CN101463091A - Method for separating stalk carboxymethylation components and preparing stalk carboxymethyl cellulose - Google Patents
Method for separating stalk carboxymethylation components and preparing stalk carboxymethyl cellulose Download PDFInfo
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Abstract
The invention relates to a method for separating straw carboxymethylated components to prepare carboxymethyl cellulose. The method comprises the following steps: ethanol is added to steam exploded straw to be taken as a reaction medium, carboxymethylation reaction occurs in the presence of sodium hydroxide and sodium monochloroacetate to obtain a solid containing the carboxymethyl cellulose, carboxymethylated hemicellulose and carboxymethylated lignin; the solid is moistened with water, added with hydrochloric acid for precipitation, added with the sodium hydroxide to adjust the pH value, and centrifuged to collect supernatant and precipitate; the ethanol is used for washing the supernatant to produce the precipitate, and the precipitate (sodium carboxymethyl cellulose) is obtained by vacuum filtration; and the centrifuged precipitate part is the carboxymethylated hemicellulose and the carboxymethylated lignin; the precipitate is subject to solvent extraction, the component insoluble in a solvent is the carboxymethylated lignin, and the rest components are the carboxymethylated hemicellulose. The method solves the limitation that a single component is used in the traditional component separation methods, the obtained carboxymethyl cellulose can be applied to enzymolysis, fermentation and industries, the carboxymethylated lignin and the like have more properties after modification, and the method realizes the straw component separation.
Description
Technical field
The invention belongs to straw refuse utilization of resources field, particularly a kind of combination preprocessing means that comprises steam explosion and carboxymethylation reaction realizes that stalk prepares carboxymethyl cellulose and reaches the isolating method of component.
Background technology
Agricultural crop straw is modal ligno-cellulosic materials, also is the extremely abundant biomass resource of quantity, and China's stalk average year output can reach 700,000,000 tons, occupies first of the world.As a kind of important recyclability resource, stalk has comprised Mierocrystalline cellulose, hemicellulose and xylogen three big components, and the investigator has carried out more comprehensive research from each subject angle both at home and abroad.But, emphasize the utilization of Mierocrystalline cellulose one-component wherein for a long time excessively and do not have the coupling of technology to make all also not realize competitive breakthrough aspect product performance, Technological Economy and the environment so far based on the stalk resource development product because the component of stalk resource is abundant, complex structure.And if can effectively utilize stalk resource by the integrated use of means such as preconditioning technique, fermentation technique, physical chemistry and biotechnology, will turn waste into wealth for realizing, advance industrial society to enter the biorefinery epoch and make huge contribution.
Carboxymethyl cellulose is to be most widely used, the most representative ionic ether of cellulose.Carboxymethyl cellulose aqueous solution has thickening, bonding, film forming, protection glue, keeps effects such as moisture, emulsification and suspension; be widely used in multiple industry such as washing composition, food, weaving, printing and dyeing, papermaking, oil, mining, makeup, the good reputation of " industrial monosodium glutamate " is arranged.The raw material of preparation carboxymethyl cellulose requires the alpha-cellulose content of cellulosic material to be not less than 88%, the polymerization degree 500-2000 mainly with linters and wood pulp through refining (purifying) usually.This has just caused raw materials cost high, Mierocrystalline cellulose pre-treatment difficulty and environment caused great pollution.Thereby the exploitation cheap raw material reduces pretreated cost, optimizes technological process and has become the task of top priority.
Proposed to produce the method for carboxymethyl cellulose among the patent CN1410451A with straw, the basic raw materials pretreatment process is for boiling through acid or soda boiling extracts wherein alpha-cellulose component after handling, again the alpha-cellulose component being carried out etherificate handles, though raw materials cost descends to some extent, but operational path complexity, the treatment condition harshness, seriously polluted.Method with microwave radiation among the patent CN101230547A is handled lignocellulosic material, remove the xylogen composition by hydrogen peroxide effect under the high temperature and obtain purer cellulosic component, carry out carboxymethylation reaction again, shortened the reaction times, but still be to concentrate on the single utilization of cellulosic component and the complete utilization of stalk three components that are unrealized.
It is by stalk being carried out pre-treatment, then it is carried out direct carboxymethylation that steam puffed stalk etherificate component is separated, and utilizes the difference of straw component carboxymethyl after product physico-chemical property and separates.Stalk carboxymethylation mainly is hydroxyl and the sodium chloroacetate reaction in the components such as Mierocrystalline cellulose in the stalk, hemicellulose, xylogen, obtaining carboxymethylated Mierocrystalline cellulose is Xylo-Mucine, carboxymethylated xylogen (making xylogen obtain modification) and other carboxymethylation products.
Mierocrystalline cellulose, hemicellulose and xylogen are interweaved by effects such as hydrogen bond, chemical bonds and form complexity cell wall structure closely, make the natural fiber feed composition separate and the utilization difficulty.If directly utilize natural stalk to carry out carboxymethylation reaction, reaction conversion ratio is low, and long reaction time.Therefore to realize the carboxymethylation reaction of stalk, must carry out the pre-activated of stalk earlier and handle.
Component is separated the comprehensive utilization that will realize biomass exactly, with each component in the maximum yield separating natural cellulose raw material, to keep the integrity of molecule as much as possible, with maximum optimization utilization and the final maximum value that realizes biomass.Pretreated purpose is exactly the strong bond combination of opening between the straw component, destroys xylogen to cellulosic package action and cellulosic crystalline texture, and component is activated.Thereby selection is reasonable, economical, environmentally friendly pretreatment process is the key of carboxymethylation reaction.
Under this thinking, at abundant, the baroque characteristics of component of stalk lignocellulose raw material, we have developed new component isolation technique system.
Summary of the invention
One of [purpose of the present invention] purpose of the present invention is at this multi-component lignocellulose raw material of stalk, developed the component separation method that is adapted to its special construction, thereby can realize that straw component separates, can obtain the carboxymethyl cellulose of high added value again, separate the utilization that other components that obtain also obtain maximum value simultaneously, the limitation that has overcome the one-component utilization of traditional components separation method reaches the significant damage that environment is caused.
The biomass complete utilization of [design of the present invention] stalk resource requires to realize the utilization respectively of each component in the stalk, yet, present pretreatment mode still concentrates on the acquisition of Mierocrystalline cellulose one-component or only adopts single pretreatment mode, and the former has caused the waste latter of other component resource then to be difficult to obtain good separating effect.Adopt steam explosion activation treatment stalk, make stalk three big component functionization by etherification reaction then, by separating the utilization that realizes different components, this just provides new thinking for the comprehensive utilization stalk resource again.
[technical solution of the present invention] technical scheme of the present invention is as follows:
Straw carboxymethylation components provided by the invention separates and prepares the method for carboxymethyl cellulose, and its step is as follows:
1) the straw particle is carried out the steam explosion pre-activated and handle, and oven dry;
2) steam explosion of step 1) being activated pretreated straw material carries out carboxymethylation and handles;
Activating the ethanol and the sodium chloroacetate that add certain volume in the pretreated straw material at the steam explosion of step 1) disperses, add then that sodium hydroxide solution alkalizes and carboxymethylation is handled, generation contains the solid of carboxymethyl cellulose, carboxymethylation hemicellulose and carboxymethylation xylogen, its temperature of reaction is at 40-100 ℃, reaction times 0.5-8 hour, reaction was under agitation carried out; After reaction finishes, with acetic acid conditioned reaction pH value to neutral, in the ethanol adding reactor with the 70%-95% of 2-15 times of volume, agitator treating 0.5-3 hour.After washing finishes,, reclaim filtrate, will be deposited in 50-60 ℃ of vacuum-drying and spend the night with suction filtration reaction solution under the vacuum pump decompression.
3) separation of carboxymethylcellulocomponent component
Method 1: with step 2) solid of dried carboxymethyl cellulose, carboxymethylation hemicellulose and carboxymethylation xylogen is 100-200 distilled water vigorous stirring dissolving doubly with 80-100 ℃ of volume ratio, use G2 sand core funnel filtered while hot then, collect filtrate and precipitation respectively.The precipitation part is the carboxymethyl cellulose of carboxymethylated hemicellulose and xylogen and part substitution value＜0.3.
Filtrate is boiled off most of solvent by underpressure distillation concentrate, be concentrated into about the 1/5-1/10 of initial soln volume.95% ethanol that adds 10-20 times of volume then washs, and filtrate produces precipitation after adding ethanol, carries out suction filtration then and obtains precipitation, and this precipitation promptly is a carboxymethyl cellulose.
Method 2: with the water-wet of carboxymethylation product, add the salt Acid precipitation then, add the sodium hydroxide stirring and dissolving again and regulate pH to 8-10, pour in the centrifuge tube centrifugally, separate supernatant and precipitation, collect supernatant and precipitation.The precipitation part is carboxymethylated hemicellulose and xylogen.Mix with supernatant with 95% ethanol, supernatant precipitates.Carry out suction filtration then and obtain precipitation, this precipitation promptly is a carboxymethyl cellulose.
4) carboxymethylation xylogen and hemicellulose component separates
Precipitation after centrifugal in step 3) part is used solvent extraction 0.5-4 hours in Soxhlet extractor, extracting is dissolved in the solute of this solvent, and this solute is carboxymethylated xylogen, is insoluble to the carboxymethylated hemicellulose that is of this solvent; Described solvent is the lower alcohol that comprises ethanol.
Described straw is maize straw, wheat stalk or rice straw.
Straw carboxymethylation components provided by the invention separates and prepares the method for carboxymethyl cellulose, after the described step 1), also comprises the pretreated steam-puffed plant straw and stalk of activation, carries out long and short fiber comb and divides; In step 2) in respectively the steam-puffed plant straw and stalk of long and short fiber is carried out carboxymethylation and handles.
The method that [the present invention has the following advantages] straw carboxymethylation components of the present invention separates and prepare carboxymethyl cellulose has the following advantages:
(1) utilizes steam explosion that straw is carried out pre-treatment, can break the structure of stalk inner tight, increased the reactive behavior of stalk greatly.
(2) correspondingly separate and utilization at the different characteristics of carboxymethylation stalk product, not only opened up an isolating new road of straw component, can also obtain products such as the carboxymethyl cellulose of high added value, carboxymethylated lignin, thereby can substitute raw materials such as part timber, cotton as the raw material of industrial production carboxymethyl cellulose with stalk, realize saving high-quality resource, waste is made full use of.
(3) overcome the pollution of conventional physical chemical composition separation method and the limitation that one-component utilizes, realized the clean biometric amount complete utilization of stalk.
[description of drawings]
The FTIR spectrogram of Fig. 1 α-Mierocrystalline cellulose CMC (SC CMC) and the quick-fried maize straw CMC of vapour (SE CMC)
Fig. 2 α-Mierocrystalline cellulose CMC (a) compares with the scanning electron microscope image of the quick-fried maize straw CMC of vapour (b)
[embodiment]
Below the present invention is further elaborated by specific embodiment.
Embodiment 1
Quick-fried maize straw 5g of the vapour of drying and crushing and Monochloro Acetic Acid sodium 5.4g are added in the three-necked flask, add the 55ml dehydrated alcohol then, fully stir 30min down in 25 ℃, add sodium hydroxide 1.85g (being dissolved in the 5mL deionized water) then,, be warming up to 75 ℃ then in 25 ℃ of abundant down alkalization 45min that stir, be incubated 2 hours, extremely neutral after reaction finishes with the vinegar acid for adjusting pH value, be cooled to room temperature then, add 180mL80% washing with alcohol 30min; With the reaction solution decompress filter, obtain filtrate and precipitation then, keep precipitation, reclaim filtrate.To precipitate 60 ℃ of vacuum-dryings spends the night.
Take by weighing the exsiccant solid,, use G2 sand core funnel filtered while hot then, collect filtrate and precipitation respectively with the deionized water vigorous stirring dissolving of 20 times of mass volume ratios of 80-100 ℃.The precipitation part is the carboxymethyl cellulose of carboxymethylated hemicellulose and xylogen and part substitution value＜0.3.
Filtrate is boiled off most of solvent by underpressure distillation concentrate, be concentrated into about the 1/5-1/10 of initial soln volume.95% ethanol that adds 10-20 times of volume then washs, and filtrate produces precipitation after adding ethanol, carries out suction filtration then and obtains precipitation, and this precipitation promptly is a carboxymethyl cellulose.
Gained carboxymethyl cellulose and separation degree index are as follows:
Rate of body weight gain: 16.3%
DS：0.77
Carboxymethyl cellulose yield: 24.5%
Embodiment 2
Quick-fried maize straw 10g of the vapour of drying and crushing and Monochloro Acetic Acid sodium 10.8g are added in the three-necked flask, add the 55ml dehydrated alcohol then, fully stir 30min down in 25 ℃, add sodium hydroxide 1.85g (being dissolved in the 5mL deionized water) then,, be warming up to 75 ℃ then in 25 ℃ of abundant down alkalization 45min that stir, be incubated 2 hours, extremely neutral after reaction finishes with the vinegar acid for adjusting pH value, be cooled to room temperature then, add 180mL80% washing with alcohol 30min; With the reaction solution decompress filter, obtain filtrate and precipitation then, keep precipitation, reclaim filtrate.To precipitate 60 ℃ of vacuum-dryings spends the night.
With the water-wet of carboxymethylation product, add the salt Acid precipitation then, add the sodium hydroxide stirring and dissolving again and regulate pH to 8-10, pour in the centrifuge tube centrifugally, separate supernatant and precipitation, collect supernatant and precipitation.The precipitation part is carboxymethylated hemicellulose and xylogen.Mix with supernatant with 95% ethanol, supernatant precipitates.Carry out suction filtration with the G3 sand core funnel then, and, use 95% washing with alcohol at last once with 80% washing with alcohol 3 times.Oven dry is weighed.Resulting product is Xylo-Mucine.
Gained carboxymethyl cellulose and separation degree index are as follows:
Rate of body weight gain: 56.5%
DS：1.45
Carboxymethyl cellulose yield: 37.5%
Embodiment 3
Quick-fried maize straw 4g of the vapour of drying and crushing and Monochloro Acetic Acid sodium 5.75g are added in the three-necked flask, add the 64ml dehydrated alcohol then, fully stir 30min down in 25 ℃, add sodium hydroxide 1.97g (being dissolved in the 8mL deionized water) then,, be warming up to 75 ℃ then in 25 ℃ of abundant down alkalization 45min that stir, be incubated 2 hours, extremely neutral after reaction finishes with the vinegar acid for adjusting pH value, be cooled to room temperature then, add 144mL80% washing with alcohol 60min; With the reaction solution decompress filter, obtain filtrate and precipitation then, keep precipitation, reclaim filtrate.To precipitate 60 ℃ of vacuum-dryings spends the night.
The carboxymethylation product is wetting with deionized water, add the salt Acid precipitation then, add the sodium hydroxide stirring and dissolving again and regulate pH to 8-10, pour in the centrifuge tube centrifugally, separate supernatant and precipitation, collect supernatant and precipitation.The precipitation part is carboxymethylated hemicellulose and xylogen.Mix with supernatant with 95% ethanol, supernatant precipitates.Carry out suction filtration with the G3 sand core funnel then, and, use 95% washing with alcohol at last once with 80% washing with alcohol 3 times.Oven dry is weighed.Resulting product is Xylo-Mucine.The precipitation part is used the ethanol extracting, can separate obtaining carboxymethylated xylogen and hemicellulose.Adopt the structure of Infrared spectroscopy product.
Gained carboxymethyl cellulose and separation degree index are as follows:
Rate of body weight gain: 15.0%
DS：0.91
Carboxymethyl cellulose yield: 32.2%
Embodiment 4
Quick-fried maize straw 4g of the vapour of drying and crushing and Monochloro Acetic Acid sodium 5.75g are added in the three-necked flask, add the 68ml dehydrated alcohol then, fully stir 30min down in 25 ℃, add sodium hydroxide 1.97g (being dissolved in the 4mL deionized water) then,, be warming up to 75 ℃ then in 25 ℃ of abundant down alkalization 45min that stir, be incubated 2 hours, extremely neutral after reaction finishes with the vinegar acid for adjusting pH value, be cooled to room temperature then, add 144mL80% washing with alcohol 60min; With the reaction solution decompress filter, obtain filtrate and precipitation then, keep precipitation, reclaim filtrate.To precipitate 60 ℃ of vacuum-dryings spends the night.
The carboxymethylation product is wetting with deionized water, add the salt Acid precipitation then, add the sodium hydroxide stirring and dissolving again and regulate pH to 8-10, pour in the centrifuge tube centrifugally, separate supernatant and precipitation, collect supernatant and precipitation.The precipitation part is carboxymethylated hemicellulose and xylogen.Mix with supernatant with 95% ethanol, supernatant precipitates.Carry out suction filtration with the G3 sand core funnel then, and, use 95% washing with alcohol at last once with 80% washing with alcohol 3 times.Oven dry is weighed.Resulting product is Xylo-Mucine.The precipitation part is used the ethanol extracting, can separate obtaining carboxymethylated xylogen and hemicellulose.Adopt the structure of Infrared spectroscopy product.
Gained carboxymethyl cellulose and separation degree index are as follows:
Rate of body weight gain: 24.3%
DS：0.93
Carboxymethyl cellulose yield: 35.5%.
Claims (3)
1, a kind of stalk carboxymethylation components separates and prepares the method for stalk carboxymethyl cellulose, and its step is as follows:
1) the straw particle is carried out the steam explosion pre-activated and handle, and oven dry;
2) steam explosion of step 1) being activated pretreated straw material carries out carboxymethylation and handles;
Activating the ethanol and the sodium chloroacetate that add certain volume in the pretreated straw material at the steam explosion of step 1) disperses, add then that sodium hydroxide solution alkalizes and carboxymethylation is handled, generation contains the solid of carboxymethyl cellulose, carboxymethylation hemicellulose and carboxymethylation xylogen, its temperature of reaction is at 40-100 ℃, reaction times 0.5-8 hour, reaction was under agitation carried out; After reaction finishes, with acetic acid conditioned reaction liquid pH value to neutral, in the ethanol adding reactor with the 70%-95% of 2-15 times of volume, agitator treating 0.5-3 hour, after washing finishes, with suction filtration reaction solution under the vacuum pump decompression, reclaim filtrate, be deposited in 50-60 ℃ of vacuum dried overnight;
3) separation of carboxymethylcellulocomponent component:
Method 1: with step 2) solid of dried carboxymethyl cellulose, carboxymethylation hemicellulose and carboxymethylation xylogen is 100-200 distilled water vigorous stirring dissolving doubly with 80-100 ℃ of volume ratio, and suction filtration is while hot collected filtrate and precipitation respectively then;
The filtrate distillation is concentrated into about the 1/5-1/10 of initial soln volume.Add 10-20 times of volume of ethanol washing and produce precipitation, suction filtration obtains precipitation then, is carboxymethyl cellulose;
Method 2: with step 2) the solid water-wet of dried carboxymethyl cellulose, carboxymethylation hemicellulose and carboxymethylation xylogen, add the salt Acid precipitation, add the sodium hydroxide stirring and dissolving again and regulate pH to 8-10, centrifugation, collect supernatant and precipitation, the washing with alcohol supernatant produces precipitation, and suction filtration obtains precipitation then, is carboxymethyl cellulose;
4) separating of carboxymethylation xylogen and hemicellulose component:
Centrifugal being deposited in of obtaining in the step 3) used solvent extraction 0.5-4 hours in the Soxhlet extractor, extracting is dissolved in the solute of this solvent, and this solute is carboxymethylated xylogen, is insoluble to the carboxymethylated hemicellulose that is of this solvent; Described solvent is the lower alcohol that comprises ethanol.
2, separate and prepare the method for carboxymethyl cellulose by the described straw carboxymethylation components of claim 1, it is characterized in that described straw is maize straw, wheat stalk or rice straw.
3, separate and prepare the method for carboxymethyl cellulose by the described straw carboxymethylation components of claim 1, it is characterized in that, after the described step 1), also comprise, carry out long and short fiber comb and divide the pretreated steam-puffed plant straw and stalk of activation; In step 2) in respectively the steam-puffed plant straw and stalk of long and short fiber is carried out carboxymethylation and handles.
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| CN101985479A (en) * | 2010-12-10 | 2011-03-16 | 西北师范大学 | Preparation and application of carboxymethyl cellulose of wheat straw |
| CN101985479B (en) * | 2010-12-10 | 2012-08-22 | 西北师范大学 | Preparation and application of carboxymethyl cellulose of wheat straw |
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