CN105624337A - Method for preparing xylose functional sugar by hemicellulose polysaccharide in hydrolyzed agricultural wastes - Google Patents

Abstract

The invention discloses a method for preparing xylose functional sugar by hemicellulose polysaccharide in hydrolyzed agricultural wastes, belonging to the field of xylose. The method comprises the following steps: selecting wheat straws, performing processes such as drying, smashing and alkaline extraction to obtain hemicellulose crude polysaccharide, then purifying, adding hemicellulose pure polysaccharide into a cellulose enzyme degradation agent and an ethanol solvent for ultrasound degradation, pressurizing and concentrating the degradation liquid, then performing membrane separation by using an ultrafiltration membrane, so as to obtain a xylose product, and concentrating and drying. According to a preparation process, after hydrolysis, redundant byproducts can be removed and the xylose with the purity of 90-95 percent is obtained; the xylose is added into food and can be widely used; the ultrafiltration membrane is adopted to remove enzyme in xylooligosaccharide liquid and non-degraded xylan, the loss of the xylose is reduced, preparation sources are rich, and the cost is low.

Description

A kind of method that in hydrolysing agricultural garbage, Hemicellulose Polysaccharide prepares xylose functional sugar

Technical field

The invention discloses a kind of method that in hydrolysing agricultural garbage, Hemicellulose Polysaccharide prepares xylose functional sugar, belong to xylose field.

Background technology

Lignocellulose-like biomass is mainly made up of cellulose, hemicellulose and lignin, and wherein hemicellulose typically constitutes from 20��35%. Hemicellulose can as Cholesterol Inhibitor and tablet distintegrant etc. It can prepare functional oligose through hydrolysis, can produce xylose, arabinose and galactose etc. But, hemicellulose is due to the difference of its composition, structure, character and reaction condition, and hydrolyzate complexity is various, thus constraining production and the application of each useful constituent of hemicellulose. Therefore the hydrolysis studying hemicellulose contributes to the efficient utilization of hemicellulose resource.

Oligomeric xylose is directly entered large intestine because of very difficult by human digestive enzymes's system decomposition, a large amount of probiotic bifidobacterias bred in intestinals and lactic acid bacteria, its tunning short-chain fatty acid such as lactic acid, acetic acid, propanoic acid, butanoic acid etc. on the one hand can reduce the pH value in intestinal, thus promoting function of intestinal canal, lipid metabolism, assisting and the absorption of mineral and preventing colon cancer. On the other hand, the growth of the pathogenic bacterium such as clostridium being suppressed, prevent abdomen gulf and the formation of constipation, minimizing toxic metabolic products (such as amine), thus alleviating liver to decompose toxin burden, playing liver-protective effect. Additionally, oligomeric xylose also has blood fat reducing, reduces cholesterol, controls the physiological propertys such as blood sugar level, antiallergic, antioxidation, infection, immunomodulating. Therefore in food, pharmacy, animal feed etc., has important application.

In traditional degradation treatment, due to multiple hemicellulose saccharic composition, such as dissolutions that is all degraded such as glucose, galactose, xylose, arabinose, hydrolyzed solution exists more saccharic composition, this causes in the process that follow-up xylose crystalline precipitates out, and owing in the hydrolyzed solution after purification, the purity of xylose is relatively low, relatively xylan is difficult to be crystallized precipitation, it is left in remaining mixed sugar liquid, reduces the yield of crystalline xylose.

Summary of the invention

The technical problem that present invention mainly solves: for due in Hemicellulose Polysaccharide component such as glucose, galactose, xylose, easy dissolution during the degraded such as arabinose, cause that hydrolyzed solution exists more saccharic composition, make in the process that follow-up xylose crystalline precipitates out, owing in the hydrolyzed solution after purification, the purity of xylose is relatively low, relatively xylan is difficult to be crystallized precipitation, remain in remaining mixed sugar liquid, the problem reducing the yield of crystalline xylose, provide a kind of method that in hydrolysing agricultural garbage, Hemicellulose Polysaccharide prepares xylose functional sugar, the present invention chooses wheat stalk, through drying, pulverize, the techniques such as alkalescence extraction obtain hemicellulose crude polysaccharides, purify again, cellulose holosaccharide is added cellulose degraded agent and alcoholic solution carries out ultrasonotomography, membrance separation is carried out with ultrafilter membrane after degradation solution pressurization concentration, xylose product can be obtained, concentrate drying, unnecessary by-product can be removed after the preparation technology hydrolysis of the present invention, obtain the xylose that purity is 90��95%, it is added on food always to have a wide range of applications, ultrafilter membrane is adopted the enzyme in oligomeric xylose liquid and undegradable xylan to be removed, reduce the loss of xylose, and prepare abundance, cost is low.

In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:

(1) 200��300g wheat stalk is taken, pulverize after being dried, sieve to obtain 50��60 order particles, at room temperature taking 500��600mL concentration is 5mol/L sodium hydroxide solution and 1000��1200mL mass fraction 3% hydrogen peroxide, 3��5h is soaked after mix and blend, put in centrifuge centrifugation 15��20min under 4000��4500r/min rotating speed after immersion, obtain supernatant;

(2) by supernatant with glacial acetic acid regulate pH value be 4.5��5.5, dialysis, solution after dialysis is rotated at 55��65 DEG C and is evaporated to the 20% of original volume, concentrated solution 1:5 by volume after evaporation is joined in the ethanol of mass fraction 95%, sealing carries out precipitate with ethanol 3��5h, alcohol deposit fluid high speed centrifuge after centrifugal treating 15��20min, is removed supernatant and is precipitated thing, precipitate is carried out lyophilization and obtains hemicellulose crude polysaccharides under the rotating speed of 5500��6000r/min;

(3) 1��3g Hemicellulose Polysaccharide obtained above is taken, it is added thereto to 200��300mLpH4.0��5.0 disodium hydrogen phosphate-citrate buffer solution, after stirring, mixed liquor is joined equipped with the ion exchange column of storng-acid cation exchange resin carries out adsorption and purification, flow velocity is 3��5mL/min, eluting 1��2h is carried out with the pH4.0��5.0 disodium hydrogen phosphate-citrate buffer solution containing 10��15% v aqueous sodium, collect after eluting containing Hemicellulose Polysaccharide eluent, eluent is heated at 60��70 DEG C concentration, concentrated solution lyophilization is obtained hemicellulose holosaccharide, the volume of described mixed liquor is 10��15 times of storng-acid cation exchange resin volume,

(4) polysaccharide obtained above is added deionization by solid-to-liquid ratio 1:5, freezing at-5 DEG C, at room temperature slowly melt again after freezing completely, sucrose solution after melting is carried out centrifugation under 4000��5000r/min rotating speed, remove precipitate, supernatant liquid will add gross mass 0.5��0.8% cellulose degraded agent, it is under 25��35kHz, carry out ultrasonic degradation at 35��45 DEG C and supersonic frequency, and in sucrose solution, add gross mass 50��60% mass fraction 80% alcoholic solution, gross mass 30��50% dehydrated alcohol is added after ultrasonic 30��40min, continue ultrasonotomography 1��2h, after degraded terminates, polysaccharide degradation solution can be obtained,

(5) by above-mentioned polysaccharide degradation solution in vacuum for for-0.04��-0.02MPa, temperature is at 20��30 DEG C, it is evaporated to the 10��15% of extracting liquid volume, add equal-volume deionized water to concentrated solution, remove insoluble matter after stirring mixing, be that 0.5��0.8 ��m of ultrafilter membrane carries out membrance separation then through molecular diameter, the pressure reduction of operation is 0.1��0.5MPa, retain small-molecular-weight, xylose product can be obtained, finally product concentrated, dry to obtain xylose functional sugar.

The application process of the present invention: it is upper that the xylose that the present invention prepares can apply to food, for instance replace the 20��30% of original white sugar at beverage xylose, can preserve at 10��30 DEG C 10��12 months, and mouthfeel is more preferably; It is added in cream, the 40��50% of original Saccharum Sinensis Roxb. can be replaced by xylose, the emulsibility of product can be improved, and eat and avoid greasy mouthfeel; It is added in pudding, xylose and Saccharum Sinensis Roxb. is changed in the ratio of 30��40%, not only there is tasty and refreshing effect, but also increase the freshness date of food.

The invention has the beneficial effects as follows:

(1) preparation technology of the present invention can remove unnecessary by-product, obtains the xylose that purity is 90��95%, has wider application;

(2) present invention adopts ultrafilter membrane the enzyme in oligomeric xylose liquid and undegradable xylan to be removed so that the loss amount of xylose reduces, and prepares abundance, and cost is low.

Detailed description of the invention

First 200��300g wheat stalk is taken, pulverize after being dried, sieve to obtain 50��60 order particles, at room temperature taking 500��600mL concentration is 5mol/L sodium hydroxide solution and 1000��1200mL mass fraction 3% hydrogen peroxide, 3��5h is soaked after mix and blend, put in centrifuge centrifugation 15��20min under 4000��4500r/min rotating speed after immersion, obtain supernatant, it is 4.5��5.5 by supernatant regulates pH value with glacial acetic acid, dialysis, solution after dialysis is rotated at 55��65 DEG C and is evaporated to the 20% of original volume, concentrated solution 1:5 by volume after evaporation is joined in the ethanol of mass fraction 95%, sealing carries out precipitate with ethanol 3��5h, alcohol deposit fluid high speed centrifuge after centrifugal treating 15��20min, is removed supernatant and is precipitated thing, precipitate is carried out lyophilization and obtains hemicellulose crude polysaccharides under the rotating speed of 5500��6000r/min, take 1��3g Hemicellulose Polysaccharide obtained, it is added thereto to 200��300mLpH4.0��5.0 disodium hydrogen phosphate-citrate buffer solution, after stirring, mixed liquor is joined equipped with the ion exchange column of storng-acid cation exchange resin carries out adsorption and purification, flow velocity is 3��5mL/min, eluting 1��2h is carried out with the pH4.0��5.0 disodium hydrogen phosphate-citrate buffer solution containing 10��15% v aqueous sodium, collect after eluting containing Hemicellulose Polysaccharide eluent, eluent is heated at 60��70 DEG C concentration, concentrated solution lyophilization is obtained hemicellulose holosaccharide, the volume of described mixed liquor is 10��15 times of storng-acid cation exchange resin volume, the polysaccharide obtained is added deionization by solid-to-liquid ratio 1:5, freezing at-5 DEG C, at room temperature slowly melt again after freezing completely, sucrose solution after melting is carried out centrifugation under 4000��5000r/min rotating speed, remove precipitate, supernatant liquid will add gross mass 0.5��0.8% cellulose degraded agent, it is under 25��35kHz, carry out ultrasonic degradation at 35��45 DEG C and supersonic frequency, and in sucrose solution, add gross mass 50��60% mass fraction 80% alcoholic solution, gross mass 30��50% dehydrated alcohol is added after ultrasonic 30��40min, continue ultrasonotomography 1��2h, after degraded terminates, polysaccharide degradation solution can be obtained, by polysaccharide degradation solution in vacuum for being-0.04��-0.02MPa, temperature is at 20��30 DEG C, it is evaporated to the 10��15% of extracting liquid volume, add equal-volume deionized water to concentrated solution, remove insoluble matter after stirring mixing, be that 0.5��0.8 ��m of ultrafilter membrane carries out membrance separation then through molecular diameter, the pressure reduction of operation is 0.1��0.5MPa, retain small-molecular-weight, xylose product can be obtained, finally product concentrated, dry to obtain xylose functional sugar.

Example 1

First 200g wheat stalk is taken, pulverize after being dried, sieve to obtain 50 order particles, at room temperature taking 500mL concentration is 5mol/L sodium hydroxide solution and 1000mL mass fraction 3% hydrogen peroxide, 3h is soaked after mix and blend, put in centrifuge centrifugation 15min under 4000r/min rotating speed after immersion, obtain supernatant, it is 4.5 by supernatant regulates pH value with glacial acetic acid, dialysis, solution after dialysis is rotated at 55 DEG C and is evaporated to the 20% of original volume, concentrated solution 1:5 by volume after evaporation is joined in the ethanol of mass fraction 95%, sealing carries out precipitate with ethanol 3h, alcohol deposit fluid high speed centrifuge after centrifugal treating 15min, is removed supernatant and is precipitated thing, precipitate is carried out lyophilization and obtains hemicellulose crude polysaccharides under the rotating speed of 5500r/min, take the 1g Hemicellulose Polysaccharide obtained, it is added thereto to 200mLpH4.0 disodium hydrogen phosphate-citrate buffer solution, after stirring, mixed liquor is joined equipped with the ion exchange column of storng-acid cation exchange resin carries out adsorption and purification, flow velocity is 3mL/min, eluting 1h is carried out with the pH4.0 disodium hydrogen phosphate-citrate buffer solution containing 10% v aqueous sodium, collect after eluting containing Hemicellulose Polysaccharide eluent, eluent is heated at 60 DEG C concentration, concentrated solution lyophilization is obtained hemicellulose holosaccharide, the volume of described mixed liquor is 10 times of storng-acid cation exchange resin volume, the polysaccharide obtained is added deionization by solid-to-liquid ratio 1:5, freezing at-5 DEG C, at room temperature slowly melt again after freezing completely, sucrose solution after melting is carried out centrifugation under 4000r/min rotating speed, remove precipitate, supernatant liquid will add gross mass 0.5% cellulose degraded agent, it is under 25kHz, carry out ultrasonic degradation at 35 DEG C and supersonic frequency, and in sucrose solution, add gross mass 50% mass fraction 80% alcoholic solution, gross mass 30% dehydrated alcohol is added after ultrasonic 30min, continuing ultrasonotomography 1h, degraded can obtain polysaccharide degradation solution after terminating, by polysaccharide degradation solution in vacuum for being-0.04MPa, temperature is at 20 DEG C, it is evaporated to the 10% of extracting liquid volume, add equal-volume deionized water to concentrated solution, remove insoluble matter after stirring mixing, be that 0.5 ��m of ultrafilter membrane carries out membrance separation then through molecular diameter, the pressure reduction of operation is 0.1MPa, retain small-molecular-weight, xylose product can be obtained, finally product concentrated, dry to obtain xylose functional sugar.

It is upper that the xylose that the present invention prepares can apply to food, for instance replaces the 20% of original white sugar at beverage xylose, can preserve 12 months, and mouthfeel is more preferably at 10 DEG C; It is added in cream, xylose can be replaced by by the 40% of original Saccharum Sinensis Roxb., the emulsibility of product can be improved, and eat and avoid greasy mouthfeel; It is added in pudding, xylose and Saccharum Sinensis Roxb. is changed in the ratio of 30%, not only there is tasty and refreshing effect, but also increase the freshness date of food.

Example 2

First 250g wheat stalk is taken, pulverize after being dried, sieve to obtain 55 order particles, at room temperature taking 550mL concentration is 5mol/L sodium hydroxide solution and 1100mL mass fraction 3% hydrogen peroxide, 4h is soaked after mix and blend, put in centrifuge centrifugation 17min under 4250r/min rotating speed after immersion, obtain supernatant, it is 5.0 by supernatant regulates pH value with glacial acetic acid, dialysis, solution after dialysis is rotated at 60 DEG C and is evaporated to the 20% of original volume, concentrated solution 1:5 by volume after evaporation is joined in the ethanol of mass fraction 95%, sealing carries out precipitate with ethanol 4h, alcohol deposit fluid high speed centrifuge after centrifugal treating 17min, is removed supernatant and is precipitated thing, precipitate is carried out lyophilization and obtains hemicellulose crude polysaccharides under the rotating speed of 5750r/min, take the 2g Hemicellulose Polysaccharide obtained, it is added thereto to 250mLpH4.5 disodium hydrogen phosphate-citrate buffer solution, after stirring, mixed liquor is joined equipped with the ion exchange column of storng-acid cation exchange resin carries out adsorption and purification, flow velocity is 4mL/min, eluting 1.5h is carried out with the pH4.5 disodium hydrogen phosphate-citrate buffer solution containing 13% v aqueous sodium, collect after eluting containing Hemicellulose Polysaccharide eluent, eluent is heated at 65 DEG C concentration, concentrated solution lyophilization is obtained hemicellulose holosaccharide, the volume of described mixed liquor is 13 times of storng-acid cation exchange resin volume, the polysaccharide obtained is added deionization by solid-to-liquid ratio 1:5, freezing at-5 DEG C, at room temperature slowly melt again after freezing completely, sucrose solution after melting is carried out centrifugation under 4500r/min rotating speed, remove precipitate, supernatant liquid will add gross mass 0.6% cellulose degraded agent, it is under 30kHz, carry out ultrasonic degradation at 40 DEG C and supersonic frequency, and in sucrose solution, add gross mass 55% mass fraction 80% alcoholic solution, gross mass 40% dehydrated alcohol is added after ultrasonic 35min, continuing ultrasonotomography 1.5h, degraded can obtain polysaccharide degradation solution after terminating, by polysaccharide degradation solution in vacuum for being-0.03MPa, temperature is at 25 DEG C, it is evaporated to the 13% of extracting liquid volume, add equal-volume deionized water to concentrated solution, remove insoluble matter after stirring mixing, be that 0.7 ��m of ultrafilter membrane carries out membrance separation then through molecular diameter, the pressure reduction of operation is 0.3MPa, retain small-molecular-weight, xylose product can be obtained, finally product concentrated, dry to obtain xylose functional sugar.

It is upper that the xylose that the present invention prepares can apply to food, for instance replaces the 25% of original white sugar at beverage xylose, can preserve 11 months, and mouthfeel is more preferably at 20 DEG C; It is added in cream, xylose can be replaced by by the 45% of original Saccharum Sinensis Roxb., the emulsibility of product can be improved, and eat and avoid greasy mouthfeel; It is added in pudding, xylose and Saccharum Sinensis Roxb. is changed in the ratio of 35%, not only there is tasty and refreshing effect, but also increase the freshness date of food.

Example 3

First 300g wheat stalk is taken, pulverize after being dried, sieve to obtain 60 order particles, at room temperature taking 600mL concentration is 5mol/L sodium hydroxide solution and 1200mL mass fraction 3% hydrogen peroxide, 5h is soaked after mix and blend, put in centrifuge centrifugation 20min under 4500r/min rotating speed after immersion, obtain supernatant, it is 5.5 by supernatant regulates pH value with glacial acetic acid, dialysis, solution after dialysis is rotated at 65 DEG C and is evaporated to the 20% of original volume, concentrated solution 1:5 by volume after evaporation is joined in the ethanol of mass fraction 95%, sealing carries out precipitate with ethanol 5h, alcohol deposit fluid high speed centrifuge after centrifugal treating 20min, is removed supernatant and is precipitated thing, precipitate is carried out lyophilization and obtains hemicellulose crude polysaccharides under the rotating speed of 6000r/min, take the 3g Hemicellulose Polysaccharide obtained, it is added thereto to 300mLpH5.0 disodium hydrogen phosphate-citrate buffer solution, after stirring, mixed liquor is joined equipped with the ion exchange column of storng-acid cation exchange resin carries out adsorption and purification, flow velocity is 5mL/min, eluting 2h is carried out with the pH5.0 disodium hydrogen phosphate-citrate buffer solution containing 15% v aqueous sodium, collect after eluting containing Hemicellulose Polysaccharide eluent, eluent is heated at 70 DEG C concentration, concentrated solution lyophilization is obtained hemicellulose holosaccharide, the volume of described mixed liquor is 15 times of storng-acid cation exchange resin volume, the polysaccharide obtained is added deionization by solid-to-liquid ratio 1:5, freezing at-5 DEG C, at room temperature slowly melt again after freezing completely, sucrose solution after melting is carried out centrifugation under 5000r/min rotating speed, remove precipitate, supernatant liquid will add gross mass 0.8% cellulose degraded agent, it is under 35kHz, carry out ultrasonic degradation at 45 DEG C and supersonic frequency, and in sucrose solution, add gross mass 60% mass fraction 80% alcoholic solution, gross mass 50% dehydrated alcohol is added after ultrasonic 40min, continuing ultrasonotomography 2h, degraded can obtain polysaccharide degradation solution after terminating, by polysaccharide degradation solution in vacuum for being-0.02MPa, temperature is at 30 DEG C, it is evaporated to the 15% of extracting liquid volume, add equal-volume deionized water to concentrated solution, remove insoluble matter after stirring mixing, be that 0.8 ��m of ultrafilter membrane carries out membrance separation then through molecular diameter, the pressure reduction of operation is 0.5MPa, retain small-molecular-weight, xylose product can be obtained, finally product concentrated, dry to obtain xylose functional sugar.

It is upper that the xylose that the present invention prepares can apply to food, for instance replaces the 30% of original white sugar at beverage xylose, can preserve 12 months, and mouthfeel is more preferably at 30 DEG C; It is added in cream, xylose can be replaced by by the 50% of original Saccharum Sinensis Roxb., the emulsibility of product can be improved, and eat and avoid greasy mouthfeel; It is added in pudding, xylose and Saccharum Sinensis Roxb. is changed in the ratio of 40%, not only there is tasty and refreshing effect, but also increase the freshness date of food.

Claims (1)

1. the method that in a hydrolysing agricultural garbage, Hemicellulose Polysaccharide prepares xylose functional sugar, it is characterised in that concrete preparation process is:

(1) 200��300g wheat stalk is taken, pulverize after being dried, sieve to obtain 50��60 order particles, at room temperature taking 500��600mL concentration is 5mol/L sodium hydroxide solution and 1000��1200mL mass fraction 3% hydrogen peroxide, 3��5h is soaked after mix and blend, put in centrifuge centrifugation 15��20min under 4000��4500r/min rotating speed after immersion, obtain supernatant;

(2) by supernatant with glacial acetic acid regulate pH value be 4.5��5.5, dialysis, solution after dialysis is rotated at 55��65 DEG C and is evaporated to the 20% of original volume, concentrated solution 1:5 by volume after evaporation is joined in the ethanol of mass fraction 95%, sealing carries out precipitate with ethanol 3��5h, alcohol deposit fluid high speed centrifuge after centrifugal treating 15��20min, is removed supernatant and is precipitated thing, precipitate is carried out lyophilization and obtains hemicellulose crude polysaccharides under the rotating speed of 5500��6000r/min;

(3) 1��3g Hemicellulose Polysaccharide obtained above is taken, it is added thereto to 200��300mLpH4.0��5.0 disodium hydrogen phosphate-citrate buffer solution, after stirring, mixed liquor is joined equipped with the ion exchange column of storng-acid cation exchange resin carries out adsorption and purification, flow velocity is 3��5mL/min, eluting 1��2h is carried out with the pH4.0��5.0 disodium hydrogen phosphate-citrate buffer solution containing 10��15% v aqueous sodium, collect after eluting containing Hemicellulose Polysaccharide eluent, eluent is heated at 60��70 DEG C concentration, concentrated solution lyophilization is obtained hemicellulose holosaccharide, the volume of described mixed liquor is 10��15 times of storng-acid cation exchange resin volume,

(4) polysaccharide obtained above is added deionization by solid-to-liquid ratio 1:5, freezing at-5 DEG C, at room temperature slowly melt again after freezing completely, sucrose solution after melting is carried out centrifugation under 4000��5000r/min rotating speed, remove precipitate, supernatant liquid will add gross mass 0.5��0.8% cellulose degraded agent, it is under 25��35kHz, carry out ultrasonic degradation at 35��45 DEG C and supersonic frequency, and in sucrose solution, add gross mass 50��60% mass fraction 80% alcoholic solution, gross mass 30��50% dehydrated alcohol is added after ultrasonic 30��40min, continue ultrasonotomography 1��2h, after degraded terminates, polysaccharide degradation solution can be obtained,

(5) by above-mentioned polysaccharide degradation solution in vacuum for for-0.04��-0.02MPa, temperature is at 20��30 DEG C, it is evaporated to the 10��15% of extracting liquid volume, add equal-volume deionized water to concentrated solution, remove insoluble matter after stirring mixing, be that 0.5��0.8 ��m of ultrafilter membrane carries out membrance separation then through molecular diameter, the pressure reduction of operation is 0.1��0.5MPa, retain small-molecular-weight, xylose product can be obtained, finally product concentrated, dry to obtain xylose functional sugar.