CN105884907A - Method for separating components of straws to prepare ultralow-viscosity carboxymethyl cellulose - Google Patents
Method for separating components of straws to prepare ultralow-viscosity carboxymethyl cellulose Download PDFInfo
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- CN105884907A CN105884907A CN201610508682.6A CN201610508682A CN105884907A CN 105884907 A CN105884907 A CN 105884907A CN 201610508682 A CN201610508682 A CN 201610508682A CN 105884907 A CN105884907 A CN 105884907A
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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]
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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
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
Abstract
The invention discloses a method for separating components of straws to prepare ultralow-viscosity carboxymethyl cellulose. The method comprises the following steps: first performing acid hydrolysis on hemicellulose of the straws to obtain fermentable monosaccharide; then extracting lignin of the straws to obtain high-activity lignin by adopting an organic solvent method; next refining cellulose to obtain high-purity and low-polymerization-degree straw cellulose by adopting an alkaline oxidation method; finally performing etherifying modification on the straw cellulose to prepare the carboxymethyl cellulose. According to the method, the ultralow-viscosity carboxymethyl cellulose can be obtained, the hemicelluloses and the lignin of the straws can be separated and resourcefully utilized, and the prepared ultralow-viscosity carboxymethyl cellulose is apparently in a white or yellowish powder state, and has the characteristics of high purity, low viscosity, high dissolution speed and high transparency.
Description
Technical field
The present invention relates to agricultural-forestry biomass utilization of resources field, be specifically related to a kind of straw component separation and prepare ultra low viscosity carboxymethyl
The method of cellulose.
Background technology
Carboxymethyl cellulose owing to there is excellent thickening, disperseing, suspend, bond, protect the performance such as moisture, protecting colloid,
Have been widely used for food, medicine, daily chemical industry, textile industry, paper industry and field of petrochemical industry.Along with
The market difference to carboxymethyl cellulose quality requirements so that it is be gradually divided into the different viscosities scope such as high, medium and low, ultralow many
Plant type product.Ultra low viscosity carboxymethyl cellulose is as in the sizing agent of painting processing paper production process, Process of Oil Well Drilling
Sizing agent in fluid loss additive and fabrication processes has higher economic worth and the bigger market demand.
The raw material preparing carboxymethyl cellulose at present is usually purified cotton and wood pulp, its starving, and production cost is higher.
Additionally, ultra low viscosity carboxymethyl cellulose to be produced, the later stage needs to use oxidant that carboxymethyl cellulose is carried out viscosity reduction, causes
Whole production technology is complex.China is large agricultural country, can produce 6～700,000,000 tons of agricultural crop straws every year, but these resources
Not obtaining rational development and utilization, except small part is used for making fertilizer and feedstuff, major part is incinerated, abandons and cause sternly
The wasting of resources of weight and environmental pollution.Agricultural crop straw belongs to lignocellulose raw material, mainly by cellulose, hemicellulose and
The big component of lignin three is constituted.All there are 3 hydroxyls on cellulose each glucose basic ring, can be etherified, be esterified, be grafted altogether
Poly-grade is reacted, thus synthesizes the cellulose-based derivatives such as carboxymethyl cellulose, cellulose acetate.Hemicellulose is non-homogeneous polysaccharide,
Mainly it is made up of unit such as xylose, arabinose, glucose, mannose, galactose, is easily acid hydrolysis generation fermentable
Monosaccharide.Hemicellulose hydrolysate can produce the chemical products such as biogas, ethanol, butanol by microbial metabolism.Lignin is benzene
Base propane construction unit is by ester bond, ehter bond and the macromolecule polyalcohol of carbon-carbon bond composition.Use the lignin of organic solvent extraction
Remain various active group, be a kind of good industrial chemicals, can pass through alcoholysis, sulfonation, acylated, alkylation, halogenation,
The lignin-base derivants such as the multiple chemical reactive synthesis phenols fuel such as polycondensation and graft copolymerization, lignosulfonates, epoxy resin.
Owing in stalk, cellulose, hemicellulose and the big component of lignin three are mutually wound around composition again by hydrogen bond and chemical bond
Miscellaneous structure, causes using single preprocess method cannot realize straw component and separates and comprehensive utilization.
Chinese patent application CN101985479A discloses preparation and the application of carboxymethyl cellulose of wheat straw, by wheat stalk
Use diluted alkaline pretreatment after pulverizing, bleach, alkalize after with chloroacetate reaction, then etherificate obtain carboxymethyl cellulose of wheat straw.
Chinese patent application CN103408671A utilizes the method that agricultural crop straw produces carboxymethyl cellulose and sodium lignin sulfonate, adopts
Producing sodium lignin sulfonate with one kettle way, its residual fiber element is through bleaching, then pulverizes, and is then etherified, produces carboxymethyl
Cellulose.Chinese patent application CN104894185A discloses a kind of method preparing sodium carboxymethyl cellulose from straw, uses
Compound bio catalyst and composite reaction catalyst prepare stalk cellulose, and then etherification modified prepare carboxymethyl cellulose.Above-mentioned
Patent application does not make full use of agricultural crop straw hemicellulose and lignin component, and resource utilization is relatively low.Chinese patent application
CN101857639A discloses a kind of method that residue using corn straw to produce biological butanol prepares sodium carboxymethyl cellulose,
Use steam explosion to extract the hydrolysis of hemicellulose desmoenzyme and obtain fermentable sugars, then utilize alkali density lignin to obtain slag charge warp again
Bleaching washing obtains the fibre stuff for preparing sodium carboxymethyl cellulose.Steam explosion pretreatment needs under high-temperature and high-pressure conditions
Carry out (170 DEG C, 15～17kg/cm2), its energy consumption is higher, and the hemicellulose of gained need to use relatively costly enzyme hydrolysis further
Mode obtains fermentable sugars；Secondly using alkali density lignin can produce a large amount of black liquor, alkali collection cost is high, black liquor difficult treatment；
Additionally, making the carboxymethyl cellulose viscosity obtained in aforementioned manners is 35～6500mPa.s, it is impossible to obtain the carboxymethyl of ultra-low viscosity
Cellulose.Chinese patent application CN102367279A discloses a kind of cotton fiber and prepares the system of ultralow-viscosity sodium carboxymethyl cellulose
Preparation Method, uses thinner that gossypin and etherification product have been carried out twice viscosity reduction and obtains ultralow-viscosity sodium carboxymethyl cellulose
(8～17mPa.s), the method needs repeatedly viscosity reduction and follow-up needs to remove thinner.
Summary of the invention
For solving the problems referred to above, the invention provides a kind of method that ultra low viscosity carboxymethyl cellulose is prepared in straw component separation,
The monosaccharide that can ferment is obtained initially with Acid hydrolysis stalk hemicellulose；Secondly use organic solvent method to extract straw lignin to obtain
High activity lignin；Then alkaline oxygenated method refined cellulose is used, it is thus achieved that high-purity, the stalk cellulose of low polymerization degree；?
Stalk cellulose carries out etherification modified carboxymethyl cellulose of preparing afterwards, and the application can not only obtain the carboxymethyl cellulose of ultra-low viscosity
Element, and achieve stalk hemicellulose and the separation of lignin and recycling.
The present invention is achieved by the following technical programs:
It is an object of the invention to provide a kind of method that ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, including walking as follows
Rapid:
(1) preparation of hemicellulose hydrolysate: by crushed stalk to 20～80 mesh, add mass fraction be 0.5%～5% inorganic
Acid solution, described straw is 1:5～20 with the solid-to-liquid ratio of described inorganic acid solution, and reaction temperature is 100 DEG C～150 DEG C, during reaction
Between be 0.5h～5h, obtain hemicellulose hydrolysate after filtration, filtering residue washes with water, is filtrated to get a pretreatment filtering residue；
(2) preparation of lignin: adding mass fraction in the pretreatment filtering residue obtained in step (1) is 30%～80%
Organic solvent, the solid-to-liquid ratio of a described pretreatment filtering residue and described organic solvent solution is 1:6～20, and reaction temperature is
140 DEG C～200 DEG C, the response time is 0.5h～3h, obtains reactant liquor and secondary pretreatment filtering residue, described secondary pretreatment after filtration
Filtering residue is first with the organic solvent washing that mass fraction is 30%～80%, then with 80 DEG C of hot washes, is filtrated to get secondary pretreatment
Residue and organic solvent washing liquid, merge described reactant liquor and organic solvent washing liquid, add 2 times of volumes of this merging solution
Being adjusted to pH2～3 with acid after water, lignin containing organic solvent is collected by filtration, organic solvent is reclaimed by decompression distillation,
Obtain lignin；
(3) preparation of stalk cellulose: adding mass fraction in step (2) described secondary pretreatment residue is 0.5%～5%
Alkali and the aqueous solution of hydrogen peroxide that mass fraction is 1%～5%, solid-to-liquid ratio is 1:6～15, and reaction temperature is 50 DEG C～100 DEG C,
Response time is 2h～8h, washes solid residue with water and dries, obtain stalk cellulose after filtration；
(4) preparation of ultra low viscosity carboxymethyl cellulose: step (3) described stalk cellulose is carried out etherification modified, including
Following steps,
A) described stalk cellulose carrying out basification, the mass ratio of described stalk cellulose and alkali is 0.5:2, cellulose with
The ratio of organic solvent is 1:10～16, and alkalization temperature is 20 DEG C～40 DEG C, and the time is 0.5h～3h；
B) in the alkalizing solution of described step a, add sodium chloroacetate and carry out etherification reaction, described stalk cellulose and described chlorine
The mass ratio of sodium acetate is 1:1～2, and etherification reaction temperature is 40 DEG C～80 DEG C, and the etherification reaction time is 0.5h～3h；
C) after etherification reaction terminates, being neutralized with acid, being adjusted to pH is 7～8, precipitates 2～3 with organic solvent washing after sucking filtration
Secondary, then dry, obtain ultra low viscosity carboxymethyl cellulose.In the application, solid-to-liquid ratio refers to the mixed proportion of solid and liquid,
Unit is g/mL.
The application uses acid hydrolysis and alkaline oxygenated bleaching protocols reduce cellulosic degree of polymerization, successfully prepare ultra low viscosity carboxymethyl
Cellulose, prepared sodium carboxymethyl cellulose, apparent condition is white or micro-yellow powder, have that purity is high, viscosity is low,
The feature that dissolution velocity is fast, transparency is good.
Preferably, described straw one in wheat stalk, rice straw, corn straw or bagasse.
Preferably, mineral acid one in hydrochloric acid, sulphuric acid, nitric acid or phosphoric acid in described step (1).
Preferably, organic solvent one in methanol, ethanol, isopropanol or acetone in described step (2).
Preferably, alkali one in sodium hydroxide, potassium hydroxide, calcium hydroxide in described step (3).
Preferably, alkali one in sodium hydroxide or potassium hydroxide in described step (4).
Preferably, in described step (4), organic solvent is selected from the one in ethanol, isopropanol, the tert-butyl alcohol.
The invention has the beneficial effects as follows:
1, the invention provides a kind of method that ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, described method uses useless
The agricultural crop straw abandoned is raw material, it is to avoid the waste of resource, effectively reduces production cost；
2, the invention provides a kind of method that ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, described method uses acid
Hydrolyzing straw hemicellulose obtains the monosaccharide that can ferment, and organic solvent extracting straw lignin obtains high activity lignin, remains straw
Cellulose obtains carboxymethyl cellulose through refining with etherification modified, it is achieved that straw component separates and recycling, improves straw
Stalk utilization rate；
3, the invention provides a kind of method that ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, described method uses acid
Hydrolysis and two kinds of means of alkaline oxygenated method reduce cellulosic degree of polymerization, are successfully prepared ultra low viscosity carboxymethyl cellulose；
4, the invention provides a kind of method that ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, prepare in this way
Sodium carboxymethyl cellulose, apparent condition is white or micro-yellow powder, have that purity is high, viscosity is low, dissolution velocity is fast,
The feature that transparency is good.
Detailed description of the invention
Below in conjunction with instantiation, it is further elucidated with the present invention.It should be understood that these embodiments are merely to illustrate the present invention, and
It is not intended to limit the scope of the invention.Technical staff makes according to the present invention in actual applications improvement and adjustment, still belong to
In protection scope of the present invention.
Except special instruction, equipment and raw material that the present invention uses are the art routine commercial products.
A kind of method that ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, comprises the steps:
(1) preparation of hemicellulose hydrolysate: by crushed stalk to 20～80 mesh, add the nothing that mass fraction is 0.5%～5%
Machine acid solution, described straw is 1:5～20 with the solid-to-liquid ratio of described inorganic acid solution, and reaction temperature is 100 DEG C～150 DEG C, reaction
Time is 0.5h～5h, obtains hemicellulose hydrolysate after filtration, and filtering residue washes with water, is filtrated to get a pretreatment filtering residue；
(2) preparation of lignin: adding mass fraction in the pretreatment filtering residue obtained in step (1) is 30%～80%
Organic solvent, the solid-to-liquid ratio of a described pretreatment filtering residue and described organic solvent solution is 1:6～20, and reaction temperature is
140 DEG C～200 DEG C, the response time is 0.5h～3h, obtains reactant liquor and secondary pretreatment filtering residue, described secondary pretreatment after filtration
Filtering residue is first with the organic solvent washing that mass fraction is 30%～80%, then with 80 DEG C of hot washes, is filtrated to get secondary pretreatment
Residue and organic solvent washing liquid, merge described reactant liquor and organic solvent washing liquid, add 2 times of volumes of this merging solution
Being adjusted to pH2～3 with acid after water, lignin containing organic solvent is collected by filtration, organic solvent is reclaimed by decompression distillation,
Obtain lignin；
(3) preparation of stalk cellulose: adding mass fraction in step (2) described secondary pretreatment residue is 0.5%～5%
Alkali and the aqueous solution of hydrogen peroxide that mass fraction is 1%～5%, solid-to-liquid ratio is 1:6～15, and reaction temperature is 50 DEG C～100 DEG C,
Response time is 2h～8h, washes solid residue with water and dries, obtain stalk cellulose after filtration；
(4) preparation of ultra low viscosity carboxymethyl cellulose: step (3) described stalk cellulose is carried out etherification modified, including
Following steps,
A) described stalk cellulose carrying out basification, the mass ratio of described stalk cellulose and alkali is 0.5:2, cellulose with
The ratio of organic solvent is 1:10～16, and alkalization temperature is 20 DEG C～40 DEG C, and the time is 0.5h～3h；
B) in the alkalizing solution of described step a, add sodium chloroacetate and carry out etherification reaction, described stalk cellulose and described chlorine
The mass ratio of sodium acetate is 1:1～2, and etherification reaction temperature is 40 DEG C～80 DEG C, and the etherification reaction time is 0.5h～3h；
C) after etherification reaction terminates, being neutralized with acid, being adjusted to pH is 7～8, precipitates 2～3 with organic solvent washing after sucking filtration
Secondary, then dry, obtain ultra low viscosity carboxymethyl cellulose.
Embodiment 1
Take wheat stalk that 300g sieves in autoclave, add the sulfuric acid solution 1500mL that mass fraction is 0.5%,
Being incubated 2h under the conditions of 150 DEG C, reaction end carries out solid-liquid separation, collects hemicellulose hydrolysate, and filtering residue washes with water, obtains
Pretreatment filtering residue.
Joining in autoclave by a pretreatment filtering residue, adding mass fraction is 30% methanol solution 3000mL, at 200 DEG C
Under the conditions of be incubated 0.5h, reaction end carry out solid-liquid separation, obtain methanol reactant liquor and secondary pretreatment filtering residue after filtration, use matter
Amount mark is 80% methanol solution washing secondary pretreatment filtering residue, then washs secondary pretreatment filtering residue with 80 DEG C of hot water,
To methanol cleaning mixture and secondary pretreatment residue, merge methanol reactant liquor and methanol cleaning mixture, add 2 times of volumes of solution after merging
Water and with acid for adjusting pH 2～3, solid-liquid separation obtains the lignin containing methanol, and methanol reclaims, i.e. through decompression distillation
Prepare lignin.
Secondary pretreatment residue adds and contains the sodium hydroxide that mass fraction is 0.5% and the hydrogen peroxide that mass fraction is 5%
Alkaline oxygenated solution 2500mL, reacts 6h under the conditions of 100 DEG C, and reaction end carries out solid-liquid separation, washes solid residue with water,
Pulverize after solid residue is dried, obtain stalk cellulose.
Stalk cellulose carries out basification, and stalk cellulose is 1:0.5, stalk cellulose and second with the mass ratio of sodium hydroxide
The solid-to-liquid ratio of alcoholic solution is 1:16 (g/mL), and alkalization temperature is 20 DEG C, and the time is 3h, adds sodium chloroacetate in alkalizing solution
Carrying out etherification reaction, stalk cellulose is 1:2 with the mass ratio of sodium chloroacetate, and etherification reaction temperature is 60 DEG C, during etherification reaction
Between be 2h.After etherification reaction terminates, being neutralized with the acetic acid solution that mass fraction is 90%, regulation pH is 7～8, sucking filtration
Precipitating 2～3 times by washing with alcohol that mass fraction is 80% afterwards, then dry, obtaining substitution value is 0.90 and viscosity is 18mPa s
Carboxymethyl cellulose.
Embodiment 2
Take rice straw that 300g sieves in autoclave, add the hydrochloric acid solution 2500mL that mass fraction is 1.5%,
Being incubated 0.5h under the conditions of 140 DEG C, reaction end carries out solid-liquid separation, collects hemicellulose hydrolysate, and filtering residue washes with water, obtains
Pretreatment filtering residue.
Pretreatment filtering residue is joined in autoclave, adds the aqueous isopropanol 1500mL that mass fraction is 55%,
Being incubated 1.5h under the conditions of 170 DEG C, reaction end carries out solid-liquid separation, obtains isopropanol reaction liquid and secondary pretreatment after filtration
Filtering residue, washs secondary pretreatment filtering residue with the aqueous isopropanol that mass fraction is 55%, then filters secondary pretreatment with 80 DEG C of hot water
Slag washs, and obtains isopropanol cleaning mixture and secondary pretreatment residue, merges isopropanol reaction liquid and isopropanol cleaning mixture, adds
Entering the water of 2 times of volumes of solution after merging and with acid for adjusting pH 2～3, solid-liquid separation obtains the lignin containing isopropanol, in liquid
Isopropanol through decompression distillation reclaim, i.e. prepare lignin.
Secondary pretreatment residue adds and contains the potassium hydroxide that mass fraction is 2% and the alkali of the hydrogen peroxide that mass fraction is 3%
Property oxidation solution 2500mL, under the conditions of 70 DEG C react 6h, reaction end carry out solid-liquid separation, wash solid residue with water,
Pulverize after solid residue is dried, obtain stalk cellulose.
Stalk cellulose carries out basification, and stalk cellulose is 1:0.8 with the mass ratio of potassium hydroxide, and stalk cellulose is with different
The ratio of propanol solution is 1:12 (g/mL), and alkalization temperature is 30 DEG C, and the time is 2h, adds sodium chloroacetate and enter in alkalizing solution
Row etherification reaction, the mass ratio of cellulose and sodium chloroacetate is 1:1.5, and etherification reaction temperature is 40 DEG C, and the etherification reaction time is
3h.After etherification reaction terminates, being neutralized with the acetic acid solution that mass fraction is 90%, regulation pH is 7～8, uses matter after sucking filtration
Amount mark is the isopropanol washing precipitation 2～3 times of 80%, then dries, and obtaining substitution value is 0.77 and viscosity is 18mPa s
Carboxymethyl cellulose.
Embodiment 3
Take corn straw that 300g sieves in autoclave, add the phosphoric acid solution 3000mL that mass fraction is 4%,
Being incubated 5h under the conditions of 100 DEG C, reaction end carries out solid-liquid separation, collects hemicellulose hydrolysate, and filtering residue washes with water, obtains
Pretreatment residue.
Pretreatment residue is joined in autoclave, adds the acetone soln 1500mL that mass fraction is 45%,
Being incubated 3h under the conditions of 150 DEG C, reaction end carries out solid-liquid separation, obtains acetone reactant liquor and secondary pretreatment filtering residue after filtration,
Wash secondary pretreatment filtering residue with the acetone soln that mass fraction is 45%, then with 80 DEG C of hot water, secondary pretreatment filtering residue is washed
Wash, obtain washing with acetone liquid and secondary pretreatment residue, merge acetone reactant liquor and washing with acetone liquid, add solution 2 after merging
The water of times volume with acid for adjusting pH 2～3, solid-liquid separation obtains the lignin containing acetone, by the acetone in liquid through decompression
Distillation is reclaimed, and i.e. prepares lignin.
Secondary pretreatment residue adds and contains the calcium hydroxide that mass fraction is 2% and the alkali of the hydrogen peroxide that mass fraction is 4%
Property oxidation solution 2500mL, under the conditions of 75 DEG C react 8h, reaction end carry out solid-liquid separation, wash solid residue with water,
Pulverize after solid residue is dried, obtain stalk cellulose.
Stalk cellulose carries out basification, and cellulose is 1:1 with the mass ratio of sodium hydroxide, cellulose and t-butanol solution
Ratio is 1:10 (g/mL), and alkalization temperature is 30 DEG C, and the time is 1h, adds sodium chloroacetate and carry out etherification reaction in alkalizing solution,
Cellulose is 1:1.2 with the mass ratio of sodium chloroacetate, and etherification reaction temperature is 65 DEG C, and the etherification reaction time is 2.5h.Etherification reaction
After end, being neutralized with the acetic acid solution that mass fraction is 90%, regulation pH is 7～8, is 80% with mass fraction after sucking filtration
The tert-butyl alcohol washing precipitation 2～3 times, then dry, obtain the carboxymethyl cellulose that substitution value is 0.83 and viscosity is 12mPa s.
Embodiment 4
Take bagasse that 300g sieves in autoclave, add the salpeter solution 6000mL that mass fraction is 3%,
Being incubated 2.5h under the conditions of 125 DEG C, reaction end carries out solid-liquid separation, collects hemicellulose hydrolysate, and filtering residue washes with water, obtains
Pretreatment filtering residue.
Pretreatment filtering residue is joined in autoclave, adds the ethanol solution 2000mL that mass fraction is 80%,
Being incubated 5h under the conditions of 140 DEG C, reaction end carries out solid-liquid separation, obtains ethanol synthesis liquid and secondary pretreatment filtering residue after filtration,
Wash secondary pretreatment filtering residue with the ethanol solution that mass fraction is 30%, then with 80 DEG C of hot water, secondary pretreatment filtering residue is washed
Wash, obtain ethanol washes and secondary pretreatment residue, merge ethanol synthesis liquid and ethanol washes, add solution 2 after merging
The water of times volume with acid for adjusting pH 2～3, solid-liquid separation obtains the lignin containing ethanol, and the ethanol in liquid steams through decompression
Evaporate and reclaim, i.e. prepare lignin.
Secondary pretreatment residue adds and contains the calcium hydroxide that mass fraction is 5% and the alkali of the hydrogen peroxide that mass fraction is 3%
Property oxidation solution 2500mL, under the conditions of 80 DEG C react 2h, reaction end carry out solid-liquid separation, wash solid residue with water,
Pulverize after solid residue is dried, obtain stalk cellulose.
Stalk cellulose is carried out the ratio that mass ratio is 1:2, cellulose and ethanol solution of basification, cellulose and potassium hydroxide
For 1:15 (g/mL), alkalization temperature is 40 DEG C, and the time is 0.5h.In alkalizing solution, add sodium chloroacetate carry out etherification reaction,
Cellulose is 1:1 with the mass ratio of sodium chloroacetate, and etherification reaction temperature is 80 DEG C, and the etherification reaction time is 0.5h.Etherification reaction
After end, being neutralized with the acetic acid solution that mass fraction is 90%, regulation pH is 7～8, is 80% with mass fraction after sucking filtration
Washing with alcohol precipitate 2～3 times, then dry, obtain the carboxymethyl cellulose that substitution value is 0.85 and viscosity is 15mPa s.
Embodiment 5
Take wheat straw that 300g sieves in autoclave, add the phosphoric acid solution 4500mL that mass fraction is 5%,
Being incubated 3h under the conditions of 105 DEG C, reaction end carries out solid-liquid separation, collects hemicellulose hydrolysate, and filtering residue washes with water, obtains
Pretreatment filtering residue.
Pretreatment filtering residue is joined in autoclave, adds the ethanol solution 2000mL that mass fraction is 80%,
Being incubated 5h under the conditions of 160 DEG C, reaction end carries out solid-liquid separation, obtains ethanol synthesis liquid and secondary pretreatment filtering residue after filtration,
Wash secondary pretreatment filtering residue with the ethanol solution that mass fraction is 55%, then with 80 DEG C of hot water, secondary pretreatment filtering residue is washed
Wash, obtain ethanol washes and secondary pretreatment residue, merge ethanol synthesis liquid and ethanol washes, add solution 2 after merging
The water of times volume with acid for adjusting pH 2～3, solid-liquid separation obtains the lignin containing ethanol, and the ethanol in liquid steams through decompression
Evaporate and reclaim, i.e. prepare lignin.
Secondary pretreatment residue adds and contains the sodium hydroxide that mass fraction is 3% and the alkali of the hydrogen peroxide that mass fraction is 1%
Property oxidation solution 2500mL, under the conditions of 50 DEG C react 8h, reaction end carry out solid-liquid separation, wash solid residue with water,
Pulverize after solid residue is dried, obtain stalk cellulose.
Stalk cellulose is carried out the ratio that mass ratio is 1:2, cellulose and ethanol solution of basification, cellulose and potassium hydroxide
For 1:15 (g/mL), alkalization temperature is 40 DEG C, and the time is 0.5h.In alkalizing solution, add sodium chloroacetate carry out etherification reaction,
Cellulose is 1:1 with the mass ratio of sodium chloroacetate, and etherification reaction temperature is 70 DEG C, and the etherification reaction time is 2h.Etherification reaction is tied
Shu Hou, is neutralized with the acetic acid solution that mass fraction is 90%, and regulation pH is 7～8, is 80% with mass fraction after sucking filtration
Washing with alcohol precipitate 2～3 times, then dry, obtain the carboxymethyl cellulose that substitution value is 0.82 and viscosity is 13mPa s.
This application discloses a kind of method that ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, cellulosic degree of polymerization is with viscous
Degree is relevant, uses acid hydrolysis can obtain the monosaccharide that can ferment, reduces cellulosic degree of polymerization simultaneously, and the addition of hydrogen peroxide reduces further
Cellulosic degree of polymerization, the application first reduces cellulosic degree of polymerization with acid and hydrogen peroxide and carries out etherification reaction again, can obtain ratio of viscosities relatively
Stable carboxymethyl cellulose.The application can not only obtain the carboxymethyl cellulose of ultra-low viscosity, and achieves straw half fiber
Element and the separation of lignin and recycling, preparing low viscosity carboxymethyl cellulose apparent condition be white or micro-yellow powder,
Have the advantages that purity is high, viscosity is low, dissolution velocity is fast, transparency is good.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and this embodiment also is not used to limit the special of the present invention
Profit scope, all equivalences done without departing from the present invention are implemented or change, are intended to be limited solely by the scope of patent protection of this case.
Claims (7)
1. the method that ultra low viscosity carboxymethyl cellulose is prepared in a straw component separation, it is characterised in that comprise the steps:
(1) preparation of hemicellulose hydrolysate: by crushed stalk to 20～80 mesh, add the nothing that mass fraction is 0.5%～5%
Machine acid solution, described straw is 1:5～20 with the solid-to-liquid ratio of described inorganic acid solution, and reaction temperature is 100 DEG C～150 DEG C, reaction
Time is 0.5h～5h, obtains hemicellulose hydrolysate after filtration, and filtering residue washes with water, is filtrated to get a pretreatment filtering residue；
(2) preparation of lignin: adding mass fraction in the pretreatment filtering residue obtained in step (1) is 30%～80%
Organic solvent, the solid-to-liquid ratio of a described pretreatment filtering residue and described organic solvent solution is 1:6～20, and reaction temperature is
140 DEG C～200 DEG C, the response time is 0.5h～3h, obtains reactant liquor and secondary pretreatment filtering residue, described secondary pretreatment after filtration
Filtering residue is first with the organic solvent washing that mass fraction is 30%～80%, then with 80 DEG C of hot washes, is filtrated to get secondary pretreatment
Residue and organic solvent washing liquid, merge described reactant liquor and organic solvent washing liquid, add 2 times of volumes of this merging solution
Being adjusted to pH2～3 with acid after water, lignin containing organic solvent is collected by filtration, organic solvent is reclaimed by decompression distillation,
Obtain lignin；
(3) preparation of stalk cellulose: adding mass fraction in step (2) described secondary pretreatment residue is 0.5%～5%
Alkali and the aqueous solution of hydrogen peroxide that mass fraction is 1%～5%, solid-to-liquid ratio is 1:6～15, and reaction temperature is 50 DEG C～100 DEG C,
Response time is 2h～8h, washes solid residue with water and dries, obtain stalk cellulose after filtration；
(4) preparation of ultra low viscosity carboxymethyl cellulose: step (3) described stalk cellulose is carried out etherification modified, including
Following steps,
A) described stalk cellulose carrying out basification, the mass ratio of described stalk cellulose and alkali is 0.5:2, cellulose with
The ratio of organic solvent is 1:10～16, and alkalization temperature is 20 DEG C～40 DEG C, and the time is 0.5h～3h；
B) in the alkalizing solution of described step a, add sodium chloroacetate and carry out etherification reaction, described stalk cellulose and described chlorine
The mass ratio of sodium acetate is 1:1～2, and etherification reaction temperature is 40 DEG C～80 DEG C, and the etherification reaction time is 0.5h～3h；
C) after etherification reaction terminates, being neutralized with acid, being adjusted to pH is 7～8, precipitates 2～3 with organic solvent washing after sucking filtration
Secondary, then dry, obtain ultra low viscosity carboxymethyl cellulose.
The method that the most according to claim 1, ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, it is characterised in that institute
State straw one in wheat stalk, rice straw, corn straw or bagasse.
The method that the most according to claim 1, ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, it is characterised in that institute
State mineral acid one in hydrochloric acid, sulphuric acid, nitric acid or phosphoric acid in step (1).
The method that the most according to claim 1, ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, it is characterised in that institute
State organic solvent one in methanol, ethanol, isopropanol or acetone in step (2).
The method that the most according to claim 1, ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, it is characterised in that institute
State alkali one in sodium hydroxide, potassium hydroxide, calcium hydroxide in step (3).
The method that the most according to claim 1, ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, it is characterised in that institute
State alkali one in sodium hydroxide or potassium hydroxide in step (4).
The method that the most according to claim 1, ultra low viscosity carboxymethyl cellulose is prepared in straw component separation, it is characterised in that institute
State organic solvent in step (4) and be selected from the one in ethanol, isopropanol, the tert-butyl alcohol.
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| CN106632736A (en) * | 2016-12-09 | 2017-05-10 | 广西壮族自治区中国科学院广西植物研究所 | Preparation method for carboxymethyl xylan |
| CN106770687A (en) * | 2016-12-16 | 2017-05-31 | 张静 | A kind of preparation method of the special couplant of rough surface ultrasonic inspection |
| CN107347288A (en) * | 2017-07-04 | 2017-11-17 | 丁广礼 | A kind of method of saving water, resisting drought rice direct-sowing dry soil moisturizing closing weeding |
| CN109569461A (en) * | 2018-12-06 | 2019-04-05 | 武汉科丝力纤维制造有限公司 | A kind of technique of organic solvent-free environment separation polyhydroxy aldehyde |
| CN110016488A (en) * | 2019-04-18 | 2019-07-16 | 中国科学院广州能源研究所 | The method of separating lignin coproduction xylo-oligosaccharide from lignocellulosic alkaline oxygenated pretreatment fluid |
| CN112500502A (en) * | 2020-12-25 | 2021-03-16 | 重庆力宏精细化工有限公司 | Sodium carboxymethylcellulose and preparation method and application thereof |
| CN112724265A (en) * | 2020-12-25 | 2021-04-30 | 农业农村部环境保护科研监测所 | Carboxymethyl cellulose, film formed by carboxymethyl cellulose, preparation method and application of carboxymethyl cellulose |
| CN115160445A (en) * | 2022-08-05 | 2022-10-11 | 湖北江汉利达石油物资装备有限公司 | Carboxymethyl cellulose and preparation process thereof |
| CN115521383A (en) * | 2022-10-31 | 2022-12-27 | 徐州创力纤维有限公司 | Preparation method of polyanion modified cellulose |
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| CN106632736A (en) * | 2016-12-09 | 2017-05-10 | 广西壮族自治区中国科学院广西植物研究所 | Preparation method for carboxymethyl xylan |
| CN106770687A (en) * | 2016-12-16 | 2017-05-31 | 张静 | A kind of preparation method of the special couplant of rough surface ultrasonic inspection |
| CN106770687B (en) * | 2016-12-16 | 2019-10-11 | 江苏三合声源超声波科技有限公司 | A kind of preparation method of the dedicated couplant of rough surface ultrasonic inspection |
| CN107347288A (en) * | 2017-07-04 | 2017-11-17 | 丁广礼 | A kind of method of saving water, resisting drought rice direct-sowing dry soil moisturizing closing weeding |
| CN109569461A (en) * | 2018-12-06 | 2019-04-05 | 武汉科丝力纤维制造有限公司 | A kind of technique of organic solvent-free environment separation polyhydroxy aldehyde |
| CN110016488A (en) * | 2019-04-18 | 2019-07-16 | 中国科学院广州能源研究所 | The method of separating lignin coproduction xylo-oligosaccharide from lignocellulosic alkaline oxygenated pretreatment fluid |
| CN110016488B (en) * | 2019-04-18 | 2021-03-09 | 中国科学院广州能源研究所 | Method for separating lignin and co-producing xylo-oligosaccharide from lignocellulose alkaline oxidation pretreatment liquid |
| CN112500502A (en) * | 2020-12-25 | 2021-03-16 | 重庆力宏精细化工有限公司 | Sodium carboxymethylcellulose and preparation method and application thereof |
| CN112724265A (en) * | 2020-12-25 | 2021-04-30 | 农业农村部环境保护科研监测所 | Carboxymethyl cellulose, film formed by carboxymethyl cellulose, preparation method and application of carboxymethyl cellulose |
| CN115160445A (en) * | 2022-08-05 | 2022-10-11 | 湖北江汉利达石油物资装备有限公司 | Carboxymethyl cellulose and preparation process thereof |
| CN115521383A (en) * | 2022-10-31 | 2022-12-27 | 徐州创力纤维有限公司 | Preparation method of polyanion modified cellulose |
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