Bio-enzyme catalysis process for reducing agent modification

Abstract

The invention relates to the field of bio-enzyme catalysis, and discloses a bio-enzyme catalysis process for reducing agent modification, which comprises the following steps: S1, enzyme solution preparation: mixing a bio-enzyme preparation with a buffer solution with the pH value of 5-8 to prepare an enzyme solution with the enzyme concentration of 0.5-5.0 g / L; the biological enzyme preparation is a compound enzyme composed of one or more of cellulase, hemicellulase and lignin degrading enzyme; s2, enzymolysis modification: mixing a carbonaceous reducing agent raw material with the enzyme solution prepared in the step S1 according to a mass ratio of 1: 5-1: 20, carrying out an enzymolysis reaction at 40-60 DEG C, and meanwhile, applying ultrasonic waves to carry out auxiliary treatment; the power of the ultrasonic waves is 100-500 W, and the frequency of the ultrasonic waves is 20-40 kHz And S3, solid-liquid separation: after the reaction is finished, separating the modified reducing agent from the enzymatic hydrolysate to obtain the solid modified reducing agent. Compared with the prior art, the method has the advantages that a biological enzyme catalysis process for modifying the reducing agent is provided, the energy consumption is low, the environment is protected, the cost is low, and the performance of the reducing agent can be remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of bio-enzyme catalysis technology, specifically to a bio-enzyme catalysis process for modifying reducing agents. Background Technology

[0002] Industrial silicon, a key raw material in photovoltaics, semiconductors, and alloy materials, relies on the reduction reaction between carbonaceous reducing agents (such as charcoal, petroleum coke, anthracite, and biochar) and silica during its smelting process. However, traditional carbonaceous reducing agents face significant technical bottlenecks:

[0003] (1) The reaction efficiency is low. Traditional reducing agents (such as charcoal and petroleum coke) have poor reactivity and the effective carbon utilization rate is less than 60%, resulting in a total power consumption of more than 12,000 kWh per ton of silicon, which seriously restricts smelting efficiency and product competitiveness.

[0004] (2) Existing reducing agent modification methods are difficult to balance "high efficiency" and "environmental protection and low cost":

[0005] Physical modification (such as high-temperature calcination activation) requires a large amount of energy and is prone to thermal stress damage to the microstructure of the reducing agent, resulting in limited structural improvement.

[0006] While chemical modification (such as acid and alkali impregnation) can improve activity, it requires a large amount of corrosive chemicals, and the subsequent wastewater and waste residue treatment is complicated, resulting in serious secondary pollution and high environmental protection costs.

[0007] (3) The application of bio-enzyme technology is lagging behind. Although the international community started research on bio-enzyme catalysis technology in mineral processing and carbon material modification earlier, special enzyme preparations and mature enzyme modification processes for the characteristics of carbonaceous reducing agents used in industrial silicon smelting have not yet been formed. In China, physical modification is still the main method, and the industrial application of bio-enzyme catalysis technology is lacking. Most enterprises still face problems such as low utilization rate of reducing agents and high power consumption per ton of silicon. Summary of the Invention

[0008] (a) Technical problems to be solved

[0009] The technical problem to be solved by the present invention is to provide a bio-enzyme catalytic process for modifying reducing agents, which is low in energy consumption, environmentally friendly, low in cost, and can significantly improve the performance of reducing agents.

[0010] (II) Technical Solution

[0011] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a bio-enzyme catalysis process for modifying reducing agents, comprising the following steps:

[0012] S1. Enzyme solution preparation: The biological enzyme preparation is mixed with a buffer solution with a pH of 5-8 to prepare an enzyme solution with an enzyme concentration of 0.5-5.0 g / L; the biological enzyme preparation is a complex enzyme composed of one or more of cellulase, hemicellulase, and lignin-degrading enzyme.

[0013] S2. Enzymatic hydrolysis modification: The carbonaceous reducing agent raw material is mixed with the enzyme solution prepared in step S1 at a mass ratio of 1:5 to 1:20, and the enzymatic hydrolysis reaction is carried out at 40-60℃, while ultrasound is applied for auxiliary treatment; the ultrasonic power is 100-500W and the frequency is 20-40kHz.

[0014] S3. Solid-liquid separation: After the reaction is complete, the modified reducing agent is separated from the enzymatic hydrolysate to obtain a solid modified reducing agent;

[0015] S4. Enzyme recovery: The enzyme hydrolysate separated in step S3 is recovered using immobilized enzyme technology and used to prepare enzyme solutions again.

[0016] As an improvement, in step S1, the composite enzyme is composed of cellulase, hemicellulase, and lignin-degrading enzyme in a mass ratio of (3-5):(2-4):(1-2).

[0017] As an improvement, in step S2, the enzymatic hydrolysis reaction time is 4 to 12 hours.

[0018] As an improvement, in step S2, the ultrasonic-assisted treatment adopts an intermittent working mode, with a working interval of 1 to 5 minutes and an interval of 1 to 3 minutes.

[0019] As an improvement, in step S4, the carrier used for the immobilized enzyme technology is chitosan microspheres, calcium alginate gel, or modified diatomaceous earth.

[0020] As an improvement, the enzyme preparation recovered in step S4 can be recycled at least 5 times.

[0021] As an improvement, the biological enzyme preparation described in step S1 is prepared autonomously by a method including the following steps:

[0022] a. Using Aspergillus niger or Trichoderma reesei as enzyme-producing strains, fermentation culture is carried out in a fermentation medium;

[0023] b. Inducing enzyme production in strains by optimizing fermentation temperature, pH, and aeration parameters;

[0024] c. After fermentation, the fermentation broth is separated and purified to obtain the biological enzyme preparation.

[0025] As an improvement, the carbonaceous reducing agent raw material is one or more of petroleum coke, anthracite, or biochar.

[0026] As an improvement, in step S2, the pH of the reaction system is maintained in the range of 5-8 by online pH monitoring and the addition of acid or alkali solutions during the enzymatic hydrolysis reaction.

[0027] As an improvement, when the enzyme preparation recovered in step S4 is used to prepare enzyme solutions again, its enzyme activity is not less than 70% of the initial enzyme activity.

[0028] (III) Beneficial Effects

[0029] The advantages of this invention compared to the prior art are:

[0030] (1) By using a complex enzyme system with a specific composition, the reducing agent is catalytically degraded under mild conditions (40-60℃, pH5-8), and combined with ultrasonic-assisted treatment, the pore structure and surface properties of the reducing agent can be effectively improved, thereby enhancing its reactivity.

[0031] (2) Ultrasonic-assisted technology enhances the mass transfer process and improves the contact efficiency between enzyme and substrate, thereby increasing the enzymatic reaction rate and modification effect. The mild reaction conditions also reduce energy consumption.

[0032] (3) By using immobilized enzyme technology (such as using inexpensive carriers like chitosan microspheres) to recover enzymes, the enzyme preparations were recycled in multiple rounds (no less than 5 times). At the same time, the enzyme preparations were prepared by self-fermentation, which significantly reduced the cost of enzymes modified by reducing agent and reduced waste emissions. Detailed Implementation

[0033] The invention will now be described in further detail with reference to specific embodiments, but this should not be construed as limiting the scope of the subject matter of the invention to the following embodiments.

[0034] Example 1

[0035] A bio-enzyme catalytic process for modifying reducing agents includes the following steps:

[0036] S1. Enzyme solution preparation: The biological enzyme preparation is mixed with a buffer solution with a pH of 5 to prepare an enzyme solution with an enzyme concentration of 0.5 g / L; the biological enzyme preparation is a complex enzyme composed of one or more of cellulase, hemicellulase, and lignin-degrading enzyme, and the complex enzyme is composed of cellulase, hemicellulase and lignin-degrading enzyme in a mass ratio of 3:2:1.

[0037] The bio-enzyme preparation is prepared autonomously using a method comprising the following steps:

[0038] a. Using Aspergillus niger or Trichoderma reesei as enzyme-producing strains, fermentation culture is carried out in a fermentation medium;

[0039] b. Inducing enzyme production in strains by optimizing fermentation temperature, pH, and aeration parameters;

[0040] c. After fermentation, the fermentation broth is separated and purified to obtain the biological enzyme preparation.

[0041] S2. Enzymatic hydrolysis modification: The carbonaceous reducing agent raw material is mixed with the enzyme solution prepared in step S1 at a mass ratio of 1:5, and the enzymatic hydrolysis reaction is carried out at 40°C for 4 hours. Ultrasonic waves are applied simultaneously for auxiliary treatment. The ultrasonic power is 100W and the frequency is 20kHz. The ultrasonic auxiliary treatment adopts an intermittent working mode, with a 1-minute working interval and a 1-minute pause. The carbonaceous reducing agent raw material is one or more of petroleum coke, anthracite, or biochar. During the enzymatic hydrolysis reaction, the pH value of the reaction system is maintained within the range of 5 by online pH monitoring and the addition of acid or alkali solutions.

[0042] S3. Solid-liquid separation: After the reaction is complete, the modified reducing agent is separated from the enzymatic hydrolysate to obtain a solid modified reducing agent;

[0043] S4. Enzyme recovery: The enzyme hydrolysate separated in step S3 is recovered using immobilized enzyme technology for the preparation of enzyme solutions again. The carrier used in the immobilized enzyme technology is chitosan microspheres, calcium alginate gel or modified diatomaceous earth. The recovered enzyme preparation can be recycled at least 5 times. When the recovered enzyme preparation is used to prepare enzyme solutions again, its enzyme activity is not less than 70% of the initial enzyme activity.

[0044] Example 2

[0045] A bio-enzyme catalytic process for modifying reducing agents includes the following steps:

[0046] S1. Enzyme solution preparation: The biological enzyme preparation is mixed with a buffer solution with a pH of 6 to prepare an enzyme solution with an enzyme concentration of 3g / L; the biological enzyme preparation is a complex enzyme composed of one or more of cellulase, hemicellulase, and lignin-degrading enzyme, and the complex enzyme is composed of cellulase, hemicellulase and lignin-degrading enzyme in a mass ratio of 4:3:2.

[0047] The bio-enzyme preparation is prepared autonomously using a method comprising the following steps:

[0048] a. Using Aspergillus niger or Trichoderma reesei as enzyme-producing strains, fermentation culture is carried out in a fermentation medium;

[0049] b. Inducing enzyme production in strains by optimizing fermentation temperature, pH, and aeration parameters;

[0050] c. After fermentation, the fermentation broth is separated and purified to obtain the biological enzyme preparation.

[0051] S2. Enzymatic hydrolysis modification: The carbonaceous reducing agent raw material is mixed with the enzyme solution prepared in step S1 at a mass ratio of 1:10, and the enzymatic hydrolysis reaction is carried out at 50°C for 8 hours. Ultrasonic waves are applied simultaneously for auxiliary treatment. The ultrasonic power is 300W and the frequency is 30kHz. The ultrasonic auxiliary treatment adopts an intermittent working mode, with a 3-minute working interval followed by a 2-minute interval. The carbonaceous reducing agent raw material is one or more of petroleum coke, anthracite, or biochar. During the enzymatic hydrolysis reaction, the pH value of the reaction system is maintained within the range of 6 by online pH monitoring and the addition of acid or alkali solutions.

[0052] S3. Solid-liquid separation: After the reaction is complete, the modified reducing agent is separated from the enzymatic hydrolysate to obtain a solid modified reducing agent;

[0053] S4. Enzyme recovery: The enzyme hydrolysate separated in step S3 is recovered using immobilized enzyme technology for the preparation of enzyme solutions again. The carrier used in the immobilized enzyme technology is chitosan microspheres, calcium alginate gel or modified diatomaceous earth. The recovered enzyme preparation can be recycled at least 5 times. When the recovered enzyme preparation is used to prepare enzyme solutions again, its enzyme activity is not less than 70% of the initial enzyme activity.

[0054] Example 3

[0055] A bio-enzyme catalytic process for modifying reducing agents includes the following steps:

[0056] S1. Enzyme solution preparation: The biological enzyme preparation is mixed with a buffer solution with a pH of 8 to prepare an enzyme solution with an enzyme concentration of 5.0 g / L; the biological enzyme preparation is a complex enzyme composed of one or more of cellulase, hemicellulase, and lignin-degrading enzyme, and the complex enzyme is composed of cellulase, hemicellulase and lignin-degrading enzyme in a mass ratio of 5:4:2.

[0057] The bio-enzyme preparation is prepared autonomously using a method comprising the following steps:

[0058] a. Using Aspergillus niger or Trichoderma reesei as enzyme-producing strains, fermentation culture is carried out in a fermentation medium;

[0059] b. Inducing enzyme production in strains by optimizing fermentation temperature, pH, and aeration parameters;

[0060] c. After fermentation, the fermentation broth is separated and purified to obtain the biological enzyme preparation.

[0061] S2. Enzymatic hydrolysis modification: The carbonaceous reducing agent raw material is mixed with the enzyme solution prepared in step S1 at a mass ratio of 1:5 to 1:20, and the enzymatic hydrolysis reaction is carried out at 60°C for 12 hours. Ultrasonic waves are applied simultaneously for auxiliary treatment. The ultrasonic power is 500W and the frequency is 40kHz. The ultrasonic auxiliary treatment adopts an intermittent working mode, with a 5-minute working interval followed by a 3-minute interval. The carbonaceous reducing agent raw material is one or more of petroleum coke, anthracite, or biochar. During the enzymatic hydrolysis reaction, the pH value of the reaction system is maintained within the range of 8 by online pH monitoring and the addition of acid or alkali solutions.

[0062] S3. Solid-liquid separation: After the reaction is complete, the modified reducing agent is separated from the enzymatic hydrolysate to obtain a solid modified reducing agent;

[0063] S4. Enzyme recovery: The enzyme hydrolysate separated in step S3 is recovered using immobilized enzyme technology for the preparation of enzyme solutions again. The carrier used in the immobilized enzyme technology is chitosan microspheres, calcium alginate gel or modified diatomaceous earth. The recovered enzyme preparation can be recycled at least 5 times. When the recovered enzyme preparation is used to prepare enzyme solutions again, its enzyme activity is not less than 70% of the initial enzyme activity.

[0064] Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents. In short, if those skilled in the art are inspired by these claims and design similar structural methods and embodiments without departing from the inventive spirit of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A bio-enzyme catalytic process for modifying reducing agents, characterized in that, Includes the following steps: S1. Enzyme solution preparation: The biological enzyme preparation is mixed with a buffer solution with a pH of 5-8 to prepare an enzyme solution with an enzyme concentration of 0.5-5.0 g / L; the biological enzyme preparation is a complex enzyme composed of one or more of cellulase, hemicellulase, and lignin-degrading enzyme. S2. Enzymatic hydrolysis modification: The carbonaceous reducing agent raw material is mixed with the enzyme solution prepared in step S1 at a mass ratio of 1:5 to 1:20, and the enzymatic hydrolysis reaction is carried out at 40-60℃, while ultrasound is applied for auxiliary treatment; the ultrasonic power is 100-500W and the frequency is 20-40kHz. S3. Solid-liquid separation: After the reaction is complete, the modified reducing agent is separated from the enzymatic hydrolysate to obtain a solid modified reducing agent; S4. Enzyme recovery: The enzyme hydrolysate separated in step S3 is recovered using immobilized enzyme technology and used to prepare enzyme solutions again.

2. The bio-enzyme catalytic process for modifying a reducing agent according to claim 1, characterized in that, In step S1, the complex enzyme is composed of cellulase, hemicellulase and lignin-degrading enzyme in a mass ratio of (3-5):(2-4):(1-2).

3. The bio-enzyme catalytic process for modifying a reducing agent according to claim 1, characterized in that, In step S2, the enzymatic hydrolysis reaction takes 4 to 12 hours.

4. The bio-enzyme catalytic process for modifying a reducing agent according to claim 1, characterized in that, In step S2, the ultrasonic-assisted treatment adopts an intermittent working mode, with a working interval of 1 to 5 minutes and an interval of 1 to 3 minutes.

5. The bio-enzyme catalytic process for modifying a reducing agent according to claim 1, characterized in that, In step S4, the carrier used in the immobilized enzyme technology is chitosan microspheres, calcium alginate gel, or modified diatomaceous earth.

6. The bio-enzyme catalytic process for modifying a reducing agent according to claim 1, characterized in that, The enzyme preparation recovered in step S4 can be recycled at least 5 times.

7. The bio-enzyme catalytic process for modifying a reducing agent according to claim 1, characterized in that, The bio-enzyme preparation described in step S1 is prepared autonomously using a method comprising the following steps: a. Using Aspergillus niger or Trichoderma reesei as enzyme-producing strains, fermentation culture is carried out in a fermentation medium; b. Inducing enzyme production in strains by optimizing fermentation temperature, pH, and aeration parameters; c. After fermentation, the fermentation broth is separated and purified to obtain the biological enzyme preparation.

8. The bio-enzyme catalytic process for modifying a reducing agent according to claim 1, characterized in that, The carbonaceous reducing agent raw material is one or more of petroleum coke, anthracite, or biochar.

9. The bio-enzyme catalytic process for modifying a reducing agent according to claim 1, characterized in that, In step S2, the pH of the reaction system is maintained within the range of 5-8 by monitoring the pH online and adding acid or alkali solutions during the enzymatic hydrolysis reaction.

10. A bio-enzyme catalytic process for modifying a reducing agent according to claim 1, characterized in that, When the enzyme preparation recovered in step S4 is used to prepare enzyme solutions again, its enzyme activity shall not be less than 70% of the initial enzyme activity.