CN102887957A - Method for preparing sodium carboxymethyl cellulose from furfural slag - Google Patents
Method for preparing sodium carboxymethyl cellulose from furfural slag Download PDFInfo
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- CN102887957A CN102887957A CN2012104232579A CN201210423257A CN102887957A CN 102887957 A CN102887957 A CN 102887957A CN 2012104232579 A CN2012104232579 A CN 2012104232579A CN 201210423257 A CN201210423257 A CN 201210423257A CN 102887957 A CN102887957 A CN 102887957A
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Abstract
The invention belongs to the field of preparation of sodium carboxymethyl cellulose, and particularly discloses a method for preparing sodium carboxymethyl cellulose from furfural slag. The method comprises the following steps: (1) extracting furfural slag with a solvent, separating, washing, and drying to obtain cellulose; (2) bleaching the cellulose with alkaline oxydol, separating, washing, and drying to obtain refined cellulose; and (3) alkalizing the refined cellulose, etherifying, neutralizing with acid, separating, washing, and drying to obtain the sodium carboxymethyl cellulose finished product. The coarse fiber treated by formic acid and oxydol can react with the alkaline oxydol more easily, thereby generating favorable bleaching effect; the invention has the advantages of simple equipment, mild reaction conditions, recoverable solvent, low production cost and high lignin recovery rate; and the operation is carried out under atmospheric pressure, and thus, is convenient and safe.
Description
Technical field
The invention belongs to the preparation field of Xylo-Mucine, be specifically related to a kind of method of utilizing furfural dregs to prepare Xylo-Mucine.
Background technology
Xylo-Mucine (CMC) is described as " industrial monosodium glutamate ", is widely used in the industries such as oil, geology, daily use chemicals, light industry, food, medicine.Because its excellent performance and purposes widely, with and also open up new Application Areas constantly, it is had a high potential, market outlook are very wide.
Furfural, chemical name is furaldehyde, is a kind of important industrial chemicals.Producing furfural in northern China mainly is to utilize corn cob, produce 1 ton of furfural and probably need 11～12 tons of corn cobs, so just produced a lot of furfural dregs, therefore, economy is isolated a large amount of furfural dregs in the processing production process properly, both can solve a large amount of furfural dregs and pile up the environmental problem that causes, realize again economic benefit.
At present the main purposes of furfural dregs of report is to make soil improvement agent or do fuel by mixing with coal, and also useful furfural dregs separates the patent report for preparing Microcrystalline Cellulose and cellulose ethanol (CN101413016), does culture medium of edible fungus (CN1049518) and make granulated active carbon (CN88101457) etc. with furfural dregs with compound furfural dregs.Measure by analysis, cellulosic content is more than 40% in the furfural dregs, the content of xylogen is about 30%, if wherein abundant Mierocrystalline cellulose is extracted synthetic Xylo-Mucine, the xylogen of stripping is done material of construction etc., when having realized economic benefit, solved again a large amount of furfural dregs and stacked the environmental problem that causes.
Report prepares in the method for Xylo-Mucine with straw, bagasse, potato slag etc. before, separated fiber element and the used method of xylogen mostly are with alkaline boiling and steam explosion, these methods need to consume a large amount of alkali and the energy, and pressurized operation also has potential safety hazard.Experiment finds, it is also not so good that these methods are used for separating in the furfural dregs effect of Mierocrystalline cellulose and xylogen.
Summary of the invention
The purpose of this invention is to provide a kind ofly reduce production costs, Mierocrystalline cellulose and xylogen have the good separation effect in the furfural dregs the furfural dregs that utilizes prepares the method for Xylo-Mucine, also realized simultaneously the refuse reclamation of furfural dregs, both realized economic benefit, environment protection significance had been arranged again.
The manufacturer of China's furfural adopts the sulfuric acid catalysis method more than 95% at present, gained aldehyde slag is measured by analysis, contain the Mierocrystalline cellulose more than 40%, the content of xylogen is about 30%, acid hydrolysis has also destroyed the cellulosic reticulated structure of parcel in the plant cell wall when removing a large amount of hemicelluloses, provide favourable condition for utilizing Mierocrystalline cellulose.
According to the composition and structure of above-mentioned furfural dregs, the present invention proposes following technical scheme and fully utilizes the method that furfural dregs prepares Xylo-Mucine, may further comprise the steps:
(1) solvent extraction furfural dregs, separation, washing, the dry Mierocrystalline cellulose that gets;
(2) Mierocrystalline cellulose is bleached through alkaline hydrogen peroxide, separation, washing, the dry refined cellulose that gets;
(3) refined cellulose is through alkalization, etherificate, and sour neutralization, separation, washing, drying make the Xylo-Mucine finished product.
Further, the solvent extraction furfural dregs described in the step (1) is: take the hydrogen peroxide of formic acid and mass concentration 10 ~ 30% as solvent, and the extraction furfural dregs; Wherein, formic acid is 7:1～16:1 with the volume mass of furfural dregs than ml/g, and hydrogen peroxide is 0.8:1～1.6:1 with the volume mass of furfural dregs than ml/g, and extraction temperature is 60～95 ℃, and extraction time is 3～7h.
Further, the bleaching of the alkaline hydrogen peroxide described in the step (2) is: Mierocrystalline cellulose adds the sodium hydroxide solution of 1 ~ 20g/L and the hydrogen peroxide of mass concentration 10 ~ 30% is bleached; Wherein adding hydrogen peroxide is 10:1～20:1 with cellulosic volume mass than ml/g, and institute's hydro-oxidation sodium solution and cellulosic mass ratio are 0.6～1.2:1, and bleaching temperature is 25～65 ℃, bleaching time 50～120min.
Further, the alkalization described in the step (3), etherificate are: refined cellulose drips chloroacetic ethanolic soln and carries out etherification reaction after the sodium hydroxide solution alkalization; Wherein, alkalization temperature is 10～35 ℃, and alkalization time is 40～80min; Refined cellulose is 1:0.8～2.0 with the ratio of chloroacetic amount of substance, and etherification temperature is 60～80 ℃, etherificate time 90～150min.
Preferably, in the step (3), the concentration of sodium hydroxide solution is 100 ~ 200g/L, alkalizes to pH value 10 ~ 12; The concentration of chloroacetic ethanolic soln is 60 ~ 160g/L.
Preferably, described step (1) is front carrying out, the processing of first furfural dregs being removed sand, then dry, pulverize, sieve.
Better, in the step (1), during separation, underpressure distillation filtrate is reclaimed formic acid, and then the vacuum-drying distillation residue obtain xylogen.
Preferably, distillation temperature is 80～100 ℃.
The inventor is through exploring, proposed a kind of with Mierocrystalline cellulose and xylogen in the solvent method separation furfural dregs, and make the method for Xylo-Mucine, have the following advantages: (1) produces good bleaching effect with the easier and alkaline hydrogen peroxide reaction of robust fibre that formic acid, hydrogen peroxide obtain after processing; (2) equipment is simple, and reaction conditions is gentle, atmospheric operation, and convenient and safe, solvent is recyclable, and production cost is low; (3) the lignin recovery rate is high, can reach 83 ~ 97%.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is done further in detail introduction, but protection scope of the present invention is not limited to this.
Embodiment 1
With furfural dregs remove sand process after, dry, pulverize, sieve, take the hydrogen peroxide of formic acid and mass concentration 20% as solvent boiling dissolving, the material after the suction filtration boiling is isolated Mierocrystalline cellulose, the washing Mierocrystalline cellulose is to neutral, then dry Mierocrystalline cellulose; Suction filtration liquid is carried out 85 ℃ of underpressure distillation, reclaim formic acid, isolate xylogen, 65 ℃ of vacuum-dryings get xylogen (rate of recovery 88.1%).Add formic acid and furfural dregs volume mass be 7:1 than ml/g, add hydrogen peroxide and furfural dregs volume mass be 1:1 than ml/g, 75 ℃ of extraction temperature, extraction time 6h.
Alkaline hydrogen peroxide (hydrogen peroxide of sodium hydroxide solution+mass concentration 20% of 5g/L) is bleached dried Mierocrystalline cellulose, suction filtration, washing, the dry refined cellulose that gets; It is 12:1 with cellulosic volume mass than ml/g that institute adds hydrogen peroxide, and institute's hydro-oxidation sodium solution and cellulosic mass ratio are 0.6:1,30 ℃ of bleaching 90min.。
Refined cellulose after 25 ℃ of lower alkalization 70min to pH values 11, drips the chloroacetic ethanolic soln of 80g/L through the sodium hydroxide solution of 120g/L, and refined cellulose is 1:1.2 with the ratio of chloroacetic amount of substance, is warming up to 65 ℃, behind the constant temperature, and etherificate 150min.With hydrochloric acid soln neutralization reaction liquid, suction filtration, washing, the dry Xylo-Mucine finished product that gets.
Embodiment 2
With furfural dregs remove sand process after, dry, pulverize, sieve, take the hydrogen peroxide of formic acid and mass concentration 30% as the high boiling dissolving of solvent, the material after the suction filtration boiling is isolated Mierocrystalline cellulose, the washing Mierocrystalline cellulose is to neutral, then dry Mierocrystalline cellulose; Suction filtration liquid is carried out 90 ℃ of underpressure distillation, reclaim formic acid, isolate xylogen, 70 ℃ of vacuum-dryings get xylogen (rate of recovery 94.8%).Add formic acid and furfural dregs volume mass be 9:1 than ml/g, add hydrogen peroxide and furfural dregs volume mass be 1.2:1 than ml/g, 85 ℃ of extraction temperature, extraction time 5h.
Alkaline hydrogen peroxide (hydrogen peroxide of sodium hydroxide solution+mass concentration 30% of 10g/L) is bleached dried Mierocrystalline cellulose, suction filtration, washing, the dry refined cellulose that gets.It is 14:1 with cellulosic volume mass than ml/g that institute adds hydrogen peroxide; Institute's hydro-oxidation sodium solution and cellulosic mass ratio are 0.8:1; 45 ℃ of bleaching 60min.
Refined cellulose after 30 ℃ of lower alkalization 60min to pH values 11, drips the chloroacetic ethanolic soln of 100g/L through the sodium hydroxide solution of 150g/L, and refined cellulose is 1:1.5 with the ratio of chloroacetic amount of substance, is warming up to 70 ℃, behind the constant temperature, and etherificate 150min.With hydrochloric acid soln neutralization reaction liquid, suction filtration, washing, the dry Xylo-Mucine finished product that gets.
Embodiment 3
With furfural dregs remove sand process after, dry, pulverize, sieve, take the hydrogen peroxide of formic acid and mass concentration 30% as solvent boiling dissolving, the material after the suction filtration boiling is isolated Mierocrystalline cellulose, the washing Mierocrystalline cellulose is to neutral, then dry Mierocrystalline cellulose; Suction filtration liquid is carried out 95 ℃ of underpressure distillation, reclaim formic acid, isolate xylogen, 75 ℃ of vacuum-dryings get xylogen (rate of recovery 96.5%).Add formic acid and furfural dregs volume mass be 11:1 than ml/g, add hydrogen peroxide and furfural dregs volume mass be 1.4:1 than ml/g, 95 ℃ of extraction temperature, extraction time 4h.
Alkaline hydrogen peroxide (hydrogen peroxide of sodium hydroxide solution+mass concentration 30% of 15g/L) is bleached dried Mierocrystalline cellulose, suction filtration, washing, the dry refined cellulose that gets.It is 16:1 with cellulosic volume mass than ml/g that institute adds hydrogen peroxide; Institute's hydro-oxidation sodium solution and cellulosic mass ratio are 1.2:1; 60 ℃ of bleaching 50min.
Refined cellulose after 35 ℃ of lower alkalization 50min to pH values 11, drips the chloroacetic ethanolic soln of 120g/L through the sodium hydroxide solution of 180g/L, and refined cellulose is 1:1.8 with the ratio of chloroacetic amount of substance, is warming up to 75 ℃, behind the constant temperature, and etherificate 120min.With hydrochloric acid soln neutralization reaction liquid, suction filtration, washing, the dry Xylo-Mucine finished product that gets.
Claims (8)
1. method of utilizing furfural dregs to prepare Xylo-Mucine is characterized in that may further comprise the steps:
The solvent extraction furfural dregs, separation, washing, the dry Mierocrystalline cellulose that gets;
Mierocrystalline cellulose is bleached through alkaline hydrogen peroxide, separation, washing, the dry refined cellulose that gets;
Refined cellulose is through alkalization, etherificate, and sour neutralization, separation, washing, drying make the Xylo-Mucine finished product.
2. the method for utilizing furfural dregs to prepare Xylo-Mucine as claimed in claim 1 is characterized in that the solvent extraction furfural dregs described in the step (1) is: take the hydrogen peroxide of formic acid and mass concentration 10 ~ 30% as solvent, and the extraction furfural dregs; Wherein, formic acid is 7:1～16:1 with the volume mass of furfural dregs than ml/g, and hydrogen peroxide is 0.8:1～1.6:1 with the volume mass of furfural dregs than ml/g, and extraction temperature is 60～95 ℃, and extraction time is 3～7h.
3. the method for utilizing furfural dregs to prepare Xylo-Mucine as claimed in claim 2, it is characterized in that the alkaline hydrogen peroxide bleaching described in the step (2) is: Mierocrystalline cellulose adds the sodium hydroxide solution of 1 ~ 20g/L and the hydrogen peroxide of mass concentration 10 ~ 30% is bleached; Wherein adding hydrogen peroxide is 10:1～20:1 with cellulosic volume mass than ml/g, and institute's hydro-oxidation sodium solution and cellulosic mass ratio are 0.6～1.2:1, and bleaching temperature is 25～65 ℃, bleaching time 50～120min.
4. the method for utilizing furfural dregs to prepare Xylo-Mucine as claimed in claim 3, it is characterized in that the alkalization described in the step (3), etherificate are: refined cellulose drips chloroacetic ethanolic soln and carries out etherification reaction after the sodium hydroxide solution alkalization; Wherein, alkalization temperature is 10～35 ℃, and alkalization time is 40～80min; Refined cellulose is 1:0.8～2.0 with the ratio of chloroacetic amount of substance, and etherification temperature is 60～80 ℃, etherificate time 90～150min.
5. the method for utilizing furfural dregs to prepare Xylo-Mucine as claimed in claim 4, it is characterized in that: in the step (3), the concentration of sodium hydroxide solution is 100 ~ 200g/L, alkalizes to pH value 10 ~ 12; The concentration of chloroacetic ethanolic soln is 60 ~ 160g/L.
6. such as the described method of utilizing furfural dregs to prepare Xylo-Mucine of any one of claim 1 ~ 5, it is characterized in that: described step (1) is front carrying out, the processing of first furfural dregs being removed sand, then dry, pulverize, sieve.
7. the method for utilizing furfural dregs to prepare Xylo-Mucine as claimed in claim 6 is characterized in that: in the step (1), during separation, underpressure distillation filtrate is reclaimed formic acid, and then the vacuum-drying distillation residue obtain xylogen.
8. the method for utilizing furfural dregs to prepare Xylo-Mucine as claimed in claim 7, it is characterized in that: distillation temperature is 80～100 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435817A (en) * | 2013-09-18 | 2013-12-11 | 湖北博斐逊生物新材料有限公司 | Method for directly extracting lignin in process of using corn bran to prepare low-molecular-weight mixed ether |
| CN103806318A (en) * | 2014-01-16 | 2014-05-21 | 北京林业大学 | Method for extracting cellulose from furfural residues |
| CN109502622A (en) * | 2018-11-21 | 2019-03-22 | 上海碳酸钙厂有限公司 | A kind of preparation method of medicinal precipitated calcium carbonate |
| CN109731888A (en) * | 2019-01-29 | 2019-05-10 | 郗丹 | A kind of chromium slag innocent treatment method |
| CN114874343A (en) * | 2022-05-30 | 2022-08-09 | 河南工业大学 | Spherical nanocrystalline cellulose based on furfural residues and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435817A (en) * | 2013-09-18 | 2013-12-11 | 湖北博斐逊生物新材料有限公司 | Method for directly extracting lignin in process of using corn bran to prepare low-molecular-weight mixed ether |
| CN103435817B (en) * | 2013-09-18 | 2015-07-08 | 湖北博斐逊生物新材料有限公司 | Method for directly extracting lignin in process of using corn bran to prepare low-molecular-weight mixed ether |
| CN103806318A (en) * | 2014-01-16 | 2014-05-21 | 北京林业大学 | Method for extracting cellulose from furfural residues |
| CN109502622A (en) * | 2018-11-21 | 2019-03-22 | 上海碳酸钙厂有限公司 | A kind of preparation method of medicinal precipitated calcium carbonate |
| CN109731888A (en) * | 2019-01-29 | 2019-05-10 | 郗丹 | A kind of chromium slag innocent treatment method |
| CN109731888B (en) * | 2019-01-29 | 2020-11-20 | 湖南福尔程环保科技有限公司 | Harmless treatment method for chromium slag |
| CN114874343A (en) * | 2022-05-30 | 2022-08-09 | 河南工业大学 | Spherical nanocrystalline cellulose based on furfural residues and preparation method thereof |
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Application publication date: 20130123 |