method of a high-viscosity sodium carboxymethyl cellulose is characterized in that:
Cotton fibre with 1 times of quality of tearing up, 1.5 doubly quality 55% aqueous sodium hydroxide solution and 3 times of 90% ethanolic soln drop in the kneader simultaneously, get rid of air in the kneader, make vacuum tightness reach 0.002MPa, inert nitrogen gas is charged in the kneader, pressure reaches 0.1MPa, and vacuumize more than repeating, filling with inert gas operation 2-3 time, stir alkalization after 120 minutes, 0.8 times of chloroacetic ethanolic soln of cotton quality was sprayed to kneader in 60 minutes equably, strength of solution is 50-80%, controlled temperature is warming up to 75-80 ℃ then gradually less than 60 ℃, continues reaction 80 minutes, obtain rough Xylo-Mucine, through washing, neutralization, centrifugal, dry, obtain refining Xylo-Mucine finished product after the pulverizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100693368A CN101220099B (en) | 2008-01-31 | 2008-01-31 | Production method for high viscosity sodium carboxymethylcellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100693368A CN101220099B (en) | 2008-01-31 | 2008-01-31 | Production method for high viscosity sodium carboxymethylcellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101220099A CN101220099A (en) | 2008-07-16 |
| CN101220099B true CN101220099B (en) | 2011-01-26 |
Family
ID=39630198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100693368A Active CN101220099B (en) | 2008-01-31 | 2008-01-31 | Production method for high viscosity sodium carboxymethylcellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101220099B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735324B (en) * | 2010-01-13 | 2012-07-04 | 北京理工大学 | Carboxymethyl cellulose nitrate and preparation method thereof |
| CN101830989B (en) * | 2010-04-14 | 2011-05-25 | 兰州大学 | Method for preparing high-viscosity sodium carboxymethyl cellulose by utilizing potato starch residues |
| CN101967231B (en) * | 2010-09-30 | 2012-06-20 | 华南理工大学 | Production method of sodium carboxymethyl cellulose with low sodium content |
| US9181659B2 (en) * | 2011-10-17 | 2015-11-10 | Cp Kelco Oy | Compositions having increased concentrations of carboxymethylcellulose |
| CN103242453A (en) * | 2012-08-14 | 2013-08-14 | 常熟威怡科技有限公司 | Method for preparing low-viscosity sodium carboxymethylcellulose |
| CN104086658B (en) * | 2013-07-11 | 2016-05-18 | 上海长光企业发展有限公司 | A kind of preparation method of food grade sodium carboxymethylcellulose |
| CN104072621A (en) * | 2014-06-30 | 2014-10-01 | 泸州北方化学工业有限公司 | Method for preparing ultrahigh-viscosity sodium carboxymethyl cellulose |
| CN104592399B (en) * | 2015-02-03 | 2017-03-15 | 重庆力宏精细化工有限公司 | A kind of preparation method for improving sodium carboxymethyl cellulose solution wandering fibre silk |
| CN104592398B (en) * | 2015-02-03 | 2016-08-24 | 重庆力宏精细化工有限公司 | A kind of preparation method of sodium carboxymethyl cellulose |
| CN105330751A (en) * | 2015-11-05 | 2016-02-17 | 重庆力宏精细化工有限公司 | Continuous production method of carboxymethylcellulose lithium for lithium batteries |
| CN106699901A (en) * | 2016-12-21 | 2017-05-24 | 天津润圣纤维素科技有限公司 | Production technology of high viscosity sodium carboxymethyl cellulose |
| CN111187355A (en) * | 2018-11-14 | 2020-05-22 | 河南正弘药用辅料股份有限公司 | Production method of sodium carboxymethylcellulose |
| CN110079327B (en) * | 2019-05-30 | 2021-01-05 | 北京理工大学 | Preparation method and application of straw sodium water retention and conditioning material |
| CN114685688B (en) * | 2022-03-30 | 2023-09-01 | 大连中比动力电池有限公司 | Sodium carboxymethyl cellulose and preparation method and application thereof |
| CN117164728A (en) * | 2023-09-06 | 2023-12-05 | 山东扬子生物科技有限公司 | Production process for preparing CMC (CMC) for lithium battery by slurry method |
-
2008
- 2008-01-31 CN CN2008100693368A patent/CN101220099B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101220099A (en) | 2008-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101220099B (en) | Production method for high viscosity sodium carboxymethylcellulose | |
| CN102675474B (en) | Preparation method of ultrahigh-viscosity sodium carboxymethyl cellulose | |
| YU66003A (en) | Method for separating hemicelluloses from a biomass containing hemicelluloses and biomass and hemicelluloses obtaining by said method | |
| CN103539868B (en) | A kind of method of preparing CMC | |
| CN111560079B (en) | Preparation method of Iota carrageenan glue solution | |
| KR20010080592A (en) | Method for the Production of Low-viscous Water-soluble Cellulose Ethers | |
| CN105542017B (en) | The preparation technology of sodium carboxymethylcellulose | |
| CN101648131A (en) | Preparation method of high effective retention and filtration agent cationic guar gum | |
| CN101712774A (en) | Method for preparing modified watermelon peel fiber and cornstarch edible film | |
| CN106632736A (en) | Preparation method for carboxymethyl xylan | |
| CN104672341B (en) | A kind of preparation method of carboxymethylhydroxyethylguar | |
| CN105661621B (en) | A kind of preparation method of full stalk papermaking-method reconstituted tobaccos | |
| AU2005318574A1 (en) | Method for production of hemicellulose from lignocellulose material | |
| CN105777917A (en) | Preparation method of carboxymethyl starch used for reactive dye printing | |
| CN1490337A (en) | Superhigh viscosity carboxymethyl sodium starch and its preparation | |
| CN104592398A (en) | Method for preparing sodium carboxymethyl cellulose | |
| CN105949329A (en) | Production process of ultrahigh viscosity sodium carboxymethyl cellulose | |
| CN105713098A (en) | Method for preparing sodium carboxymethyl cellulose by fermenting bagasse | |
| CN1281627C (en) | Process for preparing pre-dextrinized hydropropyl di-starch phosphoric ester | |
| CN104558204A (en) | Green quick high-efficiency methylation method of cellulose | |
| CN101215383A (en) | Method for preparing acid and base amphiprotic dissoluble chitosan | |
| CN108157582A (en) | It is a kind of that the method for improving sesame protein gelation is modified using immobilised enzymes | |
| CN106832057A (en) | A kind of preparation method of low polymerization degree chitin | |
| CN104630305A (en) | Production method of gamma-cyclodextrin | |
| CN103059144B (en) | Preparation method of high-viscosity pelletizing sodium carboxymethylcellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |