CN101792542A - Method for preparing water soluble mixed ether by using corn bran and wheat bran - Google Patents
Method for preparing water soluble mixed ether by using corn bran and wheat bran Download PDFInfo
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Abstract
The invention relates to a method for preparing water soluble mixed ether by using corn bran and wheat bran, wherein the corn bran is the by-product obtained during the preparation of corn starch and the wheat bran is the by-product obtained during the preparation of wheat starch. The invention provides a method for directly synthesizing water soluble mixed ether formed by Arabic xylan ether, cellulose ether, hemicellulose-lignin ether, starch ether and the like by taking the corn bran and the wheat bran as raw materials, solves the problem that the by-products of the corn and wheat processing industry cannot be processed into products with high added values, and widens the application scope of the corn bran and the wheat bran. The preparation of water soluble mixed ether by using the corn bran and the wheat bran is conducted according to the following technological processes that: the corn bran and the wheat bran are crushed into 40-200 mesh powder and water soluble mixed ether is prepared through alkalization or alkaline catalyst activation and etherification in inert organic solvent. The invention has the advantages that protein and fat in the bran can be directly hydrolyzed in the process of alkalization or alkaline catalyst activation and hydrolysate and color are removed in the process of times of mixed ether washing and purification.
Description
Technical field
The present invention relates to a kind ofly prepare water-soluble mixed ether with corn bran and Testa Tritici
Background technology
Corn bran and Testa Tritici are mainly used in feed at present, because the protein content of Testa Tritici is higher than corn bran, and extensively because in the feed; Because corn bran is of low nutritive value, and contains a certain amount of xylogen, be used for feed and be restricted, extract araboxylan and mainly use Testa Tritici, seldom use corn bran, cause corn bran seriously superfluous.The present invention is a raw material with corn bran (or Testa Tritici), and organic solvent is a solvent, and by alkalization (or with base catalysis activation), the etherifying agent etherificate generates water-soluble complex etherified material.This etherificate product, water-soluble fully, form colloidal solution with certain viscosity.With different etherifying agents, prepared different water-soluble mixed ether, for example: carboxymethyl mixed ether, hydroxyethyl mixed ether, hydroxyethyl-carboxymethyl mixed ether, methyl mixed ether, positively charged ion mixed ether etc., the characteristic of every kind of mixed ether is all different, that is to say and have different purposes, can be widely used in: industries such as petroleum drilling, thermal insulation mortar tamanori, emulsion paint, coating for internal and external wall, papermaking, washing composition, wall putty powder, building glue replace a large amount of industrial chemicals.The present invention finds one to be raw material with corn bran (or Testa Tritici), produces the industry of high value added product, and can drive the development of corn planting industry.
Summary of the invention
Purpose of the present invention is not in order to separate crude protein, fat and the xylogen of corn bran (or Testa Tritici) before reaction, in the inertia organic solvent aqueous solution, directly generate water-soluble high-molecular compound-mixed ether by alkalization (or alkali activating catalytic), etherificate; When corn bran (or Testa Tritici) alkalization (or base catalysis activation), with protein and fat splitting, separate and repeatedly wash purifying simultaneously at mixed ether, hydrolyzate is separated remove, and slough the color of mixed ether.
The main component of anhydrous corn bran is formed table 1
| Project | Protein powder (%) | Crude fat (%) | Ash content (%) | Robust fibre (%) | Nitrogen-free extract (%) |
| Content | ??8.66 | ??6.35 | ??1.11 | ??18.00 | ??63.85 |
Nitrogen-free extract is followed successively by by the content size in the table 1: araboxylan-glucal
Acid araboxylan (glucuronoarabinoxylans, abbreviation G) about 45%, half fiber-xylogen (hemicellulose-lignin, abbreviation H) is about 15%, starch (starch, abbreviation S) about 4%.Robust fibre (Cellulose, abbreviation C).
The main component of anhydrous Testa Tritici is formed table 2
| Project | Protein (%) | Fat (%) | Starch (%) | Mierocrystalline cellulose (%) | Dietary cellulose (%) |
| Content | ??12-18 | ??3-5 | ??10-15 | ??5-12 | ??35-50 |
Dietary cellulose mainly is made up of araboxylan-glucuronic acid araboxylan (G) and hemicellulose-xylogen (H).
From table 1 and table 2 as can be seen, can have by the component of alkalization, etherificate generation water-soluble high-molecular compound-mixed ether: dietary cellulose is mainly by araboxylan-glucuronic acid araboxylan (G), Mierocrystalline cellulose (C), hemicellulose-xylogen (H), starch (S), we are GCHS with above-mentioned four kinds of components by english abbreviation, GCHS is by the mixture of water-soluble polymer of alkalization, etherificate preparation, be called mixed ether, i.e. GCHS ether.
Protein is unstable in strongly basic medium with fat, and hydrolysis reaction takes place, and the hydrolysis resolvent is water-soluble, can not generate macromolecular compound, but consumes etherifying agent.
The present invention adopts inert organic solvents: methyl alcohol, ethanol, propyl alcohol and isomer, C4-C6 alcohol and isomer, acetone, hexanaphthene, toluene, polyoxyethylene glycol, glycol dimethyl ether, C4-C12 alkane, sherwood oil are action solvent, epistasis mineral alkalis such as dissolving quantitative NaOH, KOH, yellow soda ash in the presence of water, 5-60 ℃ of (or the base catalysis activation) 20-150 minute of alkalizing down, the mass ratio of above-mentioned organic solvent and corn bran (or Testa Tritici) is: (0.5-15): 1 to 40-200 order corn bran (or Testa Tritici); NaOH or KOH and corn bran (or Testa Tritici) mass ratio is: (0.1-2): 1, adopt Mono Chloro Acetic Acid (or its sodium salt), oxyethane, propylene oxide, butylene oxide ring, methyl chloride, monochloroethane, chloroethanol, 3-chloro-2 hydroxypropyl tri alkyl ammomium chlorides (alkyl is C1-C12), 2,3-epoxypropyl tri alkyl ammomium chloride (alkyl is C1-C12) is an etherifying agent, etherifying agent and corn bran (or Testa Tritici) mass ratio is: (0.2-2.0): 1,35-120 ℃ of etherificate 0.5-12 hour with middle table 1 in 18% robust fibre (celluose, abbreviation C) reacts many water of constitution of generation dissolubility mixed ether with 63.85% nitrogen-free extract, filter, filter cake (is mainly used methyl alcohol with 3-15 times of 30-90% aqueous solutions of organic solvent of corn bran (or Testa Tritici), ethanol, Virahol, hexanaphthene, aqueous acetone solution) washs 2-4 time at normal temperatures, filter, filter cake is following dry 2 hours at 105 ℃, can obtain 98% water-soluble mixed ether, 2% solution viscosity of this mixed ether is in (under 20 ℃ of conditions, the NDJ-1 viscometer determining) between the 2-15000cps; Simultaneously under strong alkaline condition with table 1, table 2 in protein separate with crude fat hydrolysis washing and remove, and flush away product colour.
The objective of the invention is to produce wheat bran that corn and wheat starch produce, the insoluble in water wheat bran tankage during the water-soluble araboxylan food fibre of vinasse, beer vinasse, extraction during with corn fermentation alcohol, by alkalization (or base catalysis activation), the etherifying agent etherificate prepares serial GCHS water-soluble ethers series products, produces high value added product with the corn bran (or Testa Tritici) of low value and replaces ether of cellulose series product of producing with purified cotton with similar functions, is the starch ethers series product of raw material production and the chemical products with similar functions with starch.
This patent is ground into 40-120 order powder with corn bran, with ethanol or methyl alcohol, Virahol is action solvent, will be by alkali activatory corn bran (or Testa Tritici) and Mono Chloro Acetic Acid (or sodium chloroacetate) reaction, temperature is 40-85 ℃, pressure 0-0.2Mpa, and corn bran (or Testa Tritici) and solvent mass ratio are 1: between the 1-10, wherein with 1: 4-1: 6 is more suitable, reaction obtains carboxymethyl GCHS ether, and (abbreviation: CMGCHS), the CMGCHS substitution value is 0.5-2.3, viscosity 5-500cps.
This patent is ground into 120 order powder with corn bran (or Testa Tritici), with Virahol or hexanaphthene is action solvent, will be by alkali activatory corn bran (or Testa Tritici) and oxyethane (or propylene oxide) reaction, temperature is 30-85 ℃, pressure 0.2-0.6Mpa, corn bran (or Testa Tritici) and solvent mass ratio are 1: between the 1-15, wherein with 1: 6-1: 8 is more suitable, reaction obtains hydroxyethyl (or hydroxypropyl) GCHS ether (abbreviation: HEGCHS or HPGCHS), HEGCHS or HPGCHS molar substitution are 1.4-2.5, viscosity 5-10000cps.
After above-mentioned reaction finishes, be cooled to 10-40 ℃, add quantitative Mono Chloro Acetic Acid or sodium chloroacetate, 60-90 ℃ of reaction down, obtain hydroxyethyl-carboxymethyl or hydroxypropyl carboxy methyl GCHS ether (abbreviation: HECMGCHS or HPCMGCHS), degree of substitution by carboxymethyl generally is controlled between the 0.3-1.0.
After above-mentioned HEGCHS or HPGCHS reaction end, be cooled to 10-40 ℃, add quantitative 3-chloro-2 hydroxypropyl-trimethyl ammonium chlorides,, obtain hydroxyethyl hydroxypropyl-trimethyl ammonium chloride positively charged ion GCHS or hydroxypropyl hydroxypropyl-trimethyl ammonium chloride positively charged ion GCHS ether product 50-100 ℃ of reaction.The nitrogen content of positively charged ion ether generally is controlled between the 1.0-3.5%.
This patent is broken into 120 order powder with corn bran powder (or Testa Tritici), with ethanol or methyl alcohol, Virahol, hexanaphthene is action solvent, will be by alkali activatory corn bran (or Testa Tritici) and 3-chloro-2 hydroxypropyl-trimethyl ammonium chlorides (CHPTMHC) reaction, temperature is 50-90 ℃, pressure 0-0.20Mpa, wheat bran and solvent mass ratio are 1: between the 1-8, wherein with 1: 5-1: 8 is more suitable, reaction obtains the (abbreviation: CHPTMHCGCHS) of hydroxypropyl-trimethyl ammonium chloride positively charged ion GCHS ether, the CHPTMHCGCHS nitrogen content is 1.5-3.5%, viscosity 5-300cps.
This patent is ground into 120 order powder with corn bran (or Testa Tritici), mix by a certain percentage as action solvent with Virahol and hexanaphthene, will be by alkali activatory corn bran and methyl chloride reaction, temperature is 60-90 ℃, pressure 0.3-0.5Mpa, and wheat bran and solvent mass ratio are 1: between the 1-13, wherein with 1: 8-1: 11 is more suitable, reaction obtains methyl GCHS ether, and (abbreviation: MGCHS), the methoxy content of MGCHS is 22-30%, viscosity 5-10000cps.
In above-mentioned reaction system, add quantitative propylene oxide simultaneously at the adding methyl chloride, temperature of reaction is 45-90 ℃, pressure 0.30-0.60Mpa, reaction obtains hydroxypropylmethyl GCHS (abbreviation: HPMGCHS), the methyl oxygen base content of HPMGCHS is 18-30%, and propoxyl content is suitable at 5-14%.
GCHS water-soluble ethers series products has biodegradability, equally with ether of cellulose, starch ethers product belong to environmentally friendly polymer novel material product, can be widely used in industries such as food, petroleum drilling, papermaking, thermal insulation mortar, putty powder, emulsion paint, coating, washing powder, washing composition, shampoo, makeup.
Embodiment
Example 1
Add 91% ethanol 2.5L in the 5L autoclave pressure, under agitation hydro-oxidation sodium 285g is heated to 50-70 ℃ and makes its whole dissolvings, is cooled to 25 ℃ again, adds 80 order 500g corn brans (or Testa Tritici), and under agitation 10-40 ℃ alkalized 40 minutes down.Under logical water coolant condition, Dropwise 5 0% Mono Chloro Acetic Acid ethanolic soln 670g, temperature is controlled between 25-45 ℃ during dropping, drips time 20-30 minute.
After dripping the Mono Chloro Acetic Acid spirituous solution, be warming up to 55 ℃ in 20 minutes, constant temperature etherificate 30 minutes directly is warming up to 82 ℃, isothermal reaction 60 minutes.
When being cooled to 30-35 ℃, with Glacial acetic acid neutralization value PH=6.5-8.5, filter, filter cake is 80 ℃ of dryings.Obtain 75% left and right sides substitution value DS=0.80,850g carboxymethyl mixed ether (CMGCHS).
With 65% aqueous ethanolic solution 2.5L,, filter 30 ℃ of following agitator treatings 60 minutes.Repeated washing three times both can obtain 〉=98% faint yellow CMGCHS mixed ether product.At 20 ℃, 2% solution viscosity of surveying CMGCHS is 150cps with DNJ-1 type viscometer.
Example 2
Sodium hydroxide in the example 1 is added 145g, and alkalization directly adds 413g sodium chloroacetate powder after finishing, and other obtains CMGCHS ether product DS=0.75 with example 1, uses the NDJ-1 viscometer, and 20 ℃, 2% solution viscosity is 250cps.
Example 3
Add 92% Virahol 3.2L in the 5L autoclave pressure, under agitation hydro-oxidation sodium 200g is heated to 50-70 ℃ and makes its whole dissolvings, is cooled to 25 ℃ again, adds 100-120 order 400g corn bran, and under agitation 10-40 ℃ alkalized 60 minutes down.Under logical water coolant condition, be cooled to 20 ℃, be evacuated to-0.06Mpa, vacuumized 10 minutes, under the autoclave pressure air-proof condition, T-Ring oxidative ethane jar added oxyethane 350g in 30-50 minute, 25-30 ℃ of reaction 40 minutes,
Heat up gradually, the still internal pressure must not surpass 0.40Mpa, and 45-65 ℃ was reacted 4-8 hour down.Be cooled to 25 ℃, add 95% acetate 310g, be neutralized to PH=6.5-8.5, filter, filter cake dry 4 hours, obtains 75-80% crude product hydroxyethyl mixed ether (HEGCHS) 600g at 80 ℃.
With 75% Virahol 2.5L, wash crude product HEGCHS at normal temperatures three times, both can obtain 95% faint yellow HEGCHS mixed ether product.At 20 ℃, 2% solution viscosity of surveying HEGCHS is 4000cps, molar substitution MS=1.8 with DNJ-1 type viscometer.
Example 4
Change the oxyethane equivalent in the example 3 into propylene oxide, other reaction conditions is identical with example 3, obtains hydroxypropyl mixed ether (HPGCHS), uses DNJ-1 type viscometer at 20 ℃, 2% solution viscosity of surveying HPGCHS is 1200cps, molar substitution MS=1.5.
Example 5
Finish in example 3 reactions, be cooled to 25 ℃, be evacuated to-0.06Mpa, in 10 minutes pumpdown times, the Mono Chloro Acetic Acid ethanolic soln 500g of Dropwise 5 0%, controlled temperature dripped at 30-45 ℃ in 20 minutes.Be warming up to 75-85 ℃, reacted 90 minutes.Be cooled to 30-40 ℃, with in 95% acetate and PH=6.5-8.5.Filter, filter cake washed 100 minutes at normal temperatures with 75% ethanol 2.5L, repeated washing three times.Can obtain purity 95% carboxymethyl hydroxyethyl mixed ether (CMHEGCHS) dry product 720g, degree of substitution by carboxymethyl DS=0.5-0.6, at 20 ℃, 2% solution viscosity of surveying CMHEGCHS is 150cps with DNJ-1 type viscometer.
Example 6
After example 4 reactions finish, be cooled to 25 ℃, other operational condition and example 5 are identical.Can obtain purity is 95% carboxy-methyl hydroxy propyl mixed ether (CMHPGCHS) dry product 670g, degree of substitution by carboxymethyl DS=0.5-0.6, and at 20 ℃, 2% solution viscosity of surveying CMHPGCHS is 215cps with DNJ-1 type viscometer.
Example 7
Finish in example 3 reactions, be cooled to 25 ℃, be evacuated to-0.06Mpa, in 10 minutes pumpdown times, 3-chloro-2 hydroxypropyl-trimethyl ammonium chlorides (CHPTMHC) the isopropanol water solution 760g of adding 50% is warming up to 85-105 ℃, reacts 80 minutes.Be cooled to 30-40 ℃, with in 95% acetate and PH=6.5-8.5.Filter, filter cake washed 100 minutes at normal temperatures with 75% ethanol 2.5L, repeated washing three times.Can obtain purity 96% cationic hydroxyethyl mixed ether (CHPTMHCHEGCHS) dry product 810g, the nitrogen content of pure product cationic hydroxyethyl mixed ether is 2.1%, and at 20 ℃, 2% solution viscosity of surveying CHPTMHCHEGCHS is 55cps with DNJ-1 type viscometer.
Example 8
Change the addition amount of sodium hydroxide in the example 1 into 145g, after alkalization finishes, the 3-chloro-2 hydroxypropyl-trimethyl ammonium chloride ethanolic soln 760g of adding 50%, other is with example 1, obtain purity and be 98% positively charged ion mixed ether (CHPTMHCGCHS) 560g, CHPTMHCGCHS mixed ether product nitrogen content is 3.5%
At 20 ℃, 2% solution viscosity of surveying CHPTMHCGCHS is 45cps with DNJ-1 type viscometer.
Example 9
In the 5L autoclave pressure, add hexanaphthene and Virahol mixing water solvent 2.5kg (hexanaphthene: Virahol: water=80: 15: 5), hydro-oxidation sodium 200g under agitation, be heated to 60-70 ℃ and make its whole dissolvings, be cooled to 25 ℃ again, add 100 order 300g wheat brans, under agitation 25-30 ℃ alkalized 40 minutes down.Under logical water coolant condition, be evacuated to-0.06Mpa, add propylene oxide 100g, methyl chloride 240g, temperature is controlled between 20-35 ℃, reacts 60-90 minute.Be warming up to 50-55 ℃, reacted 3 hours; Intensification 75-90 ℃, to react 3 hours, reaction pressure is controlled at below the 0.60Mpa.
When being cooled to 30-35 ℃, with 95% Glacial acetic acid 30g neutralization value PH=6.5-8.5, filter, filter cake is 80 ℃ of dryings.Obtain the faint yellow hydroxypropylmethyl mixed ether of 72% left and right sides 420g (HPMGCHS).
At 20 ℃, 2% solution viscosity of surveying HPMGCHS is 1200cps with DNJ-1 type viscometer; Methoxy content 22-24%, propoxyl content 5-6%.
Example 10
Oxyethane in the example 9 is removed, and other condition is identical with example 9, obtains methyl mixed ether (MGCHS) 370g, and at 20 ℃, 2% solution viscosity of surveying MGCHS is 900cps with DNJ-1 type viscometer; Methoxy content 22-24%.
Example 11
Change the propylene oxide in the example 9 into monochloroethane, other condition is identical with example 9, obtains methylethyl mixed ether 430g, and at 20 ℃, 2% solution viscosity of surveying MGCHS is 10cps with DNJ-1 type viscometer; Methoxy content 19-21%, oxyethyl group content 7-8%.
Application example 1
CMGCHS, CMHEGCHS, the direct substitution CMC-LVT of CMHPGCHS are used for oil drilling slurry; This product can partly replace can disperse rubber powder to be used for building heat-insulating mortar; CMGCHS can replace CMS and CMC fully and be used for the putty powder binding agent.CMGCHS, CMHEGCHS, CMHPGCHS have stronger alkali resistance, are used for building glue, can use with grey calcium, cement mixing, and its performance is better than CMS and CMC product, can partly replace PVA, can disperse rubber powder.This product can be used for industries such as papermaking, washing powder, washing composition, pottery.
Application example 2HEGCHS, MGCHS, HPMGCHS are used for emulsion paint and coating, can replace chemical benzene emulsion; But replaced C MC, CMS, HPMC, MC are used for inner and external wall putty powder; Can replace HEC, PAC, CMC, CMS to be used for oil drilling slurry.
Application example 3
CHPTMHCGCHS, CHPTMHCHEGCHS, CHPTMHCHPGCHS are used for products such as hair jelly, shampoo, makeup, papermaking, washing composition, can replace hydroxyethyl cationic cellulose, cationic starch ether.
Application example 4
MEGCHS has strong emulsifying property, is excellent emulsifier such as cream, ice cream, bread.
Claims (15)
1. method for preparing water-soluble mixed ether with corn bran and Testa Tritici, it is characterized in that with processing W-Gum byproduct corn bran and wheat starch byproduct wheat bran, be broken into 40-200 purpose powder, in inert organic solvents aqueous solution solvent, prepare water-soluble mixed ether by alkalization or alkali activating catalytic, etherificate, directly with corn bran and protein in wheat bran and fat splitting, water-soluble mixed ether is removed the method for hydrolyzate and color in aqueous solutions of organic solvent washing purge process in alkalization or alkali activating catalytic process.The main component of water-soluble mixed ether is by (the abbreviation: G), ether of cellulose (abbreviation: C), (abbreviation: H), starch ethers (abbreviation: S), be called GCHS ether by the big minispread abbreviation of composition content of half fiber-xylogen ether of araboxylan and derivative ether thereof.
2. the method for preparing water-soluble GCHS ether with corn bran and Testa Tritici, one, be solvent with the inert organic solvents aqueous solution, inert organic solvents methyl alcohol, ethanol, propyl alcohol and isomer (Virahol), C4-C6 alcohol and isomer, acetone, hexanaphthene, toluene, chloroform, polyoxyethylene glycol, glycol dimethyl ether, C2-C6 alkyl oxide, sherwood oil that present method is selected for use, the C4-C12 alkanes.Two, corn bran and Testa Tritici alkalize or activating catalytic in the above-mentioned inert organic solvents aqueous solution, and present method adopts inorganic strong alkali sodium hydroxide, potassium hydroxide, yellow soda ash.Three, corn bran and Testa Tritici are solvent with the inert organic solvents aqueous solution, behind above-mentioned highly basic alkalization or alkali activating catalytic, present method adopts Mono Chloro Acetic Acid, sodium chloroacetate, oxyethane, propylene oxide, butylene oxide ring, methyl chloride, monochloroethane, chloroethanol, 3-chloro-2 hydroxypropyl tri alkyl ammomium chlorides (alkyl is C1-C12), 2,3-epoxypropyl tri alkyl ammomium chloride (alkyl is C1-C12) is an etherifying agent, etherificate is carried out in alkalization or base catalysis activatory corn bran and Testa Tritici, promptly generate water-soluble GCHS ether product.
3. according to claim 1 and 2, the mass ratio of corn bran (or Testa Tritici) powder and the inert organic solvents aqueous solution is 1: 15; The mass ratio of corn bran in the reaction system (or Testa Tritici) and water is 1: (0.1-3) (water is added water from organic solvent and alkali lye or processing requirement); Corn bran (or Testa Tritici) is 1 with the mass ratio of etherifying agent: (0.20-2.0); Corn bran (or Testa Tritici) is 1 with the mass ratio of alkali: (0.12-2.0).
4. according to claim 2 and 3, corn bran (or Testa Tritici) alkalization or base catalysis activation temperature are at 5-45 ℃, and the time is 30-180 minute; Etherification temperature is at 35-120 ℃, and the etherificate time is 0.5-10 hour, and reaction pressure is at 0-0.80Mpa.Excessive alkali in the reaction system is neutralized to PH=6.0-8.5 with Glacial acetic acid, hydrochloric acid, dilute sulphuric acid, and the neutralizing acid consumption is: corn bran (or Testa Tritici) is 1 with the mass ratio of acid: 0-3.0.
5. according to claim 2,3 and 4 described, the preparation of the water-soluble mixed ether of carboxymethyl (CMGCHS), inert organic solvents we to adopt methyl alcohol, ethanol, C3-C4 alcohol and isomer thereof be solvent, corn bran (or Testa Tritici) is 1 with the mass ratio of the pure solvent aqueous solution: (1-10), adjust the ratio of sodium hydroxide (or potassium hydroxide, yellow soda ash) and Mono Chloro Acetic Acid (or sodium chloroacetate), obtaining substitution value is the CMGCHS ether product of 0.3-2.3.Excessive alkali neutralizes with hydrochloric acid or Glacial acetic acid, with 40-80% methyl alcohol or aqueous ethanolic solution under 10-50 ℃, repeat 2-4 washing, the mass ratio of methyl alcohol or aqueous ethanolic solution and corn bran (or Testa Tritici) is (4-15): 1, flush away protein and fat splitting thing and color obtain high-purity performance number carboxymethyl mixed ether product.
6. according to claim 2,3 and 4 described, the preparation of the water-soluble mixed ether of hydroxyethyl (HEGCHS), inert organic solvents we to adopt Virahol, acetone, butyl alcohol-tert be solvent, corn bran (or Testa Tritici) is 1 with the mass ratio of solvent: (2-15), sodium hydroxide (or potassium hydroxide, yellow soda ash) is adopted in alkalization, alkalization temperature is 10-35 ℃, and alkalization time is 30-180 minute; Etherifying agent adopts oxyethane (or chloroethanol), etherification temperature is 45-90 ℃, adjust sodium hydroxide (or potassium hydroxide, yellow soda ash) and oxyethane (or chloroethanol) consumption proportion, obtain molar substitution (MS) and be the water-soluble GCHS ether of hydroxyethyl of 1.2-2.5.With the Virahol of 60-80% (or acetone, butyl alcohol-tert) solution washing 2-4 time, corn bran (or Testa Tritici) is 1 with the mass ratio of the inertia solvent aqueous solution: (5-15), wash temperature 0-40 ℃, washing time 1-3 hour, flush away protein and fat splitting thing and color obtain high purity HEGCHS ether.
7. according to claim 2,3 and 4 described, the preparation of the water-soluble mixed ether of hydroxypropyl (or hydroxyl butyl) (HPGCHS or HBGCHS), inert organic solvents we to adopt hexanaphthene, Virahol, acetone, butyl alcohol-tert be solvent, corn bran (or Testa Tritici) is 1 with the mass ratio of the solvent aqueous solution: (2-15), sodium hydroxide (or potassium hydroxide, yellow soda ash) is adopted in alkalization, alkalization temperature is 10-35 ℃, and alkalization time is 30-180 minute; Etherifying agent adopts propylene oxide (or butylene oxide ring), etherification temperature is 45-100 ℃, adjust the ratio of sodium hydroxide (or potassium hydroxide, yellow soda ash) and propylene oxide alkane (or butylene oxide ring), obtain the HPGCHS that molar substitution is 1.2-2.5 (or HBGCHS) ether.With the hexanaphthene of 60-80% (or Virahol, acetone, butyl alcohol-tert) solution washing 2-4 time, corn bran (or Testa Tritici) is 1 with the mass ratio of above-mentioned solvent aqueous solution: (5-15), wash temperature 0-40 ℃, washing time 1-3 hour, obtain high purity hydroxypropyl (or hydroxyl butyl) GCHS ether.
8. according to claim 2,3,4,6 and 7 is described, at preparation hydroxyethyl GCHS ether (or hydroxypropyl GCHS ether, hydroxyl butyl GCHS ether), after etherification reaction finishes, be cooled to 0-35 ℃, be evacuated to-0.06Mpa, add a certain amount of Mono Chloro Acetic Acid (or sodium chloroacetate) aqueous solutions of organic solvent, at 55-90 ℃, continued etherificate 30-120 minute, be cooled to 10-45 ℃, be neutralized to PH=6.5-8.5 with Glacial acetic acid, obtain hydroxyethyl (or hydroxypropyl, the hydroxyl butyl) molar substitution is 0.2-2.3, and degree of substitution by carboxymethyl is the water-soluble GCHS ether of the hydroxyethyl-carboxymethyl of 0.2-2.3 (or the water-soluble GCHS ether of hydroxypropyl carboxy methyl and the water-soluble GCHS ether of hydroxyl butyl carboxymethyl).With the 60-80% solution washing of methyl alcohol, ethanol, Virahol, hexanaphthene, acetone 2-4 time, corn bran (or Testa Tritici) is 1 with the mass ratio of washings: (5-15), obtain high purity product.
9. according to claim 2,3,4,6 and 7 is described, at preparation hydroxyethyl GCHS ether (or hydroxypropyl GCHS ether, hydroxyl butyl GCHS ether) after etherification reaction finishes, be cooled to 0-45 ℃, be evacuated to-0.06Mpa, add a certain amount of 3-chloro-2 hydroxypropyl tri alkyl ammomium chlorides (alkyl is C1-C12) or 2,3-epoxypropyl tri alkyl ammomium chloride (alkyl is C1-C12) aqueous solutions of organic solvent, at 55-120 ℃, continued etherificate 30-120 minute, be cooled to 10-45 ℃, be neutralized to PH=6.5-8.5 with Glacial acetic acid, obtain hydroxyethyl (or hydroxypropyl, the hydroxyl butyl) molar substitution is 0.2-2.3, and nitrogen content is hydroxyethyl hydroxypropyl trialkyl (C1-C12) the water-soluble cationic GCHS ether (or hydroxypropyl hydroxypropyl trialkyl (C1-C12) water-soluble cationic GCHS ether and hydroxyl butyl hydroxypropyl trialkyl water-soluble cationic GCHS ether) of 0.5-3.5%.With the 60-80% solution washing of methyl alcohol, ethanol, Virahol, acetone, hexanaphthene 2-4 time, corn bran (or Testa Tritici) is 1 with the mass ratio of washings: (5-15), obtain high purity product.
10. according to claim 2,3 and 4 is described, the preparation of hydroxypropyl tri alkyl ammomium chloride water-soluble cationic GCHS ether, we adopt methyl alcohol inert organic solvents, ethanol, C3-C4 alcohol and isomer thereof, acetone, hexanaphthene, glycol dimethyl ether is a solvent, corn bran (or Testa Tritici) is 1 with the mass ratio of solvent solvent: (1-15), adjust sodium hydroxide (or potassium hydroxide, yellow soda ash) with 3-chloro-2 hydroxypropyl tri alkyl ammomium chlorides (alkyl is C1-C12) or 2, the ratio of 3-epoxypropyl tri alkyl ammomium chloride (alkyl is C1-C12), obtaining nitrogen content is 1.3-3.5% hydroxypropyl trialkyl positively charged ion mixed ether product.With 40-80% methyl alcohol, ethanol, Virahol, aqueous acetone solution under 10-50 ℃, repeat 2-4 washing, the mass ratio of methyl alcohol, ethanol, Virahol, aqueous acetone solution and corn bran (or Testa Tritici) is (4-15): 1, obtain high-purity product hydroxypropyl trialkyl (alkyl is C1-C12) GCHS ether product.
11. according to claim 2,3 and 4 described, the preparation of the water-soluble GCHS ether of hydroxypropylmethyl, inert organic solvents we to adopt Virahol and hexanaphthene, Virahol and acetone, Virahol and toluene, butyl alcohol-tert and hexanaphthene, butyl alcohol-tert and acetone, butyl alcohol-tert and toluene be double solvent, corn bran (or Testa Tritici) is 1 with the mass ratio of double solvent: (2-15), sodium hydroxide (or potassium hydroxide, yellow soda ash) is adopted in alkalization, alkalization temperature is 10-35 ℃, and alkalization time is 30-180 minute; Etherifying agent adopts propylene oxide and methyl chloride to add simultaneously, etherification temperature is 35-90 ℃, 3-10 hour etherification reaction time, reaction pressure is less than 0.80Mpa, adjust the ratio of sodium hydroxide (or potassium hydroxide, yellow soda ash) and propylene oxide and methyl chloride, obtaining methoxy content is 14-32%, and propoxyl content is the water-soluble GCHS ether of the hydroxypropylmethyl of 2-14%.With the Virahol of 60-80% (or acetone, butyl alcohol-tert) solution washing 2-4 time, corn bran (or Testa Tritici) is 1 with the mass ratio of the solvent aqueous solution: (5-15), wash temperature 10-40 ℃, washing time 1-3 hour, obtain high purity hydroxypropylmethyl GCHS ether.
12. according to claim 11, change propylene oxide into butylene oxide ring, we can obtain hydroxyl butyl methyl GCHS ether, and hydroxy butoxy content is 2-18%, and methoxy content is 14-32%.
13. according to claim 11, change propylene oxide into monochloroethane, we can obtain the water-soluble GCHS ether of methylethyl, and methoxy content is 13-24%, and oxyethyl group content is 3-10%.
14. according to claim 1,2,3 and 4 described, corn bran (or Testa Tritici) alkalizes in the inertia organic solvent aqueous solution or the base catalysis activation, by highly basic with protein in the corn bran (or Testa Tritici) and fat hydrolysis simultaneously, in the mixed ether purge process, protein separated with the hydrolyzate of fat and remove, remove product colour by washing repeatedly.
15. according to claim 1,2,3 and 4 described, the present invention is fit to pulverize the vinasse of direct fermentation alcohol and brewer's grains that wheat is pulverized direct fermentation maltose prepare water-soluble mixed ether with corn.With maize alcohol stillage (or wheat beer poor) prepare the method for mixed ether and method that corn bran (or Testa Tritici) prepares mixed ether in full accord.
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