阅读说明：本技术 采用酸性电解水实现废弃生物质再生利用的方法 (Method for realizing regeneration and utilization of waste biomass by adopting acidic electrolyzed water ) 是由 陈珂 肖伟 李信 沈民越 于 2019-11-11 设计创作，主要内容包括：本发明公开了一种采用酸性电解水实现废弃生物质再生利用的方法,包括：将废弃生物质粉碎,加入过氧化氢溶液中,进行辐照处理,过滤干燥,得到预处理废弃生物质；将预处理废弃生物质和酸性电解水A加入到高压反应器中,向反应器内注入高压二氧化碳,在一定温度和压力下保持,泄压,加入路易斯酸和酸性电解水B,再次向反应器内注入高压二氧化碳,在一定温度和压力下保持,泄压,泄压后将反应物料进行固液分离,液体回收,固体烘干,得到产物；本发明采用辐照对废弃生物质进行预处理,然后采用酸性电解水和超临界二氧化碳对废弃生物质进行预处理,该过程增加了原料的利用率,提高了木质素和半纤维素的降解。(The invention discloses a method for realizing regeneration and utilization of waste biomass by adopting acidic electrolyzed water, which comprises the following steps: crushing the waste biomass, adding the crushed waste biomass into a hydrogen peroxide solution, carrying out irradiation treatment, filtering and drying to obtain pretreated waste biomass; adding the pretreated waste biomass and acidic electrolyzed water A into a high-pressure reactor, injecting high-pressure carbon dioxide into the reactor, keeping at a certain temperature and pressure, releasing pressure, adding Lewis acid and acidic electrolyzed water B, injecting high-pressure carbon dioxide into the reactor again, keeping at a certain temperature and pressure, releasing pressure, carrying out solid-liquid separation on reaction materials after pressure release, recovering liquid, and drying solid to obtain a product; according to the method, the waste biomass is pretreated by irradiation, and then is pretreated by acidic electrolyzed water and supercritical carbon dioxide, so that the utilization rate of raw materials is increased, and the degradation of lignin and hemicellulose is improved.)

1. A method for realizing the recycling of waste biomass by adopting acidic electrolyzed water is characterized by comprising the following steps:

crushing waste biomass, adding the crushed waste biomass into a hydrogen peroxide solution, performing irradiation treatment, filtering, and drying to obtain pretreated waste biomass;

adding the pretreated waste biomass and acidic electrolyzed water A into a high-pressure reactor, injecting high-pressure carbon dioxide into the reactor, keeping the temperature at 50-65 ℃ and the pressure at 10-20 MPa for 90-120 min, releasing the pressure, then adding Lewis acid and acidic electrolyzed water B, injecting the high-pressure carbon dioxide into the reactor again, keeping the temperature at 80-100 ℃ and the pressure at 12-22 MPa for 30-60 min, opening a valve to release the pressure after the supercritical carbon dioxide treatment is finished, performing solid-liquid separation on the reaction material after the pressure is released, recovering the liquid, and drying the solid to obtain a product;

the method comprises the following steps of (1) electrolyzing sodium chloride serving as electrolyte to obtain an acidic stock solution, and diluting the acidic stock solution by 10-15 times to obtain acidic electrolyzed water A; diluting the acidic stock solution by 30-45 times to obtain acidic electrolyzed water B;

the oxidation-reduction potential ORP of the acidic stock solution is 900 mv-1250 mv; the pH of the acidic stock solution is 1.3-2.5.

2. The method for realizing the recycling of the waste biomass by using the acidic electrolyzed water as the claim 1 is characterized in that in the process of obtaining the acidic stock solution by using sodium chloride as electrolyte through electrolysis: the concentration of the adopted sodium chloride solution is 0.05-0.15 kg/L, the flow rate of the sodium chloride solution introduced into the electrolytic cell is 5-10L/min, the current of electrolysis is 5-10A, and the voltage is 10-18V.

3. The method for realizing the recycling of the waste biomass by adopting the acidic electrolyzed water as claimed in claim 1, wherein in the first step, the mass fraction of the hydrogen peroxide solution is 15-30%; the mass ratio of the waste biomass to the hydrogen peroxide solution is 1: 5-8; the irradiation treatment is carried out for 30-60 min by adopting gamma rays with the irradiation dose of 5-15 kGy.

4. The method for recycling waste biomass by using acidic electrolyzed water as claimed in claim 1, wherein in the second step, the weight ratio of the pretreated waste biomass to the acidic electrolyzed water A is 1: 8-12; the weight ratio of the pretreated waste biomass to the acidic electrolyzed water B is 1: 3 to 5.

5. The method for realizing the recycling of the waste biomass by using the acidic electrolyzed water as claimed in claim 1, wherein the lewis acid is any one of aluminum trichloride, magnesium dichloride, zirconium chloride, zinc dichloride, zinc acetate, antimony trioxide, stannous octoate, stannic chloride and chromium oxide; the weight ratio of the Lewis acid to the acidic electrolyzed water B is 1: 15-20.

6. The method for realizing the recycling of waste biomass by using acidic electrolyzed water as claimed in claim 1, wherein before the solid-liquid separation, the acidic electrolyzed water C is added into the reaction material, and then the reaction material is added into a vacuum packaging bag for vacuum packaging, and the vacuum degree is controlled to be 0.1 MPa; and (3) putting the vacuum packaging bag into high static pressure treatment equipment, sealing the pressurizing cavity, and pressurizing to perform high static pressure treatment.

7. The method for realizing the recycling of the waste biomass by using the acidic electrolyzed water as claimed in claim 6, wherein the parameters of the high static pressure treatment are as follows: raising the pressure to 500-600 MPa at a pressure raising speed of 4-6 MPa/s, and carrying out pressure maintaining treatment for 10-20 min at normal temperature.

8. The method for realizing the recycling of the waste biomass by adopting the acidic electrolyzed water as claimed in claim 6, wherein the acidic electrolyzed water C is obtained by diluting 20-25 times of the acidic stock solution; the mass ratio of the reaction materials to the acidic electrolyzed water C is 1: 8-12.

9. The method for recycling waste biomass through acidic electrolyzed water as claimed in claim 1, wherein the waste biomass is any one of straw, processing residues of forest products and landscaping garbage.

10. The method for realizing the recycling of waste biomass by using the acidic electrolyzed water as claimed in claim 1, wherein the straw is any one of corn straw, wheat straw, sorghum straw and bamboo straw.

Technical Field

The invention relates to the technical field of waste biomass recycling, in particular to a method for realizing waste biomass recycling by adopting acidic electrolyzed water.

Background

The waste biomass is considered as a high-value biological material, can be regenerated, is low in price, can be used as a substrate to extract high value-added products, and can effectively avoid solid waste pollution caused by the waste biomass due to comprehensive utilization. For example, most biomass wastes slowly release harmful methane greenhouse gases, and their incineration disposal also produces many atmospheric pollutants. Thus, improper disposal of biomass waste can adversely affect the climate, water, soil, and air environment. The method is a high-efficiency biomass resource utilization technology for preparing reducing sugar by hydrolyzing waste biomass and then fermenting to produce fuel ethanol. However, since the carbohydrates in the biomass are mostly in the form of polymers, the direct hydrolysis conditions are harsh and inefficient. If the biomass is pretreated appropriately and then subjected to hydrolysis reaction, the hydrolysis conditions are expected to be improved and the efficiency is expected to be improved.

At present, the pretreatment methods for biomass mainly comprise acid-base pretreatment, steam explosion pretreatment and ammonia fiber explosion pretreatment. The acid-base pretreatment process is mature, but has corrosion problem to equipment, neutralization treatment is needed after pretreatment, the steps are complex, and the waste liquid pollutes the environment. Steam explosion and ammonia fiber explosion pretreatment have the advantages of high treatment speed and the like, but the conditions are harsh and a high-pressure container is required. The steam explosion energy consumption is large, and the temperature is high; the ammonia gas in the ammonia fiber explosion is toxic and pollutes the environment, and the equipment investment is increased by recycling. In recent years, a novel pretreatment method which is environmentally friendly and has mild conditions has been developed and is highly preferred.

When the electrolyte dilute solution is electrolyzed by using a special electrolysis device under the conditions of certain voltage and current, products with special physicochemical properties are generated on the electrodes at the two sides, namely the electrolyzed water. The active components of the water are unstable, and the water can form nontoxic and residue-free common water after use, has no pollution after discharge, and does not cause harm to human and ecological environment. The acidic electrolyzed water has the characteristics of low pH value, high oxidation-reduction potential, active oxygen, active chlorine and the like, and has very wide application prospects in the fields of medical sanitation, agricultural production, food processing, livestock breeding, catering industry and the like. At present, the acidic electrolyzed water is widely applied to the fields of vegetable sterilization, plant cultivation, medical instrument disinfection and the like, and a literature report of treating waste biomass by using the acidic electrolyzed water is not disclosed in the prior art; in addition, the supercritical carbon dioxide is a green solvent and can generate swelling effect on the polymer, so that the crystallinity, the glass transition temperature and the like of the polymer are changed. The invention combines the supercritical carbon dioxide and the acidic electrolyzed water to pretreat the biomass, can exert the advantages of the supercritical carbon dioxide and the acidic electrolyzed water, further promotes the hydrolysis reaction of the biomass to prepare reducing sugar, simultaneously reserves the cellulose in the waste biomass as much as possible, and reduces the content of lignin and hemicellulose.

Disclosure of Invention

An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.

To achieve these objects and other advantages in accordance with the present invention, there is provided a method for recycling waste biomass using acidic electrolyzed water, comprising the steps of:

crushing waste biomass, adding the crushed waste biomass into a hydrogen peroxide solution, performing irradiation treatment, filtering, and drying to obtain pretreated waste biomass;

adding the pretreated waste biomass and acidic electrolyzed water A into a high-pressure reactor, injecting high-pressure carbon dioxide into the reactor, keeping the temperature at 50-65 ℃ and the pressure at 10-20 MPa for 90-120 min, releasing the pressure, then adding Lewis acid and acidic electrolyzed water B, injecting the high-pressure carbon dioxide into the reactor again, keeping the temperature at 80-100 ℃ and the pressure at 12-22 MPa for 30-60 min, opening a valve to release the pressure after the supercritical carbon dioxide treatment is finished, performing solid-liquid separation on the reaction material after the pressure is released, recovering the liquid, and drying the solid to obtain a product;

the method comprises the following steps of (1) electrolyzing sodium chloride serving as electrolyte to obtain an acidic stock solution, and diluting the acidic stock solution by 10-15 times to obtain acidic electrolyzed water A; diluting the acidic stock solution by 30-45 times to obtain acidic electrolyzed water B;

the oxidation-reduction potential ORP of the acidic stock solution is 900 mv-1250 mv; the pH of the acidic stock solution is 1.3-2.5.

Preferably, in the process of obtaining the acidic stock solution by electrolysis with sodium chloride as an electrolyte: the concentration of the adopted sodium chloride solution is 0.05-0.15 kg/L, the flow rate of the sodium chloride solution introduced into the electrolytic cell is 5-10L/min, the current of electrolysis is 5-10A, and the voltage is 10-18V.

Preferably, in the first step, the mass fraction of the hydrogen peroxide solution is 15-30%; the mass ratio of the waste biomass to the hydrogen peroxide solution is 1: 5-8; the irradiation treatment is carried out for 30-60 min by adopting gamma rays with the irradiation dose of 5-15 kGy.

Preferably, in the second step, the weight ratio of the pretreated waste biomass to the acidic electrolyzed water a is 1: 8-12; the weight ratio of the pretreated waste biomass to the acidic electrolyzed water B is 1: 3 to 5.

Preferably, the lewis acid is any one of aluminum trichloride, magnesium dichloride, zirconium chloride, zinc dichloride, zinc acetate, antimony trioxide, stannous octoate, stannic chloride and chromium oxide; the weight ratio of the Lewis acid to the acidic electrolyzed water B is 1: 15-20.

Preferably, before solid-liquid separation, adding acidic electrolyzed water C into the reaction material, then adding the reaction material into a vacuum packaging bag for vacuum packaging, and controlling the vacuum degree to be 0.1 MPa; and (3) putting the vacuum packaging bag into high static pressure treatment equipment, sealing the pressurizing cavity, and pressurizing to perform high static pressure treatment.

Preferably, the parameters of the high static pressure treatment are as follows: raising the pressure to 500-600 MPa at a pressure raising speed of 4-6 MPa/s, and carrying out pressure maintaining treatment for 10-20 min at normal temperature.

Preferably, the acidic electrolyzed water C is obtained by diluting the acidic stock solution by 20-25 times; the mass ratio of the reaction materials to the acidic electrolyzed water C is 1: 8-12.

Preferably, the waste biomass is any one of straw, processing residues of forest products and landscaping garbage.

Preferably, the straw is any one of corn stalk, wheat stalk, sorghum stalk and bamboo stalk.

The invention at least comprises the following beneficial effects: according to the invention, firstly, the waste biomass is treated by irradiation, and becomes crisp through irradiation pretreatment, so that the hydrolysis of the subsequent waste biomass is greatly improved, the waste biomass is pretreated by acidic electrolyzed water and supercritical carbon dioxide, the structure of the biomass can be effectively destroyed, and convenient conditions are provided for the subsequent hydrolysis reaction, the supercritical carbon dioxide which is a green solvent is utilized to explode biomass fibers, so that the biomass is favorably loosened by winding a compact spatial structure, and meanwhile, the Lewis acid is adopted to play a role in catalysis, so that the degradation of the acidic electrolyzed water on the waste biomass is improved; the process further improves the yield of reducing sugar of the waste biomass, increases the utilization rate of raw materials, and improves the degradation of lignin and hemicellulose; meanwhile, the harsh conditions of ordinary high-temperature (more than 280 ℃) hydrolysis are improved.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

The specific implementation mode is as follows:

the present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.

It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.