CN103435817A - Method for directly extracting lignin in process of using corn bran to prepare low-molecular-weight mixed ether - Google Patents
Method for directly extracting lignin in process of using corn bran to prepare low-molecular-weight mixed ether Download PDFInfo
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- CN103435817A CN103435817A CN201310427259XA CN201310427259A CN103435817A CN 103435817 A CN103435817 A CN 103435817A CN 201310427259X A CN201310427259X A CN 201310427259XA CN 201310427259 A CN201310427259 A CN 201310427259A CN 103435817 A CN103435817 A CN 103435817A
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Abstract
The invention discloses a method for directly extracting lignin in the process of using corn bran to prepare low-molecular-weight mixed ether and belongs to the field of lignin extraction by using the corn bran or wheat bran. The method comprises the steps of: using the corn bran to prepare the low-molecular-weight mixed ether, and simultaneously hydrolyzing the lignin from the corn bran structure by alkalization, hydrolysis and oxidization, wherein the hydrolyzed lignin is dissolved in alcohol as medium; distilling organic alcohol solution after centrifugal separation of the low-molecular-weight mixed ether, recovering a part of organic alcohol, distilling the reminding part, adjusting pH of the solution by using an acid regulating agent, filtering and recovering the lignin, washing the lignin to be neutral, and drying to obtain medicine-grade or food-grade low-molecular-weight corn-bran mixed ether. The method disclosed by the invention has the advantages that the extraction cost of the lignin is greatly reduced, and simultaneously the quality of the low-molecular-weight corn-bran mixed ether is improved.
Description
Technical field
The invention belongs to corn bran or Testa Tritici and extract the xylogen field, especially relate to a kind of with in the low molecular mixing ether process of corn bran preparation, directly extracting the method for xylogen.
Background technology
Extracting the high purity araboxylan or prepare the high quality mixed ether with corn bran or Testa Tritici all needs first by lignin extraction out.With corn bran and Testa Tritici, extract in the araboxylan process at present, extract xylogen xylogen method a lot, extract and send out etc. such as: chlorous acid extraction method, high-boiling point alcohol High Temperature High Pressure, all adopt special process first to extract xylogen, these methods are used a large amount of water or high-boiling point alcohol, very difficult when reclaiming xylogen and reclaiming high-boiling point alcohol, consume mass energy, greatly improve extraction cost.
Corn bran is only used for low-grade feed at present, corn bran is transformed to the problem that high additional series product are whole world research, no matter be to extract araboxylan or the macromolecular compound of processing substituted chemistry product, the for example preparation of mixed ether, all need first lignin extraction out, by corn bran, prepared in low molecular mixing ether process by the present invention, directly extract separating lignin, making to extract xylogen technique oversimplifies more, the generation waste liquid is few, on the quality base that improves low molecule corn bran mixed ether, do not increase the production cost of mixed ether, extract water-insoluble xylogen, further improved the economic benefit of corn bran deep-processing process, for corn bran, with the Testa Tritici process change, become high value added product to find a new way, the present invention is to promoting the corn planting industry, the corn deep processing industry is significant.American National Ministry of Energy, american corn plantation association, U.S. ADM company develop jointly the work that corn bran transforms high value added product, and using this project as energy reserves project focus development.The xylogen that corn bran extracts, the low molecular mixing ether product of processing etc. can replace with derivative products such as timber, purified cotton, starch, mixed ether series product, lignin product that corn bran transforms can replace petroleum chemicals in a large number: polyvinyl alcohol, can disperse rubber powder, chemical tamanori etc., just equal to reduce the produced quantity of oil.China is global corn yield the second big country, and 2009 annual production reach 1.6 hundred million tons, promotes the corn processed industry, transforms the work that improves the corn value-added product, protects corn producing industry not invaded by developed country's technology extremely urgent.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of with in the low molecular mixing ether process of corn bran preparation, directly extracting the method for xylogen, solve current method and used a large amount of water or high-boiling point alcohol, very difficult when reclaiming xylogen and reclaiming high-boiling point alcohol, consume mass energy, greatly improve the problem of extraction cost.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind ofly by the direct method of extraction xylogen in the low molecular mixing ether process of corn bran preparation, it is characterized in that, comprise the following steps:
1) choose organic alcohol solvent, and alkalized with mineral alkali, obtain the Organic Alcohol alkaline solution, the corn bran powder is added in the Organic Alcohol alkaline solution, add oxygenant, carry out alkalization and hydrolysis, oxidation, xylogen is separated from corn bran, described alkalization and oxidizing temperature are 0-120 ℃, and the reaction times is 0.5-4 hour;
2) temperature is controlled to 0-35 ℃, with etherifying agent, then is warming up to 65-95 ℃, etherificate 1-8 hour, generate mixed ether; Lignin dissolution is in the ethanolic soln medium;
3) centrifugation mixed ether: repeatedly wash mixed ether with the ethanolic soln of 50-80%, xylogen in mixed ether is all washed off; Merge the repeatedly ethanolic soln of washing, Distillation recovery ethanol recycles;
4) by 3) middle still kettle remainder solution, adjust PH=3-8 with acid regulator, stir acidifying 20-120 minute, filter, reclaim xylogen;
5) wash xylogen with water to PH=6-8, dry, pulverize into finished product, be the low molecule corn bran mixed ether of medicine or food grade.
Preferably, in described step 1), organic alcohol solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, C4-C6 alcohol and isomery alcohol thereof, propylene glycol, glycerol.
Preferably, in described step 1), mineral alkali is: sodium hydroxide, strong potassium oxide, sodium carbonate.
Preferably, in described step 1), oxygenant is hydrogen peroxide, Textone, clorox.
Preferably, described step 2) in, etherifying agent is Mono Chloro Acetic Acid, sodium chloroacetate, oxyethane, propylene oxide, butylene oxide ring, methyl chloride, monochloroethane, chloroethanol, the chloro-2 hydroxypropyl tri alkyl ammomium chlorides of 3-(alkyl is C1-C12), 2,3-epoxypropyl tri alkyl ammomium chloride (alkyl is C1-C12).
Preferably, described acid regulator is hydrochloric acid, hydrogen chloride gas, sulfuric acid, phosphoric acid, formic acid, formic acid, acetic acid, oxyacetic acid, propionic acid.
Preferably, the mass ratio of described corn bran powder and Organic Alcohol alkaline solution is 1:(1-20);
In reaction system, the mass ratio of corn bran and water is 1:(0.1-3), wherein, water is added water from Organic Alcohol and alkali lye or processing requirement);
The mass ratio of corn bran and oxygenant is 1:(0.005-1), wherein, hydrogen peroxide concentration is by 30%, and clorox concentration is by 12%, and chlorous acid is by 90%;
The mass ratio of corn bran and etherifying agent is 1:(0.20-3.0);
The mass ratio of corn bran and mineral alkali alkali is 1:(0.12-2.0).
Above-mentioned method also can be used for directly extracting xylogen in Testa Tritici, brewer's grains, rice husk, Pericarppium arachidis hypogaeae, wheat straw, reed, the low molecular mixing ether process of timber preparation.
Adopted technique scheme, beneficial effect of the present invention is: take full use corn bran and Testa Tritici as purpose, with the low molecule corn bran mixed ether of corn bran preparation the time, direct extraction, separating lignin, greatly reduce the cost that extracts xylogen, improved the quality of low molecule corn bran mixed ether simultaneously, make the low molecule corn bran mixed ether of preparation reach the Application standard of medical auxiliary materials and foodstuff additive, but ether of cellulose and the starch ethers of purified cotton, starch, wood pulp cellulose production for Partial Replacement.The xylogen extracted belongs to water-insoluble xylogen, can be used for the industries such as rubber ingredients, building, oil paint, Self-leveling base-material, intermediate, has higher use value.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1, extract the method for xylogen during with the low molecule carboxymethyl mixed ether of corn bran preparation:
In the 50L reactor, add 92% ethanol 25L, add sodium hydroxide 3.5kg under stirring, be heated to 70 ℃ of cholines 30 minutes, be cooled to 35 ℃ and add the 5kg corn bran, quaternization 0.5 hour, then add 30% hydrogen peroxide 0.5kg, oxidation 30 minutes, the 72 ℃ of oxidations 30 minutes that heat up, begin to cool down, and within 30 minutes, is cooled to 25 ℃, be evacuated to-0.05Mpa 10 minutes.Add 50% Mono Chloro Acetic Acid ethanolic soln 7.85kg, start to heat up, within 30 minutes, rise to 55 ℃, react 30 minutes, within 15 minutes, rise to 78 ℃, react 2 hours.Be cooled to 45 ℃, molecule corn bran carboxymethyl mixed ether is hanged down in centrifugation, and xylogen is dissolved in ethanol filtrate.With 75% aqueous ethanolic solution 25L, washing mixed ether, repeated washing secondary.Merging filtrate and secondary washing liquid, Distillation recovery ethanol recycles; Steam to alcohol concn at the bottom of still be 10-25%, at the bottom of cooling reactor, residuum, to 35-55 ℃, adds 35% hydrochloric acid to adjust distillation residuum PH=3-6, acidifying 30 minutes, the centrifugation xylogen, to neutral, dry, be ground into the water-insoluble xylogen powder of 300-350g finished product with warm water washing xylogen.By the de-ethanol of washed corn bran mixed ether vacuum, dry, pulverizing obtains the low molecule corn bran carboxymethyl mixed ether of 6.5kg.
The 2% solution viscosity 2-3mpa.s with the NDJ-1 viscometer at 25 ℃ of mensuration corn bran mixed ethers.
The xylogen that the present embodiment extracts is ideal for auto-flowing floor material, paint property coating, seepage control and crack resistance concrete, thermal insulation mortar basic unit, sprayed concrete, gypsum product texts.Lower molecular weight corn bran carboxymethyl mixed ether replaces and can disperse the rubber powder effect very good for thermal insulation mortar, and reduces use cost.Low molecule product can be used for the industries such as foodstuff additive, medical auxiliary materials, petroleum drilling, papermaking, building glue simultaneously.
Embodiment 2, extract the method for xylogen while with corn bran, preparing low molecular weight hydroxypropyl carboxymethyl mixed ether:
Change 92% ethanol in embodiment 1 into 92% Virahol, after exhausting vacuum, add propylene oxide 1.8kg, under normal temperature, stirring reaction is 20 minutes, is warming up to 45-55 ℃, reacts 2 hours, be cooled to 25 ℃, add 50% Mono Chloro Acetic Acid aqueous isopropanol 7.2kg, remaining reaction condition and example 1 are identical.Obtain the water-insoluble xylogen 300-350kg of finished product; Hydroxypropyl carboxy methyl mixed ether finished product 6.8kg; The 2% solution viscosity 3-7mpa.s with the NDJ-1 viscometer at 25 ℃ of mensuration corn bran mixed ethers.
Embodiment 3, extract the method for xylogen while with corn bran, preparing low molecular weight hydroxyethyl carboxymethyl mixed ether:
Change propylene oxide in embodiment 2 into oxyethane, other conditionally complete is identical.Obtain the water-insoluble xylogen 300-350kg of finished product; Hydroxyethyl-carboxymethyl mixed ether finished product 6.3kg; The 2% solution viscosity 3-5mpa.s with the NDJ-1 viscometer at 25 ℃ of mensuration corn bran hydroxyethyl-carboxymethyl mixed ethers.
Embodiment 4, extract the method for xylogen while with corn bran, preparing the low molecular weight hydroxypropyl mixed ether:
In the 50L reactor, add 92% Virahol 25L, add sodium hydroxide 1.8kg under stirring, be heated to 70 ℃ of cholines 30 minutes, be cooled to 35 ℃ and add the 5kg corn bran, quaternization 0.5 hour, add again 30% hydrogen peroxide 0.5kg, oxidation 30 minutes, the 72 ℃ of oxidations 30 minutes that heat up, begin to cool down, within 30 minutes, be chilled to 25 ℃, be evacuated to-0.06mpa 7 minutes pumpdown times, triplicate.Add propylene oxide 3.5kg, stir at normal temperatures 25 minutes, start to heat up, within 30 minutes, rise to 45 ℃, 45 ℃ of reactions 2.5 hours, heat up 55 ℃ and react 2 hours.Be cooled to 25-45 ℃, use in Glacial acetic acid and PH=7.0-8.5; , molecule corn bran hydroxypropyl mixed ether is hanged down in centrifugation, and xylogen is dissolved in ethanol filtrate.With 70% isopropanol water solution 25L, the low molecular mixing ether of washing, repeated washing secondary.Merging filtrate and secondary washing liquid, the Distillation recovery Virahol recycles; Steam to isopropyl alcohol concentration at the bottom of still be 10-20%, at the bottom of cooling reactor, residuum, to 35-55 ℃, adds 35% hydrochloric acid to adjust distillation residuum PH=3-6, acidifying 30 minutes, the centrifugation xylogen, to neutral, dry, be ground into the water-insoluble xylogen powder of 300-350g finished product with warm water washing xylogen.By the de-Virahol of washed corn bran hydroxypropyl mixed ether vacuum, dry, pulverizing obtains the low molecule corn bran hydroxypropyl mixed ether of 6.2kg.
Embodiment 5, extract the method for xylogen while with corn bran, preparing the low molecular weight hydroxyethyl mixed ether:
Change the propylene oxide in embodiment 4 into oxyethane, all the other conditionally completes are identical, obtain the water-insoluble xylogen powder of finished product 300-350g.By the de-Virahol of washed corn bran hydroxypropyl mixed ether vacuum, dry, pulverizing obtains the low molecule corn bran hydroxyethyl mixed ether of 6.0kg.
As the present invention is not limited to above-mentioned concrete embodiment, those of ordinary skill in the art is from above-mentioned design, and without performing creative labour, all conversion of having done, within all dropping on protection scope of the present invention.
Claims (8)
1. one kind is hanged down with the corn bran preparation method of directly extracting xylogen in molecular mixing ether process, it is characterized in that, comprises the following steps:
1) choose organic alcohol solvent, and alkalized with mineral alkali, obtain the Organic Alcohol alkaline solution, the corn bran powder is added in the Organic Alcohol alkaline solution, adds oxygenant, carry out alkalization and hydrolysis, oxidation, described alkalization and oxidizing temperature are 0-120 ℃, and the reaction times is 0.5-4 hour;
2) temperature is controlled to 0-35 ℃, with etherifying agent, then is warming up to 65-95 ℃, etherificate 1-8 hour, generate mixed ether;
3) centrifugation mixed ether: repeatedly wash mixed ether with the ethanolic soln of 50-80%, merge the repeatedly ethanolic soln of washing, Distillation recovery ethanol recycles;
4) by 3) middle still kettle remainder solution, adjust PH=3-8 with acid regulator, stir acidifying 20-120 minute, filter, reclaim xylogen;
5) wash xylogen with water to PH=6-8, dry, pulverize into finished product, be the low molecule corn bran mixed ether of medicine or food grade.
2. method according to claim 1, is characterized in that, in described step 1), organic alcohol solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, C4-C6 alcohol and isomery alcohol thereof, propylene glycol, glycerol.
3. method according to claim 1, is characterized in that, in described step 1), mineral alkali is: sodium hydroxide, strong potassium oxide, sodium carbonate.
4. method according to claim 1, is characterized in that, in described step 1), oxygenant is hydrogen peroxide, Textone, clorox.
5. method according to claim 1, it is characterized in that, described step 2) in, etherifying agent is Mono Chloro Acetic Acid, sodium chloroacetate, oxyethane, propylene oxide, butylene oxide ring, methyl chloride, monochloroethane, chloroethanol, the chloro-2 hydroxypropyl tri alkyl ammomium chlorides of 3-(alkyl is C1-C12), 2,3-epoxypropyl tri alkyl ammomium chloride (alkyl is C1-C12).
6. method according to claim 1, is characterized in that, described acid regulator is hydrochloric acid, hydrogen chloride gas, sulfuric acid, phosphoric acid, formic acid, formic acid, acetic acid, oxyacetic acid, propionic acid.
7. method according to claim 1, is characterized in that, the mass ratio of described corn bran powder and Organic Alcohol alkaline solution is 1:(1-20);
In reaction system, the mass ratio of corn bran and water is 1:(0.1-3), wherein, water is added water from Organic Alcohol and alkali lye or processing requirement);
The mass ratio of corn bran and oxygenant is 1:(0.005-1), wherein, hydrogen peroxide concentration is by 30%, and clorox concentration is by 12%, and chlorous acid is by 90%;
The mass ratio of corn bran and etherifying agent is 1:(0.20-3.0);
The mass ratio of corn bran and mineral alkali is 1:(0.12-2.0).
8. according to the described method of any claim of claim 1-7, it is characterized in that, described method also can be used for directly extracting xylogen in Testa Tritici, brewer's grains, rice husk, Pericarppium arachidis hypogaeae, wheat straw, reed, the low molecular mixing ether process of timber preparation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10240006B2 (en) | 2014-05-01 | 2019-03-26 | Renmatix, Inc. | Upgrading lignin from lignin-containing residues through reactive extraction |
| CN111206448A (en) * | 2020-01-19 | 2020-05-29 | 陕西科技大学 | Lignin separation method based on binary catalytic ethanol method |
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Patent Citations (6)
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| CN1779070A (en) * | 2005-08-09 | 2006-05-31 | 华南理工大学 | Full component separation for cell wall of agricultural refuse |
| CN1844167A (en) * | 2006-03-03 | 2006-10-11 | 才景志 | Sodium carboxymethyl hemicellulose with paper-making black liquor as raw material and producing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10240006B2 (en) | 2014-05-01 | 2019-03-26 | Renmatix, Inc. | Upgrading lignin from lignin-containing residues through reactive extraction |
| CN111206448A (en) * | 2020-01-19 | 2020-05-29 | 陕西科技大学 | Lignin separation method based on binary catalytic ethanol method |
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Effective date of registration: 20190821 Address after: 518052 Guangdong city of Shenzhen province Qianhai Shenzhen Hong Kong cooperation zone before Bay Road No. 1 building 201 room A (located in Shenzhen Qianhai business secretary Co. Ltd.) Patentee after: Shenzhen Mo Dun environmental protection new material Co., Ltd. Address before: No. 168 Airway Road, Liuhe Industrial Park, Xiaogan City, Hubei Province, 432000 Patentee before: Hubei Professional New Biological Material Co., Ltd. |