CN108633880A - Seawater molluscicide and its preparation method and application - Google Patents
Seawater molluscicide and its preparation method and application Download PDFInfo
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- CN108633880A CN108633880A CN201810352694.3A CN201810352694A CN108633880A CN 108633880 A CN108633880 A CN 108633880A CN 201810352694 A CN201810352694 A CN 201810352694A CN 108633880 A CN108633880 A CN 108633880A
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- Prior art keywords
- seawater
- molluscicide
- quaternary ammonium
- ammonium salt
- bleeding agent
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Classifications
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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
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Abstract
The present invention relates to seawater taking system marine growth suppression technology fields, and in particular to a kind of seawater molluscicide and its preparation method and application for sea water desalination water intake system.The present invention provides a kind of seawater molluscicide, the seawater molluscicide includes quaternary ammonium salt, bleeding agent, deionized water and organic solvent, wherein, by weight percentage, the quaternary ammonium salt is 9 55%, the bleeding agent is 1 8%, and the organic solvent 3 20%, surplus is deionized water.The quaternary ammonium salt of different alkyl chains is used in compounding by seawater molluscicide of the present invention, and it is subject to the effect of bleeding agent, biological clay and biomass can be effectively peeled off, allow quaternary ammonium salt component is significantly more efficient to act on biological tissue, play effect of preferably killing livestock, under complicated seawater condition of water quality, remain to keep good effect of killing livestock.
Description
Technical field
The present invention relates to seawater taking system marine growth suppression technology fields, and in particular to one kind is fetched water for sea water desalination
Seawater molluscicide of system and its preparation method and application.
Background technology
Sea water desalination is a water technology increased income, and can increase fresh water overall supplies, opens up new freshwater resources,
Gradually become a kind of important channel that countries in the world solve " water crisis ".However, desalination technology is deposited in its water intake system
In large-scale molluscan pollution and breed this serious problem.It usual this kind of system intake, the pump housing, water intake conduit and changes
In thermotube wall easily grow seashells, cause system water delivery to be obstructed, equipment corrosion and heat conductive efficiency decline, cause greatly
Economic loss.Shell is easily stuck in heat exchanger tube nozzle simultaneously, and under water impact, the shell of cutting edge of a knife or a sword thorn generates vibration and displacement, mill
Heat exchange tube wall is worn, security risk is serious.
The past country is widely used chlorination and carries out source control, though with control bacterium algae effect, it is relatively difficult to achieve to shellfish
Equal Macro-fouling Organismss being effectively peeled off or killing, and chlorine is serious to metal equipment corrosion, operational hazards, and it is easy to be discharged into marine site
Generate carcinogen.
For oxidizing biocides there are the drawbacks of, in order to preferably to attachment shell-fish control, it is non-in recent years
The research and development of oxidisability molluscicide make some progress, as CN101830543B proposes a kind of sea of seawater direct-current cooling system
BIOLOGICAL CONTROL technique, the biocide for using polyquaternium and bleaching water to form.CN104798803A discloses one kind with poly- six
Methylguanidine and the thio benzothiazole of 2- mercapto cyano methyls marine growth biocide as main component.
CN105766984A discloses one kind with polyquaternium and quaternary ammonium salt marine growth biocide as main component, medication
There can be preferable killing effect to green mouth when 10ppm.CN105165835A discloses a kind of seawater direct-current cooling system Hai Sheng
Object inhibitor, active ingredient are dodecyl dimethyl benzyl ammonium chloride, alkyl aminoethyl glycine, imidazolines cycloamination
Close object.
However, the seawater molluscicide research for sea water desalination water intake system is relatively fewer, it is contemplated that engineer application needs,
Such medicament is other than should have to the good inhibition of Macro-fouling Organismss, bio-toxicity, the influence to environment, and with
The compatibility of other medicaments is also direction needed to be considered.
Invention content
For this purpose, the present invention is in view of the deficiencies in the prior art or insufficient, provide a kind of for seawater taking system
Seawater molluscicide, the seawater molluscicide is a kind of water treatment agent that suitable variation water quality range is wide, have it is efficient, low
The features such as malicious, without phosphorus, degradable, is compounded by Multiple components and improves drug effect, and realization and other medicament matched wells, to pacify
Efficiently realize engineer application entirely.
The present invention provides a kind of seawater molluscicide, it includes quaternary ammonium salt, bleeding agent, deionized water and organic solvent,
In, by weight percentage, the quaternary ammonium salt is 9-55%, and the bleeding agent is 1-8%, organic solvent 3-20%, and surplus is
Deionized water.
The present invention also provides the preparation methods of seawater molluscicide, and it includes following step：
(1) it is mixed quaternary ammonium salt and deionized water to obtain mixture A；
(2) bleeding agent and organic solvent are mixed to get mixture B, are then added to mixture B mixed in step (1)
It closes in object A and obtains seawater molluscicide.
Specifically, the present invention proposes following technical solution.
The present invention provides a kind of seawater molluscicides, which is characterized in that the seawater molluscicide includes quaternary ammonium salt, infiltration
Agent, deionized water and organic solvent, wherein by weight percentage, the quaternary ammonium salt is 9-55%, and the bleeding agent is 1-
8%, the organic solvent 3-20%, surplus is deionized water.
Preferably, for the seawater molluscicide, wherein the quaternary ammonium salt is single-stranded quaternary ammonium salt, preferably C12~C16
Zephiran.
Preferably, for the seawater molluscicide, wherein the quaternary ammonium salt includes dodecyl dimethyl Benzylmagnesium chloride
Ammonium, myristyl benzyl dimethyl ammonium chloride and cetalkonium chloride.
Preferably, for the seawater molluscicide, wherein by weight percentage, the dodecyl dimethyl benzyl
Ammonium chloride is 3-20%, preferably 5-20%, and the myristyl benzyl dimethyl ammonium chloride is 5-25%, preferably 15-
25%, the cetalkonium chloride is 1-10%, preferably 5-10%.
Preferably, for the seawater molluscicide, wherein the bleeding agent is nonionic surfactant, it is preferred that
The bleeding agent is selected from C12~C18Aliphatic amine polyoxyethylene ether, aliphatic acid polyethenoxy ether, fatty alcohol polyoxyethylene ether,
One or more in nonylphenol polyoxyethylene ether or castor oil polyoxyethylene ether, it is furthermore preferred that the bleeding agent is selected from
In dodecyl fatty alcohol polyoxyethylene ether, myristyl aliphatic amine polyoxyethylene ether, nonylphenol polyoxyethylene ether one kind or
More than one.
Preferably, for the seawater molluscicide, wherein the organic solvent is selected from octanol, ethyl alcohol, propyl alcohol, second
One or more in glycol, N,N-dimethylformamide or tetrahydrofuran.
The present invention provides the preparation methods of the molluscicide, and it includes following step：
(1) it is mixed quaternary ammonium salt and deionized water to obtain mixture A；
(2) bleeding agent and organic solvent are mixed to get mixture B, are then added to mixture B mixed in step (1)
It closes in object A and obtains seawater molluscicide.
Preferably, for the preparation method, wherein in step (1), rotating speed of the stirring at 50-70 revs/min
Under be stirred.
Preferably, for the preparation method, wherein in step (1), the stirring is in the case where temperature is 20-35 DEG C
Stirring.
The present invention provides application of the seawater molluscicide in seawater taking system.
Preferably, for the application, wherein dosage of the seawater molluscicide in seawater taking system is 2-
10mg/L。
Advantageous effect obtained by the present invention is：
The quaternary ammonium salt of different alkyl chains is used in compounding by the seawater molluscicide of the present invention, and is subject to the effect of bleeding agent, energy
It is enough effectively peeled off biological clay and biomass, allows quaternary ammonium salt component is significantly more efficient to act on biological tissue, is played more preferable
Effect of killing livestock remain to keep good effect of killing livestock under complicated seawater condition of water quality.
Description of the drawings
Fig. 1-1 is death rate schematic diagram of the seawater molluscicide to green mouth killing test of various concentration in embodiment one；
Fig. 1-2 is death rate schematic diagram of the seawater molluscicide to clam son's killing test of various concentration in embodiment one；
Fig. 1-3 is the schematic diagram of the green mouth and clam son killed using the seawater molluscicide of embodiment one.
Fig. 2 is seawater molluscicide in embodiment one to byssus release effect schematic diagram, wherein (a) is to be added in Fig. 2
Culture water tank bottom of the 0mg/L molluscicides after 96 hours, (b) is the culture water that 10mg/L molluscicides are added after 96 hours in Fig. 2
Bottom portion.
Fig. 3 is that one seawater molluscicide of embodiment uses front and back power plant's sea water service system shellfish schematic diagram, wherein (a) is in Fig. 3
Using the live body shellfish schematic diagram grown in Condenser Titanium Tube before this molluscicide, (b) is clear in pipeline after shutdown and system in Fig. 3
A large amount of shellfish schematic diagrames of reason, (c) be the heat exchanger tube pipeline signal sparkling clean after 1 year using molluscicide of the present invention in Fig. 3
Figure, in Fig. 3 (d) be using molluscicide of the present invention after 1 year without any shellfish grow into pumping grid schematic diagram.
Fig. 4 is the schematic diagram that the seawater molluscicide of the 4mg/L in embodiment one influences sea water desalination antisludging agent.
Fig. 5 is the schematic diagram that the seawater molluscicide biological degradation rate in embodiment one changes over time.The molluscicide product
The time that biological degradation rate reaches 90% is only 48 hours.
Specific implementation mode
Fig. 1-1 is death rate schematic diagram of the seawater molluscicide to green mouth killing test of various concentration in embodiment one, from
As can be seen that one obtained seawater molluscicide of embodiment has good killing effect for green mouth, by embodiment in Fig. 1-1
Respectively with 4mg/L, the commodity densimeter of 8mg/L, 10mg/L can draw one preparation-obtained seawater molluscicide in 24 hours
It is dead to play significant shellfish, killing rate can reach 87% or more within 72 hours.
Fig. 1-2 is death rate schematic diagram of the seawater molluscicide to clam son's killing test of various concentration in embodiment one, from
As can be seen that one obtained seawater molluscicide of embodiment has good killing effect for clam son, by embodiment in Fig. 1-2
Respectively with 4mg/L, the commodity densimeter of 8mg/L, 10mg/L can draw one preparation-obtained seawater molluscicide in 48 hours
It is dead to play significant shellfish, killing rate can reach 95% or more within 72 hours.
Fig. 1-3 is the dead status diagram of the green mouth and clam son after the seawater molluscicide using embodiment one.
Fig. 2 is peeling effect figure of the seawater molluscicide in embodiment one to mussel byssus, wherein (a) is to be added in Fig. 2
Culture water tank bottom of the 0mg/L molluscicides after 96 hours, it can be seen that the byssus of shellfish secretion is firmly adhered to water tank bottom, and
(b) is the culture water tank bottom that 10mg/L molluscicides are added after 96 hours in Fig. 2, and bottom is sparkling clean, illustrates no byssus attachment.
Fig. 3 is that one seawater molluscicide of embodiment uses certain front and back Seawater Desalination Project scene shellfish schematic diagram, wherein Fig. 3
In (a) be using the live body shellfish schematic diagram grown in low-temperature multiple-effect seawater desalination heat exchanger tube before this molluscicide, (b) is in Fig. 3
The a large amount of shellfish schematic diagrames cleared up in pipeline and system after shutdown, after (c) is using one seawater molluscicide of embodiment 1 year in Fig. 3
Sparkling clean heat exchanger tube piping schematic, (d) is to be grown without any shellfish using after one seawater molluscicide of embodiment 1 year in Fig. 3
It is raw into pump grid schematic diagram.
Fig. 4 is the schematic diagram that one seawater molluscicide of embodiment influences sea water desalination antisludging agent, from fig. 4, it can be seen that
In the presence of the seawater molluscicide of 4mg/L, the scale inhibition performance of the antisludging agent is 97.54%, is more than the resistance when antisludging agent is used alone
Dirty rate 96.83%, when illustrating that the obtained seawater molluscicide of the present invention is used for seawater desalination system, for sea water desalination antisludging agent
Performance do not have an impact, and there are certain facilitations.This may be with such molluscicide with surface-active with one
Surely absorption peptizaiton is related.
Fig. 5 is the schematic diagram that the biological degradation rate of the seawater molluscicide of embodiment one changes over time.
As described above, the present invention provides a kind of seawater molluscicide, it includes quaternary ammonium salt, bleeding agent and has deionized water
Solvent, wherein by weight percentage, the quaternary ammonium salt is 9-55%, and the bleeding agent is 1-8%, organic solvent 5-
15%, surplus is deionized water.
Preferably, it is described by weight percentage, the quaternary ammonium salt be 25-55%, the bleeding agent be 2-6%, it is described
Organic solvent is 5-15%, and surplus is deionized water.
In a kind of currently preferred specific implementation mode, the quaternary ammonium salt is single-stranded quaternary ammonium salt, preferably C12~C16
Zephiran, the quaternary ammonium salt include dodecyl benzyl dimethyl ammonium chloride, myristalkonium
Ammonium chloride and cetalkonium chloride, described quaternary ammonium salt one end are hydrophilic radical, and the other end is hydrophobic group,
When being organism in water contact, hydrophilic radical can combine closely aquatic organism, and the other end is outside, form the surface of hydrophobic, prevention
The transmission of water oxygen, thus make aquatic organism death by suffocation.And since cell membrane is usually negatively charged, N+It is negative easily to neutralize these
Charge destroys epicyte protein activity, cuts off the transmission of intracellular nutritional substance, reach killing effect.The introducing of benzyl is effective
Increase the bactericidal performance of quaternary ammonium salt.However carbochain long or too short (being more than 18 or less than 8) is it has been generally acknowledged that without work of killing livestock
Property, therefore, the present invention chooses C12~C16Quaternary ammonium salt as main component.Multiple components are mixed with the synergy association conducive to medicament
Same-action can develop immunity to drugs to one-component medicament to avoid system marine growth.
In a kind of preferred embodiment of the present invention, the bleeding agent is nonionic surfactant, it is preferred that
The bleeding agent is selected from C12~C18Aliphatic amine polyoxyethylene ether, aliphatic acid polyethenoxy ether, fatty alcohol polyoxyethylene ether,
One or more in nonylphenol polyoxyethylene ether or castor oil polyoxyethylene ether, the bleeding agent, which plays, helps seawater to kill
Shellfish agent infiltrates into the effect of equipment surface.Wherein, (C in polymer2H4O)nN be 6-8.
In a kind of preferred embodiment of the present invention, the organic solvent is selected from octanol, ethyl alcohol, propyl alcohol, second
One or more in glycol, n,N-Dimethylformamide or tetrahydrofuran, the organic solvent dispersion and dissolving
Effect, the effect of also acting as suds and reduce freezing point.
It is by season the present invention provides a kind of molluscicide preparation method in a kind of currently preferred embodiment
Ammonium salt is mixed with deionized water, under the conditions of 20-35 DEG C, is stirred to obtain mixture A with 50~70 revs/min of rotating speed, will
Bleeding agent is mixed to get mixture B with organic solvent, then is added to be stirred to obtain in mixture A by mixture B and kills shellfish
Agent.
The obtained seawater molluscicide of the present invention, the dosage in seawater taking system are 2-10mg/L.
The obtained seawater molluscicide of the present invention can be used cooperatively when in use with sodium hypochlorite.
In a kind of currently preferred specific implementation mode, the present invention provides one kind adding scheme, for annual
1,2,3,7,8, December molluscicide 2-10mg/L was periodically added with monthly 4~8 hours frequencies, auxiliary adds time
10~15mg/L of sodium chlorate, three times/moon, time per treatment are 2~6 hours；Annual 4,5,6,9,10, November, with
Monthly 4~8 hours frequencies periodically add 2~10mg/L of molluscicide twice, and auxiliary launches sodium hypochlorite 10~15mg/L, and two
Secondary/moon, time per treatment are 2~6 hours.
The equipment and analysis that the manufacturer to raw material and equipment used in the present embodiment and product analysis use below
Method is described as follows, wherein the chemical substance do not indicate be conventional reagent the pure rank of chemistry.Wherein, real
The information for applying the raw material used in example is as shown in table 1.
The information of raw material used in 1 embodiment of table
| Material name | Purity | Manufacturer |
| Dodecyl benzyl dimethyl ammonium chloride | 99% | Shandong Hao Yao new materials Co., Ltd |
| Myristyl benzyl dimethyl ammonium chloride | 99% | Chengdu Dian Chun Science and Technology Ltd.s |
| Cetalkonium chloride | 99% | Wuhan is far at creating Science and Technology Ltd. |
| Dodecyl fatty alcohol polyoxyethylene ether | 99% | Haian County of Jiangsu Province petrochemical plant |
| Myristyl aliphatic amine polyoxyethylene ether | 99% | Haian County of Jiangsu Province petrochemical plant |
| Nonylphenol polyoxyethylene ether | 99% | Shandong natural laws bioengineering Co., Ltd |
| Castor oil polyoxyethylene ether | 99.8% | Shandong natural laws bioengineering Co., Ltd |
One molluscicide of embodiment and preparation method thereof
Molluscicide includes following raw materials by weight percentage：20% dodecyl benzyl dimethyl ammonium chloride, 25%
Myristyl benzyl dimethyl ammonium chloride, 5% cetalkonium chloride, 38% deionized water, 2% ooze
Saturating agent and 10% organic solvent, wherein the bleeding agent is dodecyl fatty alcohol polyoxyethylene ether, and the organic solvent is
Ethyl alcohol,
Preparation method is：
(1) by above-mentioned dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, cetyl
Dimethyl benzyl ammonium chloride is once put into reaction kettle with deionized water, and under 60 revs/min of rotating speed, stirring is warming up to 30 DEG C and fills
Divide dissolving, forms stable mixture A；
(2) above-mentioned bleeding agent and organic solvent are added to stirring and dissolving in reaction vessel and form stable mixture B,
Then mixture B is added in reaction kettle after being stirred with mixture A and obtains molluscicide.
Two molluscicide of embodiment and preparation method thereof
Molluscicide includes following raw materials by weight percentage：10% dodecyl benzyl dimethyl ammonium chloride, 15%
Myristyl benzyl dimethyl ammonium chloride, 8% cetalkonium chloride, 46% deionized water, 6% ooze
Saturating agent and 15% organic solvent, wherein the bleeding agent is myristyl aliphatic amine polyoxyethylene ether, and the organic solvent is
The volume ratio of the mixture of ethyl alcohol and ethylene glycol, ethyl alcohol and ethylene glycol is 3:1
Preparation method is：
(1) by above-mentioned dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, cetyl
Dimethyl benzyl ammonium chloride is once put into reaction kettle with deionized water, and under 50 revs/min of rotating speed, stirring is warming up to 30 DEG C and fills
Divide dissolving, forms stable mixture A；
(2) above-mentioned bleeding agent and organic solvent are added to stirring and dissolving in reaction vessel and form stable mixture B,
Then mixture B is added in reaction kettle after being stirred with mixture A and obtains molluscicide.
Three molluscicide of embodiment and preparation method thereof
Molluscicide includes following raw materials by weight percentage：5% dodecyl benzyl dimethyl ammonium chloride, the ten of 20%
Tetraalkyl dimethyl benzyl ammonium chloride, 10% cetalkonium chloride, 56% deionized water, 4% ooze
Saturating agent and 5% organic solvent, wherein the bleeding agent is nonylphenol polyoxyethylene ether, and the organic solvent is propyl alcohol,
Preparation method is：
(1) by above-mentioned dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, cetyl
Dimethyl benzyl ammonium chloride is once put into reaction kettle with deionized water, and under 70 revs/min of rotating speed, stirring is warming up to 30 DEG C and fills
Divide dissolving, forms stable mixture A；
(2) above-mentioned bleeding agent and organic solvent are added to stirring and dissolving in reaction vessel and form stable mixture B,
Then mixture B is added in reaction kettle after being stirred with mixture A and obtains molluscicide.
Example IV molluscicide and preparation method thereof
Molluscicide includes following raw materials by weight percentage：3% dodecyl benzyl dimethyl ammonium chloride, the ten of 10%
Tetraalkyl dimethyl benzyl ammonium chloride, 3% cetalkonium chloride, 56% deionized water, 8% infiltration
Agent and 20% organic solvent, wherein the bleeding agent be castor oil polyoxyethylene ether, the organic solvent be N, N- dimethyl
Formamide.
Preparation method is：
(1) by above-mentioned dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, cetyl
Dimethyl benzyl ammonium chloride is once put into reaction kettle with deionized water, and under 55 revs/min of rotating speed, stirring is warming up to 25 DEG C and fills
Divide dissolving, forms stable mixture A；
(2) above-mentioned bleeding agent and organic solvent are added to stirring and dissolving in reaction vessel and form stable mixture B,
Then mixture B is added in reaction kettle after being stirred with mixture A and obtains molluscicide.
Five molluscicide of embodiment and preparation method thereof
Molluscicide includes following raw materials by weight percentage：15% dodecyl benzyl dimethyl ammonium chloride, the ten of 5%
Tetraalkyl dimethyl benzyl ammonium chloride, 1% cetalkonium chloride, 75% deionized water, 1% infiltration
Agent and 3% organic solvent, wherein the bleeding agent be myristyl aliphatic acid polyethenoxy ether, the organic solvent be it is pungent
Alcohol.
Preparation method is：
(1) by above-mentioned dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, cetyl
Dimethyl benzyl ammonium chloride is once put into reaction kettle with deionized water, and under 60 revs/min of rotating speed, stirring is warming up to 35 DEG C and fills
Divide dissolving, forms stable mixture A；
(2) above-mentioned bleeding agent and organic solvent are added to stirring and dissolving in reaction vessel and form stable mixture B,
Then mixture B is added in reaction kettle after being stirred with mixture A and obtains molluscicide.
Six molluscicide of embodiment and preparation method thereof
Molluscicide includes following raw materials by weight percentage：5% dodecyl benzyl dimethyl ammonium chloride, the ten of 20%
Tetraalkyl dimethyl benzyl ammonium chloride, 10% cetalkonium chloride, 56% deionized water, 4% ooze
Saturating agent and 5% organic solvent, wherein the bleeding agent is myristyl aliphatic alcohol polyethenoxy acid, and the organic solvent is
Tetrahydrofuran.
Preparation method is：
(1) by above-mentioned dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, cetyl
Dimethyl benzyl ammonium chloride is once put into reaction kettle with deionized water, and under 60 revs/min of rotating speed, stirring is warming up to 35 DEG C and fills
Divide dissolving, forms stable mixture A；
(2) above-mentioned bleeding agent and organic solvent are added to stirring and dissolving in reaction vessel and form stable mixture B,
Then mixture B is added in reaction kettle after being stirred with mixture A and obtains molluscicide.
Seven molluscicide of embodiment and preparation method thereof
Molluscicide includes following raw materials by weight percentage：15% dodecyl benzyl dimethyl ammonium chloride, 20%
Myristyl benzyl dimethyl ammonium chloride, 8% cetalkonium chloride, 51% deionized water, 6% ooze
Saturating agent and 10% organic solvent, wherein the bleeding agent is dodecyl fatty alcohol polyoxyethylene ether, and the organic solvent is
Ethyl alcohol,
Preparation method is：
(1) by above-mentioned dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, cetyl
Dimethyl benzyl ammonium chloride is once put into reaction kettle with deionized water, and under 60 revs/min of rotating speed, stirring is warming up to 30 DEG C and fills
Divide dissolving, forms stable mixture A；
(2) above-mentioned bleeding agent and organic solvent are added to stirring and dissolving in reaction vessel and form stable mixture B,
Then mixture B is added in reaction kettle after being stirred with mixture A and obtains molluscicide.
Eight molluscicide of embodiment and preparation method thereof
Molluscicide includes following raw materials by weight percentage：20% dodecyl benzyl dimethyl ammonium chloride, 25%
Myristyl benzyl dimethyl ammonium chloride, 5% cetalkonium chloride, 39% deionized water, 1% ooze
Saturating agent and 10% organic solvent, wherein the bleeding agent is dodecyl fatty alcohol polyoxyethylene ether, and the organic solvent is
Ethyl alcohol,
Preparation method is：
(1) by above-mentioned dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, cetyl
Dimethyl benzyl ammonium chloride is once put into reaction kettle with deionized water, and under 60 revs/min of rotating speed, stirring is warming up to 30 DEG C and fills
Divide dissolving, forms stable mixture A；
(2) above-mentioned bleeding agent and organic solvent are added to stirring and dissolving in reaction vessel and form stable mixture B,
Then mixture B is added in reaction kettle after being stirred with mixture A and obtains molluscicide.
Nine molluscicide of embodiment and preparation method thereof
Molluscicide includes following raw materials by weight percentage：20% dodecyl benzyl dimethyl ammonium chloride, 25%
Myristyl benzyl dimethyl ammonium chloride, 10% cetalkonium chloride, 27% deionized water, 8%
Bleeding agent and 10% organic solvent, wherein the bleeding agent be dodecyl fatty alcohol polyoxyethylene ether, the organic solvent
For ethyl alcohol,
Preparation method is：
(1) by above-mentioned dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, cetyl
Dimethyl benzyl ammonium chloride is once put into reaction kettle with deionized water, and under 60 revs/min of rotating speed, stirring is warming up to 30 DEG C and fills
Divide dissolving, forms stable mixture A；
(2) above-mentioned bleeding agent and organic solvent are added to stirring and dissolving in reaction vessel and form stable mixture B,
Then mixture B is added in reaction kettle after being stirred with mixture A and obtains molluscicide.
One molluscicide of comparative example and preparation method thereof
Molluscicide includes following raw materials by weight percentage：20% dodecyl benzyl dimethyl ammonium chloride, 68%
Deionized water, 2% bleeding agent and 10% organic solvent, wherein the bleeding agent is dodecyl aliphatic alcohol polyethenoxy
Ether, the organic solvent are ethyl alcohol.
Preparation method is identical as the preparation method described in embodiment one.
Two molluscicide of comparative example and preparation method thereof
Molluscicide includes following raw materials by weight percentage：20% dodecyl benzyl dimethyl ammonium chloride, 25%
Myristyl benzyl dimethyl ammonium chloride, 43% deionized water, 2% bleeding agent and 10% organic solvent, wherein it is described
Bleeding agent is dodecyl fatty alcohol polyoxyethylene ether, and the organic solvent is ethyl alcohol.
Preparation method is identical as the preparation method described in embodiment one.
Three molluscicide of comparative example and preparation method thereof
Molluscicide includes following raw materials by weight percentage：20% dodecyl benzyl dimethyl ammonium chloride, 25%
Myristyl benzyl dimethyl ammonium chloride, 5% cetalkonium chloride, 40% deionized water, 10%
Organic solvent, wherein the organic solvent is ethyl alcohol.
Preparation method is identical as the preparation method described in embodiment one.
Four molluscicide of comparative example and preparation method thereof
Molluscicide includes following raw materials by weight percentage：22% dodecyl benzyl dimethyl ammonium chloride, 27%
Myristyl benzyl dimethyl ammonium chloride, 13% cetalkonium chloride, 23% deionized water, 10%
Bleeding agent and 5% organic solvent, wherein the bleeding agent be dodecyl fatty alcohol polyoxyethylene ether, the organic solvent
For ethyl alcohol.
Preparation method is identical as the preparation method described in embodiment one.
Five molluscicide of comparative example and preparation method thereof
Molluscicide includes following raw materials by weight percentage：2% dodecyl benzyl dimethyl ammonium chloride, the ten of 3%
Tetraalkyl dimethyl benzyl ammonium chloride, 0.5% cetalkonium chloride, 73% deionized water, 0.5%
Bleeding agent and 20% organic solvent, wherein the bleeding agent be dodecyl fatty alcohol polyoxyethylene ether, the organic solvent
For ethyl alcohol.
Preparation method is identical as the preparation method described in embodiment one.
Compliance test result is tested
1. sterilization experiment
By embodiment one to embodiment nine, comparative example one is made solvent with water to five obtained seawater molluscicide of comparative example and is matched
At certain density aqueous solution, with pipettor to equipped with 100mL seawater containing bacterium (bacteria containing amount 1 × 105CFU/mL~5 × 105CFU/
ML set amount) is pipetted in conical flask with stopper, triangular flask is placed at 30 DEG C and stands 4 hours, using in GB 17378.7-2007
10.1 colony counting methods measure the bacteria containing amount in seawater, and according to the total number of bacteria in seawater before and after addition medicament, calculating is killed
Bacterium rate (KB%), formula is as follows：
C in formula2To add bacteria containing amount in the seawater after molluscicide sample experiment, c1For not plus after water treatment agent sample experiment
Bacteria containing amount in seawater.The results are shown in Table 2：
2 embodiment of table and comparative formulation kill rate bacterium
By the experimental result of table 2 it is found that when using a concentration of 10mg/L and 20mg/L, by embodiment one and comparative example one
It is compared to three, bactericidal effect is much better than the bactericidal effect of comparative example one to three.Embodiment two to embodiment nine all has preferably
Bactericidal effect, in a concentration of 20mg/L, sterilizing rate is 80% or more.And due to active principle in the formula of comparative example five
Concentration is far below given range, bactericidal effect of the bactericidal effect far below embodiment one to embodiment nine.The sterilization of comparative example four
Rate has excellent performance, but is not suitable for engineer application from the consideration of medicament use cost, and since medicament effective concentration is excessively high,
It is possible that causing to target the avoidance of shellfish biology irritability, and reduce degradation efficiency.
2. killing shellfish experiment
Using green mouth and clam son as subjects, with reference to the 11st parts GB 17378.7-2007, in the water tank of every lattice 8L capacity
In raised and train, per lattice water tanks in place single examination by biology 60.By embodiment one to embodiment nine and comparative example one and right
Five preparation-obtained molluscicide of ratio makees solvent with water and is made into certain density aqueous solution, is pipetted and is set into water tank with pipettor
It is specified amount (4mg/L and 10mg/L) to quantify to drug concentration, replaced a test solution every 24 hours, detects the seawater molluscicide
It kills livestock effect.From experiment initial time, live body number in water tank is recorded every one section of set time, is touched not after being opened with shell
The judgment basis as shellfish death can be closed.It was found that dead individuals are sorted out in time, experimental data is as shown in table 3, by embodiment
One preparation-obtained molluscicide makees solvent with water and is made into certain density aqueous solution, and set amount is pipetted into water tank with pipettor
It is specified amount (4mg/L, 8mg/L, 10mg/L) to drug concentration, experimental result is as shown in Fig. 1-1 to Fig. 1-3 and Fig. 2.Experiment is used
Water is derived from Bohai Sea PORT OF HUANGHUA marine site seawater.
Embodiment and comparative formulation kills shellfish rate after table 3 48 hours
From table 3 it can be seen that young for green mouth and clam, in a concentration of 4mg/L and 10mg/L, embodiment one kills shellfish effect
Fruit is far superior to comparative example one and kills shellfish effect to comparative example three, in addition, embodiment two to embodiment nine kill shellfish effect also compared with
It is good.Although comparative example four is preferable for the killing effect of green mouth and clam son, since medicament effective concentration is excessively high, it is possible to cause
It targets shellfish biology irritability to avoid, and reduces degradation efficiency；And the molluscicide of comparative example five is due to being less than of the present invention group
The content range divided, kills shellfish effect and kills shellfish effect well below embodiment one to embodiment nine.
By Fig. 1-1 it is found that one obtained seawater molluscicide (substance content 50%) of embodiment for green mouth have it is good
Good killing effect.Respectively with 4mg/L, the commodity densimeter of 8mg/L, 10mg/L can cause significant shellfish in 24 hours
Death, killing rate can reach 87% or more within 72 hours.
By Fig. 1-2 it is found that one obtained seawater molluscicide (substance content 50%) of embodiment for clam son have it is good
Good killing effect.Respectively with 4mg/L, the commodity densimeter of 8mg/L, 10mg/L can cause significant shellfish in 48 hours
Death, killing rate can reach 95% or more within 72 hours.
Dead green mouth and the status diagram of clam son is shown in Fig. 1-3.
As shown in Figure 2, the molluscicide that embodiment one obtains has good peeling effect for byssus.Wherein, in Fig. 2
(a) it is the culture water tank bottom that 0mg/L molluscicides are added after 96 hours, it can be seen that the byssus of shellfish secretion is firmly adhered to water
Bottom portion, and (b) is the culture water tank bottom that 10mg/L molluscicides are added after 96 hours in Fig. 2, bottom is sparkling clean, illustrates nothing
Byssus adheres to, and illustrates that one obtained seawater molluscicide of embodiment has preferable killing effect to green mouth and clam son, and to foot
Silk has good peeling effect.
3. application experiment
Experiment is to use 20 10,000 tons Seawater Desalination Project of Bo Hai district regional.Before this programme, the factory is using daily
The continuous method for adding oxidizing biotides (sodium hypochlorite), originally there is certain control action, but target biology over time
It develops immunity to drugs, occurs water withdrawal gradually and become smaller, phenomena such as part shellfish is biological is mixed in water intaking, water withdrawal is decreased obviously and point
Hard shellfish has the danger for penetrating tube wall, seriously endangers system safety.(a) is using being grown in heat exchanger tube before this molluscicide in Fig. 3
Live body shellfish schematic diagram, (b) is a large amount of shellfish schematic diagrames cleared up in pipeline and system after shutting down, condenser cleaning in Fig. 3
About 3.5 ten thousand yuan/time of consumable material and labour cost.
To prevent drug resistance, through investigating in many ways, which finally uses one obtained seawater molluscicide of embodiment
And oxidizing biocides (10% liquor natrii hypochloritis, the prosperous Chemical Industry Science Co., Ltd of Tianjin auspicious sign) mixing add scheme into
Row improves, and it is as shown in table 4 to add scheme, after adding 1 year, in result such as Fig. 3 in (c) and Fig. 3 shown in (d)；Wherein,
(c) is using heat exchanger tube piping schematic sparkling clean after the seawater molluscicide described in embodiment one in Fig. 3, and (d) is in Fig. 3
Using after the seawater molluscicide described in embodiment one without any shellfish grow seawater into pump grid schematic diagram.System is stablized at present
Operation 3 years had not occurred large-scale maintenance, clearance activity caused by due to shellfish dirt is blocked up, and had illustrated to obtain using embodiment one is prepared
To molluscicide to kill shellfish effect preferable.
Certain Seawater Desalination Project of table 4 adds scheme using the molluscicide
4. pair corrosive experiment of seawater desalination system material
With reference to the measurement rotary hanging plate method of GB/T 18175-2014 water treatment agent corrosion inhibitions, to the embodiment of the present invention
One obtained molluscicide, the different non-oxide biocide of thiophene class (isothiazolinone, Xi'an perseverance Sheng Nuode Chemical Co., Ltd.s) and oxygen
The property changed biocide (sodium hypochlorite 10%, the prosperous Chemical Industry Science Co., Ltd of Tianjin auspicious sign) is to seawater desalination system material corrosivity
It is tested, test result see the table below：
5 medicament of table tests desalination system material corrosive nature
Test result shows the seawater molluscicide product except having the function of stronger marine organism control, contains simultaneously centainly
Corrosion mitigating effect.The medicament is added in seawer system the surface in equipment material and forms protective film, to system equipment and will not prevent
Rotten layer causes corrosion impact.
5. the matching with antisludging agent is tested
According to GB/T 34550.2-2017 seawater cooling water treatment chemical method of evaluating performance part 2s：Scale-inhibiting properties
It measures, tests whether there is or not the scale-inhibiting properties of antisludging agent in the presence of molluscicide, test result is as shown in Figure 4, wherein antisludging agent is day
The SD210 low-temperature multiple-effect seawater desalination antisludging agents that coast defence corruption technology development co. provides in Jinshi City Tanggu, experiment condition are 70 DEG C,
Seawater cycles of concentration is 2 times, a concentration of 4mg/L of the seawater molluscicide of the embodiment one.
As seen from Figure 4, in the presence of the seawater molluscicide, the scale inhibition performance of the antisludging agent is 97.54%, is more than the resistance
Scale inhibition performance 96.83% when dirty agent is used alone, when illustrating that such molluscicide acts on seawater desalination system, for sea water desalination
The performance of antisludging agent does not have an impact, and there are certain facilitations.
6. toxicity test
According to GB/T 21603-2008 chemicals acute oral toxicity test methods, with Beijing dimension tonneau China experimental animal
The SPF grade SD rats that technology finite process department provides are research system (production licence number：SCXK [capital] 2016-0011), to reality
It applies one preparation-obtained molluscicide acute oral toxicity of example to be evaluated, the medicament is to female, male SD rat oral half
Lethal dose (LD50) it is 926mg/kg BW.Judged according to the above test result, which is classified as
III class, acute toxicity are classified as low toxicity.
7. biological degradability is tested
Biological degradability experiment is carried out using one preparation-obtained molluscicide of embodiment in the present invention, as a result such as Fig. 5 institutes
Show.Test method refers to national standard GB/T 15818-2006 surfactant biodegradation test methods.
From fig. 5, it can be seen that the time that the molluscicide product biological degradation rate reaches 90% is only 48 hours.Using ring
There is preferable biocompatibility in border.
Embodiment two to nine obtained seawater molluscicide of embodiment has similar effect.
In conclusion seawater molluscicide of the present invention, is to be used in compounding the quaternary ammonium salt of different alkyl chains, and be subject to
Bleeding agent acts on, and can be effectively peeled off biological clay and biomass, plays effect of preferably killing livestock, and to seawater desalination system
Material have certain slow release effect.
The above is only the preferred embodiment that the present invention is implemented, and not does limitation in any form to the present invention, all
The modifications, equivalent substitutions and improvements etc. done within the spirit and principles in the present invention are required to the protection included in the present invention
Within the scope of.
Claims (11)
1. a kind of seawater molluscicide, which is characterized in that the seawater molluscicide includes quaternary ammonium salt, and bleeding agent and has deionized water
Solvent, wherein by weight percentage, the quaternary ammonium salt is 9-55%, and the bleeding agent is 1-8%, the organic solvent
3-20%, surplus are deionized water.
2. seawater molluscicide according to claim 1, wherein by weight percentage, the quaternary ammonium salt is 25-55%,
The bleeding agent is 2-6%, and the organic solvent is 5-15%, and surplus is deionized water.
3. seawater molluscicide according to claim 1 or 2, wherein the quaternary ammonium salt is single-stranded quaternary ammonium salt, preferably C12~
C16Zephiran.
4. seawater molluscicide according to claim 3, wherein the quaternary ammonium salt includes dodecyl dimethyl Benzylmagnesium chloride
Ammonium, myristyl benzyl dimethyl ammonium chloride and cetalkonium chloride.
5. seawater molluscicide according to claim 4, wherein by weight percentage, the dodecyl dimethyl benzyl
Ammonium chloride is 3-20%, preferably 5-20%, and the myristyl benzyl dimethyl ammonium chloride is 5-25%, preferably 15-
25%, the cetalkonium chloride is 1-10%, preferably 5-10%.
6. according to claim 1-5 any one of them seawater molluscicides, wherein the bleeding agent is non-ionic surface active
Agent, it is preferred that the bleeding agent is selected from C12~C18Aliphatic amine polyoxyethylene ether, aliphatic acid polyethenoxy ether, poly alkyl alcohol
One or more in ethylene oxide ether, nonylphenol polyoxyethylene ether or castor oil polyoxyethylene ether, it is furthermore preferred that described ooze
Saturating agent is selected from dodecyl fatty alcohol polyoxyethylene ether, myristyl aliphatic amine polyoxyethylene ether, nonylphenol polyoxyethylene ether
One or more.
7. according to claim 1-6 any one of them seawater molluscicides, wherein the organic solvent selected from octanol, ethyl alcohol,
One or more in propyl alcohol, ethylene glycol, N,N-dimethylformamide or tetrahydrofuran.
8. the preparation method of any one of the claim 1-7 seawater molluscicides, it includes following step：
(1) it is mixed quaternary ammonium salt and deionized water to obtain mixture A；
(2) bleeding agent and organic solvent are mixed to get mixture B, the mixture then mixture B being added in step (1)
Seawater molluscicide is obtained in A.
9. preparation method according to claim 8, wherein in step (1), the stirring is in the case where temperature is 20-35 DEG C
Stirring.
10. claim 1-7 any one of them seawater molluscicides or claim 8 or 9 any one of them preparation method institutes
Application of the obtained seawater molluscicide in seawater taking system.
11. application according to claim 10, wherein dosage of the seawater molluscicide in seawater taking system be
2-10mg/L。
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|---|---|---|---|---|
| CN113149250A (en) * | 2021-03-11 | 2021-07-23 | 天津国投津能发电有限公司 | Seawater intake pump forebay runner marine organism control system and control method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903740A (en) * | 2006-07-18 | 2007-01-31 | 武汉新化科技有限公司 | Method of biological inhibition using sea water cooling system |
-
2018
- 2018-04-19 CN CN201810352694.3A patent/CN108633880A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903740A (en) * | 2006-07-18 | 2007-01-31 | 武汉新化科技有限公司 | Method of biological inhibition using sea water cooling system |
Non-Patent Citations (3)
| Title |
|---|
| 严莲荷等: "《水处理药剂及配方手册》", 31 January 2004, 中国石化出版社 * |
| 何铁林等: "《水处理化学品手册》", 31 May 2000, 化学工业出版社 * |
| 潘卫三 等: "《工业药剂学》", 31 August 2015, 中国医药科技出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149250A (en) * | 2021-03-11 | 2021-07-23 | 天津国投津能发电有限公司 | Seawater intake pump forebay runner marine organism control system and control method |
| CN113149250B (en) * | 2021-03-11 | 2023-09-05 | 天津国投津能发电有限公司 | Seawater biological control system and control method for front pool runner of seawater taking pump |
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