CN103923130A - Method for separating glucose and xylose in straw fiber enzymatic hydrolysate - Google Patents

Abstract

The present invention relates to a method for separating glucose and xylose in straw fiber enzymatic hydrolysis solution. The method for separating glucose and xylose in straw fiber enzymatic hydrolysis solution is as follows: a) Preparation of feed syrup: desalting, decolorizing . The concentrated straw fiber enzymatic solution is adjusted to a concentration of 40-60%; b) Filtration: filter the syrup solution obtained in step a) with a micron filter to obtain a clear liquid without visible to the naked eye; c) . Sequential simulated moving bed chromatographic separation: the syrup obtained above is separated by sequential simulated moving bed chromatographic equipment, the eluent is deionized water, the adsorbent is strongly acidic cation exchange resin, and the separation temperature is 60-70°C. Sequential simulated moving bed chromatographic separation equipment includes 9 chromatographic columns arranged in sequence, with 2 feed ports and 2 discharge ports with sequential changes; d), concentration: concentrate the obtained component A solution to 70 %～75%, the component B obtained is mixed, and then concentrated to 70%～75%. The invention has low operation cost, high purity, concentration and yield of separated products, and can realize continuous and industrialized production.

Description

Method for separating glucose and xylose in straw fiber enzymatic hydrolysis solution

1. Technical field

The invention relates to a sequential simulated mobile chromatographic separation technology, in particular to a method for separating glucose and xylose in straw fiber enzymatic hydrolysis solution.

2. Background technology

According to incomplete statistics, my country produces 600-800 million tons of crop straw every year, and more than 2/3 of it is wasted without being effectively utilized. Most of these unused crop straws are burned directly, which not only causes a lot of waste of resources and environmental pollution, but also causes fire accidents. On the other hand, it also leads to low efficiency and low economic benefits of crop straw utilization. . Straw contains a lot of cellulose and hemicellulose, which is a good raw material for sugar production. With the development of biotechnology, the current straw enzymatic sugar production technology is basically mature, 3-4 tons of straw can produce 1 ton of 70% syrup after enzymatic hydrolysis, which shows that its application prospect is broad. However, the main components in straw enzymatic hydrolyzate are glucose and xylose. However, the physical and chemical properties of glucose and xylose are very similar and difficult to separate. Therefore, the separation technology of glucose and xylose in straw fiber enzymatic hydrolyzate has become an The key to efficient use.

Simulated moving chromatographic bed (SMB) is an advanced and efficient separation technology, which plays an important role in the development of modern functional sugars and functional sugar alcohols, glucose, sucrose and Chinese herbal medicines. At present, the most advanced simulated moving bed chromatography in the world is sequential simulated moving bed chromatography (SSMB). SSMB is much more advanced than traditional SMB. It is characterized by a reduction in the number of separation columns, a 30%-50% reduction in operating costs and a 20%-40% reduction in solvent usage compared to traditional chromatographic separation equipment. On the basis of ensuring high purity, it has high separation, high recovery, high efficiency, low cost, high stability and other performances.

Chinese patent 200910039185.6 discloses a method for preparing plant hemicellulose hydrolyzate and extracting xylose and arabinose; Chinese patent 201010000196.6 discloses a mixed enzymatic hydrolysis method of corncob acid hydrolysis residue and straw alkali cooking residue; China Patent 201210518298.6 discloses a method for increasing the reducing sugar content of straw. It can be seen from the above that the existing patents on straw sugar production in my country are mainly concentrated on the pretreatment of straw sugar production, and there are no research results on the separation of glucose and xylose in straw fiber enzymatic hydrolysis solution.

Chinese patent 200710014175.8 discloses a method for purifying xylose mother liquor using a sequential simulated moving bed, which uses a sequential simulated moving bed to simultaneously separate glucose, xylose and arabinose components, wherein the purity and concentration of glucose are 5% and 75.6 %, the purity and concentration of xylose are 90.2% and 31.5%, the purity and concentration of arabinose are 85.8% and 7.5%, the results show that the purity and concentration of xylose and arabinose are not high, and the advantages of the sequential simulated moving bed have not been fully utilized , the extraction of the glucose component lost a part of xylose and arabinose, resulting in a decrease in the yield of these two components, and a certain decline in the overall economic benefit; Chinese patent 200720141139.3 discloses a sequential simulated moving bed chromatography device ; Chinese patent 200920274899.0 discloses a sequential simulated moving bed chromatography purification device. It can be seen from the above that the current patents on sequential simulated moving bed chromatography in my country are mainly concentrated in the R&D and manufacturing of devices, and the application of sugar alcohols is not very mature. However, the use of sequential simulated moving bed chromatography to separate straw fibers Glucose and xylose in the enzymatic solution have no research results.

3. Contents of the invention

The purpose of the present invention is to provide a method for separating glucose and xylose in the straw fiber enzymatic hydrolyzate, which is used to solve the problem of glucose and xylose in the straw fiber enzymatic hydrolyzate in the prior art. The difficult problem that xylose cannot be separated efficiently.

The technical solution adopted in the present invention is: the method for separating glucose and xylose in the straw fiber enzymatic hydrolysis solution is as follows:

a) Preparation of feed syrup: the desalted, decolorized and concentrated straw fiber enzymatic solution is prepared to a concentration of 40-60%;

b), Filtration: filter the syrup solution obtained in step a) with a micron filter to obtain a clear liquid without visible to the naked eye;

c) Sequential simulated moving bed chromatographic separation: the syrup obtained above is separated by sequential simulated moving bed chromatographic equipment, the eluent is deionized water, the adsorbent is strongly acidic cation exchange resin, and the separation temperature is 60-70 ℃, the sequential simulated moving bed chromatographic separation equipment contains 9 chromatographic columns arranged in sequence, with 2 inlets and 2 outlets with sequential changes, and the position of No. 1 column is divided into the following three steps:

The first step: The material does not enter and exit, and a large circulation is carried out. The liquid flow direction is from No. 1 column to No. 9 column, and the circulation volume is 50% to 70% of the volume of the chromatographic column;

The second step: this step is a small cycle, only enters the eluent deionized water, the No. 1 column enters the eluent, and a part of component B comes out from the lower end of the No. 8 column. Component B is the glucose component, and the eluent dosage is 3% to 15% of the column volume;

The third step: feed materials, eluent, and discharge at the same time. This step is also called all-in-all-out. No. 1 column enters eluent, and component A comes out from the lower end of No. 1 column. Component A is xylose component ; No. 9 column enters the raw material, and another part of component B comes out from the lower end of No. 8 column. The elution dose is 3% to 15% of the volume of the chromatographic column, and the amount of feed is 5% to 10% of the volume of the chromatographic column;

Repeat the above three steps in order after the operation of No. 1 column, wherein, when repeating the second and third steps, each time it is repeated, the inlet and outlet positions are moved from No. 1 to No. 9 to the next column;

d) Concentration: Concentrate all the component A solutions prepared in the third step, and concentrate the concentration of the component A solution to 70% to 75%, and mix all the component B prepared in the second and third steps , and then concentrated, the concentration of component B solution was reduced to 70% to 75%.

In the above scheme, the strongly acidic cation exchange resin is any one of ZG-106Na+, UBK530 Na+, UBK550 Na+, 99 Na+-310 or 99 Na+-320.

Beneficial effect:

1. The present invention adopts sequential simulated moving bed chromatography to separate glucose and xylose in the straw fiber enzymolysis solution, and obtain component A solution and component B solution. The concentration of component A is 30% to 40%, and the purity of xylose is 80% %～90%, the yield is 80～90%, the concentration of component B is 30%～40%, the purity of glucose is 80%～90%, the yield is 75～85%, the process operation cost is low, and the purity and concentration of the separated product And the yield is high, and continuous and industrial production can be realized.

2. The present invention reduces subsequent concentration costs, simplifies operation steps, and reduces production loss.

4. Description of drawings

Fig. 1 is a flow diagram of the production method of the present invention;

Fig. 2 is the schematic diagram of the first step in sequential simulated moving bed chromatographic separation of the present invention;

Fig. 3 is the schematic diagram of the second step in the sequential simulated moving bed chromatographic separation of the present invention;

Fig. 4 is the schematic diagram of the third step in the sequential simulated moving bed chromatographic separation of the present invention;

Fig. 5 is the liquid chromatographic analysis spectrum of straw enzymolysis solution;

Fig. 6 is the liquid chromatographic analysis collection of glucose components after the sequential simulated moving bed chromatographic separation of embodiment 3;

Fig. 7 is the liquid chromatographic analysis spectrum of the xylose component after sequential simulated moving bed chromatographic separation in Example 3.

5. Specific implementation

Below in conjunction with accompanying drawing, the present invention will be further described:

Example 1

As shown in Figure 1, the method for separating glucose and xylose in straw fiber enzymatic hydrolysis solution is as follows:

a) Preparation of feed syrup: the desalted, decolorized and concentrated straw fiber enzymatic solution is prepared to a concentration of 60%;

b), Filtration: filter the syrup solution obtained in step a) with a micron filter to obtain a clear liquid without visible impurities;

c) Sequential simulated moving bed chromatographic separation: the syrup obtained above is separated by sequential simulated mobile chromatographic equipment. The eluent is water, the adsorbent is resin ZG-106 Na ⁺ , the separation temperature is 60-70 ℃, and the sequential simulated moving bed chromatographic separation equipment contains 9 chromatographic columns arranged in sequence, with sequentially changed feed ports 2 There are 2 outlets, and the position of No. 1 column is divided into the following three steps:

The first step: The material does not enter and exit, and a large circulation is carried out. The liquid flow direction is from No. 1 column to No. 9 column, and the circulation volume is 60% of the volume of the chromatographic column, see Figure 2;

The second step: this step is a small cycle, only enter the eluent deionized water, the No. 1 column enters the eluent, and a part of component B (glucose component) comes out from the lower end of the No. 8 column, and the eluent volume is the volume of the chromatographic column 5%, referring to Fig. 3, among the figure D is water;

The third step: feed materials, feed eluent, and discharge materials at the same time, this step is also called all-in-all-out. The No. 1 column enters the eluent, and the component A (xylose component) comes out from the lower end of the No. 1 column; the raw material enters the No. 6 column, and another part of the component B (glucose component) comes out from the lower end of the No. 8 column. The eluting dose is 5% of the volume of the chromatographic column, and the amount of feed is 5% of the volume of the chromatographic column. Referring to Fig. 4, D is water among the figures;

After the operation of No. 1 column, repeat the above three steps in the order of No. 2-No. The horn direction moves to the next column.

d), Concentration: Concentration: Concentrate all component A solutions prepared in the third step, and concentrate the concentration of component A solutions to 70% to 75%, and concentrate all component B obtained in the second and third steps Mix and then concentrate, and the concentration of the component B solution is reduced to 70% to 75%.

In this example, component A solution and component B solution were separated, the concentration of component A was 36.5%, the purity of xylose was 85.3%, and the yield was 82.1%, the concentration of component B was 32.0%, the purity of glucose was 86.7%, and the yield was 79.4% %.

Example 2

The method for separating glucose and xylose in straw fiber enzymatic hydrolysis solution is as follows:

a) Preparation of feed syrup: the desalted, decolorized and concentrated straw fiber enzymatic solution is prepared to a concentration of 60%;

b), Filtration: filter the syrup solution obtained in step a) with a micron filter to obtain a clear liquid without visible to the naked eye;

c) Sequential simulated moving bed chromatographic separation: the syrup obtained above is separated by sequential simulated mobile chromatographic equipment. The eluent is water, the adsorbent is resin 99 Na+-310, and the separation temperature is 60-70 °C. The sequential simulated moving bed chromatography separation equipment includes 9 chromatographic columns arranged in sequence, and 2 feed ports with sequential changes. , there are 2 outlets, and the position of No. 1 column is divided into the following three steps:

The first step: the material does not enter and exit, and a large circulation is carried out. The liquid flow direction is from No. 1 column to No. 9 column, and the circulation volume is 55% of the volume of the chromatographic column;

The second step: this step is a small cycle, only enter the eluent deionized water, the No. 1 column enters the eluent, and a part of component B (glucose component) comes out from the lower end of the No. 8 column, and the eluent volume is the volume of the chromatographic column 7.5% of

The third step: feed materials, feed eluent, and discharge materials at the same time, this step is also called all-in-all-out. The No. 1 column enters the eluent, and the component A (xylose component) comes out from the lower end of the No. 1 column; the raw material enters the No. 6 column, and another part of the component B (glucose component) comes out from the lower end of the No. 8 column. The eluting dose is 7.5% of the volume of the chromatographic column, and the amount of feed is 10% of the volume of the chromatographic column;

After the operation of No. 1 column, repeat the above three steps in the order of No. 2-No. The horn direction moves to the next column.

d) Concentration: Concentrate all the component A solutions prepared in the third step, and concentrate the concentration of the component A solution to 70% to 75%, and mix all the component B prepared in the second and third steps , and then concentrated, the concentration of component B solution was reduced to 70% to 75%.

In this example, component A solution and component B solution were separated, the concentration of component A was 39.5%, the purity of xylose was 82.6%, and the yield was 88.2%, the concentration of component B was 35.0%, the purity of glucose was 83.5%, and the yield was 75.8% %.

Example 3

The method for separating glucose and xylose in straw fiber enzymatic hydrolysis solution is as follows:

a) Preparation of feed syrup: the desalted, decolorized and concentrated straw fiber enzymatic solution is prepared to a concentration of 40%;

b), Filtration: filter the syrup solution obtained in step a) with a micron filter to obtain a clear liquid without visible to the naked eye;

c) Sequential simulated moving bed chromatographic separation: the syrup obtained above is separated by sequential simulated mobile chromatographic equipment. The eluent is water, the adsorbent is resin 99 Na+-310, and the separation temperature is 60-70 °C. The sequential simulated moving bed chromatography separation equipment includes 9 chromatographic columns arranged in sequence, and 2 feed ports with sequential changes. , there are 2 outlets, and the position of No. 1 column is divided into the following three steps:

The first step: the material does not enter and exit, and a large circulation is carried out. The liquid flow direction is from No. 1 column to No. 9 column, and the circulation volume is 55% of the volume of the chromatographic column;

The second step: this step is a small cycle, only enter the eluent deionized water, the No. 1 column enters the eluent, and a part of component B (glucose component) comes out from the lower end of the No. 8 column, and the eluent volume is the volume of the chromatographic column 5% of

The third step: feed materials, feed eluent, and discharge materials at the same time, this step is also called all-in-all-out. The No. 1 column enters the eluent, and the component A (xylose component) comes out from the lower end of the No. 1 column; the raw material enters the No. 6 column, and another part of the component B (glucose component) comes out from the lower end of the No. 8 column. The eluting dose is 5% of the volume of the chromatographic column, and the amount of feed is 10% of the volume of the chromatographic column;

After the operation of No. 1 column, repeat the above three steps in the order of No. 2-No. The horn direction moves to the next column.

d) Concentration: Concentrate all the component A solutions prepared in the third step, and concentrate the concentration of the component A solution to 70% to 75%, and mix all the component B prepared in the second and third steps , and then concentrated, the concentration of component B solution was reduced to 70% to 75%.

In this example, component A solution and component B solution were separated, the concentration of component A was 38.2%, the purity of xylose was 88.7%, and the yield was 85.4%, the concentration of component B was 30.4%, the purity of glucose was 82.6%, and the yield was 83.7% %.

Example 4

The method for separating glucose and xylose in straw fiber enzymatic hydrolysis solution is as follows:

a) Preparation of feed syrup: the desalted, decolorized and concentrated straw fiber enzymatic solution is prepared to a concentration of 50%;

b), Filtration: filter the syrup solution obtained in step a) with a micron filter to obtain a clear liquid without visible to the naked eye;

c) Sequential simulated moving bed chromatographic separation: the syrup obtained above is separated by sequential simulated mobile chromatographic equipment. The eluent is water, the adsorbent is resin 99 Na+-310, and the separation temperature is 60-70 °C. The sequential simulated moving bed chromatography separation equipment includes 9 chromatographic columns arranged in sequence, and 2 feed ports with sequential changes. , there are 2 outlets, and the position of No. 1 column is divided into the following three steps:

The first step: the material does not enter and exit, and a large circulation is carried out. The liquid flow direction is from No. 1 column to No. 9 column, and the circulation volume is 60% of the volume of the chromatographic column;

The second step: this step is a small cycle, only enter the eluent deionized water, the No. 1 column enters the eluent, and a part of component B (glucose component) comes out from the lower end of the No. 8 column, and the eluent volume is the volume of the chromatographic column 5% of

The third step: feed materials, feed eluent, and discharge materials at the same time, this step is also called all in all out. The No. 1 column enters the eluent, and the component A (xylose component) comes out from the lower end of the No. 1 column; the No. 6 column enters the raw material, and another part of the component B (glucose component) comes out from the lower end of the No. 8 column. The eluting dose is 5% of the volume of the chromatographic column, and the amount of feed is 5% of the volume of the chromatographic column;

After the operation of No. 1 column, repeat the above three steps in the order of No. 2-No. The horn direction moves to the next column.

d) Concentration: Concentrate all the component A solutions prepared in the third step, and concentrate the concentration of the component A solution to 70% to 75%, and mix all the component B prepared in the second and third steps , and then concentrated, the concentration of component B solution was reduced to 70% to 75%.

In this example, component A solution and component B solution were separated, the concentration of component A was 34.8%, the purity of xylose was 89.5%, and the yield was 81.3%, the concentration of component B was 30.3%, the purity of glucose was 80.5%, and the yield was 82.3% %.

The core technology of the present invention is sequential simulated moving bed chromatographic separation of glucose and xylose in straw fiber enzymolysis solution to obtain glucose syrup and xylose syrup with high purity and yield. This process not only guarantees glucose and xylose Its high purity and high yield also have distinct characteristics in terms of cost saving of the whole process and simple process steps.

Claims (2)

1. a method that separates glucose and xylose in stalk fibre enzymolysis solution, is characterized in that: in this separation stalk fibre enzymolysis solution, the method for glucose and xylose is as follows:

A), the allotment of charging syrup: be 40-60% by being formulated to concentration through desalination, decolouring, stalk fibre enzymolysis solution after concentrated;

B), filter: the syrup solution that step a) is obtained filters with micron order filter, make clarification without macroscopic liquid;

C), sequential type simulated moving bed chromatography separate: by syrup obtained above through sequential type simulated moving bed chromatography device separates, eluent is deionized water, sorbent material is highly acidic cation crossover resin, separation temperature is 60-70 DEG C, sequential type simulated moving bed chromatography separating device comprises 9 chromatographic columns of arranging in turn, have 2 of the opening for feeds of order conversion, 2 of discharge ports, are wherein divided into following three steps when No. 1 post position:

The first step: material can not enter, carries out systemic circulation, liquid flow path direction is to be flowed by No. 1 post to 9 post, internal circulating load is 50%～70% of chromatographic column volume;

Second step: this step is partial circulating, only enters eluent deionized water, No. 1 post enters eluent, under No. 8 posts, brings out a part of B component, and B component is glucose component, and entering amount of eluent is 3%～15% of chromatographic column volume;

The 3rd step: enter material simultaneously, enter eluent, discharging, this step claims again all-in and all-out, and No. 1 post enters eluent, brings out component A under No. 1 post, and component A is wood sugar component; No. 9 post enters raw material, brings out the B component of another part under No. 8 posts, and entering amount of eluent is 3%～15% of chromatographic column volume, and inlet amount is 5%～10% of chromatographic column volume;

After No. 1 post end of run, repeat in order above three steps, wherein, in the time repeating second step and the 3rd step, every repetition once, charging and discharging position moves to next post by No. 1 post to 9 post direction;

D), concentrated: the component A solution that all third steps are made concentrates, and component A strength of solution is concentrated into 70%～75%, and the B component that all second steps, third step are made is mixed, then concentrates, and B component strength of solution is reduced to 70%～75%.

2. the method for glucose and xylose in separation stalk fibre enzymolysis solution according to claim 1, is characterized in that: described highly acidic cation crossover resin is any one in ZG-106Na+, UBK530 Na+, UBK550 Na+, 99 Na+-310 or 99 Na+-320.