CN116195604A - Non-oxidizing bactericide for double-membrane method and preparation method thereof - Google Patents

Non-oxidizing bactericide for double-membrane method and preparation method thereof Download PDF

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CN116195604A
CN116195604A CN202310161944.6A CN202310161944A CN116195604A CN 116195604 A CN116195604 A CN 116195604A CN 202310161944 A CN202310161944 A CN 202310161944A CN 116195604 A CN116195604 A CN 116195604A
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essential oil
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史剑韬
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Inner Mongolia Nanda Environmental Protection Technology Co ltd
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Inner Mongolia Nanda Environmental Protection Technology Co ltd
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N63/50—Isolated enzymes; Isolated proteins
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    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/12—Asteraceae or Compositae [Aster or Sunflower family], e.g. daisy, pyrethrum, artichoke, lettuce, sunflower, wormwood or tarragon
    • A—HUMAN NECESSITIES
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    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/22—Lamiaceae or Labiatae [Mint family], e.g. thyme, rosemary, skullcap, selfheal, lavender, perilla, pennyroyal, peppermint or spearmint
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/40—Liliopsida [monocotyledons]
    • A01N65/44—Poaceae or Gramineae [Grass family], e.g. bamboo, lemon grass or citronella grass
    • A—HUMAN NECESSITIES
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract

The invention belongs to the field of bactericide preparation for water treatment, and discloses a non-oxidizing bactericide applied to a double-membrane method circulating water treatment process and a preparation method thereof. The non-oxidizing bactericide prepared by taking 3-phenyl-N- (3- (trimethoxy silane) propyl) prop-2-ene-1-imine, tetrakis (hydroxymethyl) phosphonium sulfate and modified nano copper particles as main sterilization components and taking the synergism of biological enzymes, plant essential oil and lignin as auxiliary components has excellent sterilization effects on bacteria, fungi, algae, protozoa and the like, has high action speed and sterilization efficiency, does not cause harm to the environment, and is not easy to generate drug resistance. Can be widely applied to the market field of water treatment double-membrane method and has wide market prospect.

Description

Non-oxidizing bactericide for double-membrane method and preparation method thereof
Technical Field
The invention relates to the field of preparation of bactericides for water treatment, in particular to a non-oxidizing bactericide applied to a double-membrane method circulating water treatment process and a preparation method thereof.
Background
Along with the increasing shortage of water resources, the industrial water is stressed, and the sewage recycling is particularly important, wherein the double-membrane method recycling technology is a hot spot for current research and application, and compared with a common double-membrane method system, the double-membrane method recycling technology comprises a desalted water system, a sewage recycling water system and a high-salt water system. The double-membrane method is a process combining different membrane technologies, has compact structure, small occupied area, low medicament consumption, stable treatment effect and safe and reliable operation management, can achieve the purposes of saving resources and reducing cost when being used for sewage regeneration, and has obvious economic and social benefits.
However, the microbial growth can be promoted for different water quality, water temperature and system environment, so that one of the most effective and most common methods for microbial growth in a double-membrane circulating cooling water system is to add bactericides. According to the principle of economy and practicality, the oxidizing bactericide is commonly used as a strong oxidant, and the aim of sterilization is mainly achieved through the oxidation with metabolic enzymes in bacteria. However, as the polyamide separation layer of the reverse osmosis membrane element in some double-membrane systems does not have oxidation resistance, the use of the oxidizing bactericide is limited, and the requirements for the non-oxidizing bactericide in the operation of more and more double-membrane systems are larger and more, so that the market share is high. Common non-oxidizing biocides are: quaternary ammonium salts, chlorophenols, organosulfur compounds, organotin compounds, organobromine compounds, isothiazolinones, glutaraldehyde, quaternary phosphonium salts, and the like. The non-oxidative germicides do not kill microorganisms by oxidation, but act as a toxicant on specific sites of microorganisms, thereby achieving the goal of killing microorganisms. CN107410358A discloses a non-oxidizing bactericide for water treatment, the formulation of which comprises 1-10% by weight of isothiazolinone; 1-5% by weight glutaraldehyde; 10-50% by weight of water; 1-4% by weight sodium bromide; 1-6% by weight of organic bromine; 1-8% by weight of SQ8 bactericide; 1-5% by weight of dicyanomethane; 1-10% by weight of an organic amine bactericide. In summary, the patent publications all have the technical effects of remarkable difficulty in generating drug resistance, low toxicity, low environmental hazard and the like, but the bactericidal substances such as bromide, organic amine, glutaraldehyde and the like contained in the formula have the advantages that the bromide cost is high, peroxide and ozone are easy to decompose, glutaraldehyde is easy to react with ammonia or amine compounds and is invalid, so that the prepared non-oxidative bactericide has short bactericidal duration and low bactericidal efficiency.
Therefore, in order to solve the problems of the prior art, it is necessary to develop a non-oxidative bactericide which is applied to the double-membrane method circulating water treatment process, has high sterilization efficiency and long sterilization duration, and does not cause harm to the environment.
Disclosure of Invention
In view of the above, the invention provides a non-oxidative bactericide which is applied to the double-membrane method circulating water treatment process, has high sterilization efficiency and long sterilization duration, and does not cause harm to the environment.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a non-oxidizing bactericide for double-membrane method comprises a component A, a component B, a biological dispersing agent and deionized water.
In a further technical scheme of the invention, the non-oxidizing bactericide for the double-membrane method comprises the following components in percentage by mass: 30-40% of component A, 5-10% of component B, 1-5% of biological dispersant and the balance of deionized water.
In a further technical scheme of the invention, the component A consists of 10-20 parts by weight of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine, 5-15 parts by weight of tetrakis (hydroxymethyl) phosphine sulfate and 3-6 parts by weight of modified nano copper particles.
In a further technical scheme of the invention, the component B consists of 0.1-1 part of biological enzyme, 1-3 parts of plant essential oil and 1-2 parts of lignin according to parts by weight.
In a further technical scheme of the invention, the plant essential oil is selected from one or more of lemon grass essential oil, oregano essential oil, rosemary essential oil, peppermint essential oil, artemisia annua essential oil and basil essential oil.
In a further technical scheme of the invention, the plant essential oil is preferably a plurality of combinations, in particular to a combination of artemisia annua, lemon grass essential oil, oregano essential oil and peppermint essential oil according to a weight ratio of 1:1:1:1.
In a further technical scheme of the invention, the preparation method of the modified nano copper particles specifically comprises the following steps:
(1) mixing fructus Momordicae Charantiae powder and water at a weight ratio of 1:10, stirring for 30-60min, boiling for 15-20min, filtering, cooling filtrate to room temperature, and refrigerating at 2-4deg.C to obtain fructus Momordicae Charantiae extract;
(2) heating the prepared Momordica Charantia extract to 40deg.C, mixing with copper sulfate at a weight ratio of 1:1, heating in 80-85deg.C water bath for 45-60min, centrifuging at high speed, filtering, and oven drying the product.
In a further aspect of the present invention, the biological enzyme is tyrosine kinase a.
In a further technical scheme of the invention, the biological dispersant is selected from one of biological dispersant JY-460 or biological dispersant KF-508.
In a further technical scheme of the invention, the preparation method of the non-oxidizing bactericide for the double-membrane method comprises the following steps:
step one: placing 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-ene-1-imine, phosphine tetrahydroxymethyl sulfate, modified nano copper particles and deionized water into a reaction kettle, uniformly stirring and heating to 45-50 ℃;
step two: adding lignin into a reaction kettle again, stirring and dispersing for 40-60min, and cooling to 20-25 ℃;
step three: then putting the biological dispersing agent, biological enzyme and plant essential oil into a reaction kettle, and uniformly stirring;
step four: after stirring evenly, filtering and discharging operation is carried out, a 100-mesh filter screen is adopted for filtering, and the filter is packaged and then stored in a storage tank.
According to the technical scheme, the invention discloses a non-oxidizing bactericide for a double-membrane method and a preparation method thereof, and compared with the prior art, the non-oxidizing bactericide has the following technical effects:
the non-oxidizing bactericide prepared by taking the component A as a main sterilization component and the component B as an auxiliary synergy component has excellent sterilization effects on bacteria, fungi, algae, protozoa and the like, has the characteristics of high action speed, high sterilization efficiency, no harm to the environment, difficult generation of drug resistance and the like, integrally solves the technical problem of poor sterilization and algae removal effects of the traditional bactericide, can be widely applied to the market field of water treatment double-membrane methods, and has wide market prospect.
The bactericidal component A in the non-oxidative bactericide prepared by the invention consists of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine, phosphine tetrahydroxymethyl sulfate and modified nano copper particles. Wherein, the imine compound synthesized by the reaction of 3- (trimethoxysilyl) propyl-1-amine and cinnamaldehyde of 3-phenyl-N- (3- (trimethoxysilyl) propyl-2-alkene-1-imine has excellent antibacterial performance, and is green and environment-friendly; the modified nano copper particles are metal nano particles prepared from balsam pear extract and copper sulfate, not only have remarkable antibacterial performance, but also improve the antifouling and corrosion resistance of the double-film system, prolong the service life of the double-film system and reduce the industrial cost.
The non-oxidizing bactericide prepared by the invention also comprises a synergistic component B, and in the component B, unique and unique biological enzyme is added, so that the microbial production can be more effectively inhibited, and the synergistic component of the phosphine tetramethylolsulfate is used as a synergistic component of the phosphine tetramethylolsulfate, so that the sterilization effect of the phosphine tetramethylolsulfate on bacteria is enhanced, meanwhile, the corrosion of organisms on a double-film system is reduced, the sterilization and bacteriostasis effects of the non-oxidizing bactericide for a double-film method are better promoted, and the service life of the double-film system is prolonged; in the component B, lignin is also added, and the lignin has various antibacterial active ingredients, so that the invention not only has the sterilization characteristic, but also can further prevent the generation of drug resistance of the non-oxidative bactericide prepared by the invention.
Detailed Description
The embodiment of the invention discloses a non-oxidizing bactericide for a double-membrane method, which comprises a component A, a component B, a biological dispersing agent and deionized water; comprises the following components in percentage by mass: 30-40% of component A, 5-10% of component B, 1-5% of biological dispersant and the balance of deionized water.
As non-limiting content of component A, preference is given to: 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%; the component A consists of 10-20 parts by weight of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine, 5-15 parts by weight of tetrakis (hydroxymethyl) phosphine sulfate and 3-6 parts by weight of modified nano copper particles, wherein the non-limiting content of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine is 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight and 20 parts by weight; wherein, the non-limiting content of the tetrakis (hydroxymethyl) phosphonium sulfate is 5 parts, 10 parts and 15 parts; wherein, the non-limiting content of the modified nano copper particles is 3 parts, 4 parts, 5 parts and 6 parts; the preparation method in the 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine preparation method reference Antifouling painting formulations containing green synthesized copper oxide nanoparticles using water extract of Ulva fasciata comprises the following specific operations: 3- (trimethoxy silicon based) propyl-1-amine and cinnamaldehyde are mixed according to the weight ratio of 2:1, reacted and condensed for 4 hours to synthesize 3-phenyl-N- (3- (trimethoxy silicon based) propyl-2-alkene-1-imine, the reaction is observed by thin layer chromatography, the mixture is filtered after the reaction, and then the filtrate is concentrated to obtain a solid product, and the obtained product is recrystallized by ethanol to obtain the product.
The preparation method of the modified nano copper particles specifically comprises the following steps:
(1) mixing fructus Momordicae Charantiae powder and water at a weight ratio of 1:10, stirring for 30-60min, boiling for 15-20min, filtering, cooling filtrate to room temperature, and refrigerating at 2-4deg.C to obtain fructus Momordicae Charantiae extract;
(2) heating the prepared Momordica Charantia extract to 40deg.C, mixing with copper sulfate at a weight ratio of 1:1, heating in 80-85deg.C water bath for 45-60min, centrifuging at high speed, filtering, and oven drying the product.
As non-limiting content of component B, it is preferred that, in mass percent: 5%, 6%, 7%, 8%, 9%, 10%; the component B consists of 0.1-1 part of biological enzyme, 1-3 parts of plant essential oil and 1-2 parts of lignin according to parts by weight; wherein, the non-limiting content of the biological enzyme is 0.1 part, 0.3 part, 0.5 part, 0.7 part and 1 part; wherein, the non-limiting content of the plant essential oil is 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts; wherein, the non-limiting content of lignin is 1 part, 1.5 parts, 2 parts; the biological enzyme is tyrosine kinase A; the plant essential oil is selected from one or more of lemon grass essential oil, oregano essential oil, rosemary essential oil, peppermint essential oil, artemisia annua essential oil and basil essential oil, preferably a plurality of combinations, and specifically, the combination of artemisia annua, lemon grass essential oil, oregano essential oil and peppermint essential oil according to a weight ratio of 1:1:1:1; the plant essential oil can be obtained by purchasing, or can be prepared by extracting by conventional continuous distillation method of essential oil.
As non-limiting content of the bio-dispersant, it is preferable that, in mass percent: 1%, 2%, 3%, 4%, 5%; the biological dispersing agent is selected from one of biological dispersing agent JY-460 or biological dispersing agent KF-508, wherein the biological dispersing agent is a commercial product, and the biological dispersing agent JY-460 is an industrial product produced by commercial Shijia donor environmental protection technology Co-efficient; the biological dispersant KF-508 is an industrial product produced by the development of fine chemical industry Co-Ltd in the Uruzu market.
The embodiment of the invention also comprises a preparation method of the non-oxidizing bactericide for the double-membrane method, which comprises the following preparation steps:
step one: placing 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-ene-1-imine, phosphine tetrahydroxymethyl sulfate, modified nano copper particles and deionized water into a reaction kettle, uniformly stirring and heating to 45-50 ℃;
step two: adding lignin into a reaction kettle again, stirring and dispersing for 40-60min, and cooling to 20-25 ℃;
step three: then putting the biological dispersing agent, biological enzyme and plant essential oil into a reaction kettle, and uniformly stirring;
step four: after stirring evenly, filtering and discharging operation is carried out, a 100-mesh filter screen is adopted for filtering, and the filter is packaged and then stored in a storage tank.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the modified nano copper particles in the following examples and comparative examples specifically comprises the following steps:
(1) mixing fructus Momordicae Charantiae powder with water at a weight ratio of 1:10, stirring for 45min, boiling for 18min, filtering, cooling filtrate to room temperature, and refrigerating at 3deg.C to obtain fructus Momordicae Charantiae extract;
(2) heating the prepared Momordica Charantia extract to 40deg.C, mixing with copper sulfate at a weight ratio of 1:1, heating in water bath at 85deg.C for 50min, centrifuging at high speed, filtering, and oven drying the product.
The preparation method of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine in the following examples and comparative examples specifically includes the following steps: 3- (trimethoxy silicon-based) propan-1-amine and cinnamaldehyde are mixed according to the weight ratio of 2:1, reacted and condensed for 4 hours to synthesize 3-phenyl-N- (3- (trimethoxy silicon-based) propyl) propan-2-alkene-1-imine, the reaction is observed to be carried out and ended by using thin layer chromatography, the mixture is filtered after the reaction, and then the filtrate is concentrated to obtain a solid product, and the obtained product is recrystallized by using ethanol to obtain the product.
Example 1
A non-oxidizing bactericide for a double-film method comprises the following components in percentage by mass: 30% of a component A, 10% of a component B, 50% of a biological dispersant KF-5081% and 59% of deionized water; the component A consists of 10 parts of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine, 5 parts of tetrakis (hydroxymethyl) phosphine sulfate and 3 parts of modified nano copper particles according to parts by weight; the component B consists of 0.1 part of tyrosine kinase A, 1 part of plant essential oil and 1 part of lignin according to parts by weight; the plant essential oil is prepared by combining artemisia annua, lemon grass essential oil, oregano essential oil and peppermint essential oil according to a weight ratio of 1:1:1:1.
The preparation method of the non-oxidizing bactericide for the double-film method in the embodiment 1 comprises the following steps:
step one: placing 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-ene-1-imine, tetrakis (hydroxymethyl) phosphonium sulfate, modified nano copper particles and deionized water into a reaction kettle, uniformly stirring and heating to 45 ℃;
step two: adding lignin into a reaction kettle again, stirring and dispersing for 40min, and cooling to 20 ℃;
step three: then putting the biological dispersing agent, biological enzyme and plant essential oil into a reaction kettle, and uniformly stirring;
step four: after stirring evenly, filtering and discharging operation is carried out, a 100-mesh filter screen is adopted for filtering, and the filter is packaged and then stored in a storage tank.
Example 2
A non-oxidizing bactericide for a double-film method comprises the following components in percentage by mass: 40% of component A, 5% of component B, JY-4601% of biological dispersant and 54% of deionized water; the component A consists of 20 parts of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine, 15 parts of tetrakis (hydroxymethyl) phosphine sulfate and 6 parts of modified nano copper particles according to parts by weight; the component B consists of 1 part of tyrosine kinase A, 3 parts of plant essential oil and 2 parts of lignin according to parts by weight; the plant essential oil is specifically prepared by combining artemisia annua, lemon grass essential oil, oregano essential oil and peppermint essential oil according to a weight ratio of 1:1:1:1.
The preparation method of the non-oxidizing bactericide for the double-film method in the embodiment 2 comprises the following steps:
step one: placing 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-ene-1-imine, tetrakis (hydroxymethyl) phosphonium sulfate, modified nano copper particles and deionized water into a reaction kettle, uniformly stirring and heating to 50 ℃;
step two: adding lignin into a reaction kettle again, stirring and dispersing for 60min, and cooling to 25 ℃;
step three: then putting the biological dispersing agent, biological enzyme and plant essential oil into a reaction kettle, and uniformly stirring;
step four: after stirring evenly, filtering and discharging operation is carried out, a 100-mesh filter screen is adopted for filtering, and the filter is packaged and then stored in a storage tank.
Example 3
A non-oxidizing bactericide for a double-film method comprises the following components in percentage by mass: 35% of component A, 7.5% of component B, JY-4603% of biological dispersant and 54.5% of deionized water; the component A consists of 15 parts by weight of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine, 10 parts by weight of tetrakis (hydroxymethyl) phosphonium sulfate and 4.5 parts by weight of modified nano copper particles; the component B consists of 0.5 part of tyrosine kinase A, 2 parts of plant essential oil and 1.5 parts of lignin according to parts by weight; the plant essential oil is specifically prepared by combining artemisia annua, lemon grass essential oil, oregano essential oil and peppermint essential oil according to a weight ratio of 1:1:1:1.
The preparation method of the non-oxidizing bactericide for the double-film method in the embodiment 3 comprises the following steps:
step one: placing 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-ene-1-imine, phosphine tetrahydroxymethyl sulfate, modified nano copper particles and deionized water into a reaction kettle, uniformly stirring and heating to 48 ℃;
step two: adding lignin into a reaction kettle again, stirring and dispersing for 50min, and cooling to 22 ℃;
step three: then putting the biological dispersing agent, biological enzyme and plant essential oil into a reaction kettle, and uniformly stirring;
step four: after stirring evenly, filtering and discharging operation is carried out, a 100-mesh filter screen is adopted for filtering, and the filter is packaged and then stored in a storage tank.
Comparative example 1
A non-oxidizing bactericide for a double-film method comprises the following components in percentage by mass: 35% of component A, 7.5% of component B, JY-4603% of biological dispersant and 54.5% of deionized water; the component A consists of 15 parts by weight of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine, 10 parts by weight of tetrakis (hydroxymethyl) phosphonium sulfate and 4.5 parts by weight of modified nano copper particles; the component B consists of 2 parts of plant essential oil and 1.5 parts of lignin according to parts by weight; the plant essential oil is specifically prepared by combining artemisia annua, lemon grass essential oil, oregano essential oil and peppermint essential oil according to a weight ratio of 1:1:1:1.
The preparation method of the non-oxidizing bactericide by the double membrane method in comparative example 1 was the same as that described in example 3.
Comparative example 2
A non-oxidizing bactericide for a double-film method comprises the following components in percentage by mass: 35% of component A, 7.5% of component B, JY-4603% of biological dispersant and 54.5% of deionized water; the component A consists of 15 parts by weight of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine and 10 parts by weight of tetrakis (hydroxymethyl) phosphine sulfate; the component B consists of 0.5 part of tyrosine kinase A, 2 parts of plant essential oil and 1.5 parts of lignin according to parts by weight; the plant essential oil is specifically prepared by combining artemisia annua, lemon grass essential oil, oregano essential oil and peppermint essential oil according to a weight ratio of 1:1:1:1.
The preparation method of the non-oxidizing bactericide by the double membrane method in comparative example 2 was the same as that described in example 3.
Comparative example 3
A non-oxidizing bactericide for a double-film method comprises the following components in percentage by mass: 35% of component A, 7.5% of component B, JY-4603% of biological dispersant and 54.5% of deionized water; the component A consists of 10 parts of tetrakis (hydroxymethyl) phosphine sulfate and 4.5 parts of modified nano copper particles according to parts by weight; the component B consists of 0.5 part of tyrosine kinase A, 2 parts of plant essential oil and 1.5 parts of lignin according to parts by weight; the plant essential oil is specifically prepared by combining artemisia annua, lemon grass essential oil, oregano essential oil and peppermint essential oil according to a weight ratio of 1:1:1:1.
The preparation method of the non-oxidizing bactericide by the double membrane method in the above comparative example 3 was the same as that described in example 3.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The non-oxidative bactericides prepared in the examples 1-3 and the comparative examples 1-2 of the invention and the quaternary ammonium salt bactericides, isothiazolinone and organic bromine complexing agents are subjected to a bactericidal performance detection comparison test.
Note that: the quaternary ammonium salt bactericide is 1227 industrial products produced by Wulumuzil petrochemical peak fine chemical factories; 1227 is known by the chemical name dodecyl dimethyl benzyl ammonium chloride.
Organic bromine complexing agent: KF-509 is produced by Urufimbriae Corp. Of Uruxoviridae, and comprises DBNPA (2, 2-dibromo-3-cyanopropionamide) as the main component.
(1) The test method comprises the following steps:
experimental water: the circulating cooling water in a process system of deep desalting treatment (ultrafiltration, primary reverse osmosis, secondary reverse osmosis and EDI) by a double membrane method for desalting and water supply of a certain steel boiler is taken.
Method for evaluating sterilization effect
The sterilization effect evaluation of the circulating cooling water is expressed by the sterilization rate of heterotrophic bacteria, and the content of the heterotrophic bacteria is about 10 5 cfu/mL～10 6 And adding a bactericide into the circulating water with the order of cfu/mL, detecting the content of heterotrophic bacteria every 6 hours, and evaluating the sterilizing effect according to the sterilizing rate of 24 hours of heterotrophic bacteria. Measurement of heterotrophic bacteria reference HG/T4207 industrial circulating cooling water heterotrophic bacteria count measurement-plate count method. The initial content of heterotrophic bacteria for experimental water taken on site on the same day is 9.76 multiplied by 10 5 cfu/mL, the following sterilization rates are calculatedThis was counted and the detection results were recorded in table 1.
The following formula is adopted: the impact dosing mode is adopted, the concentration of the impact dosing agent is controlled to be 100ppm, the time is controlled to be 2h, and the dosing amount is 50mg/L.
Table 1 comparison of the sterilizing rates of different items
Figure BDA0004094582030000151
As can be seen from the data in Table 1, the non-oxidizing bactericides prepared in the embodiments 1-3 of the invention have higher sterilizing rates than isothiazolinone, quaternary ammonium salt bactericides and organic bromine complexing agents, and the sterilizing rates reach more than 99%, and meanwhile, the non-oxidizing bactericides prepared in the invention have the advantages of long duration of drug effect, easiness in separation of thalli from a circulating water system and the like, are suitable for microbial control in double-film industrial circulating cooling water, are ideal new-generation industrial bactericides, and have certain market application prospects and popularization values.

Claims (8)

1. A non-oxidizing bactericide for a double-film method is characterized in that: comprises a component A, a component B, a biological dispersant and deionized water;
the component A consists of 10-20 parts by weight of 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-en-1-imine, 5-15 parts by weight of tetrakis (hydroxymethyl) phosphonium sulfate and 3-6 parts by weight of modified nano copper particles;
the component B consists of 0.1-1 part of biological enzyme, 1-3 parts of plant essential oil and 1-2 parts of lignin according to parts by weight.
2. The non-oxidizing bactericide for a double membrane process according to claim 1, characterized in that: according to the mass percentage, the component A comprises 30-40%, the component B comprises 5-10%, the biological dispersant comprises 1-5%, and the balance is deionized water.
3. The non-oxidizing bactericide for a double membrane process according to claim 1, characterized in that:
the plant essential oil is selected from one or more of lemon grass essential oil, oregano essential oil, rosemary essential oil, peppermint essential oil, artemisia annua essential oil and basil essential oil.
4. A non-oxidizing sterilant for a twin film method according to claim 3, wherein: the plant essential oil is preferably a plurality of combinations, specifically a combination of artemisia annua, lemon grass essential oil, oregano essential oil and peppermint essential oil according to a weight ratio of 1:1:1:1.
5. The non-oxidizing bactericide for a double membrane process according to claim 1, characterized in that: the biological enzyme is tyrosine kinase A.
6. The non-oxidizing bactericide for a double-membrane process according to claim 1, wherein the bio-dispersant is one selected from the group consisting of bio-dispersant JY-460 and bio-dispersant KF-508.
7. The non-oxidizing bactericide for a double membrane process according to claim 1, characterized in that: the preparation method of the modified nano copper particles specifically comprises the following steps:
(1) mixing fructus Momordicae Charantiae powder and water at a weight ratio of 1:10, stirring for 30-60min, boiling for 15-20min, filtering, cooling filtrate to room temperature, and refrigerating at 2-4deg.C to obtain fructus Momordicae Charantiae extract;
(2) heating the prepared Momordica Charantia extract to 40deg.C, mixing with copper sulfate at a weight ratio of 1:1, heating in 80-85deg.C water bath for 45-60min, centrifuging at high speed, filtering, and oven drying the product.
8. A method for preparing a non-oxidizing bactericide for a double membrane process according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
step one: placing 3-phenyl-N- (3- (trimethoxysilyl) propyl) prop-2-ene-1-imine, phosphine tetrahydroxymethyl sulfate, modified nano copper particles and deionized water into a reaction kettle, uniformly stirring and heating to 45-50 ℃;
step two: adding lignin into a reaction kettle again, stirring and dispersing for 40-60min, and cooling to 20-25 ℃;
step three: then putting the biological dispersing agent, biological enzyme and plant essential oil into a reaction kettle, and uniformly stirring;
step four: after stirring evenly, filtering and discharging operation is carried out, a 100-mesh filter screen is adopted for filtering, and the filter is packaged and then stored in a storage tank.
CN202310161944.6A 2023-02-23 2023-02-23 Non-oxidizing bactericide for double-membrane method and preparation method thereof Pending CN116195604A (en)

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