CN110256608B - Method for removing lignin in plant fiber prehydrolysis liquid by horse radish peroxidase treatment - Google Patents

Method for removing lignin in plant fiber prehydrolysis liquid by horse radish peroxidase treatment Download PDF

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CN110256608B
CN110256608B CN201910547020.3A CN201910547020A CN110256608B CN 110256608 B CN110256608 B CN 110256608B CN 201910547020 A CN201910547020 A CN 201910547020A CN 110256608 B CN110256608 B CN 110256608B
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李宗全
王福升
陈建松
傅英娟
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Qilu University of Technology
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Abstract

The invention discloses a method for removing lignin in plant fiber prehydrolysis liquid by horseradish peroxidase treatment, and belongs to the field of separation and purification of plant fiber components. The method comprises the following steps: s1, performing probe type ultrasonic treatment on a prehydrolysis liquid of a plant fiber raw material; s2, adding soluble calcium salt into the prehydrolysis liquid after ultrasonic treatment, and then treating by adopting horseradish peroxidase; and S3, removing precipitates from the treated hydrolysate to obtain purified prehydrolysis liquid. Compared with the prior art, the method provided by the invention has the advantages that the probe type ultrasonic treatment is combined with the horseradish peroxidase treatment in the presence of calcium ions, so that the lignin removal rate can be obviously improved, the loss of oligosaccharide is less, and the method has good popularization and application values.

Description

Method for removing lignin in plant fiber prehydrolysis liquid by horse radish peroxidase treatment
Technical Field
The invention relates to the field of separation and purification of plant fiber components, and particularly provides a method for removing lignin in plant fiber prehydrolysis liquid by horseradish peroxidase treatment.
Background
Self-hydrolysis, also called prehydrolysis, is the process of hydrolysis of plant fiber raw material using only hot water. The acetyl in the fiber raw material is deacetylated to generate acetic acid in the self-hydrolysis process, and the acetic acid can catalyze the hydrolysis and dissolution of hemicellulose, so the self-hydrolysis is considered to be an environment-friendly effective method for extracting the hemicellulose, and is also an important method for removing the hemicellulose from the raw material in the process of producing dissolving pulp by a sulfuric acid method. During autohydrolysis, the hemicellulose in the fibrous material dissolves into the prehydrolysis liquid. The hemicellulose dissolved in the prehydrolysis liquid is mostly present in the form of oligosaccharides and a small amount in the form of monosaccharides. The oligosaccharides have important application value in food, medicine and chemical industries, and the sugar in the hydrolysate can also be used for producing fuels such as ethanol and the like by fermentation. In the prehydrolysis process, part of lignin is dissolved in the prehydrolysis liquid, and the prehydrolysis liquid also contains micromolecule impurities such as furfural, hydroxymethyl furfural and acetic acid. In order to utilize the hemicellulose sugars in the prehydrolysis liquid of the fiber raw material, the prehydrolysis liquid needs to be separated and purified. The membrane filtration is an important method for removing small molecular impurities such as acetic acid and furfural in the hydrolysate and is also an important step for concentrating the hydrolysate. However, lignin in the prehydrolysis liquid causes membrane clogging, which reduces the production efficiency of membrane filtration and also shortens the life of the filtration membrane. In addition, when using hemicellulose sugars in the prehydrolysis liquid for fermentation to produce fuel, lignin in the hydrolysis liquid is also harmful to the enzymatic hydrolysis and fermentation processes. Therefore, the removal of lignin, which is a main impurity in the prehydrolysis liquid, has important significance for the separation, purification and utilization of hemicellulose sugar in the prehydrolysis liquid.
Many methods are available for removing lignin from the hydrolysate, including flocculation, adsorption, extraction, acidification, etc. Flocculation is carried out by flocculating high molecular polymer such as cation such as polyacrylamide, polydiallyldimethylammonium chloride and nonionic polymer such as polyethylene oxide; the adsorption method adopts active carbon, quicklime, zeolite, macroporous resin and the like. In addition, there is a method of removing lignin from the hydrolysate by means of a bio-enzyme treatment or a combination of a bio-enzyme treatment and cationic flocculation. In order to achieve high removal rates, a combination of methods is generally used in practice to remove lignin from the prehydrolysis liquid.
There are many prior arts disclosing lignin removal from a hydrolysate of a plant fiber raw material, and for example, chinese patent document 201610865111.8 discloses a method of removing lignin from a hydrolysate by using a pectinase pretreatment in combination with a cationic polymer flocculation treatment. The method comprises the following steps: (1) adding pectinase into the wood fiber hydrolysate for enzyme treatment, wherein the dosage of the pectinase is 20-1000 g per ton of hydrolysate, the enzyme treatment temperature is 20-70 ℃, the treatment time is 1-48 h, and the pH is 3.0-8.0, so as to obtain hydrolysate after enzyme treatment; (2) and treating the hydrolysate after the enzyme treatment by using a cationic flocculant, and standing or centrifuging the treated hydrolysate to remove precipitates to obtain the purified hydrolysate.
Chinese patent 2017111938442 discloses a method for removing lignin from plant fiber hydrolysate by using horseradish peroxidase in combination with cationic polymer for flocculation treatment, which comprises the following steps: (1) adding horseradish peroxidase into the plant fiber hydrolysate for enzyme treatment, wherein the dosage of the horseradish peroxidase is 5000-; (2) and adding one or a mixture of two of cationic flocculants poly (diallyldimethylammonium chloride), polyethyleneimine and polyamine into the hydrolysate after the enzyme treatment for treatment, and then standing or centrifuging to remove precipitates to obtain the purified hydrolysate.
Chinese patent document 201811148745.7 discloses a method for extracting xylose and lignin from a hydrolysate produced during the production of dissolving pulp. The method comprises the following steps: (1) extracting hydrolysate; (2) neutralizing the hydrolysate with calcium carbonate to pH of 2.8-3.2, decolorizing with active carbon to transparent 30%, exchanging with cation-anion resin, adjusting pH of the hydrolysate to 4.0-7.0, concentrating by vacuum evaporation to 16-20, and adjusting temperature to 28-30 deg.C; (3) filtering the hydrolysate in the step (2) to obtain filtrate and filter residue, drying the filter residue at 60-65 ℃ to obtain lignin, and decoloring the filtrate with cation-anion resin to obtain decolored solution; (4) decolorizing, evaporating at multiple effect until the refractive index is 55-60, and evaporating at single effect until the refractive index is 80-84; (5) the massecuite is crystallized in a step cooling mode; (6) and further drying the xylose crystals at 60-70 ℃ to obtain the finished product of dry xylose.
Chinese patent document 201810299860.8 discloses an ultrasonic-assisted purification method for xylose in eucalyptus hot water prehydrolysis liquid, which is a physical, chemical and biological combination method adopting calcium hydroxide in cooperation with ultrasonic treatment, two-stage activated carbon adsorption and laccase in cooperation with ultrasonic treatment to treat eucalyptus hydrothermal prehydrolysis liquid and adsorb excessive calcium hydroxide particles, so that soluble organic matters and impurities such as lignin and furfural except xylose in the prehydrolysis liquid are separated and removed to the maximum extent, and the purity of the xylose in the prehydrolysis liquid is improved.
Chinese patent 201310554290.X discloses a method for extracting oligosaccharides from plant material prehydrolysis liquid, comprising the following steps: (1) adding polyelectrolyte into the plant raw material prehydrolysis liquid, wherein the polyelectrolyte is one or a combination of polyaluminium chloride, polyaluminium sulfate, polyaluminium ferric chloride, polyaluminium ferric sulfate, polyaluminium ferric silicate, polyferric chloride and polyferric sulfate, the addition amount of the polyelectrolyte is 0.01-10g/L, stirring for 5-20 minutes, standing for 80-150 minutes, and separating to obtain supernatant; (2) filtering the supernatant by membrane separation to obtain oligosaccharide concentrate; (3) evaporating to crystallize oligosaccharide concentrated solution, and drying to obtain oligosaccharide.
Among the various technologies for separating and removing lignin from hydrolysate and improving hemicellulose sugar purity, a single treatment method has a low lignin removal rate, so that a process combining two or more methods is generally adopted. In processes where lignin is removed from the prehydrolyzate by flocculation treatment or acidification with cationic polymers, such as sulfuric acid treatment, the cationic polymers or acids have potentially deleterious effects on the environment and subsequent processing. The adsorbent is required to be regenerated and recycled by adopting methods such as activated carbon and exchange resin adsorption, and the problem of secondary pollution can be caused in the regeneration process. In addition, the more treatment steps, the more cumbersome the operation, and the more sugar is lost in the hydrolysate.
Aiming at the problems existing in the impurity removal of the prehydrolysis liquid of the existing plant fiber raw material: the single removal method has poor impurity removal effect, can not effectively remove lignin and still has impurity residues; when a combination of processes is used, the lignin removal is increased, but the loss of sugars is high, i.e. the selectivity of lignin removal is poor, the operation becomes cumbersome and other potentially harmful impurities may be introduced. Therefore, there is a need to develop a treatment method with high lignin removal rate, simple operation, low sugar loss rate and environmental protection. Has important significance for the purification and the subsequent utilization of the hemicellulose sugar in the prehydrolysis liquid.
Disclosure of Invention
The invention provides a method for removing lignin in plant fiber prehydrolysis liquid by horseradish peroxidase treatment, which has high lignin removal rate and low oligosaccharide loss, aiming at the problems of low lignin removal efficiency, poor selectivity and high oligosaccharide loss rate of main impurities in the existing process for extracting oligosaccharide from plant fiber raw material hydrolysate.
The plant fiber prehydrolysis liquid is prehydrolysis liquid obtained by carrying out self-hydrolysis treatment on plant fiber raw materials by hot water. The plant fiber raw material can be one of broad-leaved wood, bamboo, wheat straw, straw and reed non-wood raw materials. The self-hydrolysis treatment temperature is 140-: 4:1-20:1.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for removing lignin in plant fiber prehydrolysis liquid by using horseradish peroxidase treatment comprises the following steps:
s1, performing probe type ultrasonic treatment on a prehydrolysis liquid of a plant fiber raw material;
s2, adding soluble calcium salt into the prehydrolysis liquid after ultrasonic treatment, and then carrying out enzyme treatment by adopting horseradish peroxidase and hydrogen peroxide;
and S3, removing precipitates from the treated hydrolysate to obtain purified prehydrolysis liquid.
In the method, lignin in the prehydrolysis liquid is subjected to high-strength probe type ultrasonic treatment, and free radical reaction is generated in the ultrasonic treatment process to generate more phenolic hydroxyl groups and alcoholic hydroxyl groups. Carrying out horseradish peroxidase treatment on the prehydrolysis liquid after ultrasonic treatment, wherein in the presence of hydrogen peroxide, on one hand, phenolic hydroxyl is catalyzed by horseradish peroxidase to initiate phenoxy free radicals, and then lignin is subjected to polymerization, so that the molecular weight of the lignin is increased to be changed into insoluble lignin to be separated out; on the other hand, horseradish peroxidase can also cause oxidative degradation of lignin, alcohol hydroxyl and phenol hydroxyl can be oxidized into carboxyl in the oxidation process, and the carboxyl in the lignin and calcium ions form a compound in the presence of calcium ions and become insoluble lignin to be separated out, so that the removal rate of the lignin is effectively improved, and the loss of oligosaccharide is reduced.
In order to further increase the sugar content of the treated hydrolysate, the purified prehydrolysis liquid obtained in step S3 may be further subjected to anion exchange resin column treatment to obtain a high-purity prehydrolysis liquid with a lignin removal rate of greater than 94% and a sugar purity of greater than 95%.
The processing time of the probe type ultrasonic processing in the step S1 is preferably 25-90 minutes, and the optimal processing time is 30-60 minutes; the temperature is preferably 10-45 ℃, and the best is 20-40 ℃; the power is preferably 150-400W, and the optimal power is 200-300W; the pH of the prehydrolysis liquid is preferably 3.0-9.0, and most preferably 4.0-8.0.
In step S2, the soluble calcium salt is preferably calcium nitrate and/or calcium chloride, and the concentration of calcium ion is preferably 0.5-2.5g/L, and most preferably 1.0-2.0 g/L.
The dosage of the horseradish peroxidase is preferably 1000-5000U/L prehydrolysis liquid, and the best dosage is 1000-4000U/L prehydrolysis liquid.
The amount of hydrogen peroxide is preferably 0.5-5g/L, more preferably 1.0-3.0 g/L.
In the step S2, the enzyme treatment temperature is preferably 15-45 ℃, and the best is 20-40 ℃; the time is preferably 2-12 h, and the best time is 4-10 h; preferably, the pH is 3.5-7.0, and most preferably, the pH is 5.0-7.0.
In step S3, the treated hydrolysate is left to stand for 4-12 hours or centrifuged at 3000 rpm of 2000-3000 rpm to remove the precipitate, and then the purified prehydrolysis liquid is obtained.
Compared with the prior art, the method for removing lignin in the plant fiber prehydrolysis liquid by horseradish peroxidase treatment has the following outstanding beneficial effects:
firstly, the ultrasonic treatment provides more phenolic hydroxyl groups and alcoholic hydroxyl groups for the subsequent horse radish peroxidase treatment, which is beneficial to the lignin polymerization reaction and the oxidation reaction, thereby improving the enzyme treatment effect. In the enzyme treatment process, calcium ions can form an insoluble lignin compound with the generated lignin with carboxyl at any time to be separated out, so that the reaction is promoted. Therefore, the method can obviously improve the lignin removal rate, and the oligosaccharide loss is little. After the primary treatment by the method, the removal rate of lignin in the prehydrolysis liquid of the plant fiber raw materials is as high as 70-85%, and the loss of sugar is only 6-9%. After further anion exchange resin column treatment, the lignin removal rate is up to more than 94%, and the sugar purity is up to more than 95%.
Secondly, the method of the invention adopts a method of combining an ultrasonic physical treatment method with a biological enzyme treatment method, the introduced substances comprise calcium ions and a very small amount of horseradish peroxidase, and the added hydrogen peroxide can be basically consumed after the reaction. Therefore, the method of the invention introduces a small amount of substances which do not have harmful effects on the environment and subsequent treatment, and the treatment only needs two steps of ultrasonic treatment and enzyme treatment, thus being an environment-friendly and simple treatment process.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
[ term description ] to
Total sugar loss rate: the percentage of the total sugar reduction in the prehydrolysis liquid treatment process to the total sugar mass in the hydrolysis liquid is expressed in percentage.
The lignin removal rate is as follows: refers to the percentage mass reduction of lignin in the prehydrolysis liquid before and after treatment.
The total removal rate of furfural and hydroxymethyl furfural is as follows: refers to the percentage of the total mass of furfural and hydroxymethylfurfural in the prehydrolysis liquid reduced before and after treatment.
Sugar purity in prehydrolysis liquid: the ratio of the mass of total sugar in the prehydrolysis liquid to the mass of total substances except water in the prehydrolysis liquid.
Horse radish peroxidase activity: the enzyme amount catalyzing pyrogallic acid to generate 1.0mg of red gallic acid within 20 seconds at 20 ℃ and pH 6.0 is one enzyme activity unit.
Unless otherwise specified, the contents of the respective components used below are mass% contents.
[ example 1 ]
The method for removing lignin in the plant fiber prehydrolysis liquid by horse radish peroxidase treatment comprises the following steps:
the plant fiber prehydrolysis liquid is prehydrolysis liquid obtained after poplar self-hydrolysis, the total sugar content is 14.5g/L, and the lignin content is 5.9 g/L.
Step (2) processing:
(1) treating with probe type ultrasound (ultrasonic cell crusher, model SEIENTZ-II) under the following conditions: the treatment time is 45 minutes, the temperature is 30 ℃, the power is 200W, and the pH value is 6.0;
(2) Adding calcium chloride into the prehydrolysis liquid treated in the step 1, and treating by adopting horseradish peroxidase and hydrogen peroxide, wherein the dosage of the calcium chloride is 4.0g/L, and the enzyme treatment conditions are as follows: the enzyme dosage is 1500U/L, H2O2The dosage is 2.0g/L, the temperature is 30 ℃, the time is 6h, and the pH is 6.0.
(3) And (3) standing the hydrolysate treated in the step 2 for 10 hours, and decanting to remove precipitates to obtain the prehydrolysis liquid after upper layer purification.
The pre-hydrolyzed liquid after treatment is detected, the lignin removal rate is 85 percent, and the total sugar loss rate is 7.5 percent.
[ COMPARATIVE EXAMPLE 1 ]
The processing method is the same as that of the embodiment 1, except that: in the comparison example, probe type ultrasonic treatment in the step (1) is not carried out, the prehydrolysis liquid obtained after the self-hydrolysis of the poplar is directly subjected to the treatment in the steps (2) and (3), and calcium ions are not added in the treatment process.
According to detection, after the treatment of the comparative example 1, the lignin removal rate is 35%, and the total sugar loss rate in the prehydrolysis liquid is 5.2%.
[ COMPARATIVE EXAMPLE 2 ]
The processing method is the same as that of the embodiment 1, except that: in the comparison example, the prehydrolysis liquid obtained after the self-hydrolysis of the poplar was directly subjected to the treatments of the steps (2) and (3) without the probe type ultrasonic treatment of the step (1).
Through detection, after the treatment of the comparative example 2, the lignin removal rate is 66%, and the total sugar loss rate of the prehydrolysis liquid is 7.0%.
[ example 2 ]
The method for removing lignin in the plant fiber prehydrolysis liquid by horse radish peroxidase treatment comprises the following steps:
the plant fiber prehydrolysis liquid is prehydrolysis liquid obtained after self-hydrolysis of eucalyptus, and has the total sugar content of 13.2g/L and the lignin content of 5.3 g/L.
The processing steps are as follows:
(1) the prehydrolysis liquid is firstly treated by probe type ultrasound (ultrasonic cell crusher, model SEIENTZ-II), and the treatment conditions are as follows: the treatment time is 30 minutes, the temperature is 20 ℃, the power is 150W, and the pH is 7.0;
(2) after the pre-hydrolysis liquid is treated by ultrasonic wave, calcium chloride is added, and horseradish peroxidase is adoptedAnd hydrogen peroxide treatment, wherein the dosage of calcium chloride is 5.0g/L, and the enzyme treatment conditions are as follows: the enzyme dosage is 2000U/L, H2O2The dosage is 2.0g/L, the temperature is 25 ℃, the time is 8h, and the pH is 6.5.
(3) And standing the hydrolysate treated by the horseradish peroxidase for 10 hours, and decanting to remove precipitates to obtain the prehydrolysis liquid after upper layer purification.
The pre-hydrolyzed liquid after treatment is detected, the lignin removal rate is 83 percent, and the total sugar loss rate is 8.0 percent.
[ COMPARATIVE EXAMPLE 3 ]
The processing method is the same as that of the embodiment 2, except that: the method directly carries out the treatments of the steps (2) and (3) on the prehydrolysis liquid after the self-hydrolysis without the probe type ultrasonic treatment of the step (1), and calcium ions are not added in the treatment process.
According to detection, after the treatment of the comparative example 3, the lignin removal rate is 32%, and the total sugar loss rate in the prehydrolysis liquid is 5.2%.
[ COMPARATIVE EXAMPLE 4 ]
The processing method is the same as that of the embodiment 2, except that: the method directly carries out the treatment of the steps (2) and (3) on the prehydrolysis liquid after the autohydrolysis without the probe type ultrasonic treatment of the step (1).
According to detection, after the treatment of the comparative example 4, the lignin removal rate is 66%, and the total sugar loss rate in the prehydrolysis liquid is 7.0%.
[ example 3 ]
The method for removing lignin in the plant fiber prehydrolysis liquid by horse radish peroxidase treatment comprises the following steps:
the plant fiber prehydrolysis liquid is prehydrolysis liquid obtained by self-hydrolyzing wheat straws, and has the total sugar content of 14.2g/L and the lignin content of 5.6 g/L.
The method comprises the following steps:
(1) the prehydrolysis liquid is firstly treated by probe type ultrasound (ultrasonic cell crusher, model SEIENTZ-II), and the treatment conditions are as follows: the treatment time is 45 minutes, the temperature is 25 ℃, the power is 250W, and the pH value is 6.0;
(2) after the pre-hydrolysis liquid is subjected to ultrasonic treatment, adding calcium nitrate, and treating by adopting horseradish peroxidase and hydrogen peroxide, wherein the dosage of the calcium nitrate is 5.0g/L, and the enzyme treatment conditions are as follows: the enzyme dosage is 2500U/L, H2O2The dosage is 2.5g/L, the temperature is 20 ℃, the time is 8h, and the pH is 6.0.
(3) And standing the hydrolysate treated by the horseradish peroxidase for 10 hours, and decanting to remove precipitates to obtain the prehydrolysis liquid after upper layer purification.
The pre-hydrolyzed liquid after treatment is detected, the lignin removal rate is 80 percent, and the total sugar loss rate is 8.5 percent.
[ COMPARATIVE EXAMPLE 5 ]
The processing method is the same as that of the embodiment 3, except that: the method directly carries out the treatments of the steps (2) and (3) on the prehydrolysis liquid after the self-hydrolysis without the probe type ultrasonic treatment of the step (1), and calcium ions are not added in the treatment process.
After the treatment of comparative example 5, the lignin removal rate was 35% and the total sugar loss rate in the prehydrolysis liquid was 5.0%.
[ COMPARATIVE EXAMPLE 6 ]
The processing method is the same as that of the embodiment 3, except that: the method directly carries out the treatment of the steps (2) and (3) on the prehydrolysis liquid after the autohydrolysis without the probe type ultrasonic treatment of the step (1).
After the treatment of comparative example 6, the lignin removal rate was 71%, and the total sugar loss rate in the prehydrolysis liquid was 7.3%.
[ example 4 ]
And (3) treating the prehydrolysis liquid obtained in the example 1 by using an anion exchange resin column to obtain purified prehydrolysis liquid.
After the treatment of the steps, the total removal rate of lignin in the prehydrolysis liquid reaches 95.0%, and meanwhile, after the treatment of the steps, the total removal rate of impurities including furfural and hydroxymethyl furfural in the prehydrolysis liquid is 95.2%, the sugar purity in the obtained prehydrolysis liquid is 97.1%, and the loss of total sugar is 9.5%.
[ example 5 ]
The prehydrolysis liquid obtained in the example 2 is treated by an anion exchange resin column to obtain purified prehydrolysis liquid, the total removal rate of lignin in the prehydrolysis liquid reaches 94.2% after the treatment of the steps, the total removal rate of furfural and hydroxymethyl furfural is 94.8% after the treatment of the steps, the sugar purity in the purified prehydrolysis liquid is 95.4%, and the loss of total sugar is 9.8%.
[ example 6 ]
The same horseradish peroxidase treatment as described in example 1 was used to remove lignin from the prehydrolysis liquid of plant fibers, except that probe sonication was used at a temperature of 20 ℃.
And (3) detecting the treated prehydrolysis liquid, wherein the lignin removal rate is 82%, and the total sugar loss rate is 7.4%.
[ example 7 ]
The same procedure was followed as described in example 1 except that hydrogen peroxide was used in an amount of 1.0g/L in the horseradish peroxidase treatment to remove lignin from the prehydrolysis liquid of plant fibers.
And (3) detecting the treated prehydrolysis liquid, wherein the lignin removal rate is 78% and the total sugar loss rate is 7.2%.
[ example 8 ]
The method for removing lignin from the prehydrolysis liquid of plant fibers by horseradish peroxidase treatment was the same as described in example 2, except that the horseradish peroxidase treatment was carried out using 3000U/L of enzyme and 1.5g/L of hydrogen peroxide.
And (4) detecting the treated prehydrolysis liquid, wherein the lignin removal rate is 81 percent, and the total sugar loss rate is 7.8 percent.
[ example 9 ]
The same procedure as described in example 1 was followed to remove lignin from the prehydrolysis liquid of plant fibers by horseradish peroxidase treatment, except that the prehydrolysis liquid was obtained after autohydrolysis of bamboo.
The total sugar concentration in the prehydrolysis liquid before pretreatment is 13.5g/L, and the lignin concentration is 4.6 g/L.
After the pretreatment hydrolysate was treated in the same manner as in example 1, the lignin removal rate was 79% and the total sugar loss was 8.4%.

Claims (1)

1. The method for removing lignin in plant fiber prehydrolysis liquid by using horseradish peroxidase treatment is characterized by comprising the following steps of:
s1, performing probe type ultrasonic treatment on the prehydrolysis liquid of the plant fiber raw material with the pH value of 3.0-9.0 at the temperature of 10-45 ℃, wherein the treatment time is 25-90 minutes, the power is 150-,
the plant fiber raw material prehydrolysis liquid is obtained by carrying out self-hydrolysis treatment on a plant fiber raw material by hot water, the plant fiber raw material is one of broadleaf wood, bamboo, wheat straw, straw and reed non-wood raw materials, the self-hydrolysis treatment temperature is 140-190 ℃, the self-hydrolysis time is 30-180min, and the mass ratio of water to the plant fiber raw material is as follows: 4:1-20: 1;
s2, adding calcium nitrate and/or calcium chloride into the prehydrolysis liquid after ultrasonic treatment, then carrying out enzyme treatment by adopting horseradish peroxidase and hydrogen peroxide at the enzyme treatment temperature of 15-45 ℃ for 2-12 h and the pH value of 3.5-7.0,
calculated by calcium ions, the concentration of the calcium ions is 1.0-2.0g/L of the prehydrolysis liquid, the dosage of horseradish peroxidase is 1000-;
s3, standing the treated hydrolysate for 4-12 hours or centrifuging at 3000 r/min at 2000-;
and S4, treating the purified prehydrolysis liquid by using an anion exchange resin column to obtain the high-purity prehydrolysis liquid with the lignin removal rate of more than 94% and the sugar purity of more than 95%.
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