CN112120028A - Bactericide for reverse osmosis system and preparation method thereof - Google Patents
Bactericide for reverse osmosis system and preparation method thereof Download PDFInfo
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- CN112120028A CN112120028A CN202011014987.4A CN202011014987A CN112120028A CN 112120028 A CN112120028 A CN 112120028A CN 202011014987 A CN202011014987 A CN 202011014987A CN 112120028 A CN112120028 A CN 112120028A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/18—Nitro compounds
- A01N33/20—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom not containing sulfur-to-oxygen bonds, e.g. polysulfides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
- A01N47/14—Di-thio analogues thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
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- Chemical Kinetics & Catalysis (AREA)
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- Environmental & Geological Engineering (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a bactericide for a reverse osmosis system, which is mainly prepared from the following raw materials: 5-10 parts of 2, 2-dibromo-3-nitrilopropionamide, 5-15 parts of sulfur-containing bactericidal component, 4-8 parts of bromine-containing compound, 8-18 parts of alcohol, 5-10 parts of aprotic solvent and 50-65 parts of water in parts by mass. The bactericide for the reverse osmosis system is added during the reverse osmosis operation, can effectively sterilize and inhibit the growth of microorganisms, avoids and reduces the microbial pollution of the reverse osmosis system, reduces the cleaning frequency and ensures the normal operation of a reverse osmosis production device.
Description
Technical Field
The invention belongs to the technical field of water treatment reverse osmosis systems, and particularly relates to a bactericide for a reverse osmosis system.
Background
Because the industrial development speed of China is accelerated, the water consumption of cities and countryside is increased, water resources are seriously short, the water treatment technology of China is still to be improved, the membrane system is seriously polluted due to microorganism pollution, generally, sodium hypochlorite bactericide is adopted to sterilize the inlet water, but the performance of the material of the reverse osmosis membrane is damaged by reducing the residual chlorine in the water by adopting a reducing agent, the membrane is oxidized, the irreversible damage of the reverse osmosis membrane is caused, the desalination rate of the outlet water is seriously reduced, the capability of removing each ion in the water is lost, the water yield and the pressure difference are influenced, and the normal production operation is further influenced. On the other hand, microbial fouling of the membrane elements of the reverse osmosis system can be caused, the cleaning frequency is increased, although the operation condition of the system can be improved after cleaning, the maintenance time is not long because cleaning and decontamination are not thorough, the operation parameters of the system are not ideal after the system is operated for a short time, the system needs to be cleaned again, the cleaning period is too short, and the service life of the reverse osmosis membrane elements is seriously influenced.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a bactericide for a reverse osmosis system, which is prepared from 2, 2-dibromo-3-nitrilopropionamide, a sulfur-containing bactericidal component, a bromine-containing compound, alcohols, an aprotic solvent and water.
The second purpose of the invention is to provide a preparation method of the bactericide, which is simple and convenient to operate and use, and has the advantages of readily available chemical raw materials and low cost.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a bactericide for a reverse osmosis system, which is mainly prepared from the following raw materials: 5-10 parts of 2, 2-dibromo-3-nitrilopropionamide, 5-15 parts of sulfur-containing bactericidal component, 4-8 parts of bromine-containing compound, 8-18 parts of alcohol, 5-10 parts of aprotic solvent and 50-65 parts of water in parts by mass.
Preferably, 6-8 parts of 2, 2-dibromo-3-nitrilopropionamide, 8-11 parts of sulfur-containing bactericidal component, 5-7 parts of bromine-containing compound, 11-15 parts of alcohol, 6-8 parts of aprotic solvent and 55-60 parts of water by mass.
Preferably, 7 parts of 2, 2-dibromo-3-nitrilopropionamide, 9 parts of sulfur-containing bactericidal component, 6 parts of bromine-containing compound, 13 parts of alcohol, 7 parts of aprotic solvent and 58 parts of water.
In the raw material formula, the 2, 2-dibromo-3-nitrilopropionamide and the sulfur-containing bactericidal component have extremely strong bactericidal effects, and particularly, molecules of the 2, 2-dibromo-3-nitrilopropionamide can rapidly penetrate through cell membranes of microorganisms, brominate or oxidize special enzyme metabolites in the microorganisms, finally kill the microorganisms, and have a strong stripping function. A large number of experiments show that the 2, 2-dibromo-3-nitrilopropionamide and the sulfur-containing bactericidal component can be compounded to kill formed algae and prevent new algae from being generated, the compatibility of the compounded solution and the bromine-containing compound is better, the bromine-containing compound is added, the bactericidal effect is improved, the natural biodegradation can be realized, the compatibility with reverse osmosis membrane elements is good, the membrane is not damaged, and the bactericidal performance and the stability can be improved after the alcohol and the aprotic solvent are continuously added into the solution. In terms of dosage, the contents of the 2, 2-dibromo-3-nitrilopropionamide, the sulfur-containing bactericidal component and the bromine-containing compound are balanced, and the total amount of the three components is smaller relative to the total amount of the whole formula, so that the bactericidal performance of the three components is improved according to the proportion of the three components, and the bactericidal effect is very strong even if a small amount of parts is added.
Preferably, the sulfur-containing bactericidal component is one or more of dimethyl dithiodipropionate, dithiocarbamate and trichloromethyl-thio compounds; preferably, the sulfur-containing bactericidal component is dimethyl dithiodipropionate. The dimethyl dithiodipropionate is also used as an efficient bactericide, and has better bactericidal effect after being used together with the 2, 2-dibromo-3-nitrilopropionamide.
Preferably, the aprotic solvent is one or more of dimethylformamide, dimethylacetamide and dimethyl sulfoxide; preferably, the aprotic solvent is dimethylformamide. Dimethylformamide is an excellent aprotic solvent and also has good stability.
Preferably, the bromine-containing compound is any one or two of 2, 2-dibromo-2-nitroethanol and bronopol. 2, 2-dibromo-2-nitroethanol or bronopol has good compatibility, and can effectively prevent plants such as algae bacteria.
Preferably, the alcohol is one or more of ethanol, glycerol, diethylene glycol and 1, 3-butanediol. The alcohols have good safety performance and low price.
In addition, the invention also provides a preparation method of the bactericide, which comprises the following steps:
mixing and dissolving 2, 2-dibromo-3-nitrilopropionamide and alcohols, sequentially adding an aprotic solvent, a bromine-containing compound, a sulfur-containing bactericidal component and water, and stirring for 0.5-2 h.
Preferably, the mixing temperature of the 2, 2-dibromo-3-nitrilopropionamide and the alcohol is 30-35 ℃;
preferably, the aprotic solvent, the bromine-containing compound, the sulfur-containing bactericidal component and water are sequentially added and stirred at a temperature of 30-35 ℃.
The bactericide prepared by the preparation method has good sterilization effect and good compatibility with reverse osmosis membrane elements, and can avoid and reduce reverse osmosis membrane faults.
Compared with the prior art, the invention has the beneficial effects that:
the bactericide for the reverse osmosis system prepared by the formula is added during reverse osmosis operation, so that the sterilizing effect is enhanced, the propagation of microorganisms is inhibited, the pH application range is wider, the bactericide can be naturally biodegraded, the compatibility with reverse osmosis membrane elements is good, the faults of the reverse osmosis membrane can be avoided and reduced, the membrane operation pressure is stable, the rising trend is not obvious, and the chemical cleaning times of the membrane elements are greatly reduced. And the manufacturing method is simple and the cost is low.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Adding 5 parts of 2, 2-dibromo-3-nitrilopropionamide and 18 parts of glycerol into a reaction kettle, after the 2, 2-dibromo-3-nitrilopropionamide is completely dissolved, sequentially adding 5 parts of dimethylformamide, 4 parts of 2, 2-dibromo-2-nitroethanol, 15 parts of dimethyl dithiodipropionate and 53 parts of water, and stirring the solution at the temperature of 30-35 ℃ for 0.5-2 h.
Example 2
Adding 6 parts of 2, 2-dibromo-3-nitrilopropionamide and 11 parts of glycerol into a reaction kettle, after the 2, 2-dibromo-3-nitrilopropionamide is completely dissolved, sequentially adding 6 parts of dimethylformamide, 5 parts of 2, 2-dibromo-2-nitroethanol, 8 parts of dimethyl dithiodipropionate and 64 parts of water, and stirring the solution at the temperature of 30-35 ℃ for 0.5-2 h.
Example 3
Adding 7 parts of 2, 2-dibromo-3-nitrilopropionamide and 13 parts of glycerol into a reaction kettle, after the 2, 2-dibromo-3-nitrilopropionamide is completely dissolved, sequentially adding 7 parts of dimethylformamide, 6 parts of 2, 2-dibromo-2-nitroethanol, 9 parts of dimethyl dithiodipropionate and 58 parts of water, and stirring for 0.5-2h while keeping the temperature of the solution at 30-35 ℃.
Example 4
Adding 8 parts of 2, 2-dibromo-3-nitrilopropionamide and 15 parts of glycerol into a reaction kettle, after the 2, 2-dibromo-3-nitrilopropionamide is completely dissolved, sequentially adding 8 parts of dimethylformamide, 7 parts of bronopol, 11 parts of dimethyl dithiodipropionate and 51 parts of water, and stirring for 0.5-2 hours while keeping the temperature of the solution at 30-35 ℃.
Example 5
Adding 10 parts of 2, 2-dibromo-3-nitrilopropionamide and 8 parts of glycerol into a reaction kettle, after the 2, 2-dibromo-3-nitrilopropionamide is completely dissolved, sequentially adding 10 parts of dimethylformamide, 8 parts of bronopol, 5 parts of dimethyl dithiodipropionate and 61 parts of water, and stirring the solution for 0.5 to 2 hours at the temperature of between 30 and 35 ℃.
Example 6
The only difference from example 3 is that the sulphur-containing biocidal ingredient was selected as: dimethyl dithiodipropionate and dithiocarbamate.
Example 7
The only difference from example 3 is 6 parts of 2, 2-dibromo-3-nitrilopropionamide.
Example 8
The only difference from example 3 is 10 parts of dimethyl dithiodipropionate.
Example 9
The only difference from example 3 is 7 parts of 2, 2-dibromo-2-nitroethanol.
Comparative example 1
The procedure was as in example 3 except that 2, 2-dibromo-3-nitrilopropionamide was not added.
Comparative example 2
The specific procedure is identical to that of example 3, except that dimethyl dithiodipropionate is not added.
Comparative example 3
The procedure was as in example 3 except that 2, 2-dibromo-2-nitroethanol was not added.
Comparative example 4
The specific operation steps are the same as those in example 3, except that 3 parts of 2, 2-dibromo-3-nitrilopropionamide, 2 parts of 2, 2-dibromo-2-nitroethanol and 3 parts of dimethyl dithiodipropionate are used.
Comparative example 5
The specific operation steps are the same as those in example 3, except that 12 parts of 2, 2-dibromo-3-nitrilopropionamide, 10 parts of 2, 2-dibromo-2-nitroethanol and 18 parts of dimethyl dithiodipropionate are used.
Comparative example 6
Commercial product 1: a reverse osmosis bactericide of the corridor mall environmental protection technology limited company.
Comparative example 7
Commercial product 2: reverse osmosis bactericide from Shandong Huate Water treatment science and technology Co.
Experimental example 1
The bactericides of the embodiments 1 to 5 and the comparative examples 1 to 7 are compared in bactericidal performance, the experimental method refers to the industrial standard SY/T5890 + 1993 'bactericide performance evaluation method' to carry out performance experiment, the specific method adopts the higher water quality of the reverse osmosis water inlet microorganism to culture heterotrophic bacteria, and the number of the bacteria reaches 106-107After CFU/mL, the bactericide of the invention is added, and the total number of the residual heterotrophic bacteria in the conical bottle is determined after 15min, 1h, 8h, 24h and 48h respectively under the condition of room temperature. Comparative experiments were carried out under the same conditions and the results are shown in table 1:
TABLE 1 results of the experiment
As can be seen from table 1 above, the germicide of the reverse osmosis system of the present invention has superior germicidal effect because 2, 2-dibromo-3-nitrilopropionamide, the sulfur-containing germicidal component, and the bromine-containing compound are compatible with each other and act together, and each component needs to be in a proper amount range. It can be seen from example 6 that the sulfur-containing bactericidal component has a better bactericidal effect than the single sulfur-containing bactericidal component after two components are selected for compounding. As can be seen from the examples 7 to 9, the component content ratio in the example 3 is the optimal ratio, and the best sterilization effect is achieved. By comparing the data of comparative examples 1-3 with those of examples 1-9, it was shown that the absence of any of the three components reduced the efficiency of sterilization. Comparing the data of comparative examples 4 to 5 with those of examples 1 to 9, it was found that if the amounts of 2, 2-dibromo-3-nitrilopropionamide, the sulfur-containing bactericidal component and the bromine-containing compound are too small or too large, the bactericidal efficiency of the bactericide decreases, because if the amounts are not controlled within the proper ratio of the present invention, the bactericidal effect of the three components after the combination is rather decreased by the excessive amount. As can be seen by comparing examples 6-7 with examples 1-9, the reverse osmosis system of the present invention has significantly higher biocidal efficacy than commercial products 1 and 2. Therefore, the raw materials of the bactericide formula disclosed by the invention are specific in component selection and the dosage of each component, and cannot be changed randomly, and only the bactericide for preparing the reverse osmosis system disclosed by the invention has the highest bactericidal rate which can reach 99.9%.
In a word, the bactericide for the reverse osmosis system prepared by the formula is added during reverse osmosis operation, so that the sterilizing effect is enhanced, the propagation of microorganisms is inhibited, the application range of pH is wider, the bactericide can be naturally biodegraded, the compatibility with reverse osmosis membrane elements is good, the faults of the reverse osmosis membrane can be avoided and reduced, the membrane operation pressure is stable, the rising trend is not obvious, and the chemical cleaning times of the membrane elements are greatly reduced. And the manufacturing method is simple and the cost is low.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (9)
1. The bactericide for the reverse osmosis system is characterized by being mainly prepared from the following raw materials: 5-10 parts of 2, 2-dibromo-3-nitrilopropionamide, 5-15 parts of sulfur-containing bactericidal component, 4-8 parts of bromine-containing compound, 8-18 parts of alcohol, 5-10 parts of aprotic solvent and 50-65 parts of water in parts by mass.
2. The bactericide according to claim 1, which is characterized by comprising, by mass, 6-8 parts of 2, 2-dibromo-3-nitrilopropionamide, 8-11 parts of a sulfur-containing bactericide, 5-7 parts of a bromine-containing compound, 11-15 parts of an alcohol, 6-8 parts of an aprotic solvent, and 55-60 parts of water.
3. The bactericide according to claim 1, which comprises 7 parts by mass of 2, 2-dibromo-3-nitrilopropionamide, 9 parts by mass of a sulfur-containing bactericide component, 6 parts by mass of a bromine-containing compound, 13 parts by mass of an alcohol, 7 parts by mass of an aprotic solvent, and 58 parts by mass of water.
4. The bactericide according to claim 1, wherein the sulfur-containing bactericidal component is one or more of dimethyl dithiodipropionate, dithiocarbamate and trichloromethyl-thionyle compound;
preferably, the sulfur-containing bactericidal component is dimethyl dithiodipropionate.
5. The bactericide as claimed in claim 1, wherein the aprotic solvent is one or more of dimethylformamide, dimethylacetamide and dimethylsulfoxide;
preferably, the aprotic solvent is dimethylformamide.
6. The bactericide according to claim 1, wherein the bromine-containing compound is either or both of 2, 2-dibromo-2-nitroethanol and bronopol.
7. The bactericide as claimed in claim 1, wherein the alcohol is one or more of ethanol, glycerol, diethylene glycol, and 1, 3-butanediol.
8. The method for producing a bactericide as claimed in any of claims 1 to 8, comprising the steps of:
mixing and dissolving 2, 2-dibromo-3-nitrilopropionamide and alcohols, sequentially adding an aprotic solvent, a bromine-containing compound, a sulfur-containing bactericidal component and water, and stirring for 0.5-2 h.
9. The process according to claim 8, wherein the temperature at which the 2, 2-dibromo-3-nitrilopropionamide and the alcohol are mixed is 30 to 35 ℃;
preferably, the aprotic solvent, the bromine-containing compound, the sulfur-containing bactericidal component and water are sequentially added and stirred at a temperature of 30-35 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112868650A (en) * | 2021-02-03 | 2021-06-01 | 山东华特水处理科技有限公司 | Bactericide and preparation method and application thereof |
| CN114375953A (en) * | 2021-12-30 | 2022-04-22 | 上海丰信环保科技有限公司 | Reverse osmosis/nanofiltration bactericide suitable for alkaline water and preparation method thereof |
| CN114794109A (en) * | 2022-06-13 | 2022-07-29 | 山东天庆科技发展有限公司 | Reverse osmosis special bactericide and preparation method thereof |
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| CN112868650A (en) * | 2021-02-03 | 2021-06-01 | 山东华特水处理科技有限公司 | Bactericide and preparation method and application thereof |
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| CN114794109A (en) * | 2022-06-13 | 2022-07-29 | 山东天庆科技发展有限公司 | Reverse osmosis special bactericide and preparation method thereof |
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