CN102939973A - Compound type sterilizing algaecide and application thereof - Google Patents
Compound type sterilizing algaecide and application thereof Download PDFInfo
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Abstract
Compound type sterilizing algaecide is composed of isothiazolinone, glutaraldehyde, benzimidazole salt and polyether by mass ratio of 1:(1.0-2.0):(1.0-1.5):(1.0-2.0). The isothiazolinone is formed by mixing 5-chlorine-2-methyl-4-isothiazolin-3-ketone and 2-methyl-4-isothiazolin-3-ketone with the mass ratio of 3:1, wherein the benzimidazole salt is 1- ethyl methyl ether -2-methyl-3-R-based benzimidazole quaternary ammonium salt. The compound type sterilizing algaecide is applied in industrial recycling cooling water.
Description
One, technical field
The present invention relates to a kind of New Type Water Treatment Chemicals, particularly the industrial circulating cooling water inorganic agent exactly is a kind of composite sterilizer algicide and uses thereof.
Two, background technology
Technology on circulating cooling water treatment is one of main method of Industrial Water Saving.Because industrial colling accounts for the 70-80% of industrial water consumption, thereby realize the water circuit utilization, improve concentration rate to be the key of Industrial Water Saving; On the other hand, cooling water is to the requirement of water quality relatively not high (the major control index has turbidity, COD etc.), and this is just so that reusing sewage becomes possibility in cooling water system, for the approach after the waste water treatment provides guarantee.
But in recirculating cooling water system, burn into sediments, microorganism are three subject matters that water technology is faced, and the interaction between them and impact have consisted of the hidden danger of the safe long-term operation of cooling water system.For corrosion and sediments problem, can filter out suitable corrosion-mitigation scale-inhibition medicament according to water quality, process conditions, such as efficient corrosion inhibiter, antisludging agent, dispersant, on the other hand by preliminary treatment (as softening etc.), operation control (such as acid adding etc.) or adopt the new type corrosion resistant material to realize the corrosion of water system and the control of dirt.Yet in various degree corrosion and sediments phenomenon in the field of cooling water system, still can occur, differ larger with the possibility of result in laboratory.Through field assay, the corrosion that microorganism causes and foundry loam are one of chief reasons, this also be in the past nearly half a century microorganism and biological clay, fouling problem cause the main cause that people pay attention to.
If general circulating cooling system is fetched water when making supplementing water from urban water supply or from well, the amount of microorganism is normally seldom in the supplementing water., unlimited recirculating cooling water system constantly has dust to enter to have sent into simultaneously microorganism, when having a certain amount of nutrients, then can breed rapidly, thereby causing many bad effects, impact is cooling effectively.Because factors such as the material from leakage (ammonia, wet goods organic matter) in the water source, air, production, water treatment agents, under the dissolved oxygen of abundance, suitable temperature condition, microorganism is growth and breeding very easily.When using the water that reclaims, when cooling off such as the water that flows out with B-grade sewage treatment plant, it is more serious that problem just becomes.When being rich in more phosphate and organic matter in these water, they are polytrophic medium concerning many microorganisms.
In fact, people have many On-site Experiences in this respect, be that the trouble that microorganism causes in the cooling water system is the fastest, the most obvious, can cause rapidly the bacterium algae to grow and the water quality deterioration problems such as foundry loam, in case and biological clay generates in a large number, corrosion-mitigation scale-inhibition medicament that is inefficacy demonstrate corrosion and sediments problem at macroscopical treatment effect, cause the error in judgement to the water treatment effect.Therefore as seen, the cooling water system problem that microorganism causes relates to dirt, deposition and corrosion, therefore, must grasp the microbial growth rule, selects suitable microbe controlling method, to guarantee the safe operation of cooling water system.
Adopting biocide that the microorganism in the cooling water system is controlled is a kind of generally the use at present and effective method; namely by in cooling water, adding the not biocide of same-action; to disturbing even destroy in some aspect of microbial life activity; thereby reach the effect of control microbial reproduction, this to protection equipment, extension device service life, boost productivity, save water and energy, increase economic efficiency significant.
Because the oxidisability biocide has inexpensive, efficient characteristics, this high P/C is than making it still dominate so far the control of cooling water system microorganism.For large-scale cooling water system, the applicant do not see so far without the oxidisability biocide, and only uses the report of non-oxidative bactericide.Non-oxidative bactericide is another large class biocide in the cold water process, and they are organic compound basically, and with regard to some aspect, it uses more convenient and effective than oxidisability biocide.In present employed non-oxidative bactericide, the quaternary ammonium salt biocide has the wide spectrum bactericidal performance, all effective to bacterium, algae, fungi, different from the oxidisability biocide, affected by pH little,, environmental friendliness low to the toxicity of environment, P/C is than good, and being easy to use and storing, being most widely used, is one of the main focus of research and application of killing livestock at present.And the non-oxidative bactericide that uses at present mostly is single and plants medicament, and the composite collaborative of several non-oxidative bactericides has better killing action to the bacterium algae.
Three, summary of the invention
The present invention is directed to the deficiency of existing water quality condition and traditional non-oxidative bactericide, being intended to provides better compound non-oxidizable Biocidal algae-killing agent of a kind of performance for the circulation application, problem to be solved is to select new compound, and confirms its effect by the field.
This composite sterilizer algicide is the composition that is mixed by the mass ratio of 1:1.0-2.0:1.0-1.5:1.0-2.0 by isothiazolinone, glutaraldehyde, benzoglioxaline salt and polyethers.
Described polyethers claims again PPG, be to be made through sudden reaction in the presence of catalyzer by initiator (compound that contains active hydrogen group) and oxirane (EO), expoxy propane (PO), epoxy butane (BO) etc., common are polyoxypropyleneglycol, polytetrahydrofuran diol and oxolane-propylene oxide copolymerization glycol etc.Polyethers can be used as dispersant and defoamer uses.
Isothiazolinone is a kind of non-oxidative bactericide, mainly is comprised of CMIT (CMI) and MIT (MI).The mass ratio of CMI and MI is 3:1 during mixing.Isothiazolinone is to work the effect of killing livestock by the key that disconnects bacterium and algae protein matter.The isothiazolinone handling safety, compatibility is good, stability is strong, with after microorganism contacts, can promptly irreversibly suppress its growth, thereby cause the death of microbial cell, therefore common bacteria, fungi, algae etc. are had very strong inhibition and killing action.
Glutaraldehyde is a kind of high effect disinfectants, have wide spectrum, efficient, low toxicity, little to metal protection, be subjected to the characteristics such as organic substance influence is little, good stability.Glutaraldehyde mainly relies on aldehyde radical to the killing action of microorganism, and this type of drug main will act on thin base, hydroxyl, carboxyl and the amino of mycoprotein, can make it alkylation, causes that protein coagulating causes bacterium dead.
Described benzoglioxaline salt is chemical name: 1-the first and second ethers-2-methyl-3-R base benzimidazole quaternary ammonium salt have following chemical formula:
X-the first and second ether (CH
2OCH
2CH
3), R-alkyl (C
3-C
16); The preferred C of R
8-C
16The alkyl of carbon.
Its preparation method is at first to generate intermediate (I) 2-tolimidazole by o-phenylenediamine and acetic acid ring-closure reaction, and reaction equation is as follows:
Then, intermediate (I) generates intermediate (II) 1-the first and second ethers-2-tolimidazole with the chloromethyl ether substitution reaction, and reaction equation is as follows:
At last, intermediate (II) generates target product with bromoalkane (RBr, R are the alkyl of 3-16 carbon) quaternary ammonium salinization reaction in acetonitrile solvent, and reaction equation is as follows:
This benzoglioxaline salt and preparation method thereof is applied for patent of invention in addition.
The purposes of this composite sterilizer algicide is exactly as the application of Biocidal algae-killing agent in industrial circulating cooling water system.
Unique distinction of the present invention is that the introducing of aromatic ring in the component benzoglioxaline salt and N atom can improve the compound bactericidal activity preferably, long alkyl chain length structure can better act on microorganism, and benzoglioxaline salt is the structure with electron withdraw group, and its bacteriostatic activity also can improve a lot.In addition, it is good water-soluble that the ether that contains in the benzoglioxaline salt has it, and with polyethers, isothiazolinone and glutaraldehyde good compatibility and Synergistic biocidal algae removal ability are arranged, and can play better sterilization algae removal effect in water.
This composite sterilizer algicide bactericidal property is good, foundry loam is peeled off effective, and consumption is low, and the effect of killing livestock in the water body with middle aqueous nature is still good, and and anti-incrustation corrosion inhibitor commonly used good compatibility is arranged.In addition, the environmental protection of this composite sterilizer algicide is easy to degraded, and is environmentally friendly.The oral acute poisoning LD50 value of small white mouse is 3310mg/L, and the oral acute poisoning LD50 value of corrosion inhibiter BTA small white mouse commonly used is 937mg/L, and toxicity is far above the present invention.
This composite sterilizer algicide bactericidal property is estimated:
Compare with composite sterilizer algicide and common fungicide 1227 (dodecyl benzyl dimethyl ammonium chloride) germicidal efficiency to heterotroph, find:
(1) the composite sterilizer algicide has certain germicidal efficiency to heterotroph, and the sterilizing ability of heterotroph obviously is better than 1227, and action time is longer, still keeps 99% germicidal efficiency after 48 hours;
(2) the minimum using dosage of composite sterilizer algicide is 50mg/L, and 1227 is 100mg/L.
Germicidal efficiency with composite sterilizer algicide and 1227 pairs of sulfate reducing bacterias compares, and finds:
(1) the composite sterilizer algicide all has certain germicidal efficiency to sulfate reducing bacteria, and the sterilizing ability of sulfate reducing bacteria obviously is better than 1227, and action time is longer, still keeps 90% germicidal efficiency after 24 hours;
(2) the minimum using dosage of composite sterilizer algicide is 100mg/L, and 1227 is 150mg/L.
This composite sterilizer algicide and common anti-incrustation corrosion inhibitor compatibility are estimated:
The employing biocide can suppress the growth of bacterium in the cooling water effectively, but the compatibility problem of biocide and other medicament of system is the important content in the water technology research always, when jointly using between the medicament, may produce the anti-effect of tangerine, and drug effect is reduced.This also is some outstanding water treatment agent prescriptions when experiment and dynamic simulation experiment property indices is all very outstanding, but when actual motion a unsatisfactory major reason.
As cationic surfactant, the quaternary ammonium salt biocide is by electronegative group effect on its positive charge and the microorganism wall, causes the death of bacteriolysis and cell.But present organic phosphine corrosion inhibiting and descaling agent commonly used in the cooling water system such as HEDP, ATMP, PBTCA etc., is that the chelating by its anion and calcium ion, iron ion etc. plays inhibition and scale effect.Thereby the quaternary ammonium salt biocide is easy and corrosion inhibiting and descaling agent is muddy in the part generation, has reduced the valid density of organic phosphor medicament and biocide, thereby has affected the effect of water treatment.
Studied the variation of the turbidity after HEDP, PBTCA and this composite sterilizer algicide and 1227 effects by turbidimetry, through relatively finding:
(1) the composite sterilizer algicide is less on the impact of organic phosphine anti-incrustation corrosion inhibitor HEDP and PBTCA, much smaller than 1227 impacts on HEDP and PBTCA.
(2) the composite sterilizer algicide on the impact of HEDP greater than the impact on PBTCA.
Four, description of drawings
Fig. 1: add the foundry loam and the algae that peel off after the composite sterilizer algicide.
Fig. 2: add cycle water water body situation after the composite sterilizer algicide.
Five, embodiment
(1) raw material is prepared
1, the preparation of benzoglioxaline salt
(1) preparation of intermediate (I) 2-tolimidazole
In the 250mL there-necked flask, add solvent quality concentration 85% phosphoric acid and mass concentration 86% polyphosphoric acids, the volume ratio 1:1 of phosphoric acid and polyphosphoric acids, with the electric jacket heating, turn on agitator adds o-phenylenediamine and acetic acid, is warming up to 120-130 ℃, reacts 10 hours.React complete, the cooling reactant liquor is poured reactant liquor in the beaker into, drips 10% sodium hydroxide solution, regulates pH to neutral, has a large amount of faint yellow flocculent deposits to occur, and continues to drop to pH to alkalescence.Treat that it is cooled to about 20～40 ℃, suction filtration gets the thick product of faint yellow mud shape.With the crude product heating and melting, add activated carbon decolorizing after the melting, cooling after the decolouring obtains intermediate (I) with the ethanol-water solution recrystallization.
The fusing point test of intermediate (I) 2-tolimidazole is 175-176 ℃.
The peak at 2920 places is CH in the infrared analysis
3The peak, stretching vibration peak, the absworption peak of the 1470th, N-C, the 1540th, the absworption peak of phenyl ring.
Tolimidazole
1The H of contraposition on the corresponding phenyl ring in δ in the HNMR spectrogram=7.2035～7.2465, the H at ortho position on the corresponding phenyl ring in δ=7.5470～7.5773, the H of 2 upper methyl on the corresponding imidazole ring in δ=2.6283～2.6944, the active H among the corresponding N-H in δ=10.6719.
(2) preparation of intermediate (II) 1-the first and second ethers-2-tolimidazole
The sodium hydroxide that in the there-necked flask of 100mL, adds mass concentration 40%, intermediate (I) 2-tolimidazole 3g, phase transfer catalyst tetrabutyl ammonium bromide 0.05g.The heating reactant liquor is treated that the 2-tolimidazole dissolves fully and is added chloromethyl ether to about 80-100 ℃, reacted 10 hours.The cooling reactant liquor, minute oil-yielding stratum, water layer are with the toluene extraction several times.The oil reservoir told is dry with anhydrous calcium chloride, and Rotary Evaporators evaporates solvent toluene and the chloromethyl ether of complete reaction not, obtains oily liquids intermediate (II).
The upward peak 2H δ of the alkyl chain of connection=5.7473～5.8165 of imidazole ring N appear in the H place on the first and second ethers, another 2H on corresponding the first and second ethers in δ=3.2865～3.3502,3H δ=0.9805～1.1235,2 upper methyl H peak 3H δ=2.5416～2.6186 of imidazole ring.
(3) target product is synthetic
In the there-necked flask of 50mL, add intermediate (II) 1-the first and second ethers-2-tolimidazole, bromo R alkane, solvent acetonitrile is heated to 80 ℃, reacts 8-12 hour.Cool off to get white depositions, suction filtration takes out unreacted raw material and solvent, gets faint yellow head product.Obtain the crystal of white plates for three times with the acetonitrile recrystallization, suction filtration obtains product.R is selected from octane, dodecane, tridecane, the tetradecane, hexadecane.
When R is dodecane, benzoglioxaline salt
1In the HNMR spectrogram, the H peak 2H δ that is connected with imidazole ring N in the dodecyl=3.2654～3.5783, adjacent H peak 2H δ=1.5205～1.6015, C
3～C
11Upper H peak 2H δ=1.2014～1.3530,3H δ=0.8945～0.9566.H on the phenyl ring, 2H δ=6.4051～6.5124, H δ=6.5135～6.5895, H δ=6.5746～6.6621.
2, isothiazolinone
Get CMI3 part (mass parts, lower same), MI1 part is mixed to get isothiazolinone.
CMI, MI all purchase the company from Rohm and Hass.
3, glutaraldehyde
Buying is from the Dow Chemical Company.
4, polyethers
The EO/PO polyethers of n=20-30
Buying is from the Dow Chemical Company.
(2) existing take 100 parts of isothiazolinone as example, non-limiting examples is described below:
1, isothiazolinone is 100 parts, 100 parts of glutaraldehydes, 100 parts of 1-the first and second ethers-2-methyl-3-octyl benzoglioxaline salt, 100 parts of the EO/PO polyethers of n=20, stirring gets final product, n is the degree of polymerization, lower with.
2, isothiazolinone is 100 parts, 100 parts of glutaraldehydes, and 150 parts of 1-the first and second ethers-2-methyl-3-dodecyl benzoglioxaline salt, 100 parts of the EO/PO polyethers of n=25, stirring gets final product.
3, isothiazolinone is 100 parts, 150 parts of glutaraldehydes, and 120 parts of 1-the first and second ethers-2-methyl-3-tridecyl benzoglioxaline salt, 200 parts of the EO/PO polyethers of n=23, stirring gets final product.
4, isothiazolinone is 100 parts, 120 parts of glutaraldehydes, and 100 parts of 1-the first and second ethers-2-methyl-3-cetyl benzoglioxaline salt, 150 parts of the EO/PO polyethers of n=30, stirring gets final product.
5, isothiazolinone is 100 parts, 100 parts of glutaraldehydes, and 120 parts of 1-the first and second ethers-2-methyl-3-myristyl benzoglioxaline salt, 200 parts of the EO/PO polyethers of n=20, stirring gets final product.
6, isothiazolinone is 100 parts, 135 parts of glutaraldehydes, and 125 parts of 1-the first and second ethers-2-methyl-3-tridecyl benzoglioxaline salt, 180 parts of the EO/PO polyethers of n=30, stirring gets final product.
(3) this composite sterilizer algicide the field situation
Hefei Jin Yuan steam power plant production water source is comprised of water in certain river and certain sewage treatment plant, and circulating water system reclaims water from engineering industry water, air compressor cooling water and drier cooling water etc., and rate of water make-up is 300m approximately
3/ h.This Circulated water system of thermal power plant is provided with ClO
2Generator, circulation adopts and adds ClO generally speaking
2Mode carry out sterilization processing, but unit operation is after a period of time, produces more foundry loam and algae on cooling column column and the pool wall.From air cooler of generators and other subsidiary engine equipment that adopts cycle water to cool off of opened maintenance, the foundry loam at these positions is also many.This factory once added 1227 and carried out sterilization algae removal in circulation, but 1227 pairs of bacterium algaes to kill and peel off effect not too obvious, sterilizing rate generally only has about 85%.And, this factory use 1227 o'clock dosages substantially at 200mg/L(to possess watermeter) about, dosage is about 600kg each time.In addition, add at 1227 o'clock, on-the-spot circulation produces a lot of bubbles, easily causes the heat exchanger tube vent plug, causes exchange capability of heat to descend, and threatens the safe operation that follows pump.
In conjunction with the present ClO of the on-the-spot recirculating cooling water system of this steam power plant
2Loss amount is larger, and system's concentration rate is lower, and the characteristics that system's time of staying of biocide is short and operation present situation in order to guarantee good bactericidal effect, improve and implement the operation cost performance, adopt composite sterilizer algicide of the present invention to carry out sterilization algae removal.It is lower that the composite sterilizer algicide adds front on-the-spot turbidity of circulating water, is 1.82NTU; After the composite sterilizing agent algicide added, turbidity of circulating water was soaring rapidly, tended towards stability gradually, and adding of agent is after 8 hours, and it is maximum that turbidity reaches, and is approximately 17.5NTU, after reduce gradually, but all the time greater than turbidity before the adding of agent.This explanation composite sterilizer algicide causes peeling off in a large number of circulation foundry loam, foundry loam spreads out in water, cause water turbidity significantly to rise, later stage part Stickydeposit is at the bottom of the tower, cause the turbidity of circulating water slow decreasing, proved thus the respond well (see figure 1) of peeling off of composite sterilizer algicide.
From sterilizing rate, the composite sterilizer algicide added after 1 hour, this thermoelectricity circulation heterotroph number namely declines to a great extent, drop to 1.95E+02/mL from 2.2E+05/mL, sterilizing rate reaches more than 99%, illustrates that compound benzoglioxaline salt sterilization speed is very fast, and after 48 hours, system's micro organism quantity still seldom only has 2.3E+02/mL, illustrates that the duration of efficacy of composite sterilizer algicide is longer.
In addition, in the application process of composite sterilizer algicide, whole system is there are no how many Bubble formations, the many shortcoming (see figure 2)s of 1227 bubbles have been avoided, and compare 1227, the dosage of composite sterilizer algicide still less, dosage only needs 100～150mg/L(to possess watermeter) about, and sterilizing rate and foundry loam, that algae peels off effect is fine, and comparing 1227 has apparent in view superiority.
Claims (3)
1. composite sterilizer algicide is characterized in that: be the composition that is mixed by the mass ratio of 1:1.0-2.0:1.0-1.5:1.0-2.0 by isothiazolinone, glutaraldehyde, benzoglioxaline salt and polyethers; Described isothiazolinone is mixed by the 3:1 mass ratio by CMIT and MIT; Described benzoglioxaline salt is 1-the first and second ethers shown in the following chemical formula-2-methyl-3-R base benzimidazole quaternary ammonium salt:
X:-CH in the formula
2OCH
2CH
3, R is selected from C
3-C
16The alkyl of carbon.
2. Biocidal algae-killing agent according to claim 1, it is characterized in that: R is selected from C
8-C
16The alkyl of carbon.
3. the purposes of composite sterilizer algicide as claimed in claim 1 is characterized in that: the purposes of this composite sterilizer algicide is exactly as the application of Biocidal algae-killing agent in industrial circulating cooling water system.
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| CN104430501A (en) * | 2014-11-27 | 2015-03-25 | 苏州佑君环境科技有限公司 | Water treatment bromine bactericide and preparation method thereof |
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| CN108849929A (en) * | 2017-11-15 | 2018-11-23 | 上海屹屹环境科技有限公司 | A kind of environment-friendly type Biocidal algae-killing agent |
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| WO2017135974A1 (en) * | 2016-02-05 | 2017-08-10 | Dow Global Technologies Llc | Microbicidal composition |
| CN108601343A (en) * | 2016-02-05 | 2018-09-28 | 陶氏环球技术有限责任公司 | Synergistic microbicidal compositions |
| CN106577691A (en) * | 2016-11-25 | 2017-04-26 | 上海鹏图化工科技有限公司 | Environment-friendly residue-free composite bacterial depressant and preparation method thereof |
| CN106797955A (en) * | 2017-01-13 | 2017-06-06 | 上海鹏图化工科技有限公司 | Antifouling algicide of environment-protection nano and preparation method thereof |
| CN108849929A (en) * | 2017-11-15 | 2018-11-23 | 上海屹屹环境科技有限公司 | A kind of environment-friendly type Biocidal algae-killing agent |
| CN112998013A (en) * | 2021-03-22 | 2021-06-22 | 郑州市新郑梅久实业有限公司 | Efficient oilfield bactericide and preparation and application methods thereof |
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