Formaldehyde elimination agent with pure plant activity and preparation method thereof

Abstract

The invention relates to the technical field of formaldehyde treatment, in particular to a formaldehyde eliminating agent with pure plant activity and a preparation method thereof. The formaldehyde eliminating agent is prepared from the following raw materials in parts by weight: 20-30 parts of laver, 20-30 parts of oil tea meal, 10-15 parts of citrus peel, 10-15 parts of tea leaf residues, 5-10 parts of aloe leaves, 5-10 parts of mint leaves and 3-8 parts of licorice roots. According to the preparation method disclosed by the invention, the laver and the oil tea meal are subjected to mixed enzymolysis and carbonization treatment, enzymolysis provides a precursor which is easier to react for carbonization, and refined particles and released active ingredients can be subjected to pyrolysis and structural recombination more sufficiently in the carbonization process, so that a better pore structure and active site distribution are formed; and carbonization fixes and strengthens the action of active ingredients after enzymolysis, so that original water-soluble or unstable active substances are converted into a stable solid carbon-based material, the service life of the carbon-based material is prolonged, and the continuous purification capacity on formaldehyde is also improved.

Description

Technical Field

[0001] The present invention relates to the technical field of formaldehyde treatment, and specifically provides a pure plant active formaldehyde eliminator and a preparation method thereof. Background Art

[0002] Formaldehyde is one of the most common indoor air pollutants. This harmful gas mainly comes from indoor furniture and decorative materials such as wood veneers, paints, wallpapers, wall coverings, carpets, etc. Low-concentration formaldehyde can easily cause chronic respiratory diseases, reduced physical fitness of newborns, pregnancy syndromes, and may even cause cancer. High-concentration formaldehyde is even more harmful to the human nervous system, immune system, liver, etc.

[0003] In the prior art, Chinese patent: CN102989274A discloses a pure plant active formaldehyde eliminator, which is composed of the following components in weight percentages: 20 - 40% orange peel, 25 - 35% wormwood, 15 - 20% camphor tree leaves, and the balance is mint. The pure plant active formaldehyde eliminator of the present invention has no toxic and side effects on the human body and will not cause environmental pollution during the production process.

[0004] In the above patent, the plant raw materials are directly used without treatment, resulting in irregular shapes, few and small pores of the plant raw materials, limited overall specific surface area, and low proportion of the effective area that can contact formaldehyde, which limits the adsorption and decomposition efficiency of formaldehyde.

[0005] Based on this, the present invention provides a pure plant active formaldehyde eliminator and a preparation method thereof. Summary of the Invention

[0006] The purpose of the present invention is to provide a pure plant active formaldehyde eliminator and a preparation method thereof. The formaldehyde eliminator prepared by the present invention has a good formaldehyde removal rate and a high ingredient retention rate.

[0007] To achieve the above purpose, the present invention provides the following technical solution: A pure plant active formaldehyde eliminator, comprising the following raw materials in parts by weight: 20 - 30 parts of laver, 20 - 30 parts of camellia seed meal, 10 - 15 parts of citrus peel, 10 - 15 parts of tea dregs, 5 - 10 parts of aloe vera leaves, 5 - 10 parts of mint leaves, and 3 - 8 parts of licorice roots; The laver and camellia seed meal are subjected to mixed enzymatic hydrolysis and carbonization treatment; the citrus peel, tea dregs, aloe vera leaves, mint leaves, and licorice roots are subjected to pretreatment.

[0008] Preferably, the steps of mixing enzymolysis and carbonization treatment of the laver and camellia seed cake are as follows: Select dry laver, crush it with a universal crusher, and then sieve it through a 100-mesh sieve to obtain laver powder. Select the by-product camellia seed cake after pressing oil from camellia seeds, dry it in an oven at 60 °C until constant weight, take it out, crush it in a universal crusher, and sieve it through an 80-mesh sieve to obtain camellia seed cake powder. Add the camellia seed cake powder and laver powder to a stainless-steel container, stir with a mechanical stirrer at 50-100 r / min for 5-10 min to obtain a mixture. Add the composite enzyme solution to the stainless-steel container, stir with a mechanical stirrer at 100-300 r / min for 5-10 min, then place it in a water bath and carry out staged temperature control. The first stage is 40-45 °C for 3 h, the second stage is 50-55 °C for 2 h, and the third stage is 35-40 °C for 1 h. During the temperature control process, maintain the stirring speed at 100-300 r / min to obtain an enzymolysis solution and complete the mixed enzymolysis treatment.

[0009] Preferably, in the process of the mixed enzymolysis treatment, the volume-mass ratio of the composite enzyme solution to the mixture is 8:1, and the mass ratio of the camellia seed cake powder to the laver powder is 1:1.

[0010] Preferably, the preparation method of the composite enzyme solution is as follows: Add 8 g of sodium acetate and 800 ml of deionized water to a glass container, stir with a magnetic stirrer at 50-100 r / min for 5-10 min. After complete dissolution, add glacial acetic acid dropwise to adjust the pH value to 4.5-5.5, and then make up the volume to 1000 ml with deionized water and stir evenly to obtain a buffer solution. Add cellulase and alginate lyase to two new glass containers respectively, and add the buffer solution to the two new glass containers according to the mass ratio of cellulase or alginate lyase to the buffer solution of 1:10. At room temperature of 25 °C, stir and activate with a magnetic stirrer at 50-100 r / min for 30-40 min to obtain a cellulase solution and an alginate lyase solution. Add the cellulase solution, the alginate lyase solution and the remaining buffer solution to a new glass container, and stir with a magnetic stirrer at 50-80 r / min for 10-15 min to complete the preparation of the composite enzyme solution.

[0011] Preferably, the mass ratio of the cellulase solution, the alginate lyase solution and the buffer solution is (1-3):(0.5-2.5):1000.

[0012] Preferably, the carbonization treatment step is as follows: Place the enzymolysis solution in a centrifuge, centrifuge at 3000 - 5000 r / min for 10 - 15 minutes, collect the precipitate, wash it 2 - 3 times with deionized water, then place it in a forced-air drying oven and dry it at 60°C to constant weight. Then, pass nitrogen into the muffle furnace at a rate of 200 - 300 L / min in advance, with the nitrogen purity greater than 99.9%. After 30 - 60 minutes, place the dried precipitate in a crucible, put it into the muffle furnace, and heat it from room temperature to 450°C at a rate of 5°C / min. After reaching 450°C, maintain the nitrogen ventilation rate, keep it warm for 1.5 hours, and then cool it to room temperature with the furnace. During the heating, insulation, and cooling processes, continuously pass nitrogen at 200 - 300 L / min to complete the carbonization treatment.

[0013] Preferably, the pretreatment step of the citrus peel is as follows: Wash the citrus peel, cut it into small pieces, then send it into a drying oven and dry it at 60 - 70°C until the moisture content is lower than 10%. Then, place it in a universal grinder, crush it, and sieve it through a 40 - 60 mesh sieve to complete the pretreatment of the citrus peel; The pretreatment step of the tea residue is as follows: Collect the waste tea residue, rinse it 2 - 3 times with deionized water, send it into a drying oven, dry it at 70 - 80°C until the moisture content is lower than 8%, place it in a universal grinder, crush it, and sieve it through a 50 - 80 mesh sieve to complete the pretreatment of the tea residue.

[0014] Preferably, the pretreatment step of the aloe vera leaf is as follows: Wash the aloe vera leaf, peel it, take the leaf meat part, cut it into thin slices, place it in a vacuum drying oven, and dry it at a vacuum degree of -0.08 MPa to -0.1 MPa and a temperature of 50 - 60°C until the moisture content is lower than 5%. Then, place it in a universal grinder, crush it, and sieve it through a 60 - 80 mesh sieve to complete the pretreatment of the aloe vera leaf; The pretreatment step of the mint leaf is as follows: Wash the mint leaf, place it in a drying oven, dry it at 40 - 50°C until the moisture content is lower than 7%, place it in a universal grinder, crush it, and sieve it through a 40 - 60 mesh sieve to complete the pretreatment of the mint leaf.

[0015] Preferably, the pretreatment step of the licorice root is as follows: Wash the licorice root, slice it, place it in a drying oven, dry it at 60 - 70°C until the moisture content is lower than 8%, place it in a universal grinder, crush it, and sieve it through a 60 - 80 mesh sieve to complete the pretreatment of the licorice root.

[0016] A preparation method of a pure plant active formaldehyde eliminator includes the following steps: Step 1: Add the laver and camellia seed meal after hybrid enzymatic hydrolysis and carbonization treatment, the pretreated citrus peel, tea residue, aloe vera leaves, mint leaves and licorice roots and deionized water into a mixing kettle, with the material-liquid ratio of 1:(8 - 15), set the temperature at 50 - 60°C, stir with a mechanical stirrer at 200 - 500 r / min for 1 - 2 h, and then cool to room temperature to obtain a mixed solution; Step 2: Centrifuge the mixed solution at 3000 - 5000 r / min for 10 - 15 minutes by a centrifuge, collect the filtrate, and concentrate it under reduced pressure to 1 / 2 of the original volume at 50 - 60°C by a rotary evaporator to obtain a concentrated solution; Step 3: Place the concentrated solution in a spray dryer and spray dry it at 50 - 60°C to obtain a solid powder. Crush the solid powder with a universal crusher and sieve it through a 120-mesh sieve to complete the preparation of the pure plant active formaldehyde eliminator.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. In the present invention, during the enzymatic hydrolysis process, cellulase and alginase specifically decompose cell walls and cell membranes, destroy the original structures of laver and camellia seed meal, release the core active components of alginate polysaccharides, polyphenols and saponins, which contain hydroxyl and phenolic hydroxyl functional groups. Moreover, the enzymatic hydrolysis refines the raw material particles, increases the contact area. After carbonization treatment, the organic matter undergoes pyrolysis carbonization to form a rich pore structure, the specific surface area expands, enhancing the physical adsorption capacity. And the active components are reconstructed and modified to generate new functional groups of carbonyl and carboxyl, which react with formaldehyde through nucleophilic addition and oxidation-reduction reactions to achieve decomposition and transformation. The enzymatic hydrolysis provides a more reactive precursor for carbonization. The refined particles and released active components can undergo more complete pyrolysis and structural reorganization during the carbonization process, forming a better pore structure and active site distribution. Carbonization, on the other hand, fixes and strengthens the role of the active components after enzymatic hydrolysis, converting the originally water-soluble or unstable active substances into stable solid carbon-based materials, not only extending their service life but also enhancing the continuous purification ability of formaldehyde.

[0018] 2. In the present invention, after the citrus peel is dried and crushed, it forms a rich porous structure. The cellulose contained in the tea residue also has a certain porosity after pretreatment. Both can capture a large number of formaldehyde molecules through physical adsorption. The flavonoid compounds in the licorice root contain a large number of phenolic hydroxyl and carboxyl active functional groups, which can undergo addition and condensation chemical reactions with formaldehyde. The polysaccharide of aloe vera leaves has good film-forming properties and can form a protective film on the surface of objects to continuously capture the contacted formaldehyde. The volatile terpene compounds contained in mint leaves can not only adsorb formaldehyde but also cover up odors and improve air quality. The active components of various materials cooperate with the enzymatic hydrolysis and carbonization products of laver and camellia seed meal, giving full play to their respective advantages, forming a complete purification chain from adsorption to decomposition, making up for the limitations of single materials, and greatly improving the formaldehyde elimination efficiency and stability.

[0019] 3. In the present invention, all the raw materials selected in the entire preparation process, such as laver, camellia seed cake, and citrus peel, are plant-based raw materials, without adding any harmful chemical components, ensuring the safety of the product from the source. In the preparation process, the treatment methods such as enzymatic hydrolysis and carbonization adopted are relatively mild and will not produce toxic and harmful substances. Compared with traditional formaldehyde scavengers containing chemical components, this product will not release new pollutants into the environment during use, avoiding the problem of secondary pollution. Detailed implementation mode

[0020] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present invention.

[0021] Among them, it should be noted that the raw materials used in the following experiments are all commercially available raw materials.

[0022] Example 1: Weigh the following raw materials by weight as needed: 20 parts of laver, 20 parts of camellia seed cake, 10 parts of citrus peel, 10 parts of tea residue, 5 parts of aloe vera leaves, 5 parts of mint leaves, and 3 parts of licorice roots; The laver and camellia seed cake are subjected to mixed enzymatic hydrolysis and carbonization treatment; the citrus peel, tea residue, aloe vera leaves, mint leaves, and licorice roots are subjected to pretreatment.

[0023] The steps for the mixed enzymatic hydrolysis and carbonization treatment of laver and camellia seed cake are as follows: Select dry laver, crush it through a universal crusher, and sieve it through a 100-mesh sieve to obtain laver powder. Select the by-product camellia seed cake after pressing oil from camellia seeds, dry it in an oven at 60 °C to constant weight, take it out, place it in a universal crusher, crush it, and sieve it through an 80-mesh sieve to obtain camellia seed cake powder. Add the camellia seed cake powder and laver powder to a stainless steel container, stir with a mechanical stirrer at 50 r / min for 5 min to obtain a mixture. Add the compound enzyme solution to the stainless steel container, stir with a mechanical stirrer at 100 r / min for 5 - 10 min, then place it in a water bath and carry out staged temperature control. The first stage is maintained at 40 °C for 3 h, the second stage is maintained at 50 °C for 2 h, and the third stage is maintained at 35 °C for 1 h. During the temperature control process, keep the stirring speed at 100 r / min to obtain an enzymatic hydrolysate and complete the mixed enzymatic hydrolysis treatment.

[0024] During the mixed enzymatic hydrolysis treatment process, the volume-mass ratio of the compound enzyme solution to the mixture is 8:1, and the mass ratio of the camellia seed cake powder to the laver powder is 1:1.

[0025] The preparation method of the complex enzyme solution is as follows: Add 8 g of sodium acetate and 800 ml of deionized water to a glass container, stir at 50 r / min for 5 - 10 min with a magnetic stirrer. After complete dissolution, add glacial acetic acid dropwise to adjust the pH value to 4.5 - 5.5, and then make up the volume to 1000 ml with deionized water, stir evenly to obtain a buffer solution. Add cellulase and alginate lyase to two new glass containers respectively, and add the buffer solution to the two new glass containers according to the mass ratio of cellulase or alginate lyase to the buffer solution of 1:10. At room temperature of 25 °C, stir and activate at 50 r / min with a magnetic stirrer for 30 min to obtain cellulase solution and alginate lyase solution. Add the cellulase solution, alginate lyase solution and the remaining buffer solution to a new glass container, and stir at 50 r / min with a magnetic stirrer for 10 min to complete the preparation of the complex enzyme solution.

[0026] The mass ratio of the cellulase solution, alginate lyase solution and the buffer solution is 1:0.5:1000.

[0027] The carbonization treatment steps are as follows: Place the enzymolysis solution in a centrifuge, centrifuge at 3000 r / min for 10 minutes, collect the precipitate, wash it 2 times with deionized water, then place it in a blast drying oven and dry it at 60 °C to constant weight. Then, pass nitrogen into the muffle furnace at a rate of 200 L / min in advance, with the nitrogen purity greater than 99.9%. After 30 min, place the dried precipitate in a crucible, put it into the muffle furnace and heat it from room temperature to 450 °C at a rate of 5 °C / min. After reaching 450 °C, maintain the nitrogen ventilation rate, keep it warm for 1.5 hours, and then cool it to room temperature with the furnace. During the heating, insulation and cooling processes, continuously pass nitrogen at 200 L / min to complete the carbonization treatment.

[0028] The pretreatment steps of citrus peel are as follows: Wash the citrus peel, cut it into small pieces, then send it into a drying oven and dry it at 60 °C until the moisture content is lower than 10%. Then place it in a universal grinder, crush it and sieve it through a 40-mesh sieve to complete the pretreatment of the citrus peel; The pretreatment steps of tea residues are as follows: Collect the waste tea residues, rinse them 2 times with deionized water, send them into a drying oven, dry them at 70 °C until the moisture content is lower than 8%, place them in a universal grinder, crush them and sieve them through a 50-mesh sieve to complete the pretreatment of the tea residues.

[0029] The pretreatment steps of aloe leaves are as follows: Wash the aloe leaves, peel them, take the leaf meat part, cut it into thin slices, place it in a vacuum drying oven, dry it at a vacuum degree of -0.08 MPa and a temperature of 50 °C until the moisture content is lower than 5%, place it in a universal grinder, crush it and sieve it through a 60-mesh sieve to complete the pretreatment of the aloe leaves; The pretreatment steps of mint leaves are as follows: Wash the mint leaves, place them in a drying oven, dry at 40°C until the moisture content is less than 7%, place them in a universal grinder, crush them, and sieve them through a 40-mesh sieve to complete the pretreatment of mint leaves.

[0030] The pretreatment steps of licorice roots are as follows: Wash the licorice roots, slice them, place them in a drying oven, dry at 60°C until the moisture content is less than 8%, place them in a universal grinder, crush them, and sieve them through a 60-mesh sieve to complete the pretreatment of licorice roots.

[0031] A preparation method of a pure plant active formaldehyde eliminator includes the following steps: Step 1: Add the laver and camellia seed meal after mixed enzymatic hydrolysis and carbonization treatment, the pretreated citrus peel, tea residue, aloe vera leaves, mint leaves and licorice roots, and deionized water to a mixing kettle, with a material-liquid ratio of 1:8, set the temperature at 50°C, stir with a mechanical stirrer at 200 r / min for 1 h, and then cool to room temperature to obtain a mixed solution; Step 2: Centrifuge the mixed solution at 3000 r / min for 10 minutes, collect the filtrate, and concentrate it under reduced pressure to 1 / 2 of the original volume at 50°C by a rotary evaporator to obtain a concentrated solution; Step 3: Spray-dry the concentrated solution in a spray dryer at 50°C to obtain a solid powder, crush the solid powder in a universal grinder and sieve it through a 120-mesh sieve to complete the preparation of the pure plant active formaldehyde eliminator.

[0032] Example 2: Weigh the following raw materials according to requirements: 25 parts of laver, 25 parts of camellia seed meal, 12 parts of citrus peel, 12 parts of tea residue, 7 parts of aloe vera leaves, 7 parts of mint leaves and 5 parts of licorice roots; Perform mixed enzymatic hydrolysis and carbonization treatment on laver and camellia seed meal; perform pretreatment on citrus peel, tea residue, aloe vera leaves, mint leaves and licorice roots.

[0033] The steps of performing mixed enzymatic hydrolysis and carbonization treatment on laver and camellia seed meal are as follows: Select dry laver, crush it with a universal grinder, and sieve it through a 100-mesh sieve to obtain laver powder. Select the by-product camellia seed meal after pressing camellia seeds for oil, dry it in a drying oven at 60°C to constant weight, take it out, crush it in a universal grinder and sieve it through an 80-mesh sieve to obtain camellia seed meal powder. Add the camellia seed meal powder and laver powder to a stainless steel container, stir with a mechanical stirrer at 72 r / min for 7 min to obtain a mixture. Add the complex enzyme solution to the stainless steel container, stir with a mechanical stirrer at 200 r / min for 7 min, then place it in a water bath and perform staged temperature control. The first stage is 42°C for 3 h, the second stage is 52°C for 2 h, and the third stage is 38°C for 1 h. Keep the stirring speed at 200 r / min during the temperature control process to obtain an enzymatic hydrolysate and complete the mixed enzymatic hydrolysis treatment.

[0034] In the process of combined enzymatic hydrolysis treatment, the volume-to-mass ratio of the combined enzyme solution to the mixture is 8:1, and the mass ratio of camellia seed meal powder to laver powder is 1:1.

[0035] The preparation method of the combined enzyme solution is as follows: Add 8 g of sodium acetate and 800 ml of deionized water to a glass container, stir at 75 r / min for 7 min with a magnetic stirrer. After complete dissolution, add glacial acetic acid drop by drop to adjust the pH value to 4.5 - 5.5, and then make up the volume to 1000 ml with deionized water and stir evenly to obtain a buffer solution. Add cellulase and alginate lyase to two new glass containers respectively, and add the buffer solution to the two new glass containers according to the mass ratio of cellulase or alginate lyase to the buffer solution of 1:10. At room temperature of 25 °C, stir and activate at 75 r / min for 35 min with a magnetic stirrer to obtain cellulase solution and alginate lyase solution. Add the cellulase solution, alginate lyase solution and the remaining buffer solution to a new glass container, and stir at 50 - 80 r / min for 10 - 15 min with a magnetic stirrer to complete the preparation of the combined enzyme solution.

[0036] The mass ratios of the cellulase solution, alginate lyase solution and buffer solution are 5:1.5:1000.

[0037] The carbonization treatment steps are as follows: Place the enzymatic hydrolysate in a centrifuge, centrifuge at 4000 r / min for 12 minutes, collect the precipitate, wash it 3 times with deionized water, then place it in a forced-air drying oven and dry it at 60 °C to constant weight. Then, first introduce nitrogen into the muffle furnace at a rate of 250 L / min, with the nitrogen purity greater than 99.9%, for 45 min. After that, place the dried precipitate in a crucible and put it into the muffle furnace. Heat it from room temperature to 450 °C at a rate of 5 °C / min. After reaching 450 °C, maintain the nitrogen ventilation rate, keep it warm for 1.5 hours, and then cool it to room temperature with the furnace. During the heating, insulation and cooling processes, continuously introduce nitrogen at 250 L / min to complete the carbonization treatment.

[0038] The pretreatment steps of citrus peel are as follows: Wash the citrus peel, cut it into small pieces, then send it into a drying oven and dry it at 65 °C until the moisture content is lower than 10%. Then place it in a universal grinder, crush it and sieve it through a 50-mesh sieve to complete the pretreatment of the citrus peel; The pretreatment steps of tea residue are as follows: Collect the waste tea residue, rinse it 3 times with deionized water, send it into a drying oven and dry it at 75 °C until the moisture content is lower than 8%. Then place it in a universal grinder, crush it and sieve it through a 60-mesh sieve to complete the pretreatment of the tea residue.

[0039] The pretreatment steps of aloe vera leaves are as follows: Wash the aloe vera leaves, peel them, take the mesophyll part, cut it into thin slices, place it in a vacuum drying oven, dry it at a vacuum degree of -0.09 MPa and a temperature of 55 °C until the moisture content is lower than 5%, place it in a universal grinder, crush it and sieve it through a 70-mesh sieve to complete the pretreatment of aloe vera leaves; The pretreatment steps of mint leaves are as follows: Wash the mint leaves, place them in a drying oven, dry them at 45 °C until the moisture content is lower than 7%, place them in a universal grinder, crush them and sieve them through a 50-mesh sieve to complete the pretreatment of mint leaves.

[0040] The pretreatment steps of licorice roots are as follows: Wash the licorice roots, slice them, place them in a drying oven, dry them at 65 °C until the moisture content is lower than 8%, place them in a universal grinder, crush them and sieve them through a 70-mesh sieve to complete the pretreatment of licorice roots.

[0041] A preparation method of a pure plant active formaldehyde eliminator includes the following steps: Step 1: Add the laver and camellia seed meal after mixed enzymatic hydrolysis and carbonization treatment, the pretreated citrus peel, tea residue, aloe vera leaves, mint leaves and licorice roots and deionized water to a mixing kettle, with a material-liquid ratio of 1:11, set the temperature at 55 °C, stir with a mechanical stirrer at 300 r / min for 1.5 h, and then cool to room temperature to obtain a mixed solution; Step 2: Centrifuge the mixed solution at 4000 r / min for 12 minutes, collect the filtrate, and concentrate it under reduced pressure to 1 / 2 of the original volume at 55 °C by a rotary evaporator to obtain a concentrated solution; Step 3: Spray-dry the concentrated solution in a spray dryer at 55 °C to obtain a solid powder, crush the solid powder in a universal grinder and sieve it through a 120-mesh sieve to complete the preparation of the pure plant active formaldehyde eliminator.

[0042] Example 3: Weigh the following raw materials according to requirements: 30 parts of laver, 30 parts of camellia seed meal, 15 parts of citrus peel, 15 parts of tea residue, 10 parts of aloe vera leaves, 10 parts of mint leaves and 8 parts of licorice roots; Perform mixed enzymatic hydrolysis and carbonization treatment on laver and camellia seed meal; perform pretreatment on citrus peel, tea residue, aloe vera leaves, mint leaves and licorice roots.

[0043] The steps of mixed enzymatic hydrolysis and carbonization of laver and camellia seed meal are as follows: Select dried laver, crush it with a universal crusher, and sieve it through a 100-mesh sieve to obtain laver powder. Select the by-product camellia seed meal after camellia seeds are pressed for oil, dry it in an oven at 60°C until constant weight, take it out, crush it in a universal crusher, and sieve it through an 80-mesh sieve to obtain camellia seed meal powder. Add the camellia seed meal powder and laver powder to a stainless-steel container, stir with a mechanical stirrer at 100 r / min for 10 min to obtain a mixture. Add the complex enzyme solution to the stainless-steel container, stir with a mechanical stirrer at 300 r / min for 10 min, then place it in a water bath and carry out staged temperature control. The first stage is at 45°C for 3 h, the second stage is at 55°C for 2 h, and the third stage is at 40°C for 1 h. During the temperature control process, maintain the stirring speed at 300 r / min to obtain the enzyme hydrolysis solution and complete the mixed enzymatic hydrolysis treatment.

[0044] During the mixed enzymatic hydrolysis treatment process, the volume-mass ratio of the complex enzyme solution to the mixture is 8:1, and the mass ratio of the camellia seed meal powder to the laver powder is 1:1.

[0045] The preparation method of the complex enzyme solution is as follows: Add 8 g of sodium acetate and 800 ml of deionized water to a glass container, stir with a magnetic stirrer at 100 r / min for 10 min. After complete dissolution, gradually add glacial acetic acid to adjust the pH value to 4.5 - 5.5, and then make up the volume to 1000 ml with deionized water and stir evenly to obtain the buffer solution. Add cellulase and alginate lyase to two new glass containers respectively, and add the buffer solution to the two new glass containers according to the mass ratio of cellulase or alginate lyase to the buffer solution of 1:10. At room temperature of 25°C, stir and activate with a magnetic stirrer at 100 r / min for 40 min to obtain the cellulase solution and the alginate lyase solution. Add the cellulase solution, the alginate lyase solution and the remaining buffer solution to a new glass container, and stir with a magnetic stirrer at 80 r / min for 15 min to complete the preparation of the complex enzyme solution.

[0046] The mass ratio of the cellulase solution, the alginate lyase solution and the buffer solution is 3:2.5:1000.

[0047] The carbonization treatment steps are as follows: Place the enzyme hydrolysis solution in a centrifuge, centrifuge at 4000 r / min for 10 - 15 minutes, collect the precipitate, wash it 3 times with deionized water, then place it in a blast drying oven and dry it at 60°C until constant weight. Then, let the muffle furnace pass nitrogen at a rate of 300 L / min in advance, with the nitrogen purity greater than 99.9%. After 60 min, place the dried precipitate in a crucible, put it into the muffle furnace, and heat it from room temperature to 450°C at a rate of 5°C / min. After reaching 450°C, maintain the nitrogen ventilation rate, keep it warm for 1.5 hours, and then cool it to room temperature with the furnace. During the heating, insulation and cooling processes, continuously pass nitrogen at 300 L / min to complete the carbonization treatment.

[0048] The pretreatment steps of citrus peel are as follows: Wash the citrus peel, cut it into small pieces, send it into a drying oven, dry it at 70 °C until the moisture content is lower than 10%, place it in a universal crusher, crush it and sieve it through a 60-mesh sieve, then complete the pretreatment of citrus peel; The pretreatment steps of tea dregs are as follows: Collect the waste tea dregs, rinse them with deionized water 2 - 3 times, send them into a drying oven, dry them at 80 °C until the moisture content is lower than 8%, place them in a universal crusher, crush them and sieve them through an 80-mesh sieve, then complete the pretreatment of tea dregs.

[0049] The pretreatment steps of aloe vera leaves are as follows: Wash the aloe vera leaves, peel them, take the leaf meat part, cut it into thin slices, place it in a vacuum drying oven, dry it at a vacuum degree of -0.1 MPa and a temperature of 60 °C until the moisture content is lower than 5%, place it in a universal crusher, crush it and sieve it through an 80-mesh sieve, then complete the pretreatment of aloe vera leaves; The pretreatment steps of mint leaves are as follows: Wash the mint leaves, place them in a drying oven, dry them at 50 °C until the moisture content is lower than 7%, place them in a universal crusher, crush them and sieve them through a 60-mesh sieve, then complete the pretreatment of mint leaves.

[0050] The pretreatment steps of licorice roots are as follows: Wash the licorice roots, slice them, place them in a drying oven, dry them at 70 °C until the moisture content is lower than 8%, place them in a universal crusher, crush them and sieve them through an 80-mesh sieve, then complete the pretreatment of licorice roots.

[0051] A preparation method of a pure plant active formaldehyde eliminator includes the following steps: Step 1: Add the laver and camellia seed cake after mixed enzymatic hydrolysis and carbonization treatment, the pretreated citrus peel, tea dregs, aloe vera leaves, mint leaves and licorice roots and deionized water to a mixing kettle, with a material-liquid ratio of 1:15, set the temperature at 50 - 60 °C, stir with a mechanical stirrer at 500 r / min for 2 h, then cool to room temperature to obtain a mixed solution; Step 2: Centrifuge the mixed solution at 5000 r / min for 15 minutes, collect the filtrate, and concentrate it under reduced pressure to 1 / 2 of the original volume at 60 °C through a rotary evaporator to obtain a concentrated solution; Step 3: Place the concentrated solution in a spray dryer and spray dry it at 60 °C to obtain a solid powder. Crush the solid powder in a universal crusher and sieve it through a 120-mesh sieve to complete the preparation of the pure plant active formaldehyde eliminator.

[0052] Comparative Example 1. The difference between this comparative example and Experimental Example 1 is that: In this comparative example, laver was not added during the mixed enzymatic hydrolysis and carbonization treatment of laver and camellia seed cake.

[0053] Comparative Example 2: The difference between this comparative example and Experiment 1 is that: in this comparative example, no camellia seed meal was added during the mixed enzymatic hydrolysis and carbonization treatment of laver and camellia seed meal.

[0054] Comparative Example 3: The difference between this comparative example and Experiment 1 is that: in this comparative example, laver and camellia seed meal were not subjected to mixed enzymatic hydrolysis and carbonization treatment.

[0055] Comparative Example 4: The difference between this comparative example and Experiment 1 is that: licorice root was not added during the preparation process of this comparative example.

[0056] Performance test: Perform performance tests on the pure plant active formaldehyde scavengers prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4: Formaldehyde removal rate test: Refer to Appendix D “Determination of formaldehyde (phenol reagent spectrophotometry)” of “GB / T18883-2022 Indoor Air Quality Standard”. Inject formaldehyde gas into a 1m³ airtight environmental chamber (25±1°C, RH50%±5%). Weigh 1.00g of the pure plant active formaldehyde scavenger and spread it flat in a petri dish. Place it at the center of the chamber. Sample and measure the formaldehyde concentration in the chamber after 24h, and calculate the formaldehyde removal rate; Effective ingredient retention rate test: Place the pure plant active formaldehyde scavenger in an environment of 30°C and 60% humidity for 30 days (simulating daily storage). On the 30th day, take 3g of the pure plant active formaldehyde scavenger and detect its purification effect according to the “formaldehyde removal rate test” method. Compare the change in the removal rate at different time points to evaluate the attenuation degree of the active ingredient.

[0057] The obtained test data are recorded in the following table:

[0058] By comparing and analyzing the relevant data in the table, it can be seen that the formaldehyde scavenger prepared by the present invention through a pure plant active formaldehyde scavenger and its preparation method not only has a good formaldehyde removal rate but also has a high ingredient retention rate. This shows that the pure plant active formaldehyde scavenger and its preparation method provided by the present invention have a broader market prospect and are more suitable for promotion.

[0059] In the description of this specification, the descriptions referring to terms such as “one embodiment”, “example”, “specific example”, etc. mean that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0060] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A formaldehyde eliminator with pure plant activity, characterized in that: It includes the following raw materials in parts by weight: 20 - 30 parts of laver, 20 - 30 parts of camellia seed cake, 10 - 15 parts of citrus peel, 10 - 15 parts of tea dregs, 5 - 10 parts of aloe vera leaves, 5 - 10 parts of mint leaves and 3 - 8 parts of licorice roots; The laver and camellia seed cake are subjected to mixed enzymolysis and carbonization treatment; the citrus peel, tea dregs, aloe vera leaves, mint leaves and licorice roots are subjected to pretreatment.

2. The formaldehyde eliminator with pure plant activity according to claim 1, characterized in that The steps of the mixed enzymolysis and carbonization treatment of the laver and camellia seed cake are as follows: Select dry laver, crush it through a universal crusher, and sieve it through a 100 - mesh sieve to obtain laver powder. Select the by - product camellia seed cake after pressing camellia seeds for oil, dry it in an oven at 60 °C to constant weight, take it out, crush it in a universal crusher and sieve it through an 80 - mesh sieve to obtain camellia seed cake powder. Add the camellia seed cake powder and laver powder to a stainless - steel container, stir with a mechanical stirrer at 50 - 100 r / min for 5 - 10 min to obtain a mixture. Add the composite enzyme solution to the stainless - steel container, stir with a mechanical stirrer at 100 - 300 r / min for 5 - 10 min, then place it in a water - bath pot for staged temperature control. The first stage is at 40 - 45 °C for 3 h, the second stage is at 50 - 55 °C for 2 h, and the third stage is at 35 - 40 °C for 1 h. During the temperature - control process, keep the stirring speed at 100 - 300 r / min to obtain an enzymolysis solution, and complete the mixed enzymolysis treatment.

3. The formaldehyde eliminator with pure plant activity according to claim 2, characterized in that, During the mixed enzymolysis treatment process, the volume - mass ratio of the composite enzyme solution to the mixture is 8:1, and the mass ratio of the camellia seed cake powder to the laver powder is 1:

1.

4. The formaldehyde eliminator with pure plant activity according to claim 3, characterized in that, The preparation method of the composite enzyme solution is as follows: Add 8 g of sodium acetate and 800 ml of deionized water to a glass container, stir with a magnetic stirrer at 50 - 100 r / min for 5 - 10 min. After complete dissolution, add glacial acetic acid drop by drop to adjust the pH value to 4.5 - 5.5, then make up the volume to 1000 ml with deionized water and stir evenly to obtain a buffer solution. Add cellulase and alginate lyase to two new glass containers respectively, and add the buffer solution to the two new glass containers according to the mass ratio of cellulase or alginate lyase to the buffer solution of 1:

10. At room temperature of 25 °C, stir and activate with a magnetic stirrer at 50 - 100 r / min for 30 - 40 min to obtain a cellulase solution and an alginate lyase solution. Add the cellulase solution, alginate lyase solution and the remaining buffer solution to a new glass container, stir with a magnetic stirrer at 50 - 80 r / min for 10 - 15 min to complete the preparation of the composite enzyme solution.

5. The formaldehyde eliminator with pure plant activity according to claim 4, characterized in that, The mass ratio of the cellulase solution, alginate lyase solution and buffer solution is (1 - 3):(0.5 - 2.5):1000.

6. The formaldehyde eliminator with pure plant activity according to claim 1, characterized in that, The carbonization treatment step is as follows: Place the enzymatic hydrolysate in a centrifuge and centrifuge at 3000 - 5000 r / min for 10 - 15 minutes. Collect the precipitate, wash it 2 - 3 times with deionized water, then place it in a blast drying oven and dry it at 60°C until constant weight. Then, pass nitrogen into the muffle furnace at a rate of 200 - 300 L / min in advance, with the nitrogen purity greater than 99.9%. After 30 - 60 minutes, place the dried precipitate in a crucible, put it into the muffle furnace, and heat it from room temperature to 450°C at a rate of 5°C / min. After reaching 450°C, maintain the nitrogen ventilation rate, keep it warm for 1.5 hours, and then cool it to room temperature with the furnace. During the heating, insulation, and cooling processes, continuously pass nitrogen at 200 - 300 L / min to complete the carbonization treatment.

7. A formaldehyde eliminator with pure plant activity according to claim 1, characterized in that, The pretreatment step of the citrus peel is as follows: Wash the citrus peel, cut it into small pieces, then send it into a drying oven and dry it at 60 - 70°C until the moisture content is less than 10%. Then place it in a universal crusher, crush it, and sieve it through a 40 - 60 mesh sieve to complete the pretreatment of the citrus peel. The pretreatment step of the tea residue is as follows: Collect the waste tea residue, rinse it 2 - 3 times with deionized water, send it into a drying oven, dry it at 70 - 80°C until the moisture content is less than 8%, place it in a universal crusher, crush it, and sieve it through a 50 - 80 mesh sieve to complete the pretreatment of the tea residue.

8. A formaldehyde eliminator with pure plant activity according to claim 1, characterized in that, The pretreatment step of the aloe vera leaf is as follows: Wash the aloe vera leaf, peel it, take the mesophyll part, cut it into thin slices, place it in a vacuum drying oven, and dry it at a vacuum degree of -0.08 MPa to -0.1 MPa and a temperature of 50 - 60°C until the moisture content is less than 5%. Then place it in a universal crusher, crush it, and sieve it through a 60 - 80 mesh sieve to complete the pretreatment of the aloe vera leaf. The pretreatment step of the mint leaf is as follows: Wash the mint leaf, place it in a drying oven, dry it at 40 - 50°C until the moisture content is less than 7%, place it in a universal crusher, crush it, and sieve it through a 40 - 60 mesh sieve to complete the pretreatment of the mint leaf.

9. The formaldehyde eliminator with pure plant activity according to claim 1, characterized in that, The pretreatment step of the licorice root is as follows: Wash the licorice root, slice it, place it in a drying oven, dry it at 60 - 70°C until the moisture content is less than 8%, place it in a universal crusher, crush it, and sieve it through a 60 - 80 mesh sieve to complete the pretreatment of the licorice root.

10. A preparation method of a formaldehyde eliminator with pure plant activity, referring to a formaldehyde eliminator with pure plant activity described in any one of claims 1-9, characterized in that, It includes the following steps: Step 1: Add the mixed and carbonized laver and camellia seed meal, the pretreated citrus peel, tea residue, aloe vera leaf, mint leaf, and licorice root, and deionized water to a mixing kettle. The material-liquid ratio is 1:(8 - 15). Set the temperature at 50 - 60°C, stir with a mechanical stirrer at 200 - 500 r / min for 1 - 2 h, and then cool it to room temperature to obtain a mixed solution. Step 2: Centrifuge the mixed solution in a centrifuge at 3000 - 5000 r / min for 10 - 15 minutes, collect the filtrate, and concentrate it to 1 / 2 of the original volume under reduced pressure at 50 - 60°C using a rotary evaporator to obtain a concentrated solution. Step 3: Place the concentrated solution in a spray dryer and spray-dry it at 50 - 60°C to obtain a solid powder. Crush the solid powder with a universal crusher and sieve it through a 120 mesh sieve to complete the preparation of the pure plant active formaldehyde scavenger.

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