CN112106786A - Method for extracting pesticide components from biomass raw material based on pasteurization - Google Patents

Abstract

The invention relates to the technical field of biomass pesticides, in particular to a method for extracting pesticide components from biomass raw materials based on a pasteurization method, which comprises the following steps: carrying out pyrolysis treatment on the biomass raw material, and collecting pyrolysis tar; pretreating the pyrolysis tar to obtain pretreated tar; preparing an alkali washing solution, and performing alkali washing on the pretreated tar under a pasteurization heating condition to obtain a solution containing the pesticide active ingredients; adjusting the pH value to obtain an acidified component solution; carrying out organic extraction to obtain an enriched component organic phase; impurity removal treatment is carried out to obtain an organic phase after impurity removal; and (4) carrying out rotary evaporation treatment on the organic phase obtained by removing impurities to obtain the fine pesticide component. The invention separates and purifies the pesticide components from the biomass raw material, achieves the purpose of fully utilizing the biomass raw material, provides a new way for efficiently utilizing the biomass pyrolysis tar, is used for replacing the prior process for extracting high value-added chemical substances mainly by coal, petroleum and the like, and greatly enhances the extraction effect.

Description

A method for extracting pesticide components from biomass raw materials based on pasteurization

technical field

The invention relates to the technical field of biomass pesticides, in particular to a method for extracting pesticide components from biomass raw materials based on a pasteurization method.

Background technique

The information disclosed in this Background section is only for enhancement of understanding of the general background of the invention and should not necessarily be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.

With the development of industrial technology and the rapid progress of human social civilization, coal, oil and other resources are increasingly scarce. It is more and more important to develop renewable resources that can replace oil. Biomass energy is an important part of renewable resources, green and cheap. , The availability of raw materials is its advantage. At present, biomass utilization technologies mainly include direct combustion, pyrolysis, gasification and other methods. Among them, biomass pyrolysis is recognized as a relatively reliable utilization technology, because this technology can convert biomass into liquid, solid and gaseous products. Biomass tar has a complex composition and contains hundreds of chemical substances, and even contains high value-added chemical intermediate components such as amines and phenols. It can be widely used in pesticides, medicine, food and other industries.

At the same time, the inventor found that the prior art seldom mentions the extraction of pesticide components from biomass tar, and also lacks an effective method for extracting pesticide components from biological tar.

SUMMARY OF THE INVENTION

In view of the problems existing in the prior art, the present invention discloses a method for extracting pesticide components from biomass raw materials based on a pasteurization method. First, biomass tar is extracted from the biomass raw materials, and then the pesticides are separated and purified from the biomass tar. To achieve the purpose of making full use of biomass tar, it provides a new method for efficient utilization of biomass pyrolysis tar, which is used to replace the current process of extracting high value-added chemical substances from non-renewable energy sources such as coal and petroleum.

Specifically, the technical solution of the present invention is as follows:

In a first aspect of the present invention, the present invention provides a method for extracting pesticide components from biomass raw materials based on a pasteurization method, which comprises the following steps: subjecting biomass raw materials to pyrolysis to collect pyrolysis tar; De-tar is pretreated to remove water to obtain pretreated tar; configure alkaline washing solution, and carry out alkaline washing of pretreated tar under pasteurized heating conditions to obtain pesticide-containing active ingredient solution; adjust pH to obtain acidified ingredient solution; carry out organic Extraction to obtain an organic phase enriched with components; carrying out impurity removal treatment to obtain an organic phase after impurity removal; subjecting the organic phase obtained by impurity removal to rotary evaporation treatment to obtain fine pesticide components.

Further, the water removal pretreatment operation includes: adding anhydrous sodium sulfate solid powder to the pyrolysis tar, performing water removal treatment, and performing filtration treatment to obtain pretreated tar.

Further, the alkaline washing treatment step includes: mixing the alkaline washing solution and the pretreated tar in stages and performing pasteurization heating, and the stage mixing and pasteurization heating conditions are: the first stage, magnetic stirring, and the temperature is maintained at a pasteurized temperature of 56 -65°C for at least 30min; in the second stage, the glass rod is stirred, and the temperature is kept at the Pasteur temperature of 80-83°C for 10min. After the reaction, an alkaline washing mixed solution is obtained. The alkaline washing mixed solution is phase-layered in a separating funnel to obtain a pesticide-containing active ingredient solution.

Further, to adjust the pH of the solution, a sulfuric acid solution with a mass fraction of 10 wt % is used.

Further, the organic extraction agent is ethyl acetate, the liquid holding time of the contact reaction is at least 5min, and the temperature is room temperature to obtain the enriched component organic phase.

Further, the impurity removal operation includes washing the organic phase with deionized water, adding anhydrous sodium sulfate to the enriched component organic phase to remove moisture, and filtering, to achieve the purpose of removing residual inorganic salt solution, residual moisture and solid residue, and obtain Remove impurities from the organic phase.

Further, the impurity-removing organic phase is placed in a rotary evaporator for solvent evaporation, and the evaporation conditions are set as: the evaporation temperature is 55-60 ° C, the evaporation pressure is 0.024 MPa, which is about a quarter of the atmospheric pressure, and the fine pesticide composition is obtained. .

In the second aspect of the present invention, the present invention provides a fine pesticide ingredient prepared by the method of the first aspect.

In a third aspect of the present invention, the present invention provides an application of the fine pesticide component of the second aspect in controlling plant diseases and insect pests.

The specific embodiment of the present invention has the following beneficial effects:

It is innovatively proposed to link the secondary utilization of biomass tar with plant-derived pesticides, which has great promotion value; the method of extracting pesticide components from biomass tar is simple to operate, can greatly enrich the effective components, and has a wide range of applications , providing new ideas for the use of biomass pyrolysis tar.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention.

Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described can be used in the methods of the present invention. Methods and materials for preferred embodiments described herein are provided for illustrative purposes only.

As discussed in the background art, there are few studies on extracting pesticide components from biomass in the prior art, and there is a lack of effective methods for extracting pesticide components from biomass raw materials. In view of the problems existing in the prior art, the present invention discloses a method for extracting pesticide components from biomass raw materials based on a pasteurization method. The extraction method of the invention has good extraction effect.

In one embodiment of the present invention, there is provided a method for extracting pesticide components from biomass raw materials based on a pasteurization method, which comprises the following steps: subjecting biomass raw materials to pyrolysis treatment to collect pyrolysis tar; De-tar is pretreated to remove water to obtain pretreated tar; configure alkaline washing solution, and carry out alkaline washing of pretreated tar under pasteurized heating conditions to obtain pesticide-containing active ingredient solution; adjust pH to obtain acidified ingredient solution; carry out organic Extraction to obtain an organic phase enriched with components; carrying out impurity removal treatment to obtain an impurity-removed organic phase; subjecting the organic phase obtained by impurity removal to rotary evaporation treatment to obtain fine pesticide components.

In a specific embodiment, the operation of the water removal pretreatment is as follows: adding anhydrous sodium sulfate solid powder to the pyrolysis tar, performing water removal treatment, and performing filtration treatment to obtain pretreated tar.

In a specific embodiment, the alkaline washing treatment step includes: mixing the alkaline washing solution and the pretreated tar in stages and performing pasteurization heating, and the stage mixing and pasteurization heating conditions are: the first stage, magnetic stirring, The temperature is kept at 56-65°C of the pasteurized temperature for at least 30 minutes; in the second stage, the glass rod is stirred, and the temperature is kept at 80-83°C of the pasteurized temperature for 10 minutes. After the reaction, an alkaline washing mixed solution is obtained; the alkaline washing mixed solution is phase-layered in a separating funnel to obtain a solution containing the active ingredients of pesticides. The step-by-step pasteurization can make the active ingredients of pesticides in the pyrolysis tar react with the solution as much as possible to form inorganic salts, thereby separating from the tar system, promoting the complete reaction of the active ingredients, and greatly improving the extraction efficiency.

In a specific embodiment, a sulfuric acid solution with a mass fraction of 10 wt % is used to adjust the pH of the solution.

In a specific embodiment, the organic extractant used in the organic extraction is ethyl acetate, the liquid holding time of the contact reaction is at least 5 min, and the temperature is room temperature to obtain the enriched component organic phase. Organic solvent extraction can achieve the enrichment of active ingredients and ensure high extraction efficiency.

In a specific embodiment, the impurity removal operation includes washing the organic phase with deionized water, adding anhydrous sodium sulfate to the enriched component organic phase to remove moisture, and filtering to remove residual inorganic salt solution, residual moisture and The purpose of the solid residue is to obtain the impurity-removed organic phase.

In a specific embodiment, the impurity-removing organic phase is placed in a rotary evaporator for solvent evaporation, and the evaporation conditions are set as: the evaporation temperature is 55-60° C., and the evaporation pressure is 0.024 MPa, which is about a quarter of the Atmospheric pressure to obtain fine pesticide components. Rotary evaporation under the condition of about 1/4 atmospheric pressure can evaporate the organic solvent to the greatest extent and obtain fine pesticide components.

In one embodiment of the present invention, a fine pesticide ingredient prepared by the above method is provided.

In one embodiment of the present invention, there is provided an application of the above-mentioned fine pesticide components in controlling plant diseases and insect pests.

The present invention will be further described below in conjunction with specific embodiments.

Example 1

Extraction of phenolic pesticide components from pine wood pyrolysis oil:

The pine wood raw materials are crushed and screened, and then dried in a drying oven. The treated pine wood samples are placed in a pyrolysis furnace for pyrolysis treatment, and the temperature is raised to 500 ° C at a heating rate of 20 ° C/min. Simultaneously, nitrogen was introduced at a rate of 200 ml/min, and pine wood pyrolysis tar was obtained after treatment for 60 min. The pyrolyzed tar was added to anhydrous sodium sulfate solid powder to remove water, and filtered to remove impurities. Take 10 g of pretreated tar and save it to obtain sample 1. A sodium hydroxide solution with a mass fraction of 10 wt% was prepared. Take 10 g of the pretreated pine tar and 10 g of the sodium hydroxide solution, and carry out staged mixing and pasteurization in a beaker. 30min; in the second stage, the glass rod was stirred, and the temperature was kept at a Pasteur temperature of 80°C for 10min. After the reaction, the solution was placed in a separatory funnel, the lower phase was separated, and then a sulfuric acid solution with a mass fraction of 10 wt % was added to adjust the pH to 2; then the organic phase was extracted with ethyl acetate in stages to obtain enriched phenolic compounds Component solution; wash the solution with deionized water to remove residual inorganic salts, add anhydrous sodium sulfate to remove residual moisture; filter in a funnel to remove residual solid impurities. The treated organic phase with impurity removal was placed in a rotary evaporator, and the solvent was evaporated under the conditions of a heating temperature of 60° C. and a pressure of 0.024 MPa, and fine phenolic compounds were obtained after 20 minutes. An appropriate amount of dichloromethane was added to the obtained fine phenolic compound for dilution to obtain sample 2. Through GC/MS analysis, the specific composition of phenolic compounds in sample 2 was obtained as follows:

serial number substance name 2%/% of sample (remove solvent) 1 phenol 2.76 2 p-Cresol 1.34 3 3-methylphenol 2.05 4 p-Methoxyphenol 7.21 5 Maltol 3.12 6 2-Methoxy-5-methylphenol 5.43 7 Resorcinol 1.87 8 2-Methoxy-4-ethylphenol 2.49 9 4-Methylresorcinol 1.07 10 2,6-Dimethoxyphenol 9.35 11 5-tert-Butyl pyrogallol 3.38 12 2-Methyl-4-ethoxyphenol 2.76

Example 2

Extraction of phenolic pesticide components from safflower pyrolysis oil:

The safflower raw materials are crushed and screened, and then dried in a drying oven. The treated safflower samples are placed in a pyrolysis furnace for pyrolysis, and the temperature is raised to 500°C at a heating rate of 20°C/min. ℃, while passing nitrogen at a rate of 200ml/min, after treatment for 60min, safflower pyrolysis tar was obtained. The pyrolyzed tar was added to anhydrous sodium sulfate solid powder to remove water, and filtered to remove impurities. Take 10 g of pretreated tar for preservation, and obtain sample 3; take 10 g of pretreated safflower tar and 10 g of sodium hydroxide solution with a mass fraction of 10 wt %, and perform staged mixing and pasteurization in a beaker. The heating process is: In the first stage, magnetic stirring, the temperature was kept at 65°C for 30 min; in the second stage, the temperature was kept at 80°C at 80°C for 10 min. After the reaction, the solution was placed in a separatory funnel, the lower phase was separated, and then a sulfuric acid solution with a mass fraction of 10 wt % was added to adjust the pH to 2; then the organic phase was extracted with ethyl acetate in stages to obtain enriched phenolic compounds Component solution; wash the solution with deionized water to remove residual inorganic salts, add anhydrous sodium sulfate to remove residual moisture; filter in a funnel to remove residual solid impurities. The treated organic phase with impurity removal was placed in a rotary evaporator, and the solvent was evaporated under the conditions of a heating temperature of 60° C. and a pressure of 0.024 MPa, and fine phenolic compounds were obtained after 20 minutes. An appropriate amount of dichloromethane was added to the obtained fine phenolic compound for dilution to obtain sample 4. Through GC/MS analysis, the specific composition of phenolic compounds in sample 4 was obtained as follows:

Experimental Example: Insecticidal Effect Test of Fine Pesticide Components Prepared in Examples 1 and 2

Plutella xylostella larvae (2 instars) were selected for the test, and 3 suitable petri dishes were selected, all of which were covered with filter paper at the bottom of the dish, and deionized water was added to keep the filter paper moist. Cut cabbage leaves into appropriate sizes, one in each petri dish, and do cleaning and dewaxing treatment, and then use tweezers to put the cut leaves in 5ml of water, 5ml of pine wood sample 2, and 5ml of safflower sample 4. After fully infiltrating for 10s, take them back to Petri Dish 1, Petri Dish 2, and Petri Dish 3. After that, the petri dishes were placed in a cool and ventilated place to dry, and 18 healthy diamondback moth larvae (2 instars) per dish were inoculated with a soft brush. After inoculating larvae, place the petri dish in an incubator at 27°C, and cover the petri dish with a layer of moist gauze to ensure a humid environment of 30%-40% of the growth of the larvae. After 3 days of treatment, the number of live and dead insects treated was recorded. It was recorded that the insecticidal rate of clear water medium 1 was 12.5%, the insecticidal rate of pine medium 2 was 66.67%, and the insecticidal rate of safflower medium was 61.2%.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. a method for extracting pesticide components from biomass raw materials based on pasteurization, is characterized in that, described method comprises the following steps: The biomass raw material is subjected to pyrolysis treatment to collect pyrolysis tar; The pyrolysis tar is subjected to dewatering pretreatment to obtain pretreated tar; Configure a certain mass fraction of sodium hydroxide solution to obtain a standby alkaline washing solution; Using the standby alkaline washing solution to perform alkaline washing on the pretreated tar under pasteurized heating conditions to obtain a pesticide-containing active ingredient solution; Adjusting the pH of the pesticide-containing active ingredient solution to obtain an acidified ingredient solution; organically extracting the acidified component solution to obtain an organic phase enriched with components; Carrying out an impurity-removal treatment to the enriched component organic phase to obtain an impurity-removed organic phase; The impurity-removing organic phase is subjected to rotary evaporation to obtain fine pesticide components. 2. The method for extracting pesticide components from biomass raw materials based on pasteurization method according to claim 1, wherein the pretreatment operation comprises: adding anhydrous sodium sulfate solid powder to the pyrolysis tar , carry out water removal treatment, and carry out filtration treatment to obtain the pretreated tar. 3. The method for extracting pesticide components from biomass raw materials based on pasteurization method according to claim 1, wherein the step of alkaline washing comprises: performing the alkaline washing solution and the pretreated tar Stage mixing and pasteurization heating, after the reaction, an alkaline washing mixed solution is obtained; the alkaline washing mixed solution is phase-layered in a separatory funnel to obtain the pesticide-containing active ingredient solution; Preferably, the mass fraction of sodium hydroxide in the alkaline washing solution is 10 wt%. 4. the method for extracting pesticide components from biomass raw materials based on pasteurization method according to claim 3, it is characterized in that, described stage mixing and pasteurization conditions are: the first stage, magnetic stirring, temperature keeps bar In the second stage, the glass rod is stirred, and the temperature is maintained at the Pasteur temperature of 80-83 °C for 10 minutes. 5. The method for extracting pesticide components from biomass raw materials based on pasteurization method according to claim 1, wherein the step of adjusting pH comprises: carrying out a reverse reaction between dilute sulfuric acid solution and the pesticide active ingredient solution reaction to obtain the acidified component solution. 6. the method for extracting pesticide components from biomass raw materials based on pasteurization method according to claim 1, is characterized in that, the organic extractant that described organic extraction uses is ethyl acetate, and the duration of contact reaction is at least For 5 min, the temperature was room temperature to obtain an organic phase enriched with components. 7. The method for extracting pesticide components from biomass raw materials based on pasteurization according to claim 1, wherein the impurity removal operation comprises washing the organic phase with deionized water, and in the enriched component organic phase Add anhydrous sodium sulfate to remove moisture, and filter to obtain the impurity-removed organic phase. 8. the method for extracting pesticide components from biomass raw materials based on pasteurization method according to claim 1, is characterized in that, rotary evaporation condition is set as: water bath temperature is 60 ℃, evaporation pressure is 0.024Mpa, evaporation time is at least for 20min. 9. The fine pesticide components prepared by the method for extracting pesticide components from biomass raw materials based on the pasteurization method according to any one of claims 1-8. 10. The application of the fine pesticide composition of claim 9 in controlling plant diseases and insect pests.