CN114618448B - Deodorizing and purifying agent for kitchen waste and preparation method thereof - Google Patents

Deodorizing and purifying agent for kitchen waste and preparation method thereof Download PDF

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CN114618448B
CN114618448B CN202210275881.2A CN202210275881A CN114618448B CN 114618448 B CN114618448 B CN 114618448B CN 202210275881 A CN202210275881 A CN 202210275881A CN 114618448 B CN114618448 B CN 114618448B
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biomass charcoal
kitchen waste
deodorizing
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CN114618448A (en
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钱栢吉
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Shanghai Huyu Environmental Protection Group Co ltd
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Abstract

The invention discloses a kitchen waste deodorizing and purifying agent and a preparation method thereof. The kitchen waste deodorizing and purifying agent has extremely strong adsorption capacity on odor molecules, and can effectively remove odor molecules generated by kitchen waste and purify air.

Description

Deodorizing and purifying agent for kitchen waste and preparation method thereof
Technical Field
The invention relates to the field of deodorizing and purifying agents, in particular to a kitchen waste deodorizing and purifying agent and a preparation method thereof.
Background
Kitchen garbage, also called organic garbage and perishable garbage, refers to perishable biomass domestic waste such as food material waste, leftovers, expired food, melon, skin, fruit and kernel, green plants of flowers, chinese medicine dregs and the like, and has the characteristics of perishability, low calorific value, rich organic matter content and the like.
In the process of stacking kitchen waste, malodor is easy to generate, particularly in the high-temperature stage in summer, the malodor generation phenomenon is more obvious and severe, and the odor brings a plurality of annoyances to the life of people, so that the searching of a purifying agent capable of effectively purifying the kitchen waste to generate malodor is very necessary.
The existing deodorizing and sterilizing agent has various deodorizing modes, such as physical adsorption, chemical reaction deodorization, microbial catalytic degradation deodorization and the like. These deodorizing methods are generally incompatible, and one formulation can only have one deodorizing function and means, thus limiting the efficacy of the deodorizing agent.
Chinese patent No. CN112958589a discloses a deodorizing agent for garbage disposal, which comprises the following raw materials in parts by weight: 25-35 parts of super absorbent resin, 12-16 parts of cyclodextrin, 3-8 parts of potassium dichloroisocyanate, 6-9 parts of activated alumina, 3-8 parts of neutral anhydrous mirabilite, 1-5 parts of glyoxylic acid hydrate, 6-12 parts of N, N-dihydrocarbyl amino allylsulfonate, 1-3 parts of 3, 4-dihydro-2H-pyran, 1-3 parts of polyvinylpyrrolidone, 5-10 parts of 4- (1-piperidinyl) -3-nitrophenylacetamide, 3-7 parts of plant extract, 1-3 parts of nano titanium dioxide, 1-3 parts of regulating stabilizer and 0.5-2 parts of compatilizer; the deodorizing and sterilizing device can perform deodorizing and sterilizing in various modes at the same time, can ensure that the deodorizing modes performed at the same time have no interference and interaction, but has limited deodorizing effect and limited odor absorbing capability.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a kitchen waste deodorizing and purifying agent and a preparation method thereof.
The preparation method of the kitchen waste deodorizing and purifying agent comprises the following steps:
(1) Adding 30-50 parts of acrylic acid into 100-140 parts of water according to parts by weight, and regulating the pH to 7.0-8.0 by using 1-2M NaOH aqueous solution to obtain a mixed solution A;
(2) Uniformly mixing 1-3 parts of cross-linking agent, 4-6 parts of calcium propionate, 15-25 parts of modified biomass charcoal sulfonic acid and 130-160 parts of mixed solution A obtained in the step (1) by weight, stirring at the speed of 200-400 r/min and the temperature of 50-70 ℃ for 0.5-1.5 hours, then adding 2-4 parts of initiator, keeping the temperature and stirring rate unchanged, and reacting for 5-7 hours to obtain a gelatinous polymer;
(3) Granulating the gel polymer obtained in the step (2), and vacuum drying at 70-90 ℃ for 1-3 hours to obtain the kitchen waste deodorizing and purifying agent, wherein the particle size of the kitchen waste deodorizing and purifying agent is 0.4-1.0 cm.
Preparing acrylic acid into aqueous solution with a certain concentration, adjusting proper pH value by NaOH, adding a cross-linking agent and an initiator, and reacting to produce the microgel polymer. The microgel is an ultra-high molecular compound, has the molecular weight of 2000-3000 ten thousand, is colorless and odorless, is harmless to human body, has the molecular weight of common odor molecules below 400, and can generate strong intermolecular attraction due to the large molecular weight difference between molecules of the microgel, so as to adsorb odor components. However, due to the unique hollow shell structure of the microgel, the thermal collapse phenomenon is easy to generate, the internal structure of the microgel is damaged, and the adsorption capacity to odor is reduced.
The preparation method of the modified biomass charcoal sulfonic acid comprises the following steps:
s1: cleaning pine needles, airing, crushing, sieving with a 150-250 mesh sieve, and taking undersize to obtain pine needle powder;
s2: soaking 3000-5000 parts of pine needle powder obtained in the step S1 in 6500-10000 parts of 1.0-2.0M KCl water solution, stirring for 0.5-1.5 hours at a rotating speed of 200-400 r/min, filtering, taking a filter cake, and drying at 50-70 ℃ for 8-12 hours to obtain a precursor;
s3: transferring the precursor obtained in the step S2 into a tube furnace, heating to 460-500 ℃ at an initial temperature of 20-25 ℃ at a heating rate of 4-6 ℃/min, preserving heat for 1-3 hours at 460-500 ℃, then cooling to 20-25 ℃ at a cooling rate of 8-12 ℃/min, and grinding to obtain a biomass charcoal material;
s4: adding 25-35 parts by weight of the biomass charcoal material obtained in the step S3 into 300-500 parts by weight of concentrated sulfuric acid with the mass fraction of 97-98%, then transferring into a reaction kettle, keeping the temperature at 150-170 ℃ for 7-9 hours, naturally cooling to room temperature, filtering, washing to be neutral, and taking a filter cake to be dried in vacuum at 70-90 ℃ for 10-14 hours to obtain biomass charcoal sulfonic acid;
s5: according to parts by weight, mixing 15-25 parts of biomass charcoal sulfonic acid obtained in the step S4, 4-6 parts of metal organic framework ZIF-78 and 40-60 parts of water uniformly, heating to 35-45 ℃, stirring for 0.5-1.5 hours at a rotating speed of 150-250 r/min, filtering, and drying a filter cake at 45-55 ℃ for 10-14 hours to obtain the modified biomass charcoal sulfonic acid.
The biomass charcoal sulfonic acid is obtained by using pine needle powder rich in cellulose as a raw material and performing carbonization, sulfuric acid impregnation and sulfonation. Grafting the carbon skeleton with sulfonic acid group to form the two-dimensional lamellar organic covalent skeleton material containing sulfonic acid group. The two-dimensional layered carbon skeleton structure has a trapping effect on bacteria, a strong adsorption effect and a certain sterilization effect; the sulfonic acid group can enhance the interaction between the carbon skeleton and the nitrogen-containing compound, and is helpful for improving the adsorption of the carbon skeleton to odor molecules. During synthesis of the microgel, biomass charcoal sulfonic acid is added, the microgel wraps the biomass charcoal sulfonic acid in a shell-shaped structure of the microgel, so that a supporting effect is achieved on the shell structure of the microgel, the phenomenon of thermally induced collapse of the microgel is reduced, and the adsorption effect of the microgel on odor molecules is promoted.
The biomass charcoal sulfonic acid is compounded with the metal organic framework, and the metal organic framework material can interact with bacterial cell membranes, so that the sterilization effect is achieved; meanwhile, the metal organic framework can enhance the mechanical strength of the carbon framework in the biomass charcoal sulfonic acid, when the microgel coats the modified biomass charcoal sulfonic acid, the supporting effect on the shell structure of the microgel is further improved, the swelling of the microgel is increased, and the microgel is helped to adsorb surrounding odor molecules into particles.
Preferably, the preparation method of the modified biomass charcoal sulfonic acid comprises the following steps:
s1: cleaning pine needles, airing, crushing, sieving with a 150-250 mesh sieve, and taking undersize to obtain pine needle powder;
s2: soaking 3000-5000 parts of pine needle powder obtained in the step S1 in 6500-10000 parts of 1.0-2.0M KCl water solution, stirring for 0.5-1.5 hours at a rotating speed of 200-400 r/min, filtering to obtain a filter cake, and drying at 50-70 ℃ for 8-12 hours to obtain a precursor;
s3: transferring the precursor obtained in the step S2 into a tube furnace, heating to 460-500 ℃ at an initial temperature of 20-25 ℃ at a heating rate of 4-6 ℃/min, preserving heat for 1-3 hours at 460-500 ℃, then cooling to 20-25 ℃ at a cooling rate of 8-12 ℃/min, and grinding to obtain a biomass charcoal material;
s4: adding 25-35 parts by weight of the biomass charcoal material obtained in the step S3 into 300-500 parts by weight of concentrated sulfuric acid with the mass fraction of 97-98%, then transferring into a reaction kettle, keeping the temperature at 150-170 ℃ for 7-9 hours, naturally cooling to room temperature, filtering, washing to be neutral, and taking a filter cake to be dried in vacuum at 70-90 ℃ for 10-14 hours to obtain biomass charcoal sulfonic acid;
s5: according to parts by weight, uniformly mixing 15-25 parts of biomass charcoal sulfonic acid obtained in the step S4, 4-6 parts of metal organic framework ZIF-78, 1-3 parts of protein and 40-60 parts of water, heating to 35-45 ℃, stirring for 0.5-1.5 hours at a rotating speed of 150-250 r/min, filtering, and drying a filter cake at 45-55 ℃ for 10-14 hours to obtain the modified biomass charcoal sulfonic acid.
The protein is at least one of sericin, silk fibroin and soybean protein.
Preferably, the protein is a mixture of sericin and silk fibroin according to a mass ratio of 1 (2-3).
Sericin and silk fibroin are added into modified biomass charcoal sulfonic acid, and ionic bonds or hydrogen bonds are generated through the crosslinking action of sulfonate groups and proteins, so that the modified biomass charcoal sulfonic acid is fixed on the surface of the biomass charcoal sulfonic acid. The spherical structure of sericin, the biological sponge-like absorption of which can promote the load enhancement of microgel; the filiform structure of the silk fibroin can promote the molecular migration of odor molecules in the microgel, and effectively enhance the adsorption effect of the microgel; the sericin and the silk fibroin are synergistic, so that the adsorption capacity of the microgel to odor molecules is enhanced. Meanwhile, sericin and silk fibroin have good antibacterial effects on gram-negative bacteria and gram-positive bacteria, and the antibacterial effect of the modified biomass charcoal sulfonic acid can be further improved.
The cross-linking agent is at least one of N, N' -methylene bisacrylamide and ethyl orthosilicate.
Preferably, the crosslinking agent is N, N' -methylenebisacrylamide.
The initiator is at least one of ammonium persulfate and azo-diisobutylamidine hydrochloride.
Preferably, the initiator is ammonium persulfate.
The invention has the beneficial effects that: the kitchen waste deodorizing and purifying agent has extremely strong adsorption capacity on odor molecules, and can effectively remove odor molecules generated by kitchen waste and purify air. According to the invention, the microgel ultrahigh molecular compound is prepared, and the modified biomass charcoal sulfonic acid is added to support the shell structure of the microgel, so that the occurrence of thermal collapse is prevented, the internal space structure is stabilized, and the absorption effect of the microgel ultrahigh molecular compound on odor molecules is promoted.
Detailed Description
The raw materials used in the examples are as follows:
pine needles purchased from south-screen mountain agricultural products limited, breeds: pinus massoniana.
Metal organic frameworks ZIF-78 purchased from sienna ziyue biotechnology limited, model: ZIF-78, content 99.9%.
Sericin purchased from shandong hope chemical industry limited, CAS number: 60650-89-7, food grade, 99%.
Silk fibroin, purchased from shandong herd new materials limited, CAS number: 96690-41-4 food grade with 99% content.
Example 1
The preparation method of the kitchen waste deodorizing and purifying agent comprises the following steps:
(1) Adding 40 parts of acrylic acid into 120 parts of water according to parts by weight, and regulating the pH to 7.5 by using a 1M NaOH aqueous solution to obtain a mixed solution A;
(2) Uniformly mixing 2 parts of cross-linking agent, 5 parts of calcium propionate, 20 parts of modified biomass charcoal sulfonic acid and 150 parts of mixed solution A obtained in the step (1) by weight, stirring at the speed of 300r/min at 60 ℃ for 1 hour, then adding 3 parts of initiator, keeping the temperature and stirring rate unchanged, and reacting for 6 hours to obtain a gelatinous polymer;
(3) Granulating the gel polymer obtained in the step (2), and vacuum drying at 80 ℃ for 2 hours to obtain the kitchen waste deodorizing and purifying agent, wherein the particle size of the kitchen waste deodorizing and purifying agent is 0.5cm.
The preparation method of the modified biomass charcoal sulfonic acid comprises the following steps:
s1: cleaning pine needles, airing, crushing, sieving with a 200-mesh sieve, and taking the undersize to obtain pine needle powder;
s2: according to parts by weight, soaking 4000 parts of pine needle powder obtained in the step S1 in 8000 parts of 1.0M KCl water solution, stirring for 1 hour at a rotating speed of 300r/min, filtering to obtain a filter cake, and drying at 60 ℃ for 10 hours to obtain a precursor;
s3: transferring the precursor obtained in the step S2 into a tube furnace, heating to 480 ℃ at an initial temperature of 20 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours at 480 ℃, then cooling to 20 ℃ at a cooling rate of 10 ℃/min, and grinding to obtain the biomass charcoal material.
S4: adding 30 parts of the biomass charcoal material obtained in the step S3 into 400 parts of concentrated sulfuric acid with the mass fraction of 98%, transferring into a reaction kettle, keeping at 160 ℃ for 8 hours, naturally cooling to room temperature, filtering, washing to neutrality, and taking a filter cake, and vacuum drying at 80 ℃ for 12 hours to obtain the biomass charcoal sulfonic acid.
S5: and (3) uniformly mixing 20 parts of biomass charcoal sulfonic acid obtained in the step (S4), 5 parts of metal organic framework ZIF-78 and 50 parts of water according to parts by weight, heating to 40 ℃, stirring for 1 hour at a rotating speed of 200r/min, filtering, and drying a filter cake at 50 ℃ for 12 hours to obtain the modified biomass charcoal sulfonic acid.
The cross-linking agent is N, N' -methylene bisacrylamide.
The initiator is ammonium persulfate.
Example 2
The preparation method of the kitchen waste deodorizing and purifying agent comprises the following steps:
(1) Adding 40 parts of acrylic acid into 120 parts of water according to parts by weight, and regulating the pH to 7.5 by using a 1M NaOH aqueous solution to obtain a mixed solution A;
(2) Uniformly mixing 2 parts of cross-linking agent, 5 parts of calcium propionate, 20 parts of modified biomass charcoal sulfonic acid and 150 parts of mixed solution A obtained in the step (1) by weight, stirring at the speed of 300r/min at 60 ℃ for 1 hour, then adding 3 parts of initiator, keeping the temperature and stirring rate unchanged, and reacting for 6 hours to obtain a gelatinous polymer;
(3) Granulating the gel polymer obtained in the step (2), and vacuum drying at 80 ℃ for 2 hours to obtain the kitchen waste deodorizing and purifying agent, wherein the particle size of the kitchen waste deodorizing and purifying agent is 0.5cm.
The preparation method of the modified biomass charcoal sulfonic acid comprises the following steps:
s1: cleaning pine needles, airing, crushing, sieving with a 200-mesh sieve, and taking the undersize to obtain pine needle powder;
s2: according to parts by weight, soaking 4000 parts of pine needle powder obtained in the step S1 in 8000 parts of 1.0M KCl water solution, stirring for 1 hour at a rotating speed of 300r/min, filtering to obtain a filter cake, and drying at 60 ℃ for 10 hours to obtain a precursor;
s3: transferring the precursor obtained in the step S2 into a tube furnace, heating to 480 ℃ at an initial temperature of 20 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours at 480 ℃, then cooling to 20 ℃ at a cooling rate of 10 ℃/min, and grinding to obtain the biomass charcoal material.
S4: adding 30 parts of the biomass charcoal material obtained in the step S3 into 400 parts of concentrated sulfuric acid with the mass fraction of 98%, transferring into a reaction kettle, keeping at 160 ℃ for 8 hours, naturally cooling to room temperature, filtering, washing to neutrality, and taking a filter cake, and vacuum drying at 80 ℃ for 12 hours to obtain the biomass charcoal sulfonic acid.
S5: and (2) uniformly mixing 20 parts of biomass charcoal sulfonic acid obtained in the step (S4), 5 parts of metal organic framework ZIF-78, 2 parts of protein and 50 parts of water according to parts by weight, heating to 40 ℃, stirring for 1 hour at a rotating speed of 200r/min, filtering, and drying a filter cake at 50 ℃ for 12 hours to obtain the modified biomass charcoal sulfonic acid.
The cross-linking agent is N, N' -methylene bisacrylamide.
The initiator is ammonium persulfate.
The protein is sericin.
Example 3
The preparation method of the kitchen waste deodorizing and purifying agent comprises the following steps:
(1) Adding 40 parts of acrylic acid into 120 parts of water according to parts by weight, and regulating the pH to 7.5 by using a 1M NaOH aqueous solution to obtain a mixed solution A;
(2) Uniformly mixing 2 parts of cross-linking agent, 5 parts of calcium propionate, 20 parts of modified biomass charcoal sulfonic acid and 150 parts of mixed solution A obtained in the step (1) by weight, stirring at the speed of 300r/min at 60 ℃ for 1 hour, then adding 3 parts of initiator, keeping the temperature and stirring rate unchanged, and reacting for 6 hours to obtain a gelatinous polymer;
(3) Granulating the gel polymer obtained in the step (2), and vacuum drying at 80 ℃ for 2 hours to obtain the kitchen waste deodorizing and purifying agent, wherein the particle size of the kitchen waste deodorizing and purifying agent is 0.5cm.
The preparation method of the modified biomass charcoal sulfonic acid comprises the following steps:
s1: cleaning pine needles, airing, crushing, sieving with a 200-mesh sieve, and taking the undersize to obtain pine needle powder;
s2: according to parts by weight, soaking 4000 parts of pine needle powder obtained in the step S1 in 8000 parts of 1.0M KCl water solution, stirring for 1 hour at a rotating speed of 300r/min, filtering to obtain a filter cake, and drying at 60 ℃ for 10 hours to obtain a precursor;
s3: transferring the precursor obtained in the step S2 into a tube furnace, heating to 480 ℃ at an initial temperature of 20 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours at 480 ℃, then cooling to 20 ℃ at a cooling rate of 10 ℃/min, and grinding to obtain the biomass charcoal material.
S4: adding 30 parts of the biomass charcoal material obtained in the step S3 into 400 parts of concentrated sulfuric acid with the mass fraction of 98%, transferring into a reaction kettle, keeping at 160 ℃ for 8 hours, naturally cooling to room temperature, filtering, washing to neutrality, and taking a filter cake, and vacuum drying at 80 ℃ for 12 hours to obtain the biomass charcoal sulfonic acid.
S5: and (2) uniformly mixing 20 parts of biomass charcoal sulfonic acid obtained in the step (S4), 5 parts of metal organic framework ZIF-78, 2 parts of protein and 50 parts of water according to parts by weight, heating to 40 ℃, stirring for 1 hour at a rotating speed of 200r/min, filtering, and drying a filter cake at 50 ℃ for 12 hours to obtain the modified biomass charcoal sulfonic acid.
The cross-linking agent is N, N' -methylene bisacrylamide.
The initiator is ammonium persulfate.
The protein is silk fibroin.
Example 4
The preparation method of the kitchen waste deodorizing and purifying agent comprises the following steps:
(1) Adding 40 parts of acrylic acid into 120 parts of water according to parts by weight, and regulating the pH to 7.5 by using a 1M NaOH aqueous solution to obtain a mixed solution A;
(2) Uniformly mixing 2 parts of cross-linking agent, 5 parts of calcium propionate, 20 parts of modified biomass charcoal sulfonic acid and 150 parts of mixed solution A obtained in the step (1) by weight, stirring at the speed of 300r/min at 60 ℃ for 1 hour, then adding 3 parts of initiator, keeping the temperature and stirring rate unchanged, and reacting for 6 hours to obtain a gelatinous polymer;
(3) Granulating the gel polymer obtained in the step (2), and vacuum drying at 80 ℃ for 2 hours to obtain the kitchen waste deodorizing and purifying agent, wherein the particle size of the kitchen waste deodorizing and purifying agent is 0.5cm.
The preparation method of the modified biomass charcoal sulfonic acid comprises the following steps:
s1: cleaning pine needles, airing, crushing, sieving with a 200-mesh sieve, and taking the undersize to obtain pine needle powder;
s2: according to parts by weight, soaking 4000 parts of pine needle powder obtained in the step S1 in 8000 parts of 1.0M KCl water solution, stirring for 1 hour at a rotating speed of 300r/min, filtering to obtain a filter cake, and drying at 60 ℃ for 10 hours to obtain a precursor;
s3: transferring the precursor obtained in the step S2 into a tube furnace, heating to 480 ℃ at an initial temperature of 20 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours at 480 ℃, then cooling to 20 ℃ at a cooling rate of 10 ℃/min, and grinding to obtain the biomass charcoal material.
S4: adding 30 parts of the biomass charcoal material obtained in the step S3 into 400 parts of concentrated sulfuric acid with the mass fraction of 98%, transferring into a reaction kettle, keeping at 160 ℃ for 8 hours, naturally cooling to room temperature, filtering, washing to neutrality, and taking a filter cake, and vacuum drying at 80 ℃ for 12 hours to obtain the biomass charcoal sulfonic acid.
S5: and (2) uniformly mixing 20 parts of biomass charcoal sulfonic acid obtained in the step (S4), 5 parts of metal organic framework ZIF-78, 2 parts of protein and 50 parts of water according to parts by weight, heating to 40 ℃, stirring for 1 hour at a rotating speed of 200r/min, filtering, and drying a filter cake at 50 ℃ for 12 hours to obtain the modified biomass charcoal sulfonic acid.
The cross-linking agent is N, N' -methylene bisacrylamide.
The initiator is ammonium persulfate.
The protein is a mixture of sericin and silk fibroin according to a mass ratio of 1:2.4.
Comparative example 1
The preparation method of the kitchen waste deodorizing and purifying agent comprises the following steps:
(1) Adding 40 parts of acrylic acid into 120 parts of water according to parts by weight, and regulating the pH to 7.5 by using a 1M NaOH aqueous solution to obtain a mixed solution A;
(2) Uniformly mixing 2 parts of cross-linking agent, 5 parts of calcium propionate, 20 parts of biomass charcoal sulfonic acid, 5 parts of protein and 150 parts of mixed solution A obtained in the step (1) according to parts by weight, stirring at a rotating speed of 300r/min and a temperature of 60 ℃ for 1 hour, then adding 3 parts of initiator, keeping the temperature and the pressure unchanged, and reacting for 6 hours to obtain a gelatinous polymer;
(3) Granulating the gel polymer obtained in the step (2), and vacuum drying at 80 ℃ for 2 hours to obtain the kitchen waste deodorizing and purifying agent, wherein the particle size of the kitchen waste deodorizing and purifying agent is 0.5cm.
The preparation method of the biomass charcoal sulfonic acid comprises the following steps:
s1: cleaning pine needles, airing, crushing, sieving with a 200-mesh sieve, and taking the undersize to obtain pine needle powder;
s2: according to parts by weight, soaking 4000 parts of pine needle powder obtained in the step S1 in 8000 parts of 1.0M KCl water solution, stirring for 1 hour at a rotating speed of 300r/min, filtering to obtain a filter cake, and drying at 60 ℃ for 10 hours to obtain a precursor;
s3: transferring the precursor obtained in the step S2 into a tube furnace, heating to 480 ℃ at an initial temperature of 20 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours at 480 ℃, then cooling to 20 ℃ at a cooling rate of 10 ℃/min, and grinding to obtain the biomass charcoal material.
S4: adding 30 parts of the biomass charcoal material obtained in the step S3 into 400 parts of concentrated sulfuric acid with the mass fraction of 98%, transferring into a reaction kettle, keeping at 160 ℃ for 8 hours, naturally cooling to room temperature, filtering, washing to neutrality, and taking a filter cake, and vacuum drying at 80 ℃ for 12 hours to obtain the biomass charcoal sulfonic acid.
The cross-linking agent is N, N' -methylene bisacrylamide.
The initiator is ammonium persulfate.
Test example 1
Performance index tests were performed on the kitchen waste deodorizing and purifying agents in examples and comparative examples.
Determination of the removal effect of Hydrogen sulfide: the initial concentration is 0.15mg/m under the conditions of normal temperature (20 ℃) and normal pressure (1 standard atmosphere) 3 The hydrogen sulfide concentration was analyzed by circulating the gas in a large bubble absorption tube containing 10mg of physical deodorant at a flow rate of 1L/min for 24 hours, and collecting the treated gas. The hydrogen sulfide concentration was determined according to GB/T14678-1993 gas chromatography for determination of air quality hydrogen sulfide, methyl mercaptan, dimethyl sulfide and dimethyl disulfide.
Determination of ammonia removal effect: the initial concentration is 1.5mg/m under the conditions of normal temperature (20 ℃) and normal pressure (1 standard atmosphere) 3 The ammonia concentration of the gas was analyzed by circulating the gas through a large bubble absorption tube containing 10mg of a physical deodorant at a flow rate of 1L/min for 24 hours and collecting the treated gas. The ammonia concentration was measured according to HJ 533-2009 "Nahner reagent Spectrophotometry for determination of environmental air and exhaust gas ammonia".
Determination of methyl mercaptan removal effect: the initial concentration is 0.1mg/m under the conditions of normal temperature (20 ℃) and normal pressure (1 standard atmosphere) 3 The gas was circulated through a large bubble absorption tube containing 10mg of physical deodorant at a flow rate of 1L/min for 24 hours, and the treated gas was collected and analyzed for methyl mercaptan concentration. Determination of methyl mercaptan concentration according to GB/T14678-1993 "determination of air quality Hydrogen sulfide, methyl mercaptan, methyl sulfide and dimethyl disulfideGas chromatography.
Determination of the removal effect of dimethyl sulfide: the initial concentration is 0.1mg/m under the conditions of normal temperature (20 ℃) and normal pressure (1 standard atmosphere) 3 The gas was circulated through a large bubble absorption tube containing 10mg of a physical deodorant at a flow rate of 1L/min for 24 hours, and the treated gas was collected and analyzed for the concentration of dimethyl sulfide. The concentration of dimethyl sulfide was determined according to GB/T14678-1993 gas chromatography for determination of hydrogen sulfide, methyl mercaptan, dimethyl sulfide and dimethyl disulfide in air mass.
The deodorizing efficiency calculation formula: y= (c) 0 -c)/c 0 ×100％。
Wherein:
y: the removal rate.
c 0 : the concentration of hydrogen sulfide, ammonia, methyl mercaptan or methyl sulfide before treatment was 0.15mg/m respectively 3 、1.5mg/m 3 、0.1mg/m 3 、0.1mg/m 3 。
c: the concentration of the treated hydrogen sulfide, ammonia, methyl mercaptan or methyl sulfide is expressed in mg/m 3 。
TABLE 1 Performance index test
Compared with comparative example 1, the embodiment 1 is added with the biomass charcoal sulfonic acid modified by the metal organic framework, the metal organic framework further increases the mechanical strength of the modified biomass charcoal sulfonic acid, and when the microgel wraps the shell structure of the modified biomass charcoal sulfonic acid, the microgel is better mechanically supported, so that the microgel is prevented from thermally collapsing, the internal structure of the microgel is prevented from being damaged, and the absorption effect of the microgel on odor molecules is enhanced; in examples 2 to 4, sericin, silk fibroin and the combination of the two were added to the modified biomass charcoal sulfonic acid of the metal organic framework, and sericin and silk fibroin were added to the modified biomass charcoal sulfonic acid, and the sulfonate and protein were crosslinked to form ionic bonds or hydrogen bonds, thereby being fixed on the surface of the biomass charcoal sulfonic acid. The spherical structure of sericin, the biological sponge-like absorption of which can promote the load enhancement of microgel; the filiform structure of the silk fibroin can promote the molecular migration of odor molecules in the microgel, and effectively enhance the adsorption effect of the microgel; the two are synergistic, so that the adsorption capacity of the microgel to odor molecules is further enhanced.
Test example 2
The deodorizing and purifying agents for kitchen wastes in the examples and the comparative examples were subjected to antibacterial performance test, and the test standard was referred to WS/T650-2019, method for evaluating antibacterial and bacteriostatic effects.
Table 2 antibacterial property test
In the embodiment 1, the modified biomass charcoal sulfonic acid is added, and the metal organic framework is compounded on the surface of the biomass charcoal sulfonic acid, so that the sterilization effect is achieved through interaction between the metal organic framework and bacterial cell membranes, and the sterilization effect of the microgel is remarkably improved; example 4 further added sericin and silk fibroin, the sericin and silk fibroin have good antibacterial effect on gram-negative bacteria and gram-positive bacteria, so that the antibacterial property of the kitchen waste deodorizing and purifying agent in example 4 is further enhanced.

Claims (5)

1. The preparation method of the kitchen waste deodorizing and purifying agent is characterized by comprising the following steps:
(1) Adding acrylic acid into water, and regulating the pH to 7.0-8.0 by using NaOH aqueous solution to obtain a mixed solution A;
(2) Mixing a cross-linking agent, calcium propionate, modified biomass charcoal sulfonic acid and the mixed solution A obtained in the step (1), uniformly stirring, then adding an initiator, keeping the temperature and stirring speed unchanged, and reacting to obtain a gel polymer;
(3) Granulating the gel polymer obtained in the step (2), and drying in vacuum to obtain the kitchen waste deodorizing and purifying agent;
the preparation method of the modified biomass charcoal sulfonic acid comprises the following steps:
s1: cleaning pine needles, airing, crushing, sieving with a 150-250 mesh sieve, and taking undersize to obtain pine needle powder;
s2: soaking 3000-5000 parts of pine needle powder obtained in the step S1 in 6500-10000 parts of 1.0-2.0M KCl water solution, stirring for 0.5-1.5 hours at a rotating speed of 200-400 r/min, filtering to obtain a filter cake, and drying at 50-70 ℃ for 8-12 hours to obtain a precursor;
s3: transferring the precursor obtained in the step S2 into a tube furnace, heating to 460-500 ℃ at an initial temperature of 20-25 ℃ at a heating rate of 4-6 ℃/min, preserving heat for 1-3 hours at 460-500 ℃, then cooling to 20-25 ℃ at a cooling rate of 8-12 ℃/min, and grinding to obtain a biomass charcoal material;
s4: adding 25-35 parts by weight of the biomass charcoal material obtained in the step S3 into 300-500 parts by weight of concentrated sulfuric acid with the mass fraction of 97-98%, then transferring into a reaction kettle, keeping the temperature at 150-170 ℃ for 7-9 hours, naturally cooling to room temperature, filtering, washing to be neutral, and taking a filter cake to be dried in vacuum at 70-90 ℃ for 10-14 hours to obtain biomass charcoal sulfonic acid;
s5: uniformly mixing 15-25 parts by weight of biomass charcoal sulfonic acid obtained in the step S4, 4-6 parts by weight of metal organic framework ZIF-78, 1-3 parts by weight of protein and 40-60 parts by weight of water, heating to 35-45 ℃, stirring at a rotating speed of 150-250 r/min for 0.5-1.5 hours, filtering, and drying a filter cake at 45-55 ℃ for 10-14 hours to obtain modified biomass charcoal sulfonic acid;
the protein is sericin and a mixture of sericin proteins.
2. The method for preparing the kitchen waste deodorizing and purifying agent as set forth in claim 1, comprising the steps of:
(1) Adding 30-50 parts of acrylic acid into 100-140 parts of water according to parts by weight, and regulating the pH to 7.0-8.0 by using 1-2M NaOH aqueous solution to obtain a mixed solution A;
(2) Uniformly mixing 1-3 parts of cross-linking agent, 4-6 parts of calcium propionate, 15-25 parts of modified biomass charcoal sulfonic acid and 130-160 parts of mixed solution A obtained in the step (1) by weight, stirring at the speed of 200-400 r/min and the temperature of 50-70 ℃ for 0.5-1.5 hours, then adding 2-4 parts of initiator, keeping the temperature and stirring rate unchanged, and reacting for 5-7 hours to obtain a gelatinous polymer;
(3) Granulating the gel polymer obtained in the step (2), and vacuum drying at 70-90 ℃ for 1-3 hours to obtain the kitchen waste deodorizing and purifying agent, wherein the particle size of the kitchen waste deodorizing and purifying agent is 0.4-1.0 cm.
3. The method for preparing the deodorizing and purifying agent for kitchen waste according to claim 1, wherein the cross-linking agent is at least one of N, N' -methylenebisacrylamide and ethyl orthosilicate.
4. The method for preparing the deodorizing and purifying agent for kitchen waste according to claim 1, wherein the initiator is at least one of ammonium persulfate and azobisisobutyrimidine hydrochloride.
5. The kitchen waste deodorizing and purifying agent is prepared by the preparation method of the kitchen waste deodorizing and purifying agent according to any one of claims 1 to 4.
CN202210275881.2A 2022-03-21 2022-03-21 Deodorizing and purifying agent for kitchen waste and preparation method thereof Active CN114618448B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08308916A (en) * 1995-05-18 1996-11-26 Sekisui Plastics Co Ltd Deodorant gel
JP2000334033A (en) * 1999-05-26 2000-12-05 Sekisui Chem Co Ltd Deodorant
CN107383392A (en) * 2017-07-11 2017-11-24 华南农业大学 A kind of biomass-based hydrogel and preparation method and application
JP2019088499A (en) * 2017-11-15 2019-06-13 大原パラヂウム化学株式会社 Deodorant for life smell
CN113307921A (en) * 2021-06-04 2021-08-27 深圳市晶孚科技有限公司 Multifunctional modified biomass charcoal and preparation method and application thereof
CN114149944A (en) * 2021-11-30 2022-03-08 南京农业大学 Microorganism combination with tail end capable of efficiently adsorbing malodorous gas, enhanced colonization and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08308916A (en) * 1995-05-18 1996-11-26 Sekisui Plastics Co Ltd Deodorant gel
JP2000334033A (en) * 1999-05-26 2000-12-05 Sekisui Chem Co Ltd Deodorant
CN107383392A (en) * 2017-07-11 2017-11-24 华南农业大学 A kind of biomass-based hydrogel and preparation method and application
JP2019088499A (en) * 2017-11-15 2019-06-13 大原パラヂウム化学株式会社 Deodorant for life smell
CN113307921A (en) * 2021-06-04 2021-08-27 深圳市晶孚科技有限公司 Multifunctional modified biomass charcoal and preparation method and application thereof
CN114149944A (en) * 2021-11-30 2022-03-08 南京农业大学 Microorganism combination with tail end capable of efficiently adsorbing malodorous gas, enhanced colonization and application

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