CN101857639B - Method for preparing sodium carboxymethyl cellulose from the residue of bio-butanol produced from corn stalks - Google Patents

Abstract

The invention discloses a method for preparing sodium carboxymethylcellulose from residues generated by producing biobutanol from maize straw. A by-product fiber slurry during production of biobutanol from the maize straw is taken as a raw material, and is subjected to pulverization, basification, etherification, washing, centrifugation, drying, pulverization and sieving to prepare the finished sodium carboxymethylcellulose. The residues generated in the process of producing the biobutanol from the maize straw are utilized fully and changed into treasure, so the industrial development of the production of the biobutanol from the maize straw is promoted, and the problems of deficient raw materials and high production cost during the production of the sodium carboxymethylcellulose are solved. The appearance of the prepared sodium carboxymethylcellulose is white or faint yellow powder, the pH value is between 6.0 and 8.5, the moisture content is less than or equal to 10 percent, the degree of substitution is between 0.6 and 1.2, the viscosity is between 35 and 6,500 mPa.s, and the chloride content is less than or equal to 1.2 percent; and the sodium carboxymethylcellulose has excellent performance, and can be applied in the industry such as daily chemical engineering, papermaking, oil exploitation and the like.

Description

Method for preparing sodium carboxymethyl cellulose from the residue of bio-butanol produced from corn stalks

technical field

The invention relates to the field of preparation methods of sodium carboxymethyl cellulose, in particular to the reuse of wastes produced from corn stalks to produce bio-butanol.

Background technique

With the rapid development of the global economy, the increasing shortage of petroleum resources and the aggravation of environmental pollution, people pay more and more attention to the research and development of clean and renewable biomass energy. As a renewable resource with rich sources and low price, corn stalks can produce about 300 million tons per year in my country, but most of them are burned or discarded directly, causing serious resource waste and environmental pollution problems. Its research and utilization is An important research direction of biomass energy in the future. The use of corn stalks to produce the second-generation biofuel, bio-butanol, has broad application prospects. However, the amount of corn stalk residues produced during the production process is large and difficult to handle, causing great environmental pollution. This has also become a constraint for the bio-butanol industry. An important reason for industrialization. The residue contains a large amount of cellulose, which is usually not fully utilized and discarded, which is difficult to handle and causes a waste of materials.

Sodium carboxymethyl cellulose (CMC) is an important class of ionic cellulose ether, which has good properties of thickening, suspension, dispersion, adhesion and protective colloid. Usually sodium carboxymethyl cellulose is produced and prepared with refined cotton as a raw material. The raw materials are scarce and the production cost is relatively high. There are patent documents to prepare sodium carboxymethyl cellulose through simple pretreatment of bagasse, rice straw, cotton stalks, etc., such as The Chinese patents whose publication numbers are CN1439653A, CN16265555A, CN101434658A and Wang Wansen, the research on the process of preparing carboxymethyl cellulose from crop stalks. The method tried in Tianjin Chemical Industry, 2004 (1), but did not utilize the hemicellulose in the raw material, It has the disadvantage of low utilization rate of biomass resources. Moreover, in Wang Wansen's research on the process of preparing carboxymethyl cellulose from crop straw, the degree of substitution of the sodium carboxymethyl cellulose product produced from corn straw is only 0.6-0.7, and the viscosity is only 400-600mPa.s. A new method for producing sodium carboxymethyl cellulose with publication number CN1009094B discloses a method for producing sodium carboxymethyl cellulose using water-based methods using rice straw, corn bran and other plant stalks. In the patent, the hemicellulose in the straw is not fully utilized, and the sodium carboxymethylcellulose produced by the water medium method is a medium and low-grade product, and the product viscosity is low (2% aqueous solution is 30-80mPa.s), and the salt content is low. High (sodium chloride content is 16%). In this patent, after washing and refining CMC with high-concentration hydrochloric acid solution, the product is not washed and neutralized, so that the insoluble H-CMC generated during washing with hydrochloric acid solution is not reduced to soluble Na-CMC will cause degradation during drying and affect product quality.

Contents of the invention

In order to solve the disadvantage of high production cost of sodium carboxymethylcellulose existing in the prior art, the present invention provides a method for preparing sodium carboxymethylcellulose from residues of bio-butanol produced from corn stalks. Alcohol corn stalk residues are used as raw materials, turning waste into treasure, and reducing the production cost of sodium carboxymethyl cellulose.

The technical solution of the present invention is: a method for preparing sodium carboxymethyl cellulose from the residue of corn stalks to produce bio-butanol, using corn stalk fiber slurry as raw material, adopting the method of solvent kneading, after conventional alkalization, ether Sodium carboxymethyl cellulose is obtained after chemical, washing and drying steps, and the corn stalk fiber slurry is obtained after bleaching, washing and drying the residue of corn stalk production bio-butanol, and the obtained corn stalk fiber slurry is used in the production of bio-butanol The lignin and hemicellulose in the corn stover have been removed in the process, and it has been fermented in the production.

The alkalization step is as follows: crush the corn stalk fiber slurry to obtain corn stalk fiber slurry powder, weigh 75-150 parts by weight of the corn stalk fiber slurry powder and put it into a kneader, and put 70-140 parts by weight of the The sodium hydroxide solution with a mass percentage concentration of 45% to 55% wt and 120 to 240 parts by weight of industrial grade ethanol are evenly mixed, and after the stirring is started, the mixed solution of sodium hydroxide and ethanol is evenly sprinkled on the corn stalk fiber slurry powder , stirring and alkalizing at 10-30° C. for 0.5-1.5 hours, and making the cellulose in the corn stalk fiber slurry into alkali cellulose.

The etherification step is as follows: adding 37 to 180 parts by weight of an alcohol solution of monochloroacetic acid with a mass percent concentration of 70% to 80% wt to the alkalized slurry for etherification, and the temperature is controlled at 10 ~30°C, etherification for 0.5 to 1.5 hours, and then heated to 70~80°C for another 0.5 to 1.5 hours.

The washing step is as follows: the etherified material is washed with an ethanol solution with a mass percent concentration of 60% to 85% wt, the pH value is adjusted to 6.0 to 8.5, and then put into a centrifuge to dry and recover the ethanol.

Beneficial effect:

1 Using the by-products of corn stalks to produce bio-butanol as raw materials to produce sodium carboxymethyl cellulose makes full use of the residues produced by corn stalks to produce bio-butanol, turning waste into treasure and promoting the industrialization of corn stalks to produce bio-butanol , which solves the problems of lack of raw materials and high production costs for the production of sodium carboxymethyl cellulose.

2 Realized the full utilization of corn stalks. The method of the present invention uses corn stalks as raw materials to extract the hemicellulose in the stalks for the production of bio-butanol; the lignin in the stalks is extracted with lye, and can be used to prepare lignin-based derivatives after purification; the remaining slag After the raw material is washed and dried or bleached and washed and dried, the corn straw fiber slurry whose main component is cellulose is obtained, and then used to produce sodium carboxymethyl cellulose.

3. The sodium carboxymethyl cellulose prepared from the residue of corn stalks produced by the present invention is white or light yellow powder; the pH value is 6.0-8.5; the water content is ≤10%; the degree of substitution is 0.6-1.2; The viscosity is 30-6500mPa.s; the chloride content is ≤1.2%. It has excellent properties such as thickening, dispersion, suspension, adhesion, film formation, protective colloid and moisture protection. It can be used in daily chemical industry, papermaking and oil exploration, etc. industry. Increased the added value of corn stalks.

Detailed ways

The solutions and effects of the present invention are further illustrated below in conjunction with the examples, but the present invention is not limited only to the following examples.

A method for preparing sodium carboxymethyl cellulose from the residue of bio-butanol produced from corn stalks, using corn stalks as raw materials, first undergoing steam explosion, and after the steam explosion product is enzymatically hydrolyzed by hemicellulase, it is treated with Clostridium acetobutylicum Fermentation to produce bio-butanol, the slag is then used to extract lignin with alkali, and the residue is washed and dried with water or bleached and washed with water to produce corn straw fiber slurry for sodium carboxymethyl cellulose; or corn straw is directly extracted with alkali to lignin The purified material is enzymatically hydrolyzed by hemicellulase, then fermented by Clostridium acetobutylicum to produce bio-butanol, and the remaining slag is washed and dried with water or bleached and washed with water to produce corn straw for the production of sodium carboxymethyl cellulose Fiber Slurry. The fiber slurry is used as a raw material, and the method of solvent kneading is adopted to obtain the sodium carboxymethyl cellulose after conventional alkalization, etherification, washing and drying steps.

The alkalization step is as follows: crush the corn stalk fiber slurry to obtain corn stalk fiber slurry powder, weigh 75-150 parts by weight of the corn stalk fiber slurry powder and put it into a kneader, and put 70-140 parts by weight of the The sodium hydroxide solution with a mass percentage concentration of 45% to 55% wt and 120 to 240 parts by weight of industrial grade ethanol are evenly mixed, and after the stirring is started, the mixed solution of sodium hydroxide and ethanol is evenly sprinkled on the corn stalk fiber slurry powder , stirring and alkalizing at 10-30° C. for 0.5-1.5 hours, and making the cellulose in the corn stalk fiber slurry into alkali cellulose.

The etherification step is as follows: adding 37 to 180 parts by weight of monochloroacetic acid alcohol solution with a concentration of 70% to 80% wt to the alkalized slurry several times for etherification. The etherification is controlled at 10-30°C for 0.5-1.5 hours, and then the temperature is raised to 70-80°C for another 0.5-1.5 hours.

The washing step is as follows: the etherified material is washed with an ethanol solution with a mass percent concentration of 60% to 85% wt, the pH value is adjusted to 6.0 to 8.5, and then put into a centrifuge to dry and recover the ethanol. After drying, crushing and sieving, the finished product of sodium carboxymethyl cellulose is obtained.

For the method of producing butanol from corn stalks, please refer to literature: Lin Yousheng, Wang Xuming, etc., Enzymatic hydrolysis and butanol fermentation after pretreatment of corn stalks. Anhui Agricultural Sciences, 2009 (22); Li Dongmin, Chen Hongzhang, Steam-exploded straw membrane cycle enzyme Decoupling acetone-butanol fermentation. Chinese Journal of Process Engineering, 2007(6); Xian Yongping, Clostridium acetobutylicum immobilization technology for acetone-butanol fermentation research. Journal of Northwest Normal University (Natural Science Edition). 2001(3 ).

Example 1

Crush the corn stalks and put them into the steam explosion tank. After sealing it, let water steam in so that the tank pressure is 15-17kg/cm2, keep it at about 170°C for 4-5 minutes, and release the pressure quickly to make the steam-exploded corn stalks. After breaking the news through hemicellulase enzymolysis, use Clostridium acetobutylicum to ferment to produce bio-butanol, the remaining residue is extracted with alkali to extract lignin, then bleached with hydrogen peroxide, washed twice with tap water, centrifuged and dried, and dried to obtain corn Straw fiber slurry: using the fiber slurry as raw material, adopting the method of solvent kneading, and undergoing conventional alkalization, etherification, washing and drying steps to obtain sodium carboxymethyl cellulose.

The alkalization step is: after pulverizing the corn fiber slurry, weighing 75 parts by weight and putting it into a kneader, mixing 70 parts by weight of 45% to 55% wt of sodium hydroxide solution and 120 parts by weight of industrial grade Mix the ethanol evenly. After starting the stirring, sprinkle the mixture of sodium hydroxide and ethanol evenly on the corn stalk powder, stir and alkalize at 10-30°C for 0.5-1.5 hours, and make the cellulose in the slurry into alkali fiber white;

The etherification step is as follows: adding 75 parts by weight of 70% to 80% wt monochloroacetic acid alcohol solution for etherification several times, controlling the temperature at 10 to 30°C during the addition, etherifying for 0.5 to 1.5 hours, and then raising the temperature Reaction at 70-80°C for another 0.5-1.5 hours;

The washing steps are as follows: washing with 60% to 85% wt ethanol solution after discharge, and simultaneously adjusting the pH value to 6.0 to 8.5 with hydrochloric acid or sodium hydroxide solution; putting the washed and neutralized material into a centrifuge Drying, recovering ethanol at the same time; drying, crushing and sieving to obtain the finished product of sodium carboxymethyl cellulose prepared from the residue of bio-butanol produced from corn stalks.

The physicochemical data of gained product is:

Exterior pH value Moisture content (%wt) Viscosity (2%, 25℃)/(mPa.s) Chloride content (%wt) Degree of substitution Pale yellow 6.0 5.4 35 1.1 1.20

Example 2

The corn stalks are crushed and lignin is extracted with lye, and the remaining material is enzymatically hydrolyzed by hemicellulase, then fermented by Clostridium acetobutylicum to produce bio-butanol, and then washed, centrifuged and dried to obtain fiber slurry ; Taking fiber slurry as raw material, adopting the method of solvent kneading, and obtaining sodium carboxymethyl cellulose after conventional alkalization, etherification, washing and drying steps.

The alkalization step is as follows: after pulverizing the fiber slurry, weigh 150 parts by weight and put it into a kneader, mix 140 parts by weight of 45% to 55% wt of sodium hydroxide solution and 240 parts by weight of industrial grade ethanol Mix evenly. After starting the stirring, sprinkle the mixture of sodium hydroxide and ethanol evenly on the corn stalk powder, stir and alkalize at 10-30°C for 0.5-1.5 hours, and make the cellulose in the slurry into alkali cellulose ;

The etherification step: adding 180 parts by weight of 70% to 80%wt monochloroacetic acid alcohol solution etherification several times, the temperature is controlled at 10 to 30°C during the addition, etherification is carried out for 0.5 to 1.5 hours, and then the temperature is raised to Reaction at 70-80°C for another 0.5-1.5 hours;

The washing step: wash with 60%-85%wt ethanol solution after discharge, and adjust the pH value to 6.0-8.5 with hydrochloric acid or sodium hydroxide solution at the same time; put the washed and neutralized material into a centrifuge Drying, recovering ethanol at the same time; then drying; crushing; sieving. The finished product of sodium carboxymethyl cellulose prepared from the residue of bio-butanol produced from corn stalks is obtained.

The physicochemical data of gained product are:

Exterior pH value Moisture content (%wt) Viscosity (2%, 25℃)/(mPa.s) Chloride content (%wt) Degree of substitution Pale yellow 8.3 3.9 6300 0.9 0.73

Example 3

First crush the corn stalks, extract the lignin in the stalks with an alkaline solution, and after the purified materials are enzymatically hydrolyzed with hemicellulase, they are fermented with Clostridium acetobutylicum to produce bio-butanol. % hydrogen peroxide was bleached at 70°C for 2 hours, washed twice with tap water, centrifuged and dried to obtain fiber slurry; the fiber slurry was used as raw material, and the method of solvent kneading was used to undergo conventional alkalization and etherification. , washing and drying to obtain sodium carboxymethyl cellulose.

The alkalization step is: after pulverizing the fiber slurry, weighing 110 parts by weight and putting it into a kneader, mixing 110 parts by weight of 45% to 55% wt of sodium hydroxide solution and 190 parts by weight of industrial grade ethanol Mix evenly. After starting the stirring, sprinkle the mixture of sodium hydroxide and ethanol evenly on the corn stalk powder, stir and alkalize at 10-30°C for 0.5-1.5 hours, and make the cellulose in the slurry into alkali cellulose ;

The etherification step is: adding 85 parts by weight of 70% to 80% wt monochloroacetic acid alcohol solution for etherification several times, controlling the temperature at 10 to 30°C during addition, etherifying for 0.5 to 1.5 hours, and then raising the temperature Reaction at 70-80°C for another 0.5-1.5 hours;

The washing step: wash with 60%-85%wt ethanol solution after discharge, and adjust the pH value to 6.0-8.5 with hydrochloric acid or sodium hydroxide solution at the same time; put the washed and neutralized material into a centrifuge Drying, recovering ethanol at the same time; then drying; crushing; sieving. The finished product of sodium carboxymethyl cellulose prepared from the residue of bio-butanol produced from corn stalks is obtained.

The physicochemical data of gained product is:

Exterior pH value Moisture content (%wt) Viscosity (2%, 25℃)/(mPa.s) Chloride content (%wt) Degree of substitution White 7.0 4.6 1320 1.2 0.71

Example 4

The corn stalks are crushed first, and the lignin in the stalks is extracted with an alkaline solution. After the purified material is enzymatically hydrolyzed with hemicellulase, it is fermented with Clostridium acetobutylicum to produce bio-butanol, and the remaining residue is treated with 3% to 12 %wt lye was washed twice, centrifugally dried, and dried to obtain fiber slurry; the fiber slurry was used as raw material, and the method of solvent kneading was used to obtain carboxyl Sodium Methylcellulose.

The alkalization step is: after pulverizing the fiber slurry, weighing 135 parts by weight and putting it into a kneader, mixing 120 parts by weight of 45% to 55% wt of sodium hydroxide solution and 220 parts by weight of industrial grade ethanol Mix evenly. After starting the stirring, sprinkle the mixture of sodium hydroxide and ethanol evenly on the corn stalk powder, stir and alkalize at 10-30°C for 0.5-1.5 hours, and make the cellulose in the slurry into alkali cellulose ;

The etherification step is as follows: adding 110 parts by weight of 70% to 80% wt monochloroacetic acid alcohol solution for etherification several times, controlling the temperature at 10 to 30°C during the addition, etherifying for 0.5 to 1.5 hours, and then raising the temperature Reaction at 70-80°C for another 0.5-1.5 hours;

The washing steps are as follows: washing with 60% to 85% wt ethanol solution after discharge, and simultaneously adjusting the pH value to 6.0 to 8.5 with hydrochloric acid or sodium hydroxide solution; putting the washed and neutralized material into a centrifuge Shake dry and recover ethanol at the same time; then dry; pulverize; sieve. The finished product of sodium carboxymethyl cellulose prepared from the residue of bio-butanol produced from corn stalks.

The physicochemical data of gained product are:

Exterior pH value Moisture content (%wt) Viscosity (2%, 25℃)/(mPa.s) Chloride content (%wt) Degree of substitution Pale yellow 7.9 5.5 1000 1.0 0.69

Example 5

Crush the corn stalks and put them into the steam explosion tank. After sealing it, let water steam in so that the tank pressure is 15-17kg/cm2, keep it at about 170°C for 4-5 minutes, and release the pressure quickly to make the steam-exploded corn stalks. After enzymatic hydrolysis with hemicellulase, the material is fermented by Clostridium acetobutylicum to produce bio-butanol. The remaining residue is extracted with alkali to extract lignin, then bleached with hydrogen peroxide, washed twice with tap water, centrifuged and dried, and dried to obtain Fiber slurry: using fiber slurry as raw material, adopting the method of solvent kneading, and undergoing conventional alkalization, etherification, washing, and drying steps to obtain sodium carboxymethyl cellulose.

The alkalization step is: after pulverizing the fiber slurry, weighing 90 parts by weight and putting it into a kneader, mixing 85 parts by weight of 45% to 55% wt of sodium hydroxide solution and 150 parts by weight of industrial grade ethanol Mix evenly. After starting the stirring, sprinkle the mixture of sodium hydroxide and ethanol evenly on the corn stalk powder, stir and alkalize at 10-30°C for 0.5-1.5 hours, and make the cellulose in the slurry into alkali cellulose ;

The etherification step is: adding 85 parts by weight of 70% to 80% wt monochloroacetic acid alcohol solution for etherification several times, controlling the temperature at 10 to 30°C during addition, etherifying for 0.5 to 1.5 hours, and then raising the temperature Reaction at 70-80°C for another 0.5-1.5 hours;

The washing steps are as follows: washing with 60% to 85% wt ethanol solution after discharge, and simultaneously adjusting the pH value to 6.0 to 8.5 with hydrochloric acid or sodium hydroxide solution; putting the washed and neutralized material into a centrifuge Shake dry and recover ethanol at the same time; then dry; pulverize; sieve. The finished product of sodium carboxymethylcellulose prepared from the residue of bio-butanol produced from corn stalks.

The physicochemical data of gained product are:

Exterior pH value Moisture content (%wt) Viscosity (2%, 25℃)/(mPa.s) Chloride content (%wt) Degree of substitution White 8.5 4.9 800 1.2 1.01

Example 6

Crush the corn stalks and put them into the steam explosion tank. After airtight, put water vapor into the tank to make the tank pressure 15-17kg/cm2, keep it at 170°C for 4-5 minutes, and release the pressure quickly to make steam-exploded corn stalks and steam-explosion materials. After enzymatic hydrolysis with hemicellulase, use Clostridium acetobutylicum to ferment bio-butanol, extract lignin from the remaining slag with alkali, wash twice with tap water, spin and dry by centrifugation, and obtain fiber slurry; The fiber slurry is used as raw material, and the sodium carboxymethyl cellulose is obtained after conventional alkalization, etherification, washing and drying steps by means of solvent kneading.

The alkalization step is: after pulverizing the fiber slurry, weighing 120 parts by weight and putting it into a kneader, mixing 115 parts by weight of 45% to 55% wt of sodium hydroxide solution and 195 parts by weight of industrial grade ethanol Mix evenly. After starting the stirring, sprinkle the mixture of sodium hydroxide and ethanol evenly on the corn stalk powder, stir and alkalize at 10-30°C for 0.5-1.5 hours, and make the cellulose in the slurry into alkali cellulose ;

The etherification step is as follows: adding 110 parts by weight of 70% to 80% wt monochloroacetic acid alcohol solution for etherification several times, controlling the temperature at 10 to 30°C during the addition, etherifying for 0.5 to 1.5 hours, and then raising the temperature Reaction at 70-80°C for another 0.5-1.5 hours;

The washing steps are as follows: washing with 60% to 85% wt ethanol solution after discharge, and simultaneously adjusting the pH value to 6.0 to 8.5 with hydrochloric acid or sodium hydroxide solution; putting the washed and neutralized material into a centrifuge Shake dry and recover ethanol at the same time; then dry; pulverize; sieve. The finished product of sodium carboxymethyl cellulose prepared from the residue of bio-butanol produced from corn stalks is obtained.

The physicochemical data of gained product are:

Exterior pH value Moisture content (%wt) Viscosity (2%, 25℃)/(mPa.s) Chloride content (%wt) Degree of substitution Pale yellow 8.2 6.6 640 0.6 0.70

Viscosity can be controlled by controlling the conditions of alkalization and etherification, especially the amount of alkali and etherification agent.

comparative example

In Wang Wansen's research on the process of preparing carboxymethyl cellulose from crop straw, the sodium carboxymethyl cellulose prepared from corn straw only meets the CMC standard for sizing in the textile industry. The performance of the product is as follows:

Exterior pH value Moisture content (%wt) Viscosity (2%, 25℃)/(mPa.s) Chloride content (%wt) Degree of substitution Pale yellow none none 400～600 none 0.6～0.7

Adopt the method in CN1009094B to produce sodium carboxymethyl cellulose with corn stalks, the product performance of the sodium carboxymethyl cellulose that obtains is as follows:

Exterior pH value Moisture content (%wt) Viscosity (2%, 25℃)/(mPa.s) Chloride content (%wt) Degree of substitution Pale yellow ≤7.0 <15 30～80 ≤16 ≤0.9

Claims (4)

1. a residue of producing biological butanol with corn straw prepares the method for Xylo-Mucine; Use the corn straw fibre stuff to be raw material; The method that adopts solvent to mediate through obtaining Xylo-Mucine after conventional alkalization, etherificate, washing, the drying treatment step, is characterized in that; The corn straw fibre stuff is to obtain after the corn straw washing residue of producing biological butanol, the oven dry; The corn straw fibre stuff of gained has used the hemicellulase enzymolysis to remove the semicellulose in the corn straw in the process of producing biological butanol, proposes xylogen with alkali, and has passed through fermentation aborning.

2. the residue with corn straw production biological butanol as claimed in claim 1 prepares the method for Xylo-Mucine; It is characterized in that; Described alkalinization step is: obtain corn straw fibre stuff powder after the corn straw fibre stuff is pulverized; Weighing 75～150 weight part corn straw fibre stuff powder are put into kneader; With the mass percent concentration of 70～140 weight parts is that the sodium hydroxide solution of 45%～55%wt and the technical grade ethanol of 120～240 weight parts mix; After open stirring with sodium hydroxide and the even sprinkle of alcoholic acid mixed solution in corn straw fibre stuff powder, stir down at 10～30 ℃ and to alkalize 0.5～1.5 hour, process soda cellulose to the Mierocrystalline cellulose in the corn straw fibre stuff.

3. the residue with corn straw production biological butanol as claimed in claim 1 prepares the method for Xylo-Mucine; It is characterized in that; Described etherification step is: the Monochloro Acetic Acid spirituous solution to through the mass percent concentration that adds 37～180 weight parts in the slurry of alkalinisation treatment being 70%～80%wt carries out etherificate; Add fashionable temperature and be controlled at 10～30 ℃, etherificate 0.5 to 1.5 hour is warming up to then and reacted under 70～80 ℃ 0.5～1.5 hour again.

4. the residue with corn straw production biological butanol as claimed in claim 1 prepares the method for Xylo-Mucine; It is characterized in that; Described washing step is: using mass percent concentration through the material after the etherificate is the ethanolic soln washing of 60%～85%wt; Regulating the pH value is 6.0～8.5, puts into whizzer then and dries, and reclaims ethanol.