CN114931153A

CN114931153A - Bamboo-derived composite preparation and preparation method and application thereof

Info

Publication number: CN114931153A
Application number: CN202210399209.4A
Authority: CN
Inventors: 李志强; 战雅微; 王美鑫; 马腾飞
Original assignee: International Bamboo And Rattan Center
Current assignee: International Bamboo And Rattan Center
Priority date: 2022-04-15
Filing date: 2022-04-15
Publication date: 2022-08-23

Abstract

The invention relates to the technical field of agriculture and forestry biological resource utilization, and particularly discloses a bamboo-derived composite preparation and a preparation method and application thereof. The compound preparation provided by the invention can be used as mother liquor or an auxiliary agent for producing biological source pesticides, leaf fertilizers and soil conditioners. The preparation method provided by the invention is a universal method for separating the extract from the raw materials such as bamboo and felling processing residues thereof and the like and carrying out catalytic conversion to obtain the compound preparation; comprises the steps of removing an extract from bamboo in a hydrothermal mode (cooking and softening), carrying out a gasification catalytic reaction process on an extract solution, carrying out fractional condensation on a reaction product and recycling the reaction product. In the preparation method provided by the invention, the process equipment is simple, the process is stable and controllable, the route is simple and feasible, the preparation method is environment-friendly and nontoxic, the comprehensive utilization efficiency of all components of the bamboo raw material extract is high, the industrialization is easy to realize, and the application prospect is wide.

Description

Bamboo-derived composite preparation and preparation method and application thereof

Technical Field

The invention relates to the technical field of agriculture and forestry biological resource utilization, and particularly relates to a bamboo-derived composite preparation as well as a preparation method and application thereof.

Background

The bamboo industry is a well-known green industry and has great social, economic, ecological and cultural values. Due to the high growth speed and short growing period, the bamboo contains a large amount of nutrient components required for the growth of the bamboo. These nutrients make the bamboo easy to mildew if not protected after felling, and are especially easy to be infected by Trichoderma viride, Penicillium citrinum, Aspergillus niger and so on to change color, thus seriously reducing the use value. The bamboo pole mainly comprises fiber cells and parenchyma cell tissues, wherein 45-55% of parenchyma cells are filled with nutrient substances such as starch (20-60 g.kg < -1 >), sugar (20 g.kg < -1 >), protein (15-60 g.kg < -1 >), fat (20-40 g.kg < -1 >) and the like. These nutrients, especially sugars and starches, are believed to be the major contributors to bamboo decay and mildew.

From the chemical composition, bamboo mainly consists of cellulose, hemicellulose and lignin, and a small amount of extract. The bamboo wood extract contains a small amount of extract, but has complex chemical components, including wax layer, free sugar, starch, polyphenol, terpenoid, resin acid, lipid, special amino acid, carbohydrate, mineral elements and other hundreds of organic compounds. Many of the compounds can be directly used for perfumes, insecticides, preservatives, dyes, antioxidants, activators and the like, and have important utilization values of chemical engineering, medical engineering and fine chemical engineering. Depending on their nature, they may be extracted with water, alcohol, benzene, ethanol, ether or other organic solvents, or extracted with dilute alkali or steam distillation.

At present, bamboo leaves in bamboo felling residues are much researched because the bamboo leaves contain rich flavonoids. The bamboo leaf flavone and its glycoside compound have obvious blood fat reducing and serum cholesterol reducing effects, and the bamboo leaf extract rich in flavone has various biological effects, such as free radical eliminating, antioxidant, antiaging, antibacterial and antiviral effects, and is widely used in health products, cosmetics and food additives.

Therefore, nutrient component extracts in the bamboo products need to be removed before the production, so that the excellent quality of the bamboo products, such as mildew resistance, corrosion resistance, elegance, beauty and no discoloration, is ensured. Researches find that the removed nutrient solution can not be stored for a long time, and the nutrient solution needs to be converted and utilized to improve the use value of the nutrient solution and change waste into valuable. But currently there is no effective way to utilize it.

The newly felled bamboo is soaked in running water, which is a mildew-proof method widely used by bamboo processing enterprises. Different components in bamboo can be extracted by adopting different solvents. The cold water extract of bamboo wood mainly comprises monosaccharide, oligosaccharide, a small amount of tannin, amino acid, soluble pigment, salt, inorganic salt and the like. The hot water extract contains starch, gums and other polysaccharides in addition to the cold water extract. The bamboo material extracted by cold water, hot water, benzene/alcohol or alcohol/ether and the like is found to have equivalent inhibition performance on 3 test bacteria.

At present, in research and industry, a solvent is used for removing an extract in order to prevent bamboo products from discoloring and mildewing, but an extraction solution rich in nutrient components is generally discharged as waste water, so that resource waste is caused. In addition, although research is carried out to separate effective components from the extract solution for utilization, the concentration of the compound in the extract solution is too low, the components are complex, the separation and purification cost is too high, and the popularization and the application are not facilitated. Meanwhile, the fertilizer is rich in nutritional ingredients such as starch, protein and sugar, so that the fertilizer is easy to deteriorate and pollute, and therefore timely and effective treatment is urgently needed.

The use of a large amount of chemical pesticides controls crop pests to a certain extent, but causes serious problems of environmental pollution, poisoning of people and livestock, food safety and the like. It is extremely important to find a pollution-free pesticide having good environmental compatibility and a long-lasting effect on plant diseases and insect pests. Therefore, the development of environment-friendly pesticides is an urgent need. In recent years, research on the insecticidal activity of plant extracts has become one of the hot spots of agricultural and pharmaceutical research. The bamboo extract has antibacterial, antioxidant, insecticidal, and antitumor effects.

The green food trend is more and more concerned about the safety of food, wherein the concern about chemical preservatives is more and more serious, the chemically synthesized preservatives and pesticides have more or less, direct or indirect side effects on human bodies, and the development of natural, efficient, safe and nontoxic food preservatives and biological pesticides has become the key point of research and development. The search for active substances from natural sources to replace chemical food preservatives and pesticides is becoming more and more urgent.

Disclosure of Invention

The invention aims to provide a method for preparing an organic composite preparation which is easy to store and has good bactericidal activity by separating extracts rich in nutrient components from various raw materials related to bamboos and carrying out catalytic conversion on the extracts. Meanwhile, the technical problem that bamboo products are easy to discolor and mildew is solved.

In the prior art, bamboo products are easy to mildew, and are usually soaked in water to destroy nutrient components such as saccharides and protein in the bamboo and enhance the mildew-proof and corrosion-proof capability of the bamboo. However, the extract containing bamboo nutrients produced by bamboo soaking cannot be effectively used.

In the prior art, active components of bamboo extract are not developed and utilized, and the preparation source of biopesticide is single. Aiming at the defects of the prior art, the application provides a method for producing a biological source pesticide bactericide auxiliary agent by separating an extract from raw materials such as bamboo and felling processing residues thereof and the like with universality and carrying out catalytic conversion.

The invention innovatively and fully utilizes natural wood fiber raw materials such as bamboo wood and the like to obtain aqueous solution rich in extract through the existing industrial hydrothermal pretreatment extraction, converts the aqueous solution into compound bactericides such as organic acids, aldehydes, ketones and the like with stable properties by adopting an acid catalysis method in a gasification state, obtains high-concentration bactericide mother liquor after cooling, and can be subsequently used as an auxiliary agent to develop a series of biological pesticides, mildewproof agents, preservatives, leaf fertilizers, soil conditioners and the like. Meanwhile, gas obtained by gasification and condensation can be used as fuel gas, and the bamboo material after the extract is removed is not easy to mildew, so that the processing and utilization are not affected. And the environment can be further protected, the food safety is improved, and the comprehensive utilization of all components of bamboo resources is facilitated.

In a first aspect, the present invention provides a method for preparing a bamboo-derived composite preparation, comprising: soaking a bamboo raw material in water to obtain bamboo extract, carrying out gasification catalytic reaction on the bamboo extract and an acid catalyst, and condensing a gasification catalytic reaction product to obtain the bamboo-derived composite preparation.

In the preparation method provided by the invention, the reaction temperature of the gasification catalytic reaction is 120-300 ℃, preferably, the reaction temperature is 160-250 ℃; the reaction time is 5-60 min.

The invention discovers that if the reaction temperature is higher, the nutrient components (extracts) in the bamboo extract can be carbonized, and the extracts can not be converted into effective components with bacteriostatic effect. However, if the reaction temperature is low, conversion of nutrients into effective components having bacteriostatic activity cannot be achieved even if the reaction time is increased.

Because various nutrient components in the extract obtained by soaking and extracting in water are complex, the nutrient components can be successfully converted into water-soluble antibacterial substances only under the reaction temperature and time provided by the invention.

In the preparation method provided by the invention, the acid catalyst comprises an inorganic acid catalyst and an organic acid catalyst, wherein the inorganic acid catalyst is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; the organic acid catalyst is selected from one or more of formic acid, acetic acid, glycolic acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, citric acid, oxalic acid, maleic acid, acrylic acid, sulfamic acid, tartaric acid, succinic acid and salicylic acid.

In the preparation method provided by the invention, the organic acid catalyst is 0.2-0.5% of formic acid or oxalic acid.

In the preparation method provided by the invention, the bamboo extract contains bamboo starch, bamboo polysaccharide, bamboo gum, bamboo tannin, bamboo amino acid, bamboo soluble pigment and bamboo inorganic salt.

As a specific embodiment of the present invention, the preparation method of the bamboo-derived composite preparation provided by the present invention comprises:

a. soaking bamboo raw material in water for extraction to obtain extract;

b. adding acid catalyst into the extract, and carrying out gasification catalytic reaction at the temperature of 160-250 ℃ for 5-30min to obtain a gasification reaction product;

c. condensing the gasification reaction product to obtain a composite preparation solution rich in organic acids, aldehydes and ketones and organic gas;

d. the organic gas obtained in step c may be used as fuel for the gasification catalytic reaction in step b.

In the preparation method provided by the invention, the highest temperature of soaking and extracting in the step a is 180 ℃, and the soaking and extracting time is 0.5-24 h.

More specifically, step a is: soaking and extracting bamboo raw materials with water at a certain temperature; comprises soaking bamboo in water tank under normal pressure, soaking or washing bamboo in hot water in tank, rinsing bamboo with high temperature water, and removing extract from bamboo by water.

The step b is as follows: adding a certain amount of acid catalyst into the aqueous solution rich in the extract, and reacting the solution in a flowing state through a high-temperature gasification catalytic reaction device at the reaction temperature of 120-300 ℃.

In a second aspect, the invention provides a bamboo-derived composite preparation prepared by the preparation method. The compound preparation solution rich in organic acids, aldehydes and ketones obtained by the process technology can be directly used as liquid fertilizer for agricultural and forestry crops such as farmland crops, vegetables and orchards, so that the problem of water pollution caused by aggravated water eutrophication due to farmland runoff of the traditional fertilizer is solved; can also be used as a disinfectant and sterilization liquid or a deodorant and the like in the livestock raising process; it is recommendable to carry out further concentration, modification, encapsulation and other treatments, and further be used as an auxiliary agent or mother liquor production or directly be used as a biological source pesticide, a foliar fertilizer, a soil conditioner and the like. The bamboo-derived composite preparation prepared by the invention has good stability, corrosion resistance and antibacterial performance.

According to the understanding of the technical personnel in the field, the invention also claims the application of the bamboo-derived composite preparation in preparing natural biological pesticides, fertilizers or soil conditioners with high bacteriostatic ability.

In a third aspect, the invention provides a product, wherein the compound preparation prepared by the invention is used as a mother solution or an auxiliary agent of the product, and the product is a biological pesticide, a disinfectant, a bactericide, a foliar fertilizer, a deodorant and a soil conditioner.

The invention has the beneficial effects that:

the method has the advantages that the catalytic conversion reaction is carried out in a gasification state, the nutrient components of the bamboo extract can be fully reacted and converted, the efficiency is high, the speed is high, the mixture after the reaction is subjected to the step c and the step d by the step quenching process, the non-liquefiable gas is used as the fuel, and the organic matter aqueous solution rich in catalytic conversion products is obtained.

The organic compound preparation obtained by catalytic conversion of the bamboo extract obtained by the method is used as a raw material of a biological pesticide, a disinfectant, a foliar fertilizer, a deodorant, a soil conditioner and the like. Meanwhile, the organic composite solution can also be directly used for disinfection and sterilization.

The method solves the industrial problem of color change and mildew in the subsequent bamboo products after removing the nutrient component extract from the bamboo, and simultaneously provides a new product idea for green and environment-friendly biological pesticide sterilization and soil improvement through the catalytic conversion of the bamboo extract. The process has the advantages of simple equipment, stable and controllable process, simple and feasible route, environmental protection, no toxicity, high comprehensive utilization efficiency of all components of the bamboo raw material, easy realization of industrialization and wide application prospect.

Drawings

Fig. 1 is a process flow diagram of the bamboo-derived composite preparation provided by the present invention.

Detailed Description

The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.

EXAMPLE 1 catalytic conversion of bamboo tube extract

The embodiment provides a preparation method of a bamboo-derived composite preparation, a process flow chart is shown in figure 1, and the preparation method comprises the following specific steps:

(1) removing branches and leaves of 30kg of 4-year-old moso bamboos, cutting into bamboo tubes with the length of 2m, sequentially putting the bamboo tubes into a pressure tank, adding water which is over the bamboo, closing a tank door, heating to 150 ℃, keeping the temperature for 4h, and cooling to the normal temperature to obtain 300L of extract;

(2) discharging and collecting the extract in the pressure tank, adding 1.5L of 0.5% oxalic acid into the extract, transferring into a gasification catalytic reaction device for gasification catalytic reaction, heating to 250 ℃, and reacting for 30min in a heat preservation section to obtain a gasification reaction product;

(3) and (3) carrying out fractional condensation on the gasification reaction product by using water to obtain non-liquefiable gas and 100L of composite preparation solution A rich in organic acids, aldehydes and ketones.

The operation of fractional condensation comprises a three-stage process: 1min at 120 ℃, 3min at 60 ℃ and 5min at normal temperature.

The non-condensable liquefied gas was checked to be ignitable and was presumed to be CO or H ₂ Or methane, has the potential to be used as a fuel. High performance liquid chromatography detection shows that the composite preparation has complex components and consists of various organic acids, aldehydes and ketones. (Compounds capable of qualitative and quantitative detection are shown in Table 1).

TABLE 1 names and contents of some compounds in the composite formulation

Compound (I)	Content (g/L)
		Formic acid	1.29
Levulinic acid	1.75
		Furfural	2.08
5-hydroxymethylfurfural	1.24
		Vanillic acid	0.17
P-hydroxybenzaldehyde	0.55
		Syringaldehyde	0.11
Vanillyl ketone	0.07

The mildew-proof test of the treated bamboo tube proves that compared with untreated bamboo, the mildew-proof performance of the bamboo tube is greatly improved.

Example 2 catalytic conversion of bamboo shoot extracts

This example provides a method for preparing a bamboo-derived composite formulation, and differs from example 1 only in that bamboo strands processed from bamboo tubes are placed in a pressure treatment tank in step (1) to obtain a composite formulation B.

Example 3

This example provides a method for preparing a bamboo-derived composite preparation, and the only difference between this example and example 1 is that in step (1), a bamboo tube is soaked in an open water pool for 24h to obtain a composite preparation C.

Example 4

This example provides a method for preparing a bamboo-derived composite preparation, and differs from example 1 only in that 0.5% formic acid is added to the bamboo extract solution in step (2) and reacted at 200 ℃ for 30min to obtain composite preparation D.

Comparative example 1 different temperatures of gasification catalytic reaction

This comparative example is the same as example 1 except that the catalytic reaction temperatures used in this comparative example are 100 ℃ (less than 120 ℃) and 350 ℃ (greater than 300 ℃).

And obtaining the compound preparation E at the catalytic reaction temperature of 100 ℃.

And obtaining the compound preparation F at the catalytic reaction temperature of 350 ℃.

Comparative example 2 different gasification catalytic reaction times

This comparative example is the same as example 1 except that the catalytic reaction times used in this comparative example were 10min (less than 30min) and 120min (greater than 30 min).

And when the catalytic reaction time is 10min, obtaining the compound preparation G.

And when the catalytic reaction time is 120min, obtaining the compound preparation H.

Experimental example 1 composite preparation bacteriostatic properties

The sterilization performance of each composite preparation in the examples and the comparative examples is evaluated by adopting a zone of inhibition test method, which is carried out according to an antibiotic microorganism detection method in pharmacopoeia of the people's republic of China, and the zone of inhibition test method has short period and can be used for rapid primary screening of medicaments.

The bacteriostatic zone test method comprises the following specific steps:

preparing culture solution from maltose, agar and potato decoction, injecting into a culture dish (diameter is about 90mm) to obtain potato glucose agar culture medium, sterilizing with steam, inoculating decay fungi strain, and culturing in a constant temperature and humidity chamber (28 deg.C) for about one week. The bacterial strains used in the zone of inhibition test are mould, colibacillus, etc.

The cultured strains are evenly coated on a blank culture medium on a sterile workbench by using an inoculating loop, 4 Oxford cups (stainless steel small tubes with the inner diameter of 6mm, the outer diameter of 7.8mm and the height of 10 mm) are placed in each culture dish, 0.5mL of sterile distilled water, the extracting solution which is not gasified and catalyzed and various compound preparations with high concentration, medium concentration and low concentration are respectively dripped into the stainless steel small tubes by using a dropper, marks are made on the culture dishes, and each condition is repeated for 3 times. The plates were incubated in an incubator (28 ℃ soil 2 ℃). After 2 weeks of culture, the diameters of the zones were measured with a vernier caliper and compared, and the zone test is shown in table 2.

TABLE 2 bacteriostatic effect

The results in Table 2 show that the complex formulation solutions of organic acids, ketones and aldehydes obtained in examples 1 to 4 of the present invention have excellent bactericidal effects against mold and Escherichia coli. Among them, the composite preparation B obtained in example 1 exerts the most excellent bacteriostatic effect. The composite preparation H obtained in the comparative example 2 has a good antibacterial effect, but the reaction time is prolonged, so that the meaningless energy consumption investment is increased, and the reaction time is not too long from the energy-saving aspect.

Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. A preparation method of a bamboo-derived composite preparation is characterized by comprising the following steps: soaking a bamboo raw material in water to obtain bamboo extract, carrying out gasification catalytic reaction on the bamboo extract and an acid catalyst, and condensing a gasification catalytic reaction product to obtain the bamboo-derived composite preparation.

2. The preparation method as claimed in claim 1, wherein the reaction temperature of the gasification catalytic reaction is 120-300 ℃; the reaction time is 5-60 min.

3. The preparation method according to claim 1, wherein the acid catalyst comprises an inorganic acid catalyst and an organic acid catalyst, and the inorganic acid catalyst is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; the organic acid catalyst is selected from one or more of formic acid, acetic acid, glycolic acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, citric acid, oxalic acid, maleic acid, acrylic acid, sulfamic acid, tartaric acid, succinic acid and salicylic acid.

4. The method according to claim 3, wherein the organic acid-based catalyst is 0.2 to 0.5% formic acid or oxalic acid.

5. The method of claim 1, wherein the bamboo extract comprises bamboo starch, bamboo polysaccharide, bamboo gum, bamboo tannin, bamboo amino acid, bamboo soluble pigment and bamboo inorganic salt.

6. The production method according to any one of claims 1 to 5, comprising:

a. soaking and extracting bamboo raw materials with water to obtain an extract;

d. the organic gas obtained in step c can be used as fuel for the gasification catalytic reaction in step b.

7. The process according to claim 6, wherein the maximum temperature of the soaking extraction in step a is 180 ℃ and the soaking extraction time is 0.5-24 h.

8. A bamboo-derived complex preparation produced by the production method according to any one of claims 1 to 7.

9. Use of the bamboo-derived composite preparation according to claim 8 in preparation of natural biological pesticides, fertilizers or soil conditioners with high bacteriostatic ability.

10. A product characterized by using the composite preparation according to claim 8 as a mother liquor or an auxiliary for the product, which is a biological pesticide, a disinfectant, a foliar fertilizer, a deodorant, a soil conditioner.