CN107903327A - The method that stalk cellulose component separates and prepares carboxymethyl cellulose - Google Patents

The method that stalk cellulose component separates and prepares carboxymethyl cellulose Download PDF

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Publication number
CN107903327A
CN107903327A CN201711035833.1A CN201711035833A CN107903327A CN 107903327 A CN107903327 A CN 107903327A CN 201711035833 A CN201711035833 A CN 201711035833A CN 107903327 A CN107903327 A CN 107903327A
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China
Prior art keywords
cellulose
stalk
dry
cmc
carboxymethyl cellulose
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CN201711035833.1A
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Chinese (zh)
Inventor
郑庆义
兹留柱
郝明奎
韩宝征
杨磊
么传杰
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Shandong Nintaus Xinke Agricultural Development Co Ltd
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Shandong Nintaus Xinke Agricultural Development Co Ltd
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Priority to CN201711035833.1A priority Critical patent/CN107903327A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/08Alkali cellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00Preparation of cellulose ethers
    • C08B11/02Alkyl or cycloalkyl ethers
    • C08B11/04Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/10Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
    • C08B11/12Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00Preparation of cellulose ethers
    • C08B11/20Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
    • C08B11/22Isolation

Abstract

The present invention provides a kind of method that stalk cellulose component separates and prepares carboxymethyl cellulose, first separates cellulose from stalk;Then, by the cellulose of acquisition, it is prepared into carboxymethyl cellulose.The present invention separates all components in stalk, and recycling;Produced CMC is food-grade, pharmaceutical grade, and cost is low;Product purity of the present invention is high;It can reach 99.8%.Present invention process is simple, more convenient operation.

Description

The method that stalk cellulose component separates and prepares carboxymethyl cellulose
Technical field
The invention belongs to stalk resource to utilize field, be related to a kind of separation and Extraction cellulose from stalk method and The method that carboxymethyl cellulose is prepared on the basis of this.
Background technology
Carboxymethyl cellulose (CMC), is that use scope is most wide in the world today, the cellulose species of dosage maximum, has Bonding, thickening, enhancing, emulsification, water conservation, suspension etc. act on.CMC is not only good emulsion stabilizer in food applications, increases Thick dose, and freeze with excellent, melt stability, and the flavor of product can be improved, extend storage time.In medical industry In can make the emulsion stabilizer of injection, the binding agent of tablet, film forming agent and safe and reliable anticancer drug carrier.CMC is in detergent In can be used as anti-dirt redeposition agent, in oil drilling can be used for protection oil well as mud stability, water-retaining agent, weaving It is used as sizing agent, the thickener of printing paste, printing in textiles and hard finishing etc. in industry.
At present, the raw material of CMC is largely refined cotton linter and lower margin cottons, and starving is of high cost, crops straw , can be as the raw material of CMC containing abundant cellulose in stalk.Agricultural crop straw mainly contains half fiber as lignocellulose raw material Element, lignin, cellulose and other components are tieed up, so needing first to extract the cellulose in stalk, synthesis could be used as The raw material of CMC.By the use of agricultural crop straw as the synthesis material of CMC, efficiently solve that current synthesis material is of high cost, and stalk is comprehensive Close the problem of utilization rate is low.
Chinese patent application CN103224565 has opened a kind of method that straw component separation prepares ultra-low viscosity CMC, uses Sour water solution stalk hemicellulose obtains the monose that can ferment, and organic solvent extracting straw lignin obtains high activity lignin, remaining Stalk cellulose is through sour water solution and alkaline oxygenated method, etherification modified ultra low viscosity carboxymethyl cellulose.The patent is directly by stalk Powder is alkalized, etherification reaction prepares CMC.The cellulose in stalk is not separated, then prepares CMC, will be caused prepared CMC purity it is low, hemicellulose and lignin in stalk are not fully utilized, and waste of resource while also result in serious ring Pollute in border.And used epoxychloropropane toxicity big during synthesis carboxymethyl cellulose, also use nitrogen and do protection gas, into This height.The carboxymethyl cellulose produced is to belong to technical grade, and purity is low, and toxicity is big.
Chinese patent application CN105884907 discloses a kind of method for the CMC that printing gum is prepared using stalk, will Straw powder, industrial alcohol and solid NaOH mixing carry out quaternization, then add monoxone under nitrogen protection and are etherified Reaction, adding alkali twice are cured, and glacial acetic acid ethanol solution adjusts pH, then washed, centrifugation, dry, pulverization process print to obtain the final product The CMC of flower thickener.What the patent isolated the method for cellulose in stalk is organic solvent extraction, first carries lignin Take out, residue is cellulose, and inevitable residual organic solvent is unfavorable for later basification etherification procedure, and in stalk except Lignin, cellulose and hemicellulose, also have the components such as some protein, fat, pectin and inorganic salts, are not examined in separation process Consider these components, the purity of CMC that subsequently prepares will be caused low.
It can be seen from the above that stalk component separates the method for preparing CMC there are certain defect, it is necessary to further research and develop at present Technique is simple, cost is low, purity is high, food-grade, pharmaceutical grade carboxymethyl cellulose.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of stalk cellulose component separates and prepares carboxymethyl cellulose Method.The method of the present invention is existing to separate cellulose from stalk, then, by the cellulose of acquisition by alkalizing, being etherified Carboxymethyl cellulose is prepared into etc. technique.
It is of the invention to be using technical solution:First, straw component separation method, step are as follows:
(1) stalk tablet obtained by wet feed preparation is sent to digester, while adds a certain amount of clear water.It is passed through fresh steaming Vapour, keeps the temperature two hours, and boiling terminates, and whole materials are spurted spraying pot cooling preservation through putting pot pump.The material warp of spraying pot Cross acroll press washer and carry out three sections of countercurrent washings, filtrate enters submember extraction workshop section.Filtrate from hot-water extraction workshop section Settled by settling tank, submember, the raw material using this submember as degradable utensil are then extracted by membrane type system. Production fresh water is back to use hot-water extraction washing room, concentrated water circulating and recovering to membrane type system.
Solid slag from a upper workshop section freely drops to digester through acroll press washer discharge port, while adds a certain amount of Acid solution and clear water.After filling pot, live steam is passed through, pot inner liquid medicine reaches corresponding temperature, and starts to keep the temperature.Boiling knot Whole materials are spurted spraying pot cooling preservation by beam through putting pot pump.The material of spraying pot carries out three sections by acroll press washer Countercurrent washing, as far as possible cleans the xylose hydrolysis fluid in solid slag to improve xylose yield.Xylose hydrolysis fluid enters xylose essence Workshop section processed.
(2) solid slag enters alkaline cooking section, and solid slag enters digester through acroll press washer, at the same add lye and Cellulose washs one section of filtrate as cooking liquor.Steam heating is added after filling pot, reaches corresponding temperature, and start to keep the temperature.Steam End is boiled, whole materials are spurted into spraying pot through putting pot pump.The material of spraying pot carries out isolating cellulose by filter Filter cake and lignin aqueous slkali.After cellulose cake dilution three sections of countercurrent washings are carried out with acroll press washer.Next section of filtrate Washed for the preceding paragraph, the filtrate of first segment is sent into digester.Moist cellulose drying after washing is to spare after 90%.
(3) lignin aqueous slkali is after evaporation and concentrating, send to acidifying groove to add hydrochloric acid and adjust to acidity, lignin and fully separates out After be sent into filter.Wooden filter cake passes through two sections of countercurrent washings.Next section of filtrate is washed for the preceding paragraph, the filtrate of first segment It is sent into.It is spare after lignin drying to certain mass fraction after washing.
Then, cellulose above-mentioned steps (2) obtained, prepares carboxymethyl cellulose, technique includes following process: Alkalization process, etherificate process, neutralization washing refining step, rotary process, rake do process, baking operation and crush blending process. Comprise the following steps that:
(1) alkalize
In kneader, by cellulose and sodium hydroxide ethanol solution (m:M=2:1-5:1) according to mass ratio 1:2 in 30- Under the conditions of 70 DEG C, kneader rotating speed is 60-200r/min, alkalization 30-180min generation alkali cellulose.
(2) it is etherified
After the completion of alkalization, the monoxone ethanol solution (m of cellulose dosage 10-40% (mass percent) is added:M=2: 1-5:1) 40-80 DEG C, is warming up to, cocurrent adds cellulose dosage 10% (mass percent) sodium hydroxide ethanol solution (m:M=2: 1-5:1) 30-180min generation carboxyl methyl celluloses are etherified.
(3) washing is neutralized
The CMC of etherificate generation is put into sink, is added mass percent concentration and is washed simultaneously for 3-10% dilute hydrochloric acid It is 5-8.5 that excessive alkali, which is neutralized, to pH, is washed 3 times, the salinity produced in reaction process enters in solution.
(4) centrifuge
The CMC washed is put into centrifuge and carries out solid-liquor separation, the dry process of filter cake Song Zhixia roads rake.Filtrate can be used for Step (3) neutralizes washing.
(5) rake is dry
Put into after filter cake after centrifugation is torn up in the dry machine of rake, it is dry to moisture 10-20%, and recycle in CMC Alcohol.The alcohol of recycling can be used for step (3) to neutralize washing.
(6) dry
CMC (moisture content 10-20%) after harrowing and doing is put into dryer and is dried, is dried to water in product Divide less than 10%.
(7) blending is crushed
Material after drying, crushes by pulverizer, after winnowing machine, air-introduced machine, cyclone separator and vibrating screen, reaches To defined product granularity, dress bag is got product.
The present invention has the advantages that:
1st, all components in stalk are separated, and recycling;All the components in stalk are included fiber by the present invention Element, hemicellulose, lignin are first separated, and then prepare carboxymethyl cellulose again, and all the components in stalk are made full use of. The method of the present invention is suitable for all types of stalks, such as wheat stalk, maize straw, broomcorn straw, cotton stalk.
2nd, CMC is produced as food-grade, pharmaceutical grade, and cost is low;Alkaline boiling of the present invention, acidifying and etc. be nothing The soda acid and food-grade alcohol for the cheap low concentration poisoned, cost is low, nonhazardous, does not use methanol, acetone, epoxychloropropane, The noxious materials such as chlorine, thus food-grade, pharma grade product can be produced.
3rd, product purity is high;The present invention prepares carboxymethyl cellulose again after the cellulosic component in stalk is separated first Element, purity can reach 99.8%.Acid catalyst uses solid acid and liquid acid at the same time, and the percent hydrolysis of hemicellulose improves 3%.
4th, present invention process is simple, more convenient operation.In cellulose preparation, solution and reagent used are low concentration, often Reagent is advised, the reaction time is short.The existing method that cellulose is obtained from stalk generally uses the aqueous slkali of 10%-20%, secondary chlorine Sour sodium, hydrogen peroxide and dilute hydrochloric acid, and the present invention has simply used 0.5% aqueous slkali, 0.8% dilute sulfuric acid, subtracts in technique Lack environmental hazard, save a large amount of materials, it is of low cost, it is environmental-friendly.
5th, the method for the present invention is environmentally friendly, pollution-free.Used organic solvent is recycled during synthesis carboxymethyl cellulose Utilize, it is environment friendly and pollution-free.The ethanol that each equipment volatilizes in the second alcohol and water and production process of centrifuge abjection is collected to storage Tank is kept in, and is squeezed into rectifying column in due course and is purified, and the ethanol for respectively obtaining various concentrations to be produced recycles.Ethanol rectifying is adopted With dual-effect energy-saving technique, I column overhead steam provides heat source for II tower tower reactor, while I column overhead product is condensed, i.e. Diluted Alcohol. II column overhead product is dense ethanol through multi-stage condensing.The brine waste that ethanol removal process produces, through sewage-treatment plant, send to Other workshop reactions not high to water quality requirement consume, and do not have production waste.The present invention carries out discarded ethanol through rectifying Recycling, the brine waste of generation is sent to other workshops reactions not high to water quality requirement and consumed through sewage-treatment plant, It is more perfect for from technique, environmental protection.
Embodiment
Technical scheme and its caused technique effect are done further with reference to specific test method Illustrate, the following description is only intended to explain the invention, but the present invention is not any limitation as in any way, is made based on the present invention Any conversion or replacement, belong to protection scope of the present invention.The method of the invention is this area unless otherwise specified Conventional method.
Embodiment one, separate cellulose from stalk
Take stalk tablet 2t obtained by wet feed preparation to be sent to digester, while add the clear water of 5 times of amounts.It is passed through live steam, Keep the temperature 120 DEG C two hours, boiling terminates, and cooling preserves.Filtering, filtrate can be used for preparing degradable utensil.Residue washing three times, It is 0.8% (mass fraction) to add sulfuric acid Controlled acidity, and hydrolyzing 1h at 130 DEG C obtains hydrolyzate, filters, and filtrate can be used for refining Xylose.Boiling 1h, filtering, after filtrate neutralizes at 110 DEG C in 0.5% (mass percent) sodium hydroxide solution after residue washing Obtain lignin.Filter residue is washed, dry 0.67t celluloses.
Embodiment two, prepare carboxymethyl cellulose
(1) alkalize
1t celluloses are taken in 4m3In kneader with 2t sodium hydroxide ethanol solutions (m:M=2:1) under the conditions of 30 DEG C, adjust It is 60r/min to save kneader rotating speed, alkalization 30min generation alkali cellulose.
(2) it is etherified
After the completion of alkalization, 10% (the 10% of cellulose quality) monoxone ethanol solution (m is added:M=2:1), it is warming up to 40 DEG C, stream adds 10% (the 10% of cellulose quality) sodium hydroxide ethanol solution (m:M=2:1), it is etherified 30min generations CMC.
(3) washing is neutralized
The thick CMC of etherificate generation is put into sink, and it is during 3% dilute hydrochloric acid wash simultaneously to add mass percent concentration It is 7.8 with excessive alkali to pH, wash 3 times, the salinity produced in reaction process enters in solution.
(4) centrifuge
The CMC washed is put into centrifuge and carries out solid-liquor separation, filtrate is washed into wine storing jar is applied mechanically for product, The dry process of filter cake Song Zhixia roads rake.
(5) rake is dry
Put into after filter cake after centrifugation is torn up in the dry machine of rake, it is dry to moisture 20%, and recycle the wine in CMC Essence, the alcohol of recycling are washed for product.
(6) dry
By through rake it is dry after CMC put into dryer and be dried, be dried in product moisture below 10%.
(7) blending is crushed
Material after drying, crushes by pulverizer, after winnowing machine, air-introduced machine, cyclone separator and vibrating screen, reaches To defined product granularity, dress is wrapped up to product.
Embodiment three, prepare carboxymethyl cellulose
(1) alkalize
1t celluloses are taken in 4m3In kneader with 2t sodium hydroxide ethanol solutions (m:M=3:1) under the conditions of 40 DEG C, adjust It is 100r/min to save kneader rotating speed, alkalization 60min generation alkali cellulose.
(2) it is etherified
After the completion of alkalization, 20% (the 20% of cellulose quality) monoxone ethanol solution (m is added:M=3:1), it is warming up to 50 DEG C, stream adds 10% (the 10% of cellulose quality) monoxone ethanol solution (m:M=3:1), it is etherified 60min generations CMC.
(3) washing is neutralized
The thick CMC of etherificate generation is put into sink, and it is dense that mass percent is added in the case of proper proportion alcohol liquid ratio Spend for 5% dilute hydrochloric acid (addition be subject to pH value of solution testing result), wash 3 times, and neutralize excessive alkali to pH be 7, reaction During the salinity that produces enter in solution.
(4) centrifuge
The CMC washed is put into centrifuge and carries out solid-liquor separation, filtrate is washed into wine storing jar is applied mechanically for product, The dry process of filter cake Song Zhixia roads rake.
(5) rake is dry
Put into after filter cake after centrifugation is torn up in the dry machine of rake, it is dry to moisture 13%, and recycle the wine in CMC Essence, the alcohol of recycling are washed for product.
(6) dry
By through rake it is dry after CMC put into dryer and be dried, be dried in product moisture below 10%.
(7) blending is crushed
Material after drying, crushes by pulverizer, after winnowing machine, air-introduced machine, cyclone separator and vibrating screen, reaches To defined product granularity, dress is wrapped up to product.
Example IV, prepare carboxymethyl cellulose
(1) alkalize
1t celluloses are taken in 4m3In kneader with 2t sodium hydroxide ethanol solutions (m:M=4:1) under the conditions of 50 DEG C, adjust It is 150r/min to save kneader rotating speed, alkalization 90min generation alkali cellulose.
(2) it is etherified
After the completion of alkalization, 30% (the 30% of cellulose quality) monoxone ethanol solution (m is added:M=4:1), it is warming up to 60 DEG C, stream adds 10% (the 10% of cellulose quality) sodium hydroxide ethanol solution (m:M=4:1), it is etherified 90min generations CMC.
(3) washing is neutralized
The thick CMC of etherificate generation is put into sink, and adding mass percent concentration, (addition is with molten for 7% dilute hydrochloric acid Subject to liquid pH testing results) washed and neutralize excessive alkali to pH be 8, wash 3 times, the salinity produced in reaction process into Enter in solution.
(4) centrifuge
The CMC washed is put into centrifuge and carries out solid-liquor separation, filtrate is washed into wine storing jar is applied mechanically for product, The dry process of filter cake Song Zhixia roads rake.
(5) rake is dry
Put into after filter cake after centrifugation is torn up in the dry machine of rake, it is dry to moisture 16%, and recycle the wine in CMC Essence, the alcohol of recycling are washed for product.
(6) dry
By through rake it is dry after CMC put into dryer and be dried, be dried in product moisture below 10%.
(7) blending is crushed
Material after drying, crushes by pulverizer, after winnowing machine, air-introduced machine, cyclone separator and vibrating screen, reaches To defined product granularity, dress is wrapped up to product.
Embodiment five, prepare carboxymethyl cellulose
(1) alkalize
1t celluloses are taken in 4m3In kneader with 2t sodium hydroxide ethanol solutions (m:M=5:1) under the conditions of 60 DEG C, adjust The rotating speed for saving kneader is 200r/min, alkalization 120min generation alkali cellulose.
(2) it is etherified
After the completion of alkalization, 40% (the 40% of cellulose quality) monoxone ethanol solution (m is added:M=5:1), it is warming up to 70 DEG C, stream adds 10% (the 10% of cellulose quality) sodium hydroxide ethanol solution (m:M=5:1), it is etherified 120min generations CMC.
(3) washing is neutralized
The thick CMC of etherificate generation is put into sink, and adding mass percent concentration, (addition is with molten for 10% dilute hydrochloric acid Subject to liquid pH testing results) washed and neutralize excessive alkali to pH be 5, wash 3 times, the salinity produced in reaction process into Enter in solution.
(4) centrifuge
The CMC washed is put into centrifuge and carries out solid-liquor separation, filtrate is washed into wine storing jar is applied mechanically for product, The dry process of filter cake Song Zhixia roads rake.
(5) rake is dry
Put into after filter cake after centrifugation is torn up in the dry machine of rake, it is dry to moisture 20%, and recycle the wine in CMC Essence, the alcohol of recycling are washed for product.
(6) dry
By through rake it is dry after CMC put into dryer and be dried, be dried in product moisture below 10%.
(7) blending is crushed
Material after drying, crushes by pulverizer, after winnowing machine, air-introduced machine, cyclone separator and vibrating screen, reaches To defined product granularity, dress is wrapped up to product.
Comparative example one
The carboxymethyl cellulose for taking the above embodiment of the present invention two to be prepared to embodiment five, it is commercially available with purchase at random five batches Product, using GB 1886.232-2016 as foundation, contrast product physical and chemical index is as a result as shown in the table.
1 physical and chemical index of table contrasts
As seen from the above table, product of the present invention has bright in principal component content, substitution value, viscosity, loss on drying etc. It is aobvious to be better than commercial product.

Claims (4)

1. a kind of method that stalk cellulose component separates and prepares carboxymethyl cellulose, it is characterized in that, first by cellulose from Separated in stalk;Then, by the cellulose of acquisition, carboxymethyl cellulose is prepared into, is comprised the following steps that:
(1) alkalize
In kneader, by cellulose and sodium hydroxide ethanol solution according to mass ratio 1:2 under the conditions of 30-70 DEG C, kneader Rotating speed is 60-200r/min, alkalization 30-180min generation alkali cellulose;
(2) it is etherified
After the completion of alkalization, the monoxone ethanol solution of cellulose dosage 10-40% is added, is warming up to 40-80 DEG C, cocurrent adds fiber Plain 10% sodium hydroxide ethanol solution of dosage etherificate 30-180min generation carboxyl methyl celluloses;
(3) washing is neutralized
The CMC of etherificate generation is put into sink, is added mass percent concentration and is washed and neutralized for 3-10% dilute hydrochloric acid Excessive alkali is 5-8.5 to pH, is washed 3 times, and the salinity produced in reaction process enters in solution;
(4) centrifuge
The CMC washed is put into centrifuge and carries out solid-liquor separation, the dry process of filter cake Song Zhixia roads rake;
(5) rake is dry
Put into after filter cake after centrifugation is torn up in the dry machine of rake, it is dry to moisture 10-20%;
(6) dry
By through rake it is dry after CMC put into dryer and be dried, be dried in product moisture below 10%;
(7) blending is crushed
Material after drying, crushes by pulverizer, after winnowing machine, air-introduced machine, cyclone separator and vibrating screen, reaches rule Fixed product granularity, dress bag are got product.
2. the method that stalk cellulose component as claimed in claim 1 separates and prepares carboxymethyl cellulose, it is characterized in that, institute State the mass ratio m of sodium hydroxide and ethanol in sodium hydroxide ethanol solution:M=2:1-5:1.
3. the method that stalk cellulose component as claimed in claim 1 separates and prepares carboxymethyl cellulose, it is characterized in that, institute State the mass ratio m of monoxone and ethanol in monoxone ethanol solution:M=2:1-5:1.
4. the method that stalk cellulose component as claimed in claim 1 separates and prepares carboxymethyl cellulose, it is characterized in that, institute It is as follows to state the method that cellulose is separated from stalk:Take stalk tablet obtained by wet feed preparation to be sent to digester, while add 5 The clear water of amount again;Live steam is passed through, keeps the temperature 120 DEG C two hours, boiling terminates, and cooling preserves;Filtering, residue washing three times, It is 0.8% to add sulfuric acid Controlled acidity, and hydrolyzing 1h at 130 DEG C obtains hydrolyzate;Filter, in 0.5% hydroxide after residue washing Boiling 1h at 110 DEG C in sodium solution, filtering, filter residue is washed, dry cellulose.
CN201711035833.1A 2017-10-30 2017-10-30 The method that stalk cellulose component separates and prepares carboxymethyl cellulose Pending CN107903327A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1410451A (en) * 2001-10-05 2003-04-16 李长令 Method of producing carboxy methyl cellulose and xylose using straw
CN101434658A (en) * 2007-11-13 2009-05-20 宫卫东 Method for producing carboxymethyl cellulose from cotton stem
CN101456958A (en) * 2008-12-31 2009-06-17 中国科学技术大学 Method for preparing cellulose water-based solution by stalk

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1410451A (en) * 2001-10-05 2003-04-16 李长令 Method of producing carboxy methyl cellulose and xylose using straw
CN101434658A (en) * 2007-11-13 2009-05-20 宫卫东 Method for producing carboxymethyl cellulose from cotton stem
CN101456958A (en) * 2008-12-31 2009-06-17 中国科学技术大学 Method for preparing cellulose water-based solution by stalk

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
宋小平等: "《洗涤剂实用生产技术500例》", 30 March 2011, 中国纺织出版社 *

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Application publication date: 20180413