阅读说明：本技术 一种酒糟二次微生物发酵活化制备电容炭材料的方法 (Method for preparing capacitance carbon material by secondary microbial fermentation and activation of vinasse ) 是由 李永锋 黄棣 于 2021-09-27 设计创作，主要内容包括：一种酒糟二次微生物发酵活化制备电容炭材料的方法,属于生物质电容炭材料制备技术领域,目的在于提供一种采用干法混合原料和连续炭化反应器来生产高比表面积活性生物质电容炭的方法,本发明利用微生物对原材料酒糟进行二次培养纯化,对热处理或者微波辐照碳化得到的生物质酒糟粉末与KOH和/或NaOH活化剂混合,在氮气保护下升温活化,恒温120分钟,反应结束后在氮气保护下降温到室温,取出产物进行回收和水洗,进行烘干制成品。本发明产品安全可靠,提高了生产过程中的安全性生产过程更加连续,提高了生产效率,降低了生产成本,产品质量稳定,具有广泛的应用前景。(A method for preparing capacitance carbon material by vinasse secondary microbial fermentation activation belongs to the technical field of biomass capacitance carbon material preparation, and aims to provide a method for producing high-specific-surface-area active biomass capacitance carbon by adopting a dry-method mixed raw material and a continuous carbonization reactor. The invention has the advantages of safe and reliable product, improved safety in the production process, more continuous production process, improved production efficiency, reduced production cost, stable product quality and wide application prospect.)

1. A method for preparing a capacitance carbon material by secondary fermentation and activation of vinasse by microorganisms is characterized by comprising the following steps: the method comprises the following steps:

uniformly dispersing microorganisms into vinasse, adding nutrient components, and performing secondary fermentation to obtain a microorganism vinasse mixture;

secondly, drying and carbonizing the mixture to obtain biomass capacitance carbon;

dry mixing the biomass capacitance carbon and the strong base solid, and uniformly mixing the biomass capacitance carbon and the strong base solid by a high-speed pulverizer;

fourthly, loading the mixture obtained in the third step into a nickel reactor, and carrying out high-temperature activation reaction under the protection of inert gas;

and fifthly, after the reaction is finished, cooling to room temperature under the protection of nitrogen, taking out the active biomass capacitance carbon, carrying out KOH recovery and water washing, and drying to obtain a finished product.

2. The method for preparing the capacitance carbon material by the secondary microbial fermentation and activation of the vinasse according to claim 1, wherein the method comprises the following steps: in the first step the microorganism comprises Escherichia coli or yeast.

3. The method for preparing the capacitance carbon material by the secondary microbial fermentation and activation of the vinasse according to claim 1, wherein the method comprises the following steps: and thirdly, the strong base comprises one or two of potassium hydroxide and sodium hydroxide, and the weight ratio of the biomass capacitance carbon to the strong base is 1: 3-5.

4. The method for preparing the capacitance carbon material by the secondary microbial fermentation and activation of the vinasse according to claim 1, wherein the method comprises the following steps: the high-temperature activation reaction in the fourth step is as follows: the temperature rising speed is 10-12 ℃/min, and the temperature is kept constant for 1 hour for dehydration when reaching 400-500 ℃; and then, continuously heating to 750-850 ℃ at the heating rate of 10-12 ℃/min, starting activation, and keeping the temperature for 120 min.

5. The method for preparing the capacitance carbon material by the secondary microbial fermentation and activation of the vinasse according to claim 1, wherein the method comprises the following steps: in the fifth step, the washing times are 2-6.

Technical Field

The invention belongs to the technical field of preparation of biomass capacitance carbon materials, and particularly relates to a method for producing a biomass capacitance carbon material with high specific surface activity by a chemical activation method.

Background

In the existing preparation method of biomass capacitance carbon, the chemical dispersion method is most suitable for producing biomass capacitance carbon material on a large scaleThe material is especially powdered biomass capacitance carbon material. Specifically, the reduction method includes a chemical reduction method, such as using a strong reducing agent such as hydrazine hydrate, high-temperature heating treatment, microwave irradiation treatment, electrochemical reduction, and the like, and the conductive biomass capacitance carbon material with a high specific surface area can be obtained. However, the specific surface area of the biomass capacitance carbon powder obtained by the current methods is 1000 m²Less than g, generally less than 700m²Is much lower than the theoretical specific surface area of the biomass capacitance carbon. The technical bottleneck restricts the further application of the biomass capacitance carbon material.

Disclosure of Invention

The invention aims to provide a method for producing high-specific-surface-area active biomass capacitance carbon by adopting a dry-method mixed raw material and a continuous carbonization reactor, and particularly relates to a continuous preparation method for preparing high-specific-surface-area active biomass capacitance carbon by fermenting distiller grains with secondary microorganisms.

The invention adopts the following technical scheme:

a method for preparing a capacitance carbon material by secondary fermentation and activation of vinasse by microorganisms comprises the following steps:

uniformly dispersing microorganisms into vinasse, adding nutrient components, and performing secondary fermentation to obtain a microorganism vinasse mixture;

secondly, drying and carbonizing the mixture to obtain biomass capacitance carbon;

dry mixing the biomass capacitance carbon and the strong base solid, and uniformly mixing the biomass capacitance carbon and the strong base solid by a high-speed pulverizer;

fourthly, loading the mixture obtained in the third step into a nickel reactor, and carrying out high-temperature activation reaction under the protection of inert gas;

and fifthly, after the reaction is finished, cooling to room temperature under the protection of nitrogen, taking out the active biomass capacitance carbon, carrying out KOH recovery and water washing, and drying to obtain a finished product.

Further, the microorganism in the first step includes Escherichia coli or yeast.

Further, the third step is that the strong base comprises one or two of potassium hydroxide and sodium hydroxide, and the weight ratio of the biomass capacitance carbon to the strong base is 1: 3-5.

Further, the high temperature activation reaction in the fourth step is as follows: the temperature rising speed is 10-12 ℃/min, and the temperature is kept constant for 1 hour for dehydration when reaching 400-500 ℃; and then, continuously heating to 750-850 ℃ at the heating rate of 10-12 ℃/min, starting activation, and keeping the temperature for 120 min.

Further, the number of times of washing with water in the fifth step is 2 to 6.

The invention has the following beneficial effects:

the invention innovatively adopts the method that yeast is added for secondary culture and fermentation of the vinasse, so that redundant crude protein and crude fat are converted into a biochar source, and the carbon yield is greatly improved. The specific surface area is 1800-2900 m²(ii) in terms of/g. The prepared biomass capacitance carbon material with high specific surface activity keeps high conductivity of the biomass capacitance carbon material while ensuring high specific surface area.

The capacitance carbon material is used for hydrogen storage, lithium ion batteries, super capacitors or fuel batteries, nano electronic devices, high-frequency circuits, photon sensors, gene electronic sequencing and noise reduction.

Drawings

FIG. 1 is a flow chart of the preparation method of the present invention.

Detailed Description

A method for preparing a capacitance carbon material by secondary fermentation and activation of vinasse by microorganisms comprises the following steps:

uniformly dispersing microorganisms into vinasse, adding nutrient components, and performing secondary fermentation to obtain a microorganism vinasse mixture;

secondly, drying and carbonizing the mixture to obtain biomass capacitance carbon;

dry mixing the biomass capacitance carbon and the strong base solid, and uniformly mixing the biomass capacitance carbon and the strong base solid by a high-speed pulverizer;

fourthly, loading the mixture obtained in the third step into a nickel reactor, and carrying out high-temperature activation reaction under the protection of inert gas;

and fifthly, after the reaction is finished, cooling to room temperature under the protection of nitrogen, taking out the active biomass capacitance carbon, carrying out KOH recovery and water washing, and drying to obtain a finished product.

In the present invention, it is known in the art to uniformly disperse microorganisms into distiller's grains, add nutrients, and perform secondary fermentation.

Example 1

(1) Carbonizing distiller's grains cultured by escherichia coli to obtain biomass capacitance carbon, and weighing 30g of biomass capacitance carbon; mixing KOH and biomass capacitance carbon according to the weight ratio of 4: 1, mixing, adding into a grinder, quickly grinding and uniformly mixing; then, the uniformly mixed raw materials are loaded into a nickel reactor, nitrogen is introduced after the reactor is closed, air in the reactor is replaced, the temperature is raised under the protection of the nitrogen, the temperature raising speed is 10-12 ℃/min, the temperature is raised to 450 ℃, and the constant temperature is kept for 2 hours for dehydration; then, continuously heating to 850 ℃ at the heating rate of 10-12 ℃/min, starting activation, keeping the temperature for 120min, cooling to room temperature under the protection of nitrogen after the reaction is finished, taking out a product, washing with water, and drying to obtain the product, wherein the BET surface area of the product is 2240m²/g。

Example 2

(1) Carbonizing distiller's grains cultured by saccharomycetes to obtain biomass capacitance carbon, and weighing 40g of biomass capacitance carbon; mixing KOH and biomass capacitance carbon according to the weight ratio of 5: 1, mixing, adding into a grinder, quickly grinding and uniformly mixing; then, the uniformly mixed raw materials are loaded into a nickel reactor, nitrogen is introduced after the reactor is closed, air in the reactor is replaced, the temperature is raised under the protection of the nitrogen, the temperature raising speed is 10-12 ℃/min, the temperature is raised to 450 ℃, and the constant temperature is kept for 2 hours for dehydration; then, the temperature is increased to 800 ℃ at the temperature rising speed of 10-12 ℃/min, activation is started, the temperature is kept for 120min, the temperature is reduced to room temperature under the protection of nitrogen after the reaction is finished, the product is taken out, washed by water and dried to prepare the product, wherein the BET surface area is 2530m²/g。

Example 3

(1) Carbonizing distiller's grains cultured by escherichia coli to obtain biomass capacitance carbon, and weighing 40g of biomass capacitance carbon; mixing KOH and biomass capacitance carbon according to the weight ratio of 5: 1, mixing, adding into a grinder, quickly grinding and uniformly mixing; then, the uniformly mixed raw materials are loaded into a nickel reactor, the reactor is sealed, nitrogen is introduced to replace air in the reactor, the temperature is raised under the protection of the nitrogen, and the temperature raising speed is 10-12 DEG CThe water is dehydrated at the constant temperature of 450 ℃ for 2 hours in min; then, the temperature is increased to 800 ℃ at the temperature rising speed of 10-12 ℃/min, activation is started, the temperature is kept for 120min, the temperature is reduced to room temperature under the protection of nitrogen after the reaction is finished, the product is taken out, washed by water and dried to obtain the product, wherein the BET surface area is 2570m²/g。

Example 4

The method for preparing the biomass capacitance carbon material with high specific surface activity by activating KOH and NaOH mixed activators comprises the following preparation steps:

(1) carbonizing distiller's grains cultured by saccharomycetes to obtain biomass capacitance carbon, and weighing 20g of biomass capacitance carbon; KOH and NaOH are mixed according to a molar ratio of 5: 1, mixing with biomass capacitance carbon according to the weight ratio of 5: 1, mixing, adding into a grinder, quickly grinding and uniformly mixing; then, the uniformly mixed raw materials are loaded into a nickel reactor, nitrogen is introduced after the reactor is closed, air in the reactor is replaced, the temperature is raised under the protection of the nitrogen, the temperature raising speed is 10-12 ℃/min, the temperature is raised to 450 ℃, and the constant temperature is kept for 2 hours for dehydration; then, the temperature is increased to 800 ℃ at the rate of 10-12 ℃/min, activation is started, the temperature is kept for 120min, the temperature is reduced to room temperature under the protection of nitrogen after the reaction is finished, the product is taken out, washed by water and dried to obtain the product, wherein the BET surface area is 2390m²/g。

The biomass capacitance carbon material with high specific surface activity prepared in the embodiments 1-4 of the invention has a specific surface area of 1800-2900 m²Compared with the prior art, the method has the advantages of safety, reliability, continuous production, high production efficiency and low production cost; the full-automatic carbonization reactor is adopted, and the full-automatic operation from feeding to discharging is realized, so that the production efficiency is improved, and the production cost is reduced. The biomass capacitance carbon material with high specific surface activity prepared in the embodiments 1-4 of the invention maintains high conductivity of the biomass capacitance carbon material while ensuring high specific surface area.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.