CN116410340A - Method for directly preparing lithium carboxymethyl cellulose by using straw/poplar - Google Patents
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 58
- 241000219000 Populus Species 0.000 title claims abstract description 55
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 55
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 54
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 54
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims abstract description 54
- 239000010902 straw Substances 0.000 title claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 239000000243 solution Substances 0.000 claims abstract description 72
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002904 solvent Substances 0.000 claims abstract description 67
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 43
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 238000006266 etherification reaction Methods 0.000 claims abstract description 16
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims abstract description 16
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000004061 bleaching Methods 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 20
- 238000002834 transmittance Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000007935 neutral effect Effects 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 229920002678 cellulose Polymers 0.000 description 13
- 239000001913 cellulose Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 7
- 239000011449 brick Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 4
- 235000019743 Choline chloride Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 4
- 229960003178 choline chloride Drugs 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 229960000448 lactic acid Drugs 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- OHXYLFVFSUFWPO-UHFFFAOYSA-M lithium;2-chloroacetate Chemical compound [Li+].[O-]C(=O)CCl OHXYLFVFSUFWPO-UHFFFAOYSA-M 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to the technical field of preparation of lithium carboxymethyl cellulose, and discloses a method for directly preparing lithium carboxymethyl cellulose by using straws or poplar. The method comprises the steps of pretreating straws or poplar by adopting a DES solvent, bleaching the pretreated straws or poplar and carrying out secondary pretreatment; adding a lithium hydroxide aqueous solution and a lithium borate auxiliary agent into a specific solvent system to obtain a mixed solution; dispersing the straws or poplar subjected to secondary pretreatment into a mixed solution for alkalization reaction; adding chloroacetic acid solution to carry out etherification reaction after the reaction to generate carboxymethyl cellulose lithium; the specific solvent system is isopropanol/tert-butanol, and the volume ratio of isopropanol to tert-butanol is 75:25. The preparation method provided by the invention simplifies the process method, shortens the reaction period, improves the utilization rate of raw materials, reduces the use frequency of corrosive reagents, and improves the substitution degree, viscosity, transmittance and yield of the prepared finished product of the carboxymethyl cellulose lithium.
Description
Technical Field
The invention relates to the technical field of preparation of lithium carboxymethyl cellulose, in particular to a method for directly preparing lithium carboxymethyl cellulose by using straws or poplar.
Background
The cellulose material is a biomass resource with special molecular structure and material characteristics, has the characteristics of environmental friendliness, low cost, abundant resources, good mechanical properties and stable chemical properties, and is widely focused by scientific researchers in the application field of lithium ion battery binders. Among them, sodium carboxymethyl cellulose (CMC-Na) is a cellulose-based binder that has been studied in many cases, and is used in a binder for a negative electrode of a lithium battery in many cases. However, sodium ions ionized by CMC-Na may have exchange reaction with lithium ions on the surface of the carbon negative electrode, so that the deintercalation efficiency of the lithium ions is reduced; the ionized sodium ions and electrolyte are easy to react, so that free moving lithium ions in the whole system can be reduced, the radius of the sodium ions is larger, the conductivity is lower, and the advantages of small volume, light weight, high energy and the like of the lithium battery can not be fully reflected.
The CMC-Li polymer material is prepared by replacing Na in CMC-Na with lithium (Li), and is a binder with good ionic conductivity besides inheriting the excellent characteristic of CMC-Na as a battery binder, so that the quantity of free mobile lithium ions in a battery can be effectively increased, the diffusion distance between the lithium ions and the surface of an active material is reduced, the lithium deintercalation efficiency of a positive and negative electrode material is improved, and the charge and discharge capacity and the cycle performance of the battery are improved. Therefore, CMC-Li with the same molecular structure is prepared by using lithium to replace sodium as a novel lithium battery binder, which is a development direction in the field and has extremely wide application value.
In the related art, most of refined cotton is used as a raw material to prepare the lithium carboxymethyl cellulose by an indirect method. The preparation of the carboxymethyl cellulose lithium by using the raw material purified cotton has the problems of long fiber, compact structure, difficult reaction of reagents entering the structure in the reaction process, high raw material price and the like. For the preparation process, the indirect method has the problems of long process period, complicated method, low utilization rate of raw materials in the process, frequent use of corrosive reagents and the like. However, few direct methods for preparing the lithium carboxymethyl cellulose still have a series of problems of low substitution degree, poor light transmittance, low viscosity, low raw material utilization rate and the like of the prepared lithium carboxymethyl cellulose.
Disclosure of Invention
In order to solve a series of problems of low substitution degree, low light transmittance, low viscosity, low material utilization rate, low yield and the like of a product obtained by a preparation method of carboxymethyl cellulose lithium in the prior art, the invention provides a method for directly preparing carboxymethyl cellulose lithium by using straws or poplar.
In order to solve the technical problems, the invention adopts the following technical scheme:
pre-treating straw or poplar with DES solvent, bleaching the pre-treated straw or poplar, and pre-treating for the second time; adding a lithium hydroxide aqueous solution and a lithium borate auxiliary agent into a specific solvent system to obtain a mixed solution; dispersing the straws or poplar subjected to secondary pretreatment into a mixed solution for alkalization reaction; adding chloroacetic acid solution to carry out etherification reaction after the reaction to generate carboxymethyl cellulose lithium;
wherein the specific solvent system is isopropanol/tert-butanol, and the volume ratio of isopropanol to tert-butanol is 75:25.
Using alcoholic DES solvents [ ChCl ]] 1 [EG] 5 And acid DES solvent [ ChCl ]] 1 [LA] 5 Sequentially treating straw or poplar, or using alcohol DES solvent [ ChCl ]] 1 [EG] 4 And acid DES solvent [ ChCl ]] 1 [LA] 4 Sequentially treating the straw or poplar. In particular, when the raw material is straw, the pretreatment can be carried out by adopting an acid DES solution [ ChCl ]] 1 [LA] 5 Alcohol DES solution [ ChCl ]] 1 [EG] 5 The method comprises the steps of carrying out a first treatment on the surface of the When the raw material is poplar, the pretreatment can be carried out by adopting an acid DES solution [ ChCl ]] 1 [LA] 4 Alcoholic DES solution [ ChCl ]] 1 [EG] 4 。
The poplar or straw is used as a raw material, is cheap and easy to obtain and wide in source, the pretreated poplar or straw is loose in structure, penetration and absorption of alkali solution and etherifying agent are facilitated, and the reaction efficiency of alkali solution and etherifying agent with cellulose is remarkably improved. Compared with refined cotton, the method has the advantage that poplar or straw is used as a raw material to be more favorable for the reaction preparation of carboxymethyl cellulose lithium.
Further, soaking the straw or poplar powder, performing suction filtration and washing, drying, grinding in a mortar, sieving, adding the sieved straw into a DES solvent, putting the mixture into a homogeneous phase for pretreatment, and performing suction filtration and washing until the reaction is finished and the mixture is neutral and dried; pretreatment is carried out by adopting acid DES solution [ ChCl ]] 1 [LA] 5 And alcoholic DES solutions [ ChCl ]] 1 [EG] 5 And respectively stirring choline chloride, lactic acid, choline chloride and ethylene glycol solution in a certain proportion at a constant temperature of 80 ℃ until a uniform colorless transparent clear liquid is formed. The solid-to-liquid ratio of the DES solvent to the raw material is 1:30, the pretreatment temperature of the acid DES solvent is 140 ℃, the pretreatment temperature of the alcohol DES solvent is 200 ℃, and the pretreatment time of the acid DES solvent and the alcohol DES solvent is 180min. Most lignin and hemicellulose in the raw materials are removed by pretreatment, the structure of the pretreated straw becomes loose, the permeation and absorption of alkali solution and etherifying agent are facilitated, and the reaction efficiency of the alkali solution and the etherifying agent with the cellulose is remarkably improved.
Further, a mixed bleaching reagent is used in bleaching, wherein the mixed bleaching reagent is sodium hypochlorite and hydrogen peroxide solution; the secondary pretreatment uses sodium hydroxide solution with mass fraction of 5-12%, the secondary pretreatment temperature is 70-90 ℃, and the secondary pretreatment time is 30-90 min. Bleaching and secondary pretreatment are intended to further delignify, allowing the cellulose to swell and fully prepare for the next alkalization.
Further, the mass ratio of the lithium borate solid to the straw/poplar is 0.045-0.075:1, and the solid-liquid ratio of the raw material straw/poplar to the solvent system is 1:40-47 g/ml.
Further, the concentration of the lithium hydroxide aqueous solution is 0.1g/ml to 0.15g/ml; the time of the alkalization reaction is 60-210 min, the temperature of the alkalization reaction is 25-45 ℃, more preferably, the time of the alkalization reaction is 60-180 min.
Considering the complex structure of cellulose itself, the alkali solution needs to be in sufficient contact with the cellulose, swell and permeate, and the process needs enough time. During the alkalization, the use efficiency of the etherifying agent in the etherification reaction process can be improved by adding a certain proportion of auxiliary lithium borate, and the substitution reaction is more facilitated by the increase of the concentration of the lithium chloroacetate due to the reaction of excessive chloroacetic acid and the lithium borate after the addition of the lithium borate, so that the substitution degree of the carboxymethyl cellulose lithium is finally improved.
The selection of the alkalizing reaction solvent is not limited by the related technology, and the components and the proportion of the components can be compatible, and the conventional solvent used for synthesizing the carboxymethyl cellulose lithium in the field can be basically selected in the field. The invention is careful in selecting the reaction solvent system, and the dispersibility, boiling point and solubility of the system are all critical. For example, although the solubility of a pure ethanol solution system is better, the system cannot reach the target temperature when the self boiling point is lower in the liquid state, so that the solubility of the system is reduced, the contact of materials is insufficient, the mass transfer rate is also slowed down, and the substitution degree of the product is reduced. For another example, 85% ethanol is lower in cost for pure ethanol and better in dissolution capacity than pure ethanol, but forms an azeotrope with water with less than the boiling point of pure ethanol. The self boiling point of the pure isopropanol solution of the single solvent is higher, the pure isopropanol solution can reach the target temperature, has better dispersing effect, improves the substitution degree, but still has low substitution degree. The common sense of the invention adopts mixed solvents of tertiary butanol and isopropanol, and when tertiary butanol is added into isopropanol, the substitution degree and viscosity of the carboxymethyl cellulose lithium are obviously improved along with the increase of the dosage of tertiary butanol. With the improvement of the substitution degree, the substitution groups of the carboxymethyl cellulose lithium molecules are gradually crosslinked in the system, so that the viscosity of the product is greatly improved. When the volume content of the tertiary butanol reaches 25 percent, the best effect is achieved, so that 75 percent of isopropanol/25 percent of tertiary butanol is selected as a reaction solvent system.
Further, the concentration of the chloroacetic acid solution is 0.15 g/ml-0.3 g/ml, and the dripping time of the etherifying agent solution into the reaction system is 30-50 min.
Further, the etherification reaction is divided into two stages, wherein the first stage reaction temperature is 35-55 ℃, the reaction time is 30-120 min, the second stage reaction temperature is 55-80 ℃, and the reaction time is 60-120 min.
The etherification process is mainly divided into two stages: lithium hydroxide reacts with chloroacetic acid, the generated lithium chloroacetate reacts with alkalized cellulose, and the reaction time of the two stages is particularly critical. In the etherification reaction process, chloroacetic acid needs to permeate into cellulose to react, if the reaction time is insufficient, the reaction is uneven, so that the product quality is poor, the substitution degree is low, and the viscosity is insufficient; meanwhile, the etherification reaction time needs to be strictly controlled in consideration of the utilization rate of equipment and energy cost consumption.
The reaction product after etherification reaction provided by the invention is neutralized, washed and dried to obtain the lithium carboxymethyl cellulose. Further, the neutralization process is to replace hydroxyl lithium in the product with hydroxyl, the neutralization reagent is acetic acid, and the neutralization is carried out until the pH=7-8; washing with 90% ethanol for at least 5 times until the filtrate obtained by dropwise adding one drop of potassium chromate solution and one drop of silver nitrate solution is brick red; drying at 80deg.C for 240min.
The method for directly preparing the carboxymethyl cellulose lithium by using poplar or straw is characterized in that the poplar is pretreated by a DES solution, a pretreatment flow chart is shown in figure 1, then the pretreated poplar is bleached and subjected to secondary pretreatment, then an alkalization reaction is carried out, a reaction solvent with specific composition and proportion is adopted in the alkalization process, an etherification auxiliary agent is added, and finally the reaction process of preparing the carboxymethyl cellulose lithium by the etherification reaction process is shown in figure 2. Compared with the prior art, the method for directly preparing the lithium carboxymethyl cellulose by the poplar has the following advantages:
the two DES solvents are sequentially pretreated to remove most of lignin and hemicellulose in the raw materials, the pretreated poplar or straw structure becomes loose, the penetration and absorption of alkali solution and etherifying agent are more facilitated, and the reaction efficiency of alkali solution and etherifying agent with cellulose is remarkably improved. Bleaching to further remove lignin and other impurities, and the sodium hydroxide subjected to secondary pretreatment plays roles in swelling, extracting cellulose and improving the efficiency of alkalization reaction.
All lithium hydroxide is added in the alkalization process, so that the alkali liquor and cellulose react more uniformly and sufficiently, the alkali absorption, swelling and permeation reaction are ensured to be sufficient, the alkali liquor used in the etherification process advances into the cellulose in advance, and then the etherifying agent is added to react more sufficiently and uniformly, thereby reducing the occurrence of side reaction, improving the etherification effect, and improving the substitution degree, viscosity and yield of reaction products.
In the alkalization process, isopropanol with the volume ratio content of 75 percent/tert-butanol with the volume ratio content of 25 percent is selected as a reaction solvent system, so that the substitution degree and the viscosity of the lithium carboxymethyl cellulose are obviously improved. In addition, the addition of the auxiliary agent lithium borate with a certain proportion can improve the use efficiency of the etherifying agent in the etherification reaction process, and finally, the substitution degree of the carboxymethyl cellulose lithium is optimal.
The method simplifies the process, shortens the reaction period, improves the utilization rate of raw materials, reduces the use frequency of corrosive reagents, and improves the substitution degree, viscosity, transmittance and yield of the prepared carboxymethyl cellulose lithium.
Drawings
FIG. 1 is a flow chart of raw material pretreatment provided by the invention;
FIG. 2 is a reaction flow chart for directly preparing lithium carboxymethyl cellulose from straws or poplar;
FIG. 3 is a graph of lithium carboxymethyl cellulose prepared in example 2 of the present invention and its formulation into a 1wt% CMC-Li solution;
FIG. 4 is a graph of lithium carboxymethyl cellulose prepared in example 3 of the present invention and its formulation into a 1wt% CMC-Li solution.
Detailed Description
The invention discloses a method for directly preparing carboxymethyl cellulose lithium by using straw or poplar, which can be realized by appropriately improving process parameters by a person skilled in the art with reference to the content of the invention. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included herein. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
The present invention will be described in further detail with reference to specific embodiments thereof so that those skilled in the art can better understand the present invention.
Example 1
Firstly, soaking straw powder for 480min, filtering, washing, then drying at 80 ℃, grinding in a mortar, and finally screening to 40 meshes, wherein the molar ratio is 1:5, respectively stirring at constant temperature of 80 ℃ until respectively forming uniform colorless transparent clear liquid-acid DES solution [ ChCl ]] 1 [LA] 5 And alcoholic DES solutions [ ChCl ]] 1 [EG] 5 . The solid-to-liquid ratio of the straw to the DES solution is 1:30g/ml, and the alcohol DES solution [ ChCl] 1 [EG] 5 The pretreatment temperature of (C) is 200 ℃, and the acid DES solution [ ChCl ]] 1 [LA] 5 The pretreatment temperature is 140 ℃, the pretreatment time of two times is 180 minutes, and the reaction is finished, filtered and washed until the reaction is neutral and dried.
The pretreated straw is reacted for 30min at 35 ℃ by sodium hypochlorite and hydrogen peroxide solution, is filtered, washed to be neutral at 50 ℃ and dried, and is reacted for 90min at 90 ℃ by sodium hydroxide solution with mass fraction of 5%, and is washed by deionized water and filtered to be neutral.
21ml of deionized water was added to the beaker, and then 2.4g of lithium hydroxide was dissolved in deionized water and sonicated for 30min. 120ml of 75% isopropanol/25% tertiary butanol solvent system and 0.135g of lithium borate with the following volume content ratio are added into a beaker, and the mixture is stirred uniformly. Adding the mixed solution into a reaction kettle, adding 3g of pretreated straw, starting stirring, and controlling the temperature to be 30 ℃ for reaction for 120min.
After the completion, 20ml of a chloroacetic acid solution (solvent: 75% isopropyl alcohol/25% t-butanol) was added dropwise to the reaction vessel, and the addition time was controlled to be 30 minutes, and the reaction was carried out at 45℃for 60 minutes and 65℃for 60 minutes.
Cooling to room temperature, and dropwise adding acetic acid until the neutralization reagent is acetic acid, wherein the neutralization reagent is acetic acid until the pH value is 7-8; washing with 90% ethanol for at least 5 times until the filtrate obtained by dropwise adding one drop of potassium chromate solution and one drop of silver nitrate solution is brick red; drying at 80 ℃ for 240min to obtain the finished product of the lithium carboxymethyl cellulose.
Example 2
Firstly, soaking straw powder for 480min, filtering, washing, then drying at 80 ℃, grinding in a mortar, and finally screening to 40 meshes, wherein the molar ratio is 1:5, and stirring at constant temperature of 80deg.C until homogeneous colorless transparent clear liquid-acid DES solvent [ ChCl ] is formed respectively] 1 [LA] 5 And an alcoholic DES solvent [ ChCl ]] 1 [EG] 5 . The solid-to-liquid ratio of straw to DES solution is 1:30g/ml, alcohol DES solvent [ ChCl] 1 [EG] 5 The pretreatment time of (C) is 200 ℃, and the acid DES solvent [ ChCl ]] 1 [LA] 5 The pretreatment time is 140 ℃, the pretreatment time is 180min for two times in sequence, and the reaction is finished, filtered and washed until the reaction is neutral and dried.
The pretreated straw is reacted for 30min at 35 ℃ by sodium hypochlorite and hydrogen peroxide solution, is filtered, washed to be neutral and dried, and is reacted for 60min at 80 ℃ by 10% sodium hydroxide solution, and is washed by deionized water and filtered to be neutral.
34ml of deionized water was added to the beaker, and then 4.5g of lithium hydroxide was dissolved in deionized water and sonicated for 30min. 141ml of 75% isopropyl alcohol/25% tertiary butanol solvent system and 0.18g of lithium borate were added to the beaker and stirred uniformly. Adding the mixed solution into a reaction kettle, adding 3g of the straw subjected to secondary pretreatment, starting stirring, and controlling the temperature to be 25 ℃ for reaction for 180min.
After completion, 20ml of a chloroacetic acid solution (solvent: 75% isopropyl alcohol/25% t-butanol) was added dropwise to the reaction vessel, and the dropwise addition time was controlled to be 50 minutes, followed by a reaction at 50℃for 60 minutes and a reaction at 75℃for 60 minutes.
Dropping acetic acid until the neutralization reagent is acetic acid after the temperature is reduced to room temperature, and neutralizing until the pH value is 7-8; washing with 90% ethanol for at least 5 times until the filtrate obtained by dropwise adding one drop of potassium chromate solution and one drop of silver nitrate solution is brick red; drying at 80 ℃ for 240min to obtain the finished product of the lithium carboxymethyl cellulose.
Example 3
Firstly, soaking poplar powder for 480min, filtering and washing, then drying at 80 ℃, grinding in a mortar, and finally screening to 40 meshes, wherein the molar ratio is 1:4, respectively stirring the choline chloride, the ethylene glycol, the choline chloride and the lactic acid solution at a constant temperature of 80 ℃ to respectively form two uniform, colorless and transparent clear liquid-alcohol DES solvents [ ChCl ]] 1 [EG] 4 And acid DES solvent [ ChCl ]] 1 [LA] 4 . The solid-to-liquid ratio of poplar to DES solution is 1:30g/ml, alcohol DES solvent [ ChCl] 1 [EG] 4 The pretreatment temperature of (C) is 200 ℃, and the acid DES solvent [ ChCl ]] 1 [LA] 4 The pretreatment temperature is 140 ℃, the pretreatment time is 180min for two times in sequence, and the reaction is finished, filtered and washed until the reaction is neutral and dried.
The pretreated poplar is reacted for 30min at 35 ℃ by sodium hypochlorite and hydrogen peroxide solution, filtered and washed to be neutral at 50 ℃ and dried, and then the poplar is reacted for 60min at 85 ℃ by 12% sodium hydroxide solution, washed by deionized water and filtered to be neutral.
34ml of deionized water was added to the beaker, and then 4.5g of lithium hydroxide was dissolved in deionized water and sonicated for 30min. 130ml of 75% isopropyl alcohol/25% tertiary butanol solvent system and 0.18g of lithium borate with the following volume contents are added into a beaker, and the mixture is stirred uniformly. Adding the mixed solution into a reaction kettle, adding 3g of poplar after secondary pretreatment, starting stirring, and controlling the temperature to be 25 ℃ for reaction for 180min.
After completion, 20ml of a chloroacetic acid solution (solvent: 75% isopropyl alcohol/25% t-butanol) was added dropwise to the reaction vessel, and the dropwise addition time was controlled to 40min, followed by a reaction at 40℃for 90min and a reaction at 55℃for 120min.
Dropping acetic acid until the neutralization reagent is acetic acid after the temperature is reduced to room temperature, and neutralizing until the pH value is 7-8; washing with 90% ethanol for at least 5 times until the filtrate obtained by dropwise adding one drop of potassium chromate solution and one drop of silver nitrate solution is brick red; drying at 80 ℃ for 240min to obtain the finished product of the lithium carboxymethyl cellulose.
Example 4
Firstly, soaking poplar powder for 480min, filtering and washing, then drying at 80 ℃, grinding in a mortar, and finally screening to 40 meshes, wherein the molar ratio is 1:4, and stirring at constant temperature of 80 ℃ to form two homogeneous colorless transparent clear liquid-alcohol DES solvent [ ChCl ]] 1 [EG] 4 And acid DES solvent [ ChCl ]] 1 [LA] 4 . The solid-to-liquid ratio of poplar to DES solution is 1:30g/ml, alcohol DES solvent [ ChCl] 1 [EG] 4 The pretreatment temperature of (C) is 200 ℃, and the acid DES solvent [ ChCl ]] 1 [LA] 4 The pretreatment temperature is 140 ℃, the pretreatment time is 180min for two times in sequence, and the reaction is finished, filtered and washed until the reaction is neutral and dried.
The poplar is reacted for 30min at 35 ℃ by sodium hypochlorite and hydrogen peroxide solution, filtered and washed to be neutral and dried at 50 ℃, and then the poplar is reacted for 90min at 70 ℃ by 10% sodium hydroxide solution, washed by deionized water and filtered to be neutral.
34ml of deionized water was added to the beaker, and then 4.5g of lithium hydroxide was dissolved in deionized water and sonicated for 30min. Then, 120ml of a solvent system of 75% isopropyl alcohol/25% tertiary butanol and 0.18g of lithium borate were added to the beaker and stirred uniformly. Adding the mixed solution into a reaction kettle, adding 3g of pretreated poplar, starting stirring, and controlling the temperature to be 35 ℃ for reaction for 120min.
After completion, 20ml of a chloroacetic acid solution (solvent: 75% isopropyl alcohol/25% t-butanol) was added dropwise to the reaction vessel, and the dropwise addition time was controlled to be 30 minutes, followed by reaction at 55℃for 30 minutes and at 60℃for 120 minutes.
Dropping acetic acid until the neutralization reagent is acetic acid after the temperature is reduced to room temperature, and neutralizing until the pH value is 7-8; washing with 90% ethanol for at least 5 times until the filtrate obtained by dropwise adding one drop of potassium chromate solution and one drop of silver nitrate solution is brick red; drying at 80 ℃ for 240min to obtain the finished product of the lithium carboxymethyl cellulose.
Example 5
Firstly, soaking straw powder for 480min, filtering, washing, then drying at 80 ℃, grinding in a mortar, and finally screening to 40 meshes, wherein the molar ratio is 1:5, and stirring at constant temperature of 80deg.C until homogeneous colorless transparent clear liquid-acid DES solvent [ ChCl ] is formed respectively] 1 [LA] 5 And an alcoholic DES solvent [ ChCl ]] 1 [EG] 5 . The solid-to-liquid ratio of straw to DES solution is 1:30g/ml, alcohol DES solvent [ ChCl] 1 [EG] 5 The pretreatment time of (C) is 200 ℃, and the acid DES solvent [ ChCl ]] 1 [LA] 5 The pretreatment time is 140 ℃, the pretreatment time is 180min for two times in sequence, and the reaction is finished, filtered and washed until the reaction is neutral and dried.
The pretreated straw is reacted for 30min at 35 ℃ by sodium hypochlorite and hydrogen peroxide solution, is filtered, washed to be neutral at 50 ℃ and dried, and then is reacted for 60min at 75 ℃ by 10% sodium hydroxide solution, and is washed by deionized water and filtered to be neutral.
34ml of deionized water was added to the beaker, and then 4.5g of lithium hydroxide was dissolved in deionized water and sonicated for 30min. 141ml of 75% isopropyl alcohol/25% tertiary butanol solvent system and 0.18g of lithium borate in the following volume content ratio were added into the beaker, and the mixture was stirred uniformly. Adding the mixed solution into a reaction kettle, adding 3g of pretreated straw, starting stirring, and controlling the temperature to be 45 ℃ for reaction for 60min.
After the completion, 20ml of a chloroacetic acid solution (solvent: 75% isopropyl alcohol/25% t-butanol) was added dropwise to the reaction vessel, and the addition time was controlled to be 30 minutes, and the reaction was carried out at 35℃for 120 minutes and at 80℃for 60 minutes.
Dropping acetic acid until the neutralization reagent is acetic acid after the temperature is reduced to room temperature, and neutralizing until the pH value is 7-8; washing with 90% ethanol for at least 5 times until the filtrate obtained by dropwise adding one drop of potassium chromate solution and one drop of silver nitrate solution is brick red; drying at 80 ℃ for 240min to obtain the finished product of the lithium carboxymethyl cellulose.
Example 6
Soaking poplar powder for 480min, filtering, washing, stoving at 80 deg.c, grinding in mortar,finally sieving to 40 meshes, wherein the molar ratio is 1:4, and stirring at constant temperature of 80 ℃ to form two homogeneous colorless transparent clear liquid-alcohol DES solvent [ ChCl ]] 1 [EG] 4 And acid DES solvent [ ChCl ]] 1 [LA] 4 . The solid-to-liquid ratio of poplar to DES solution is 1:30g/ml, alcohol DES solvent [ ChCl] 1 [EG] 4 The pretreatment temperature of (C) is 200 ℃, and the acid DES solvent [ ChCl ]] 1 [LA] 4 The pretreatment temperature is 140 ℃, the pretreatment time is 180min for two times in sequence, and the reaction is finished, filtered and washed until the reaction is neutral and dried.
The poplar is reacted for 30min at 35 ℃ by sodium hypochlorite and hydrogen peroxide solution, filtered and washed to be neutral and dried at 50 ℃, and then the poplar is reacted for 60min at 80 ℃ by 10% sodium hydroxide solution, washed by deionized water and filtered to be neutral.
40ml of deionized water was added to the beaker, and then 6g of lithium hydroxide was dissolved in deionized water and sonicated for 30min. 140ml of 75% isopropyl alcohol/25% tertiary butanol solvent system and 0.225g of lithium borate were then added to the beaker and stirred well. Adding the mixed solution into a reaction kettle, adding 3g of pretreated poplar, starting stirring, and controlling the temperature to be 45 ℃ for reaction for 60min.
After the completion, 20ml of a chloroacetic acid solution (solvent: 75% isopropyl alcohol/25% t-butanol) of 0.3g/ml was added dropwise to the reaction vessel, and the addition time was controlled to be 50 minutes, and the reaction was carried out at 50℃for 60 minutes and at 70℃for 90 minutes.
Dropping acetic acid until the neutralization reagent is acetic acid after the temperature is reduced to room temperature, and neutralizing until the pH value is 7-8; washing with 90% ethanol for at least 5 times until the filtrate obtained by dropwise adding one drop of potassium chromate solution and one drop of silver nitrate solution is brick red; drying at 80 ℃ for 240min to obtain the finished product of the lithium carboxymethyl cellulose.
Comparative example 1
The same procedure as in example 2 was used to prepare lithium carboxymethyl cellulose by direct straw conversion using 75% isopropanol/25% t-butanol as 85% ethanol.
Comparative example 2
The same procedure as in example 2 was used to prepare lithium carboxymethyl cellulose by direct straw conversion using 75% isopropanol/25% t-butanol as 100% ethanol.
Comparative example 3
The same procedure as in example 2 was used to prepare lithium carboxymethyl cellulose by direct straw conversion by changing 75% isopropanol/25% t-butanol to 100% isopropanol.
Comparative example 4
The same method as in example 3 is used for preparing the carboxymethyl cellulose lithium by the poplar direct method without adding the auxiliary agent lithium borate.
Comparative example 5
The same method as in example 3 was used to prepare lithium carboxymethyl cellulose by the direct poplar method, except that the step of pretreatment of poplar with DES solvent was omitted.
Comparative example 6
The same procedure as in example 2 was followed except that the DES solvent in the pretreatment was changed to an acid-type DES solvent [ ChCl ]] 1 [LA] 3 And an alcoholic DES solvent [ ChCl ]] 1 [EG] 3 The method is used for preparing the lithium carboxymethyl cellulose by a straw direct method.
Test example 1
About 1.0g of the carboxymethyl cellulose lithium prepared in the examples and the comparative examples is weighed and placed in a corundum crucible, carbonized on an electric furnace until no smoke is generated, placed in a high-temperature furnace at 300 ℃, heated to 750 ℃, kept at the temperature for more than 15min, cooled to below 200 ℃, transferred into a 250mL conical flask, washed with 100mL of water for several times, 50mL of sulfuric acid standard titration solution (0.05 mol/L) is added, the beaker is placed on the electric furnace and heated, slowly boiled for 10min, 2 drops of methyl red indicator liquid (1 g/L) are added, cooled, and titrated with sodium hydroxide standard titration solution until red is just faded (0.1 mol/L).
The CMC-Li sample prepared in each example and comparative example was weighed 2.5g (0.5 wt% solution was prepared) of CMC-Li dried at 105℃for 2 hours, accurately to 0.001g for use, 492.5ml of water was measured to a jar, the jar was placed on a heating mantle, the rotational speed was adjusted to 200-400 r/min, the sample was slowly added, and the stirring speed was slowly adjusted to 900r/min until the sample was completely dissolved uniformly, until the sample was completely added to the solution. The test results are shown in Table 1.
Degree of Substitution (DS): c (C) b ＝(2V H2SO4 ×C H2SO4 -V NaOH ×C NaOH )/m；
DS＝0.162×C b /1-(0.064×C b )。
Viscosity (η): η = reading
Table 1 results of the substitution degree and viscosity test of lithium carboxymethyl cellulose prepared in examples and comparative examples
The data in Table 1 show that the lithium carboxymethyl cellulose obtained by the preparation method provided by the invention is more outstanding in terms of substitution degree and viscosity.
Test example 2
The lithium carboxymethyl cellulose prepared in each example and comparative example was prepared as a 1wt% cmc-Li solution, and the absorbance a, which is the absorption of ultraviolet light by the sample, was measured in an ultraviolet detector, so that the transmittance, transmittance and yield data of the aqueous lithium carboxymethyl cellulose solution were calculated and shown in table 2.
Transmittance (T): t=10 -A
Yield: CMC-Li yield= (actual mass of CMC-Li/theoretical mass of CMC-Li) ×100%
Table 2 results of transmittance and yield tests of lithium carboxymethyl cellulose prepared in examples and comparative examples
The data in Table 2 show that the yield and the transmittance of the carboxymethyl cellulose lithium prepared by the embodiment of the invention are better, and the method for directly preparing the carboxymethyl cellulose lithium by using the straws or poplar provided by the invention improves the yield and the quality of CMC-Li products in the aspect of transmittance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for directly preparing carboxymethyl cellulose lithium by using straw/poplar is characterized by comprising the following steps: pre-treating straw or poplar with DES solvent, bleaching the pre-treated straw or poplar, and pre-treating for the second time; adding a lithium hydroxide aqueous solution and a lithium borate auxiliary agent into a specific solvent system to obtain a mixed solution; dispersing the straws or poplar subjected to secondary pretreatment into a mixed solution for alkalization reaction; adding chloroacetic acid solution to carry out etherification reaction after the reaction to generate carboxymethyl cellulose lithium;
wherein the specific solvent system is isopropanol/tert-butanol, and the volume ratio of isopropanol to tert-butanol is 75:25.
2. The method of claim 1, wherein: using alcoholic DES solvents [ ChCl ]] 1 [EG] 5 And acid DES solvent [ ChCl ]] 1 [LA] 5 Sequentially treating straw or poplar, or using alcohol DES solvent [ ChCl ]] 1 [EG] 4 And acid DES solvent [ ChCl ]] 1 [LA] 4 Sequentially treating the straw or poplar.
3. A method according to claim 1 or 2, characterized in that: the solid-liquid ratio of the straw or poplar to the DES solvent is 1:30, the pretreatment temperature of the alcohol DES solvent is 200 ℃, the pretreatment temperature of the acid DES solvent is 140 ℃, and the pretreatment time is 180min.
4. The method of claim 1, wherein: the bleaching process uses a mixed bleaching reagent, wherein the mixed bleaching reagent is sodium hypochlorite and hydrogen peroxide solution; the secondary pretreatment uses sodium hydroxide solution with mass fraction of 5-12%, the secondary pretreatment temperature is 70-90 ℃, and the secondary pretreatment time is 30-90 min.
5. The method of claim 1, wherein: the mass ratio of the lithium borate solid to the straw/poplar is 0.045-0.075:1, and the solid-liquid ratio of the raw material straw/poplar to the solvent system is 1:40-47 g/ml.
6. The method of claim 1 or 5, wherein: the concentration of the lithium hydroxide aqueous solution is 0.1 g/ml-0.15 g/ml; the time of the alkalization reaction is 60-210 min, and the temperature of the alkalization reaction is 25-45 ℃.
7. The method of claim 1, wherein: the concentration of the chloroacetic acid solution is 0.15 g/ml-0.3 g/ml, and the dripping time of the etherifying agent solution in the reaction system is 30-50 min.
8. The method of claim 1 or 7, wherein: the etherification reaction is divided into two stages, wherein the first stage reaction temperature is 35-55 ℃, the reaction time is 30-120 min, the second stage reaction temperature is 55-80 ℃, and the reaction time is 60-120 min.
9. The method of claim 1, wherein: and neutralizing, washing and drying the reaction product after the etherification reaction to obtain the lithium carboxymethyl cellulose.
10. The method of claim 9, wherein: the neutralizing agent is acetic acid; at least 5 times of washing with 90% ethanol; the temperature of the drying is 80 ℃ and the drying time is 240min.
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