CN112741117B

CN112741117B - Preparation method of herbal antibacterial disinfectant

Info

Publication number: CN112741117B
Application number: CN202110114552.5A
Authority: CN
Inventors: 谈宇清; 任琪
Original assignee: Guangdong Paite Aier Biotechnology Co ltd
Current assignee: Guangdong Paite Aier Biotechnology Co ltd
Priority date: 2021-01-26
Filing date: 2021-01-26
Publication date: 2022-01-25
Anticipated expiration: 2041-01-26
Also published as: CN112741117A

Abstract

The invention relates to a preparation method of a composite herbal antibacterial disinfectant, which comprises the following steps: crushing the tea seed cake and camellia seed shells, wet-grinding the crushed tea seed cake and camellia seed shells into slurry, treating the slurry by microwave and ultrasonic waves, and adding an alcohol-water solvent with the concentration of 60-80% until the total weight of the slurry is 8-10 times of the net weight of the tea seed cake and the camellia seed shells; then heating to boil and condensing and refluxing; then press-filtering to obtain brown-yellow opaque filtrate; adding magnesium chloride and/or calcium hydroxide to adjust the pH value to 10, adding hydrogen peroxide to decolor, dissolving out the antibacterial components in the mangosteen shell under an acidic condition, and passing through a column to obtain the herbal antibacterial disinfectant. The preparation method has the advantages of wide raw material source, low price and environment-friendly production process. The obtained disinfectant has the functions of washing, bacteriostasis and disinfection, is similar to chemical synthesis products in the aspect of killing harmful bacteria, fungi and viruses, and has small irritation to human bodies and animals. Can change agricultural wastes into valuables, improve the income of farmers and have remarkable social and economic benefits.

Description

Preparation method of herbal antibacterial disinfectant

Technical Field

The invention relates to a method for preparing herbal antibacterial disinfectant by comprehensively utilizing camellia seed shells, tea seed cakes, mangosteen shells, shaddock peels and the like.

Background

The existing sterilization disinfectant is mostly prepared by mixing chemically synthesized surfactant and disinfectant in proportion. In order to kill harmful microorganisms such as bacteria, fungi and viruses, the prepared product has certain irritation and various degrees of irritation or damage to the skin and the body of a human body or an animal. These chemicals also present more or less environmental pollution problems during the manufacturing process.

The herbal antibacterial disinfectant has the advantages of good safety and suitability for agricultural products, food, tableware and the like. Most of the existing herbal antibacterial disinfectant adopts a plurality of traditional Chinese medicinal materials as raw materials, and the traditional Chinese medicinal materials are compounded after active ingredients are extracted. The key varieties of the traditional Chinese medicinal materials are expensive, the yield is rare, and the defects of shortage of raw material sources, high cost and high price of final products and the like exist. The extraction of effective components from the dregs of a decoction can reduce the cost of raw materials, but the yield is low, and the amount of residual solid waste after extraction is large, so that the effective treatment is difficult. And the method also has the defects of high comprehensive energy consumption, long extraction period and the like of extraction and separation purification, the production cost is high, and the obtained product is difficult to compete with the chemically synthesized sterilization disinfectant in price, so that the method is difficult to popularize and popularize.

The resources of tea-oil trees and oranges in China are very rich, and the byproducts of tea seed oil cake (more than 50 ten thousand tons per year according to estimation) and camellia seed shells are burnt as wastes, which is very pity. The tea oil cake contains a large amount of tea saponin, tea oil, protein and the like. The tea saponin molecule consists of hydrophilic saccharide and hydrophobic coordinating group, so that the tea saponin has various surface active properties of emulsification, dispersion, wetting, decontamination, foaming and the like, and is a natural nonionic surfactant. Tea saponin is widely used as a detergent in the daily chemical industry and is also used in various industrial scenes such as pesticide emulsifiers and the like. The annual output of citrus in China exceeds 4000 ten thousand tons, wherein the annual output of the grapefruit exceeds 500 ten thousand tons. The shaddock peel is discarded not less than 100 ten thousand tons every year. None of these resources are efficiently utilized.

The invention is processed by adopting tea seed oil/camellia oil and other woody oil materials as residual tea cakes (cakes) after oil extraction, and camellia seed shells, mangosteen shells, shaddock peels, citrus peels and other agricultural and sideline products as raw materials, and the raw materials are low in price and can become special high-added-value disinfection and sterilization liquid after being processed.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention discloses a method for preparing a composite herbal antibacterial disinfectant containing tea saponin and natural antibacterial components.

A preparation method of a herbal antibacterial disinfectant comprises the following steps:

the first step is as follows: crushing the tea seed cake and camellia seed shells, wet-grinding the crushed tea seed cake and camellia seed shells into slurry, treating the slurry by microwave and ultrasonic waves, and adding an alcohol-water solvent with the concentration of 60-80% until the total weight of the slurry is 8-10 times of the net weight of the tea seed cake and the camellia seed shells; then heating to boil and condensing and refluxing; then press-filtering to obtain brown-yellow opaque filtrate; adding magnesium chloride and/or calcium hydroxide to adjust the pH value to 10, adding hydrogen peroxide to decolorize, and filtering to obtain the transparent herbal antibacterial disinfectant solution.

The preparation method of the herbal antibacterial disinfectant further comprises the following steps:

the second step is that: pulverizing dried mangosteen shell, adding into the above transparent filtrate, and adding organic acid to adjust pH to 4-6;

the third step: pulverizing dried pericarpium Citri Grandis, extracting with hot water and ethanol to obtain suspension emulsion, press-filtering the suspension emulsion with plate frame to obtain filter cake, and making into packed column with the filter cake as chromatographic packing;

the fourth step: and filtering the filtrate obtained in the second step through the packed column obtained in the third step, and collecting the obtained filtrate to obtain the herbal antibacterial disinfectant solution.

In one embodiment of the present invention, the method further comprises:

the fifth step: filtering the filtrate obtained in the fourth step, or skipping the third step and the fourth step and directly filtering the filtrate obtained in the second step, or mixing the filtrate obtained in the fourth step and the filtrate obtained in the second step, and removing suspended matters through two-stage precise filtration; then controlling the temperature below 80 ℃, rectifying to remove water, adding glycerol, and continuously vacuumizing and evaporating to remove the low-boiling-point organic solvent.

In one embodiment of the present invention, in the fourth step, the filtration using the packed column is continued until the packing in the packed column is stained with the color leached by the fine powder of the mangosteen shell from top to bottom.

In another embodiment, the residual tea seed oil in the tea seed cake is removed by dimethyl carbonate before the first step.

In another embodiment, in the second step, the mangosteen shell fine powder in the clear filtrate is charged in a weight ratio of 1:1 to sasangua cake.

The 60% -80% alcohol-water solvent added in the first step can be methanol, ethanol or acetone, preferably ethanol.

and (3) eluting the filler in the used filler column with water, performing fine filtration on the obtained eluent to remove suspended insoluble substances, then performing evaporation concentration, and collecting the remaining filtrate, namely the herbal antibacterial disinfectant.

In one embodiment, the used packed column is eluted by water, and purified water which is 5-10 times of the total volume of the packing in the packed column flows through the packed column from top to bottom; and taking out the filler in the filler column, soaking the filler in water, and extruding to remove liquid.

and step three, collecting filtrate in the plate-frame filter pressing process, namely the herbal antibacterial disinfectant.

The herbal antibacterial disinfectant disclosed by the invention has the functions of washing, bacteriostasis and disinfection, is similar to or even better than a chemically synthesized product in the aspect of killing harmful bacteria, fungi and viruses, and has small irritation to human bodies and animals. The raw materials have wide sources and low price, the production process is environment-friendly, and no negative effects such as environmental pollution and the like are generated. Can improve the utilization rate of the existing agricultural and sideline products, improve the income of farmers, change the agricultural wastes into valuables and have remarkable social and economic benefits.

Drawings

FIG. 1 is a process flow diagram of an embodiment of the present invention for preparing a first dope.

FIG. 2 is a process flow diagram of an embodiment of the present invention for making filter cake B and a second dope.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings. The implementation of the invention is not limited to the embodiments described below, but can be implemented in many different forms. The following examples are put forth so as to provide a more thorough understanding of the present disclosure.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein are intended to describe specific embodiments only and are not intended to limit the present invention.

Tea saponin (Tea saponin), also known as Tea saponin, is a natural glycoside compound contained in plants of Theaceae and Camellia, and is a pentacyclic triterpenoid saponin composed of basic structures of aglycone (C30H50O6), sugar and organic acid. The tea seeds, tea leaves, tea tree stems and root systems are all distributed, and the content of the tea seeds is the largest. The tea seed contains tea saponin 12-15%, and the natural tea saponin is odorless, colorless, particulate or fine columnar crystal, and has hygroscopicity.

The tea seed cake and the camellia seed shell contain tea saponin, tannin, polysaccharide pigment, protein and the like, and the detection result of the tea seed shell shows that: the camellia seed hulls contain 11.07% of water, 1.02% of ash, 2.53% of crude fat, 2.70% of crude protein, 1.59% of reducing sugar, 10.68% of tea saponin, 22.00% of hemicellulose, 17.32% of cellulose and 31.35% of lignin. The traditional separation method adopts an organic solvent, adsorption resin and a chromatography, needs to consume expensive adsorption resin and special chromatographic packing, and is only suitable for the separation and purification of products with high added values; and the chromatographic separation has small capacity, and is not suitable for large-scale industrialization.

FIG. 1 is a flow chart of a process for preparing an embodiment of the first dope of the present invention. The process for preparing the herbal antibacterial disinfectant comprises the following working procedures:

step 101

Grinding camellia seed hulls and camellia seed hulls into powder, and adding an alcohol-water solvent with the concentration of 60-80% until the total weight of the slurry is 8-10 times of the net weight of the camellia seed hulls and the camellia seed hulls to obtain slurry A. The specific process comprises the following steps:

preparing the tea seed cake slurry by adopting wet grinding, namely: adding water, grinding into slurry emulsion by a grinding tool such as a stone mill, collecting, and adding 60-80% alcohol-water solvent to obtain slurry A. In the step, the camellia oleifera and the like are ground/milled into micron-sized suspended particles, and the total amount of the water solvent is 8-10 times of the net weight of the camellia oleifera and the camellia seeds.

In one embodiment, after the residual tea seed oil in the cold-pressed oil-tea camellia cakes is removed by dissolving and extracting dimethyl carbonate, the dimethyl carbonate is removed by heating.

Step 102

And (3) heating and refluxing the slurry A after microwave and ultrasonic treatment to obtain slurry B. The specific process comprises the following steps:

the slurry A is pumped into an extraction reaction kettle after being treated by ultrasonic waves and heated by microwaves to 80-90 ℃, and is heated and maintained to be condensed and refluxed by steam, and the extraction is carried out for 3-4 hours.

In one embodiment, heating is stopped after maintaining moderate agitation, negative pressure evaporation, and reflux condensation in the extraction reactor for 1-2 hours.

The ultrasonic wave is a sound wave with the frequency higher than 20000 Hz, and the ultrasonic wave has good directivity and strong penetrating power. The emulsion slurry is irradiated by ultrasonic waves, so that micro bubbles in the liquid can keep vibrating under the action of the sound waves. When the microbubble pressure reaches a certain level, the bubbles expand rapidly and then close abruptly. During this period, the shock wave is generated at the moment when the bubble is closed, so that 10 is generated around the bubble¹²-10¹³pa, the tremendous pressure generated by this ultrasonic cavitation can break down the insolubles in the slurry to differentiate them into solution. And the principle of microwave heating is different from ultrasonic radiation. The microwave refers to electromagnetic wave with the wavelength ranging from 1mm to 1m, and the corresponding frequency ranges from 300GHz to 300 MHz. In the electromagnetic field of a microwave, molecules of polar substances are polarized, changing with the microwave field direction hundreds of millions of times per second. Because polar molecules always try to align at the same rate, causing the polar molecules to rotate. When this rotational behavior is hindered by elastic scattering of atoms or thermal vibration of the crystal lattice, energy dissipation occurs and electromagnetic energy is converted into thermal energy, causing the temperature of the material to rise. Since the solvent in the emulsified slurry is a polar molecule, the suspension includes both polar and non-polar molecules. For substances composed of polar molecules, the microwave energy can be absorbed better. Solvents with dipoles such as water and ethanol have a heating effect when irradiated with microwaves. There are many substances in suspension, consisting of non-polar molecules, which are substantially or hardly microwave-absorbing, so that under microwave radiation the molecules of different substances have substantially different corresponding kinetic properties, which helps them to achieve molecular-level separation.

Step 103

And carrying out pressure filtration on the slurry B to obtain a brown-yellow opaque filtrate C and a filter cake A. The specific process comprises the following steps:

filtering the slurry B by a plate-and-frame filter press while heating to obtain dark brown, yellow brown or earthy yellow liquid C with suspended solid removed, wherein the residual filter residue is filter cake A.

Step 104

Adding magnesium chloride and calcium hydroxide into the brown yellow filtrate C, modulating into an alkaline material with the pH value of about 10, adding hydrogen peroxide for decolorization, and filtering again to obtain a transparent filtrate D. The specific process comprises the following steps:

and (2) putting the liquid C into a refining kettle, naturally cooling to normal temperature, adding 50-100g of alkali metal salt (including but not limited to magnesium chloride or calcium chloride) into each cubic meter of filtrate, continuously stirring for 2-4 hours until bittern is fully dissolved and uniformly mixed, adding calcium oxide or calcium hydroxide emulsion to adjust the pH value of the feed liquid to 9-10, and filtering by using a plate and frame filter again to remove solid matters. This step breaks down the colloids in the emulsion, allowing protein molecules, etc. to agglomerate into insoluble particles that can be removed by filtration; adding hydrogen peroxide (30%) which is 5% -10% of the net weight of the filtrate into the filtrate, continuously stirring and reacting for 60-90 minutes, and filtering by a precision filter such as a 0.5um ceramic membrane and the like to remove most of color-developing impurities to obtain clear and transparent filtrate D.

Step 105

Drying and pulverizing mangosteen shell, adding decolorized filtrate D, adding citric acid, and adjusting pH to 4-6 to obtain refined filtrate F. The specific process comprises the following steps:

adding at least one organic acid such as citric acid into the decolorized transparent filtrate D, adjusting pH to 4-6, adding fine powder of cortex Bambusae (weight ratio of fructus Camelliae sinensis cake to fructus Camelliae sinensis cake and fructus Camelliae sinensis seed shell is about 1:1) at 60-80 deg.C, stirring for 1-2 hr, and extracting antibacterial component (including but not limited to mangostin alpha-mangostin, etc.) from cortex Bambusae.

The fine powder of mangosteen shell is obtained by cleaning purple black shell of mangosteen shell, drying in the shade in a dry room to make its water content less than 5%, grinding, and pulverizing into fine powder (sieving with 60 mesh sieve).

And (3) putting the fine powder of the mangosteen shell into the transparent filtrate D, fully stirring and mixing (ensuring that the extraction temperature does not exceed 80 ℃) for 1-2 hours, and then adjusting the pH value of the solvent to 4-6 by using organic acid (such as any one of citric acid, oxalic acid and glacial acetic acid, preferably citric acid). Stirring for about 1 hour, and naturally cooling to about 40 deg.C to obtain refined filtrate F.

In another embodiment, the refined filtrate F is subjected to two-stage microfiltration to remove suspended matter; then controlling the temperature below 80 ℃, rectifying to remove water, adding glycerol, continuously vacuumizing and evaporating to remove the low-boiling-point organic solvent, and obtaining the herbal antibacterial disinfectant.

Step 106

Adding a proper amount of ethanol into the refined filtrate F, and obtaining a purified liquid G through a filtering process by taking the filter cake B as a chromatographic filler; the purified solution G can also be concentrated, dehydrated and de-ethanol to obtain a first stock solution. The specific process comprises the following steps:

adding ethanol which is 10-20% of the total volume of the materials into the refined filtrate F, uniformly mixing, filtering the mixed solution by a plate and frame filter press to remove insoluble substances such as mangosteen shell micro powder, filtering by a 0.5um ceramic membrane and other precise filters, and collecting the filtrate after the filtrate flows through one or more filler columns from top to bottom to obtain the purified solution G.

The filter material filled in the packed column is filter cake B.

The process for removing most of water solvent from the purified liquid G comprises the following steps: evaporating and concentrating at a temperature not higher than 80 deg.C, separating the steam condensate by rectification, removing water by single-component reflux of solvent such as ethanol, and removing water by rectification reflux of low-boiling-point solvent to remove more than 95% of water. Then removing organic solvents such as ethanol and the like. And finally, adding glycerol to protect the activity of the antibacterial component to obtain a first stock solution.

In one embodiment, the first stock solution is further processed as follows: adding glycerol, mixing, vacuumizing to remove low-boiling-point organic solvent (such as ethanol), and storing.

The obtaining of the filter cake B is shown in figure 2 and is a process flow chart of an embodiment of the invention for preparing the filter cake B and a second stock solution. The method comprises the following steps:

step 201

Drying and pulverizing the shaddock peel, and leaching with hot water and ethanol (the ethanol accounts for 5% -20%) to obtain the suspoemulsion H.

Step 202

And (4) filtering the suspension emulsion H by using a plate frame to obtain a filter cake B and an extracting solution K.

Step 203

And concentrating, dehydrating and removing ethanol from the extracting solution K to obtain a second stock solution.

In step 106, the filler column is filled with filter cake B, i.e. filter residue obtained by leaching shaddock peel, refined filtrate F is subjected to two-stage filtration and then is sent into the filler column, and the purplish red pigment dissolved out from the mangosteen shell micro powder can color the filler column. When more than 80% of the whole column body is changed into purple red or dark brown, eluting the residue in the filler column by pure water which is 5-10 times of the total volume of the filler (in the elution process, the flow rate is controlled to be not more than 0.05 m/s, and the pure water is used for rinsing from top to bottom) to obtain the eluent. Further, taking out the materials in the packed column, squeezing the liquid in the packed column by a dry-wet separator, and collecting the dry materials and the squeezed liquid; and soaking the dry materials in pure water again, extruding water out again by using a dry-wet separator, collecting the dry materials and the extruded liquid, and repeating for two to three times to obtain a combined liquid M and the dry materials. The dry material can be used for producing feed, for example, after most of water is removed by extrusion through a screw dry-wet separator, the dry material is extruded into rod-shaped particles through a die and can be used for cultivating yellow mealworms or other livestock; or after the rod-shaped particles are heated and deeply dried by infrared, the rod-shaped particles are carbonized in a high-temperature carbonization furnace with the temperature of 600-900 ℃ in an air-isolated manner to prepare the active carbon adsorbent for sewage treatment and the like.

And (4) after the combined solution M is subjected to two-stage precise filtration to remove suspended insoluble substances, performing negative pressure evaporation and concentration to obtain a third stock solution for later use.

The first stock solution, the second stock solution and the third stock solution obtained in the steps can be directly used or added with purified water and other auxiliary agents for further compounding, and various commercial-grade and consumer-grade end products can be prepared. Including but not limited to: disinfecting and sterilizing hand washing liquid, cleaning liquid special for medical instruments, pet disinfecting and mite-killing spray liquid, fruit and vegetable cleaning liquid, tableware detergent, underwear disinfecting and cleaning liquid and the like.

The invention not only simply crushes the hulls of the camellia seeds, the camellia cakes and the like, but also precisely grinds or mills the camellia seeds to obtain slurry, after the slurry is filtered, at least one alkali metal salt is added to remove the stability of protein colloid, then hydrogen peroxide is used for decoloring under the alkaline condition, and the method of plate-and-frame filter pressing, precise filtering and adsorption impurity removal of a filler chromatographic column is sequentially adopted, thereby solving the problem that the tea saponin in the camellia cakes is difficult to separate after being tightly combined with other components in a stable colloid form.

According to the method, aiming at the oil-tea camellia cake dregs obtained by a low-temperature cold pressing method, after dimethyl carbonate is dissolved and residual tea seed oil is extracted, the dimethyl carbonate is heated and volatilized to remove a solvent; and then wet grinding is adopted to obtain slurry emulsion, the slurry treated by ultrasonic wave or microwave is subjected to the processes of negative pressure evaporation and boiling reflux, the tea saponin in the tea seed cake is fully extracted, after the tea seed cake is filtered by filter cloth, the extracting solution (filtrate) flows through powdery filler columns such as the fruit shell dry powder (formed by mechanical crushing after deep drying) of the shaddock peel or the orange peel from top to bottom, and two unexpected effects can be achieved simultaneously:

1. under the action of natural surfactants such as tea saponin, and the like, most of antibacterial active substances (such as hesperidin, naringin, and the like) in shaddock peel or orange peel are eluted, and a plurality of antibacterial active substances are not dissolved in water, but can be effectively dissolved out to enter filtrate under the action of natural surfactants such as tea saponin, and the like;

2. insoluble substances and macromolecular compounds in the tea cakes are intercepted and adsorbed by porous powder derived from fruit peels and fruit shells, so that free proteins, tannin and other colloidal components in the tea cakes are effectively removed, and the process substantially plays a role in chromatographic separation (including but not limited to adsorption chromatography and perfusion chromatography) and is favorable for obtaining a clear and transparent compound liquid. And then the composite liquid is subjected to precise filtration and is evaporated and concentrated at low temperature (less than 80 ℃) to obtain the composite stock solution with the antibacterial bioactivity.

Further: adding a certain amount of cortex Garciniae micropowder into acidic solvent containing tea saponin, press-filtering with plate-and-frame filter to obtain filtrate, and performing column chromatography to obtain composite liquid containing xanthone compounds such as mangostin dissolved from cortex Garciniae.

The degerming and disinfecting concentrated solution obtained by the invention contains tea saponin and a plurality of natural antibacterial ingredients, wherein the natural antibacterial ingredients comprise but are not limited to: xanthone compounds such as alpha-mangostin, flavonoid compounds such as hesperidin, naringin and limonin, and tannic acid. The natural components have high killing and strong inhibiting effects on bacteria and fungi at very low concentration, and also have antiviral and anthelmintic effects.

The bitter components (such as naringin and limonin) in the tea seed cake and the shaddock peel are removed from the dry material obtained by the invention, but the protein components in the dry material are retained, and the dry material is used for feed components after being squeezed again and subjected to liquid removal, so that the palatability is better. Can be fermented by probiotics, so that the nutritional ingredients in the oil-tea camellia cake and the shaddock peel are easier to absorb.

The invention uses micro powder (crushed and sieved by a 60-mesh sieve) prepared by deeply drying shaddock peel (or orange and orange peel) as chromatography filler; the ethanol-water solvent with tea saponin dissolved therein is used as mobile phase, and water is used as eluent. The materials have low cost, and the problem of high cost of chromatographic separation is solved; furthermore, after the filler column is eluted by pure water, an extrusion type dry-wet separator is adopted to remove liquid in the filler, so that micromolecule compounds in the solvent are fully recovered, the residue of micromolecule components such as tea saponin, limonin and the like in the filler is reduced to the maximum extent, bitter substances in the pomelo peel powder and the oil-tea camellia cake are fully removed, and the material is more suitable to be used as a raw material of animal feed.

Yet another embodiment:

taking 1000g of tea seed cake, adding 2-3 liters of water, blending, and grinding into slurry by using a traditional stone mill. Loading into a container, placing into an ultrasonic cleaning machine, vibrating for about thirty minutes, adding 10-15L of anhydrous ethanol, putting into a reaction kettle, stirring for 2-8 hours, slowly heating until the solvent is boiled, and keeping condensation reflux for about one hour. And filtering and removing insoluble substances from the condensate by using a plate-and-frame filter press to obtain 12-18 liters of filtrate. Adding 30-50 g of sodium hydroxide solid into the filtrate, stirring to fully dissolve, slowly dropwise adding 1.5L of hydrogen peroxide (30%), maintaining stirring for 1-2 hours, heating to 60 ℃, continuously stirring for 1-2 hours, and then removing impurities through a 0.5-micron ceramic membrane precision filter to obtain refined liquid. Adding 250-300 g of citric acid into the refined liquid, and stirring until the citric acid is fully dissolved. Adding 500 g of mangosteen micropowder and 1000g of mangosteen micropowder to enable the mangosteen micropowder to be fully and uniformly suspended, keeping the temperature at about 60 ℃, continuing stirring for 1-2 hours, filtering again through a plate-and-frame filter press and a 0.5-micron ceramic membrane precision filter, and then filtering from a filler column by taking a shaddock peel filter cake as a filler to obtain a first stock solution. The contents of the filler were washed out with pure water and concentrated to a second stock solution.

The content of tea saponin in the tea seed cake is 12% -13%, the micro powder obtained by crushing the dried shaddock peel has a rich porous structure, the average pore diameter is about 2-20 microns, and the porous structure is favorable for adsorbing dye macromolecules. The content of the shaddock peel holocellulose is very high, and a large amount of hydroxyl and carbonyl groups which can be combined with dye molecules are contained. The method can adsorb purple red pigment in the mangosteen shell, and also can block colored substances from tea cake to obtain a first refined liquid with near colorless. Naringin in the fine powder of pericarpium Citri Grandis is easily soluble in hot water and ethanol solvent, can be washed out during chromatography, and enters into the first refined solution.

The cortex Bambusae is rich in oxa-allinone compounds represented by alpha-mangostin, and can be dissolved in alcohol-water solvent under acidic condition.

The method comprises the steps of firstly mixing the fine powder of the mangosteen shell with the decolorized refined liquid, then filtering the mixture through a filler column filled with the fine powder of the shaddock peel, utilizing micron-level or even nano-level micropores (composed of cell walls and high porosity) of the fine powder of the mangosteen shell and the fine powder of the dried shaddock peel, having good adsorption and interception functions on residual macromolecular impurities of refined filtrate prepared from the tea cake milling slurry, performing chromatographic separation in the process of flowing from top to bottom, and effectively solving the problems that the tea saponin is tightly combined with various impurities and is difficult to be fully and effectively separated.

By adopting a plate-and-frame filter pressing and filler column adsorption filtration method, most suspended matters in the tea dreg slurry are intercepted and removed, and meanwhile, antibacterial ingredients in micro powder such as the mangosteen shell, the shaddock peel and the like are dissolved in the first stock solution. The method has low comprehensive cost and is beneficial to continuously amplifying the productivity.

The invention extracts active ingredients from tea seed cake, mangosteen shell and shaddock peel in a low-cost way. The traditional method needs separate extraction, and has the problems of large consumption of auxiliary materials such as organic solvent and the like, high cost and the like. The process and the technology provided by the invention skillfully utilize the surface activity of the tea saponin and the adsorption capacity of the shaddock peel micro powder, improve the rapid dissolution rate of antibacterial components in the mangosteen shell and the shaddock peel, better remove macromolecular impurities in the tea saponin extraction slurry, obtain a concentrated product with good stability, and are suitable for improving the antibacterial and disinfection capacity of the existing washing products. The social significance of the invention is as follows: the comprehensive utilization rate of agricultural and sideline products is improved, the added value of agricultural and forestry products can be improved, and the cooperative development of the first, second and third industries is promoted.

The first stock solution contains some antibacterial components with good alcohol solubility extracted from the mangosteen shell and the shaddock peel. These costs are generally water-soluble and tend to precipitate in water, and it is necessary to maintain their antibacterial activity for a long period of time by dissolving in glycerin. Therefore, after the moisture and the ethanol are removed, the first stock solution is stored in the glycerol in the form of concentrated solution, can be used as an active ingredient for sterilization and disinfection, and is added into various existing products such as detergent (such as tableware cleaning agent, pet bath foam) and the like according to the proportion of 1-10 percent, so that the antibacterial and disinfection capability of the existing products is improved; the components in the second solution have good water solubility, and can be sold as a product after being directly dehydrated and concentrated, and are more used in industrial washing and sterilizing scenes such as industrial washing, disinfection and sterilization.

In order to test the bacteriostatic effect of the extracting solution, a bacteriostatic circle comparison experiment based on a filter paper sheet method is performed. Experiments show that different extracts have different inhibiting abilities on various harmful bacteria, referring to the following table I, "+" indicates that a sample has an inhibiting effect on tested bacteria, and the diameter of an inhibition zone is shown in parentheses and is in cm; "-" indicates that the sample is not inhibitory to the test bacteria.

A first table:

wherein, the diameter of the inhibition zone corresponding to +++ is larger than 16mm, the diameter of the inhibition zone corresponding to ++ is larger than 10mm, and the diameter of the inhibition zone corresponding to + is larger than 5 mm. The bacteriostatic experiment shows that: the first stock solution obtained by the invention has broad-spectrum bacteriostatic action.

Other combinations of the features of the embodiments described above are possible and not all possible combinations of features are fully described herein for the sake of brevity. It is to be understood that all combinations of the above features are included in the scope of the present specification unless they are contradictory.

The above examples specifically and in detail describe several embodiments of the invention, which are not intended to limit the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. All changes, equivalents and modifications that come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims

1. A preparation method of a herbal antibacterial disinfectant is characterized by comprising the following steps:

the first step is as follows: crushing the tea seed cake and camellia seed shells, wet-grinding the crushed tea seed cake and camellia seed shells into slurry, treating the slurry by microwave and ultrasonic waves, and adding an alcohol-water solvent with the concentration of 60-80% until the total weight of the slurry is 8-10 times of the net weight of the tea seed cake and the camellia seed shells; then heating to boil and condensing and refluxing; then press-filtering to obtain brown-yellow opaque filtrate; adding magnesium chloride and/or calcium hydroxide to adjust the pH value to 10, adding hydrogen peroxide to decolor, and filtering to obtain transparent filtrate;

the second step is that: pulverizing dried mangosteen shell, adding into the above transparent filtrate, and adding organic acid to adjust pH to 4-6; adding the fine mangosteen shell powder in the transparent filtrate, wherein the weight ratio of the fine mangosteen shell powder to the tea seed cake is 1: 1;

the fourth step: and filtering the filtrate obtained in the second step by using the packed column obtained in the third step, and collecting the obtained filtrate to obtain the herbal antibacterial disinfectant.

2. The method for preparing herbal antibacterial disinfectant as claimed in claim 1, further comprising:

the fifth step: removing suspended matters from the filtrate obtained in the fourth step by two-stage precise filtration; then controlling the temperature below 80 ℃, rectifying to remove water, adding glycerol, and continuously vacuumizing and evaporating to remove the low-boiling-point organic solvent.

3. A herbal antiseptic solution as defined in claim 1 wherein in the fourth step, the filtration using the packed column is continued until the packing in the packed column is stained with the color of the fine powder leaching of the mangosteen shell from the top to the bottom.

4. The method for preparing herbal antiseptic solution of claim 1, wherein the residual tea seed oil in the tea seed cake is removed by dimethyl carbonate before the first step.

5. A preparation method of a herbal antibacterial disinfectant is characterized by comprising the following steps:

the used filler column of claim 3, wherein the filler is eluted with water, the obtained eluent is subjected to fine filtration to remove suspended insoluble substances, and then is subjected to evaporation concentration, and the remaining filtrate is collected to obtain the herbal antibacterial disinfectant.

6. A preparation method of herbal antibacterial disinfectant as claimed in claim 5, wherein said used packed column is eluted with water by passing purified water, which is 5-10 times of the total volume of the packing in said packed column, through said packed column from top to bottom; and taking out the filler in the filler column, soaking the filler in water, and extruding to remove liquid.