CN112156645B - Composite biological enzyme deodorant and preparation method thereof - Google Patents
Composite biological enzyme deodorant and preparation method thereof Download PDFInfo
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- CN112156645B CN112156645B CN202011011104.4A CN202011011104A CN112156645B CN 112156645 B CN112156645 B CN 112156645B CN 202011011104 A CN202011011104 A CN 202011011104A CN 112156645 B CN112156645 B CN 112156645B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
- B01D53/85—Biological processes with gas-solid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/485—Sulfur compounds containing only one sulfur compound other than sulfur oxides or hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention relates to the field of biological enzyme deodorizers, in particular to a composite biological enzyme deodorizer and a preparation method thereof, wherein the composite biological enzyme deodorizer comprises solid components; the solid component comprises the following components in parts by weight: 5-12 parts of composite biological enzyme preparation and 30-50 parts of modified blast furnace slag. The composite biological enzyme deodorant also comprises liquid components, wherein the liquid components comprise the following components in parts by weight: 0.1-0.5 part of sodium lignosulfonate, 0.05-0.2 part of poly dimethyl diallyl ammonium chloride and 40-80 parts of deionized water. The invention prepares a composite biological enzyme deodorant integrating three methods of physics, chemistry and microorganism by combining the prior methods of physics deodorization, chemistry deodorization and microorganism deodorization.
Description
Technical Field
The invention relates to the field of biological enzyme deodorizers, and in particular relates to a composite biological enzyme deodorizer and a preparation method thereof.
Background
The common deodorant in the prior art mainly comprises the following types of physical deodorant, chemical deodorant, microbial deodorant and plant deodorant, wherein the physical deodorant absorbs odor substances into micropores of the absorbent by using the absorbent, but the absorbent is difficult to desorb once absorbing the odor substances, cannot be reused and is difficult to treat, so that secondary pollution to the environment is caused, and the chemical deodorant has the characteristics of strong pertinence, quick response and the like, can cover odor, but has higher cost and is easy to cause secondary pollution; although the microbial deodorant is low in cost, the rapid and efficient deodorization effect is difficult to achieve due to the difficulty in microbial mixed fermentation, instability of products and certain adaptability and growth period, and the existing preparation method of the deodorant has the technical problems of complex extraction process, high production cost, low content of effective active ingredients, incapability of fundamentally removing odor and the like.
Therefore, the development of a composite biological enzyme deodorant which has outstanding effect and can rapidly deodorize is urgent to solve the existing odor pollution problem.
Disclosure of Invention
In view of the above problems, the present invention provides a complex bio-enzyme deodorant comprising a solid component; the solid component comprises the following components in parts by weight:
5-12 parts of a composite biological enzyme preparation and 30-50 parts of modified blast furnace slag;
preferably, the composite biological enzyme deodorant also comprises a liquid component, wherein the liquid component comprises the following components in parts by weight:
0.1-0.5 part of sodium lignosulfonate, 0.05-0.2 part of poly dimethyl diallyl ammonium chloride and 40-80 parts of deionized water;
wherein the mass ratio of the solid component to the liquid component is 1: 6-20.
Preferably, the complex bio-enzyme preparation comprises lipase, protease, cellulase, hemicellulase, pectinase, oxidoreductase and laccase.
Preferably, the mass ratio of the lipase to the protease to the cellulase to the hemicellulase to the pectinase to the oxidoreductase to the laccase is 1: 0.5-0.8: 1.2-1.5: 0.7-0.9: 0.8-1: 1.3-1.6: 1.5-1.8.
Preferably, the modified blast furnace slag has a particle size of not more than 0.2 mm.
Preferably, the preparation method of the modified blast furnace slag comprises the following steps:
s1, blast furnace slag pretreatment:
(1) the method comprises the following steps of (1) recovering blast furnace slag, washing the blast furnace slag by using deionized water to remove impurities, drying the blast furnace slag in an oven at 80-100 ℃ for 5-10 hours, cooling the blast furnace slag to room temperature, and crushing the blast furnace slag and sieving the blast furnace slag by using a 100-200-mesh sieve to obtain blast furnace slag powder;
(2) adding the blast furnace slag powder into deionized water, dropwise adding concentrated sulfuric acid until the pH value of the liquid is 2.0-3.0, performing ultrasonic dispersion treatment for 3-5 h, filtering to obtain a solid, washing with water until the washing liquid is neutral, and treating in an oven at 80-100 ℃ for 5-10 h to obtain pretreated blast furnace slag; wherein the mass ratio of the blast furnace slag powder to the deionized water is 1: 5-10;
s2, modifying blast furnace slag:
weighing 5-hydroxy-6-methylnicotinic acid, adding the 5-hydroxy-6-methylnicotinic acid into deionized water, then dropwise adding a sodium hydroxide solution until the pH value of the liquid is 11.0-12.0, stirring the mixture uniformly, then adding the pretreated blast furnace slag, ultrasonically dispersing the mixture uniformly, pouring the mixture into a reaction kettle, heating the mixture to 150-180 ℃, carrying out sealing reaction on the mixture for 24-48 hours, naturally cooling the mixture to room temperature after the reaction is finished, filtering the mixture to obtain a solid, washing the solid for three times by using a saturated sodium bicarbonate solution, then washing the solid with water until the washing liquid is neutral, and drying the solid in an oven at 80-100 ℃ for 5-10 hours to obtain modified blast furnace slag;
wherein the mass ratio of the 5-hydroxy-6-methylnicotinic acid to the pretreated blast furnace slag to the deionized water is 1: 3-6: 12-15.
Another object of the present invention is to provide a preparation method of a complex biological enzyme deodorant, comprising the steps of:
step 1, weighing biological enzyme with the enzyme activity of 500-1000U/mg according to different odor components to be removed, and mixing to obtain composite biological enzyme;
step 2, adding the composite biological enzyme into deionized water at room temperature, slowly stirring and dispersing until the mixture is uniform, centrifuging to obtain supernatant, passing through a polysulfone fiber membrane, and concentrating to obtain a composite biological enzyme preparation with the enzyme activity of 5000-10000U/mL; wherein the mass ratio of the compound biological enzyme to the deionized water is 1: 10-100;
step 3, adding modified blast furnace slag into the composite biological enzyme preparation, dispersing the mixture at room temperature until the mixture is uniform, heating the mixture to 35-45 ℃, slowly stirring the mixture for 2-4 hours, cooling the mixture to room temperature, and standing the mixture for 8-10 hours to obtain a modified blast furnace slag/composite biological enzyme preparation;
step 4, carrying out vacuum drying treatment on the modified blast furnace slag/composite biological enzyme preparation to obtain a solid component;
step 5, weighing sodium lignosulfonate, poly dimethyl diallyl ammonium chloride and deionized water according to the amount, mixing and stirring the mixture uniformly to obtain a liquid component;
and 6, mixing the solid component and the liquid component until the solid component and the liquid component are uniform.
Preferably, in the step 2, the pore diameter of the polysulfone fiber membrane is 5-20 nm.
Preferably, in the step 2, the solid remaining after passing through the polysulfone fiber membrane is re-extracted with ethanol, the obtained extracting solution is centrifuged to obtain supernatant, the supernatant passes through the polysulfone fiber membrane, and the supernatant is concentrated to obtain a composite biological enzyme extracting solution with the enzyme activity of 5000-10000U/mL, and the composite biological enzyme extracting solution is mixed with the composite biological enzyme preparation for use.
Preferably, in the step 3, the modified blast furnace slag/composite biological enzyme preparation needs to be stored at 0-4 ℃.
The invention has the beneficial effects that:
1. the invention prepares a composite biological enzyme deodorant integrating three methods of physics, chemistry and microorganism by combining the prior methods of physics deodorization, chemistry deodorization and microorganism deodorization. This compound biological enzyme deodorant is at the in-process that uses, adsorbs foul smell gas through the physical method, and the chemical process combines foul smell gas, and the microbial process is detached foul smell gas, compares in single deodorization method, and adsorption function and deodorization function that can be abundant play the deodorant after this three kinds of methods combine have greatly promoted the effect efficiency of deodorant. The composite biological enzyme deodorant is divided into a solid component and a liquid component, wherein the solid component can be used independently, namely the solid component is poured into a container and is arranged nearby an odor source (the effect is better in a closed environment); the liquid component is mainly beneficial to more uniform dispersion of the solid component, the solid component and the liquid component are mixed to prepare a mixed solution, and the mixed solution is sprayed on the odor source by a spraying method or a smearing method. The selected biological enzyme can perform neutralization or condensation reaction with active groups (such as sulfydryl, amino, ammonia and the like) in the malodorous substances, simultaneously inhibit the sulfate from being converted to generate hydrogen sulfide, convert pollutants in the malodorous substances into harmless carbohydrate, eliminate the free malodorous substances in the environment and avoid any secondary pollution.
2. In the preparation process of the biological enzyme deodorant, the modified blast furnace slag with a strong adsorption function is added, and the surface of the modified blast furnace slag contains an organic ligand of N-, O-donor atoms, so that the biological enzyme deodorant not only has strong adsorption to biological enzymes, but also has strong binding capacity to odor-irritating gases (ammonia gas, hydrogen sulfide, organic amine, thioether and the like), and can stably and efficiently remove odor. After the composite biological enzyme deodorant is put into an odor source, odor substances are adsorbed and combined in the body of the composite biological enzyme deodorant, the biological enzyme carries out oxidative decomposition on the odor substances, and an environment which is not beneficial to the survival of odor-producing microorganisms can be formed, so that odor-producing microorganisms are thoroughly prevented from generating odor irritant gas again from the source. In addition, the modified blast furnace slag prepared by the invention can be recycled, and only biological enzyme needs to be supplemented and is reconfigured into a solid component according to the parts by weight and the preparation steps.
3. Blast furnace slag is a byproduct in the steel smelting process, is obtained by rapidly cooling high-temperature molten slag discharged from an iron-making blast furnace by water, and forms loose and porous granulated slag with high activity because liquid phase viscosity is rapidly increased and crystal nuclei are not formed in time and do not have an environment for crystal growth. However, the stability of blast furnace slag is poor and the adsorption properties to biological enzymes and gaseous substances are not outstanding. Therefore, the invention obtains the modified blast furnace slag by modifying the slag, thereby enhancing the stability and the adsorption performance of the slag on biological enzyme and odor gas. Firstly, physically removing impurities from blast furnace slag, drying and crushing the blast furnace slag until the particle size is less than 0.2 mm; then acid-washing to dissolve part of Ca and Al on the slag surface, increasing the surface roughness of slag particles, and activating the surface to form a crystal Structure of (SiO)4)4-Promoting the ion exchange and adsorption; and then modifying the surface of the activated blast furnace slag by using 5-hydroxy-6-methylnicotinic acid, and grafting and adsorbing the modified blast furnace slag on the surface of the activated blast furnace slag under an alkaline condition. The 5-hydroxy-6-methylnicotinic acid is used as an organic ligand simultaneously containing N-and O-donor atoms, the N-and O-atoms can be simultaneously used as proton acceptors and proton donors, and the 5-hydroxy-6-methylnicotinic acid contains multidentate coordination sites and various possible coordination modes, so that the 5-hydroxy-6-methylnicotinic acid can exert excellent adsorption performance. The invention uses blast furnace slag to prepare the modified blast furnace slag carrier, achieves the effect of treating waste by waste, not only widens the utilization mode and the approach of the blast furnace slag, but also effectively improves the benefit of the blast furnace slagThe rate of utilization has improved the absorption clearance of foul smell gas simultaneously.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A composite bio-enzyme deodorant comprising a solid component; the solid component comprises the following components in parts by weight:
8 parts of composite biological enzyme preparation and 40 parts of modified blast furnace slag;
the composite biological enzyme deodorant also comprises liquid components, wherein the liquid components comprise the following components in parts by weight:
0.3 part of sodium lignosulphonate, 0.1 part of poly dimethyl diallyl ammonium chloride and 60 parts of deionized water;
wherein the mass ratio of the solid component to the liquid component is 1: 12.
The compound biological enzyme preparation comprises lipase, protease, cellulase, hemicellulase, pectinase, oxidoreductase and laccase.
The mass ratio of the lipase to the protease to the cellulase to the hemicellulase to the pectinase to the oxidoreductase to the laccase is 1:0.6:1.4:0.8:0.9:1.5: 1.6.
The particle size of the modified blast furnace slag is not more than 0.2 mm.
The preparation method of the modified blast furnace slag comprises the following steps:
s1, blast furnace slag pretreatment:
(1) the method comprises the following steps of (1) recovering blast furnace slag, washing the blast furnace slag by using deionized water to remove impurities, drying the blast furnace slag in an oven at 80-100 ℃ for 5-10 hours, cooling the blast furnace slag to room temperature, and crushing the blast furnace slag and sieving the blast furnace slag by using a 100-200-mesh sieve to obtain blast furnace slag powder;
(2) adding the blast furnace slag powder into deionized water, dropwise adding concentrated sulfuric acid until the pH value of the liquid is 2.0-3.0, performing ultrasonic dispersion treatment for 3-5 h, filtering to obtain a solid, washing with water until the washing liquid is neutral, and treating in an oven at 80-100 ℃ for 5-10 h to obtain pretreated blast furnace slag; wherein the mass ratio of the blast furnace slag powder to the deionized water is 1: 5-10;
s2, modifying blast furnace slag:
weighing 5-hydroxy-6-methylnicotinic acid, adding the 5-hydroxy-6-methylnicotinic acid into deionized water, then dropwise adding a sodium hydroxide solution until the pH value of the liquid is 11.0-12.0, stirring the mixture uniformly, then adding the pretreated blast furnace slag, ultrasonically dispersing the mixture uniformly, pouring the mixture into a reaction kettle, heating the mixture to 150-180 ℃, carrying out sealing reaction on the mixture for 24-48 hours, naturally cooling the mixture to room temperature after the reaction is finished, filtering the mixture to obtain a solid, washing the solid for three times by using a saturated sodium bicarbonate solution, then washing the solid with water until the washing liquid is neutral, and drying the solid in an oven at 80-100 ℃ for 5-10 hours to obtain modified blast furnace slag;
wherein the mass ratio of the 5-hydroxy-6-methylnicotinic acid to the pretreated blast furnace slag to the deionized water is 1: 3-6: 12-15.
The preparation method of the composite biological enzyme deodorant comprises the following steps:
step 1, weighing biological enzyme with the enzyme activity of 500-1000U/mg according to different odor components to be removed, and mixing to obtain composite biological enzyme;
step 2, adding the composite biological enzyme into deionized water at room temperature, slowly stirring and dispersing until the mixture is uniform, centrifuging to obtain supernatant, passing through a polysulfone fiber membrane, and concentrating to obtain a composite biological enzyme preparation with the enzyme activity of 5000-10000U/mL; wherein the mass ratio of the compound biological enzyme to the deionized water is 1: 10-100;
step 3, adding modified blast furnace slag into the composite biological enzyme preparation, dispersing the mixture at room temperature until the mixture is uniform, heating the mixture to 35-45 ℃, slowly stirring the mixture for 2-4 hours, cooling the mixture to room temperature, and standing the mixture for 8-10 hours to obtain a modified blast furnace slag/composite biological enzyme preparation;
step 4, carrying out vacuum drying treatment on the modified blast furnace slag/composite biological enzyme preparation to obtain a solid component;
step 5, weighing sodium lignosulfonate, poly dimethyl diallyl ammonium chloride and deionized water according to the amount, mixing and stirring the mixture uniformly to obtain a liquid component;
and 6, mixing the solid component and the liquid component until the solid component and the liquid component are uniform.
In the step 2, the pore diameter of the polysulfone fiber membrane is 5-20 nm.
In the step 2, the solid remained after passing through the polysulfone fiber membrane is extracted again by using ethanol, the obtained extracting solution is centrifuged to obtain supernatant, the supernatant passes through the polysulfone fiber membrane, and the supernatant is concentrated to obtain composite biological enzyme extracting solution with the enzyme activity of 5000-10000U/mL, and the composite biological enzyme extracting solution is mixed with the composite biological enzyme preparation for use.
In the step 3, the modified blast furnace slag/composite biological enzyme preparation needs to be stored at 0-4 ℃.
Example 2
A composite bio-enzyme deodorant comprising a solid component; the solid component comprises the following components in parts by weight:
5 parts of composite biological enzyme preparation and 30 parts of modified blast furnace slag;
the composite biological enzyme deodorant also comprises liquid components, wherein the liquid components comprise the following components in parts by weight:
0.1 part of sodium lignosulphonate, 0.05 part of poly dimethyl diallyl ammonium chloride and 40 parts of deionized water;
wherein the mass ratio of the solid component to the liquid component is 1: 6.
The compound biological enzyme preparation comprises lipase, protease, cellulase, hemicellulase, pectinase, oxidoreductase and laccase.
The mass ratio of the lipase to the protease to the cellulase to the hemicellulase to the pectinase to the oxidoreductase to the laccase is 1:0.5:1.2:0.7:0.8:1.3: 1.5.
The particle size of the modified blast furnace slag is not more than 0.2 mm.
The preparation method of the modified blast furnace slag comprises the following steps:
s1, blast furnace slag pretreatment:
(1) the method comprises the following steps of (1) recovering blast furnace slag, washing the blast furnace slag by using deionized water to remove impurities, drying the blast furnace slag in an oven at 80-100 ℃ for 5-10 hours, cooling the blast furnace slag to room temperature, and crushing the blast furnace slag and sieving the blast furnace slag by using a 100-200-mesh sieve to obtain blast furnace slag powder;
(2) adding the blast furnace slag powder into deionized water, dropwise adding concentrated sulfuric acid until the pH value of the liquid is 2.0-3.0, performing ultrasonic dispersion treatment for 3-5 h, filtering to obtain a solid, washing with water until the washing liquid is neutral, and treating in an oven at 80-100 ℃ for 5-10 h to obtain pretreated blast furnace slag; wherein the mass ratio of the blast furnace slag powder to the deionized water is 1: 5-10;
s2, modifying blast furnace slag:
weighing 5-hydroxy-6-methylnicotinic acid, adding the 5-hydroxy-6-methylnicotinic acid into deionized water, then dropwise adding a sodium hydroxide solution until the pH value of the liquid is 11.0-12.0, stirring the mixture uniformly, then adding the pretreated blast furnace slag, ultrasonically dispersing the mixture uniformly, pouring the mixture into a reaction kettle, heating the mixture to 150-180 ℃, carrying out sealing reaction on the mixture for 24-48 hours, naturally cooling the mixture to room temperature after the reaction is finished, filtering the mixture to obtain a solid, washing the solid for three times by using a saturated sodium bicarbonate solution, then washing the solid with water until the washing liquid is neutral, and drying the solid in an oven at 80-100 ℃ for 5-10 hours to obtain modified blast furnace slag;
wherein the mass ratio of the 5-hydroxy-6-methylnicotinic acid to the pretreated blast furnace slag to the deionized water is 1: 3-6: 12-15.
The preparation method of the composite biological enzyme deodorant comprises the following steps:
step 1, weighing biological enzyme with the enzyme activity of 500-1000U/mg according to different odor components to be removed, and mixing to obtain composite biological enzyme;
step 2, adding the composite biological enzyme into deionized water at room temperature, slowly stirring and dispersing until the mixture is uniform, centrifuging to obtain supernatant, passing through a polysulfone fiber membrane, and concentrating to obtain a composite biological enzyme preparation with the enzyme activity of 5000-10000U/mL; wherein the mass ratio of the compound biological enzyme to the deionized water is 1: 10-100;
step 3, adding modified blast furnace slag into the composite biological enzyme preparation, dispersing the mixture at room temperature until the mixture is uniform, heating the mixture to 35-45 ℃, slowly stirring the mixture for 2-4 hours, cooling the mixture to room temperature, and standing the mixture for 8-10 hours to obtain a modified blast furnace slag/composite biological enzyme preparation;
step 4, carrying out vacuum drying treatment on the modified blast furnace slag/composite biological enzyme preparation to obtain a solid component;
step 5, weighing sodium lignosulfonate, poly dimethyl diallyl ammonium chloride and deionized water according to the amount, mixing and stirring the mixture uniformly to obtain a liquid component;
and 6, mixing the solid component and the liquid component until the solid component and the liquid component are uniform.
In the step 2, the pore diameter of the polysulfone fiber membrane is 5-20 nm.
In the step 2, the solid remained after passing through the polysulfone fiber membrane is extracted again by using ethanol, the obtained extracting solution is centrifuged to obtain supernatant, the supernatant passes through the polysulfone fiber membrane, and the supernatant is concentrated to obtain composite biological enzyme extracting solution with the enzyme activity of 5000-10000U/mL, and the composite biological enzyme extracting solution is mixed with the composite biological enzyme preparation for use.
In the step 3, the modified blast furnace slag/composite biological enzyme preparation needs to be stored at 0-4 ℃.
Example 3
A composite bio-enzyme deodorant comprising a solid component; the solid component comprises the following components in parts by weight:
12 parts of composite biological enzyme preparation and 50 parts of modified blast furnace slag;
the composite biological enzyme deodorant also comprises liquid components, wherein the liquid components comprise the following components in parts by weight:
0.5 part of sodium lignosulphonate, 0.2 part of poly dimethyl diallyl ammonium chloride and 80 parts of deionized water;
wherein the mass ratio of the solid component to the liquid component is 1: 20.
The compound biological enzyme preparation comprises lipase, protease, cellulase, hemicellulase, pectinase, oxidoreductase and laccase.
The mass ratio of the lipase to the protease to the cellulase to the hemicellulase to the pectinase to the oxidoreductase to the laccase is 1:0.8:1.5:0.9:1:1.6: 1.8.
The particle size of the modified blast furnace slag is not more than 0.2 mm.
The preparation method of the modified blast furnace slag comprises the following steps:
s1, blast furnace slag pretreatment:
(1) the method comprises the following steps of (1) recovering blast furnace slag, washing the blast furnace slag by using deionized water to remove impurities, drying the blast furnace slag in an oven at 80-100 ℃ for 5-10 hours, cooling the blast furnace slag to room temperature, and crushing the blast furnace slag and sieving the blast furnace slag by using a 100-200-mesh sieve to obtain blast furnace slag powder;
(2) adding the blast furnace slag powder into deionized water, dropwise adding concentrated sulfuric acid until the pH value of the liquid is 2.0-3.0, performing ultrasonic dispersion treatment for 3-5 h, filtering to obtain a solid, washing with water until the washing liquid is neutral, and treating in an oven at 80-100 ℃ for 5-10 h to obtain pretreated blast furnace slag; wherein the mass ratio of the blast furnace slag powder to the deionized water is 1: 5-10;
s2, modifying blast furnace slag:
weighing 5-hydroxy-6-methylnicotinic acid, adding the 5-hydroxy-6-methylnicotinic acid into deionized water, then dropwise adding a sodium hydroxide solution until the pH value of the liquid is 11.0-12.0, stirring the mixture uniformly, then adding the pretreated blast furnace slag, ultrasonically dispersing the mixture uniformly, pouring the mixture into a reaction kettle, heating the mixture to 150-180 ℃, carrying out sealing reaction on the mixture for 24-48 hours, naturally cooling the mixture to room temperature after the reaction is finished, filtering the mixture to obtain a solid, washing the solid for three times by using a saturated sodium bicarbonate solution, then washing the solid with water until the washing liquid is neutral, and drying the solid in an oven at 80-100 ℃ for 5-10 hours to obtain modified blast furnace slag;
wherein the mass ratio of the 5-hydroxy-6-methylnicotinic acid to the pretreated blast furnace slag to the deionized water is 1: 3-6: 12-15.
The preparation method of the composite biological enzyme deodorant comprises the following steps:
step 1, weighing biological enzyme with the enzyme activity of 500-1000U/mg according to different odor components to be removed, and mixing to obtain composite biological enzyme;
step 2, adding the composite biological enzyme into deionized water at room temperature, slowly stirring and dispersing until the mixture is uniform, centrifuging to obtain supernatant, passing through a polysulfone fiber membrane, and concentrating to obtain a composite biological enzyme preparation with the enzyme activity of 5000-10000U/mL; wherein the mass ratio of the compound biological enzyme to the deionized water is 1: 10-100;
step 3, adding modified blast furnace slag into the composite biological enzyme preparation, dispersing the mixture at room temperature until the mixture is uniform, heating the mixture to 35-45 ℃, slowly stirring the mixture for 2-4 hours, cooling the mixture to room temperature, and standing the mixture for 8-10 hours to obtain a modified blast furnace slag/composite biological enzyme preparation;
step 4, carrying out vacuum drying treatment on the modified blast furnace slag/composite biological enzyme preparation to obtain a solid component;
step 5, weighing sodium lignosulfonate, poly dimethyl diallyl ammonium chloride and deionized water according to the amount, mixing and stirring the mixture uniformly to obtain a liquid component;
and 6, mixing the solid component and the liquid component until the solid component and the liquid component are uniform.
In the step 2, the pore diameter of the polysulfone fiber membrane is 5-20 nm.
In the step 2, the solid remained after passing through the polysulfone fiber membrane is extracted again by using ethanol, the obtained extracting solution is centrifuged to obtain supernatant, the supernatant passes through the polysulfone fiber membrane, and the supernatant is concentrated to obtain composite biological enzyme extracting solution with the enzyme activity of 5000-10000U/mL, and the composite biological enzyme extracting solution is mixed with the composite biological enzyme preparation for use.
In the step 3, the modified blast furnace slag/composite biological enzyme preparation needs to be stored at 0-4 ℃.
Comparative example 1
A composite bio-enzyme deodorant comprising a solid component; the solid component comprises the following components in parts by weight:
8 parts of composite biological enzyme preparation and 40 parts of blast furnace slag;
the composite biological enzyme deodorant also comprises liquid components, wherein the liquid components comprise the following components in parts by weight:
0.3 part of sodium lignosulphonate, 0.1 part of poly dimethyl diallyl ammonium chloride and 60 parts of deionized water;
wherein the mass ratio of the solid component to the liquid component is 1: 12.
The compound biological enzyme preparation comprises lipase, protease, cellulase, hemicellulase, pectinase, oxidoreductase and laccase.
The mass ratio of the lipase to the protease to the cellulase to the hemicellulase to the pectinase to the oxidoreductase to the laccase is 1:0.6:1.4:0.8:0.9:1.5: 1.6.
The particle size of the modified blast furnace slag is not more than 0.2 mm.
The treatment method of the blast furnace slag comprises the following steps:
(1) the method comprises the following steps of (1) recovering blast furnace slag, washing the blast furnace slag by using deionized water to remove impurities, drying the blast furnace slag in an oven at 80-100 ℃ for 5-10 hours, cooling the blast furnace slag to room temperature, and crushing the blast furnace slag and sieving the blast furnace slag by using a 100-200-mesh sieve to obtain blast furnace slag powder;
(2) adding the blast furnace slag powder into deionized water, dropwise adding concentrated sulfuric acid until the pH value of the liquid is 2.0-3.0, performing ultrasonic dispersion treatment for 3-5 h, filtering to obtain a solid, washing with water until the washing liquid is neutral, and treating in an oven at 80-100 ℃ for 5-10 h to obtain pretreated blast furnace slag; the mass ratio of the blast furnace slag powder to the deionized water is 1: 5-10.
The preparation method of the composite biological enzyme deodorant comprises the following steps:
step 1, weighing biological enzyme with the enzyme activity of 500-1000U/mg according to different odor components to be removed, and mixing to obtain composite biological enzyme;
step 2, adding the composite biological enzyme into deionized water at room temperature, slowly stirring and dispersing until the mixture is uniform, centrifuging to obtain supernatant, passing through a polysulfone fiber membrane, and concentrating to obtain a composite biological enzyme preparation with the enzyme activity of 5000-10000U/mL; wherein the mass ratio of the compound biological enzyme to the deionized water is 1: 10-100;
step 3, adding blast furnace slag into the composite biological enzyme preparation, dispersing the mixture at room temperature until the mixture is uniform, heating the mixture to 35-45 ℃, slowly stirring the mixture for 2-4 hours, cooling the mixture to room temperature, and standing the mixture for 8-10 hours to obtain a blast furnace slag/composite biological enzyme preparation;
step 4, carrying out vacuum drying treatment on the blast furnace slag/composite biological enzyme preparation to obtain a solid component;
step 5, weighing sodium lignosulfonate, poly dimethyl diallyl ammonium chloride and deionized water according to the amount, mixing and stirring the mixture uniformly to obtain a liquid component;
and 6, mixing the solid component and the liquid component until the solid component and the liquid component are uniform.
In the step 2, the pore diameter of the polysulfone fiber membrane is 5-20 nm.
In the step 2, the solid remained after passing through the polysulfone fiber membrane is extracted again by using ethanol, the obtained extracting solution is centrifuged to obtain supernatant, the supernatant passes through the polysulfone fiber membrane, and the supernatant is concentrated to obtain composite biological enzyme extracting solution with the enzyme activity of 5000-10000U/mL, and the composite biological enzyme extracting solution is mixed with the composite biological enzyme preparation for use.
In the step 3, the blast furnace slag/composite biological enzyme preparation needs to be stored at 0-4 ℃.
Comparative example 2
A composite bio-enzyme deodorant comprising a solid component; the solid component comprises the following components in parts by weight:
8 parts of a compound biological enzyme preparation;
the composite biological enzyme deodorant also comprises liquid components, wherein the liquid components comprise the following components in parts by weight:
0.3 part of sodium lignosulphonate, 0.1 part of poly dimethyl diallyl ammonium chloride and 60 parts of deionized water;
wherein the mass ratio of the solid component to the liquid component is 1: 12.
The compound biological enzyme preparation comprises lipase, protease, cellulase, hemicellulase, pectinase, oxidoreductase and laccase.
The mass ratio of the lipase to the protease to the cellulase to the hemicellulase to the pectinase to the oxidoreductase to the laccase is 1:0.6:1.4:0.8:0.9:1.5: 1.6.
The preparation method of the composite biological enzyme deodorant comprises the following steps:
step 1, weighing biological enzyme with the enzyme activity of 500-1000U/mg according to different odor components to be removed, and mixing to obtain composite biological enzyme;
step 2, adding the composite biological enzyme into deionized water at room temperature, slowly stirring and dispersing until the mixture is uniform, centrifuging to obtain supernatant, passing through a polysulfone fiber membrane, and concentrating to obtain a composite biological enzyme preparation with the enzyme activity of 5000-10000U/mL; wherein the mass ratio of the compound biological enzyme to the deionized water is 1: 10-100;
step 3, carrying out vacuum drying treatment on the composite biological enzyme preparation to obtain a solid component;
step 4, weighing sodium lignosulfonate, poly dimethyl diallyl ammonium chloride and deionized water according to the amount, mixing and stirring uniformly to obtain a liquid component;
and 6, mixing the solid component and the liquid component until the solid component and the liquid component are uniform.
In the step 2, the pore diameter of the polysulfone fiber membrane is 5-20 nm.
In the step 2, the solid remained after passing through the polysulfone fiber membrane is extracted again by using ethanol, the obtained extracting solution is centrifuged to obtain supernatant, the supernatant passes through the polysulfone fiber membrane, and the supernatant is concentrated to obtain composite biological enzyme extracting solution with the enzyme activity of 5000-10000U/mL, and the composite biological enzyme extracting solution is mixed with the composite biological enzyme preparation for use.
In order to illustrate the present invention more clearly, the performance of the composite bio-enzyme deodorant prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2 was tested.
The detection method comprises the following steps:
(1) weighing solid components of 5 kinds of composite biological enzyme deodorizers and respectively marking, wherein the content of the composite biological enzyme in the 5 kinds of solid components is completely the same;
(2) then 6 sealed boxes (length multiplied by width multiplied by height is 1m multiplied by 0.5m) with the same size are taken, after the boxes are vacuumized, the same amount of odorous gas (volume concentration: 2% of ammonia gas, 5% of hydrogen sulfide, 5% of methyl mercaptan, 5% of ethylamine and the balance of air) is introduced;
(3) setting one of the sealed boxes into which the odorous gas is introduced in the step 2 as a blank control group, respectively adding the other 5 sealed boxes into the 5 solid components of the composite biological enzyme deodorant, then performing deodorization treatment for 2h/24h under the same temperature and illumination (room temperature and dark), then detecting the odorous gas components in each sealed box, and calculating the removal rate of the odorous gas, wherein the results are shown in table 1;
wherein the removal rate (%) of the odor gas is the concentration of the odor gas after the deodorization treatment/the concentration of the odor gas introduced before the deodorization treatment.
TABLE 1 results of deodorization assay
As can be seen from table 1, the composite bio-enzyme deodorant prepared in embodiments 1 to 3 of the present invention has a strong adsorption effect, can efficiently remove odorous gas in a short time (2 hours in the table), has a better deodorizing effect for a long time (24 hours in the table) (refer to comparative example 1 and comparative example 2), and achieves the purposes of outstanding effect and rapid deodorization. In addition, the deodorant prepared in the embodiments 1 to 3 of the invention has good recoverability, and the enzyme can be efficiently and repeatedly used for many times after being continuously loaded after being recovered.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A composite biological enzyme deodorant, characterized in that it comprises a solid component; the solid component comprises the following components in parts by weight:
5-12 parts of a composite biological enzyme preparation and 30-50 parts of modified blast furnace slag;
the composite biological enzyme deodorant also comprises liquid components, wherein the liquid components comprise the following components in parts by weight:
0.1-0.5 part of sodium lignosulfonate, 0.05-0.2 part of poly dimethyl diallyl ammonium chloride and 40-80 parts of deionized water;
wherein the mass ratio of the solid component to the liquid component is 1: 6-20;
the preparation method of the modified blast furnace slag comprises the following steps:
s1, blast furnace slag pretreatment:
(1) the method comprises the following steps of (1) recovering blast furnace slag, washing the blast furnace slag by using deionized water to remove impurities, drying the blast furnace slag in an oven at 80-100 ℃ for 5-10 hours, cooling the blast furnace slag to room temperature, and crushing the blast furnace slag and sieving the blast furnace slag by using a 100-200-mesh sieve to obtain blast furnace slag powder;
(2) adding the blast furnace slag powder into deionized water, dropwise adding concentrated sulfuric acid until the pH = 2.0-3.0 of the liquid, performing ultrasonic dispersion treatment for 3-5 h, filtering to obtain a solid, washing with water until the washing liquid is neutral, and placing in an oven at 80-100 ℃ for treatment for 5-10 h to obtain pretreated blast furnace slag;
s2, modified blast furnace slag:
weighing 5-hydroxy-6-methylnicotinic acid, adding the weighed 5-hydroxy-6-methylnicotinic acid into deionized water, then dropwise adding a sodium hydroxide solution until the pH of the liquid is = 11.0-12.0, stirring the mixture evenly, then adding the pretreated blast furnace slag, ultrasonically dispersing the mixture evenly, pouring the mixture into a reaction kettle, heating the mixture to 150-180 ℃, carrying out sealing reaction for 24-48 hours, naturally cooling the mixture to room temperature after the reaction is finished, filtering the mixture to obtain a solid, washing the solid for three times by using a saturated sodium bicarbonate solution, then washing the solid until the washing liquid is neutral, and placing the solid in an oven at 80-100 ℃ for drying treatment for 5-10 hours to obtain the modified blast furnace slag.
2. The compound biological enzyme deodorant according to claim 1, wherein the compound biological enzyme preparation comprises lipase, protease, cellulase, hemicellulase, pectinase, oxidoreductase and laccase.
3. The composite biological enzyme deodorant as claimed in claim 2, wherein the mass ratio of the lipase, the protease, the cellulase, the hemicellulase, the pectinase, the oxidoreductase and the laccase is 1: 0.5-0.8: 1.2-1.5: 0.7-0.9: 0.8-1: 1.3-1.6: 1.5-1.8.
4. The composite biological enzyme deodorant according to claim 1, wherein the particle size of the modified blast furnace slag is not more than 0.2 mm.
5. A preparation method of the compound biological enzyme deodorant as claimed in any one of claims 1-4, characterized by comprising the following steps:
step 1, weighing biological enzyme with the enzyme activity of 500-1000U/mg according to different odor components to be removed, and mixing to obtain composite biological enzyme;
step 2, adding the composite biological enzyme into deionized water at room temperature, slowly stirring and dispersing until the mixture is uniform, centrifuging to obtain supernatant, passing through a polysulfone fiber membrane, and concentrating to obtain a composite biological enzyme preparation with the enzyme activity of 5000-10000U/mL; wherein the mass ratio of the composite biological enzyme to the deionized water is 1: 10-100;
step 3, adding modified blast furnace slag into the composite biological enzyme preparation, dispersing the mixture at room temperature until the mixture is uniform, heating the mixture to 35-45 ℃, slowly stirring the mixture for 2-4 hours, cooling the mixture to room temperature, and standing the mixture for 8-10 hours to obtain a modified blast furnace slag/composite biological enzyme preparation;
step 4, carrying out vacuum drying treatment on the modified blast furnace slag/composite biological enzyme preparation to obtain a solid component;
step 5, weighing sodium lignosulfonate, poly dimethyl diallyl ammonium chloride and deionized water according to the amount, mixing and stirring the mixture uniformly to obtain a liquid component;
and 6, mixing the solid component and the liquid component until the solid component and the liquid component are uniform.
6. The preparation method of the composite biological enzyme deodorant according to claim 5, wherein in the step 2, the pore diameter of the polysulfone fiber membrane is 5-20 nm.
7. The preparation method of the composite biological enzyme deodorant according to claim 5, wherein in the step 2, the solid remaining after the polysulfone fiber membrane is passed through is re-extracted with ethanol, the obtained extract is centrifuged to obtain supernatant, the supernatant is passed through the polysulfone fiber membrane, the supernatant is concentrated to obtain composite biological enzyme extract with the enzyme activity of 5000-10000U/mL, and the composite biological enzyme extract is mixed with the composite biological enzyme preparation for use.
8. The preparation method of the composite biological enzyme deodorant, according to claim 5, characterized in that in the step 3, the modified blast furnace slag/composite biological enzyme preparation is stored at 0-4 ℃.
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