CN102939973B - 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 industrial circulating cooling water inorganic agent, is exactly 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, thus realize water recycle, improve the key that concentration rate is Industrial Water Saving; On the other hand, cooling water is to the requirement of water quality relatively not high (major control index has turbidity, COD etc.), and this just makes reusing sewage become possibility in cooling water system, for the approach after 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 formed 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, as efficient corrosion inhibiter, antisludging agent, dispersant, control (as acid adding etc.) or adopt new type corrosion resistant material to realize the corrosion of water system and the control of dirt by pretreatment (as softening etc.), operation on the other hand.But still there will be corrosion and sediments phenomenon in various degree in the application of the scene of cooling water system, 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, and this is also microorganism and the main cause that attracts people's attention of biological clay, fouling problem nearly half a century in the past.
If general circulating cooling system is fetched water from urban water supply or from well while making supplementing water, in supplementing water, the amount of microorganism is normally little., unlimited recirculating cooling water system constantly has dust to enter to have sent into microorganism simultaneously, in the time there is a certain amount of nutrients, can breed rapidly, thereby cause many bad effects, affect effectively cooling.Due to factors such as the material from leakage in water source, air, production (ammonia, wet goods organic matter), water treatment agents, under sufficient dissolved oxygen, suitable temperature condition, microorganism is growth and breeding very easily.When the necessary water with reclaiming, when as next cooling in the water flowing out with B-grade sewage treatment plant, it is more serious that problem just becomes.In the time being rich in more phosphate and organic matter in these water, concerning many microorganisms, they are polytrophic medium.
In fact, people have many On-site Experiences in this respect, be trouble that in cooling water system, microorganism causes the soonest, the most obvious, can cause rapidly bacterium algae to grow and the water quality deterioration problems such as foundry loam, once and biological clay generates in a large number, corrosion-mitigation scale-inhibition medicament that is inefficacy demonstrate corrosion and sediments problem on macroscopical treatment effect, cause the error in judgement to water treatment effect.Therefore the cooling water system problem visible, microorganism causes, relates to dirt, deposition and corrosion, therefore, must grasp microbial growth rule, selects suitable microbe controlling method, to ensure the safe operation of cooling water system.
Adopting biocide to control the microorganism in cooling water system is that one is generally used and effective method at present; by add the not biocide of same-action in cooling water; some aspect of microbial life activity is disturbed even and destroyed; thereby reach the effect of microbial reproduction controlled, this to protection equipment, extension device service life, boost productivity, save water and energy, increase economic efficiency significant.
Because oxidisability biocide has inexpensive, efficient feature, 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, applicant do not see so far without oxidisability biocide, and only uses the report of non-oxidative bactericide.Non-oxidative bactericide is another large class biocide in cold water process, and they are organic compound substantially, and with regard to some aspect, it uses more convenient and effective than oxidisability biocide.In current used non-oxidative bactericide, quaternary ammonium salt biocide has wide spectrum bactericidal performance, all effective to bacterium, algae, fungi, different from 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 using mostly at present is single and plants medicament, and the composite collaborative of several non-oxidative bactericides has better killing action to 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 circulation application, problem to be solved is to select new compound, and is applied and confirmed its effect by scene.
This composite sterilizer algicide is the composition being 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 under catalyzer exists by initiator (containing the compound of 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, is mainly made up of CMIT (CMI) and MIT (MI).When mixing, the mass ratio of CMI and MI is 3:1.Isothiazolinone is that the key by disconnecting bacterium and algae protein matter works the effect of killing livestock.Isothiazolinone handling safety, compatibility is good, stability is strong, contact with microorganism after, can promptly irreversibly suppress its growth, thereby cause the death of microbial cell, therefore common bacteria, fungi, algae etc. are had to 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 subject to the features 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 death.
Described benzoglioxaline salt is chemical name: 1-the first and second ethers-2-methyl-3-R base benzimidazole quaternary ammonium salt, has 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 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 chloromethyl ether substitution reaction, and reaction equation is as follows:
Finally, intermediate (II) generates target product with bromoalkane (RBr, R is 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 separately applied for patent of invention.
The purposes of this composite sterilizer algicide is exactly the application as Biocidal algae-killing agent in industrial circulating cooling water system.
Unique distinction of the present invention is that the introducing of aromatic ring in component benzoglioxaline salt and N atom can improve 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, the ether containing in benzoglioxaline salt makes it have good water-soluble, and has good compatibility and Synergistic biocidal algae removal ability with polyethers, isothiazolinone and glutaraldehyde, 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 conventional anti-incrustation corrosion inhibitor have good compatibility.In addition, the environmental protection of this composite sterilizer algicide, is easy to degraded, environmentally friendly.The oral acute poisoning LD50 value of small white mouse is 3310mg/L, and the conventional oral acute poisoning LD50 value of corrosion inhibiter BTA small white mouse is 937mg/L, and toxicity is far above the present invention.
This composite sterilizer algicide bactericidal property is evaluated:
The germicidal efficiency of heterotroph is compared with composite sterilizer algicide and common fungicide 1227 (dodecyl benzyl dimethyl ammonium chloride), finds:
(1) composite sterilizer algicide has certain germicidal efficiency to heterotroph, and the sterilizing ability of heterotroph is obviously better than to 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.
Compare with the germicidal efficiency of composite sterilizer algicide and 1227 pairs of sulfate reducing bacterias, find:
(1) composite sterilizer algicide all has certain germicidal efficiency to sulfate reducing bacteria, and the sterilizing ability of sulfate reducing bacteria is obviously better than to 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 evaluated:
Employing biocide can suppress the growth of bacterium in cooling water effectively, but the compatibility problem of biocide and other medicament of system is the important content in water technology research always, while jointly use, may produce the anti-effect of tangerine between medicament, and drug effect is reduced.This is also some outstanding water treatment agent formulas in the time of experiment and dynamic simulation experiment property indices is all very outstanding, but in the time of actual motion a unsatisfactory major reason.
As cationic surfactant, quaternary ammonium salt biocide is by electronegative group effect on its positive charge and microorganism wall, causes the death of bacteriolysis and cell.But at present conventional organic phosphine corrosion inhibiting and descaling agent in cooling water system, as HEDP, ATMP, PBTCA etc., is to play inhibition and scale effect by the chelating of its anion and calcium ion, iron ion etc.Thereby quaternary ammonium salt biocide is easy and corrosion inhibiting and descaling agent is muddy in 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) composite sterilizer algicide is less on the impact of organic phosphine anti-incrustation corrosion inhibitor HEDP and PBTCA, the impact much smaller than 1227 on HEDP and PBTCA.
(2) composite sterilizer algicide is greater than the impact on PBTCA to the impact of HEDP.
Four, brief description of the drawings
Fig. 1: add the foundry loam and the algae that peel off after composite sterilizer algicide.
Fig. 2: add cycle water water body situation after composite sterilizer algicide.
Five, embodiment
(1) raw material is prepared
1, the preparation of benzoglioxaline salt
(1) preparation of intermediate (I) 2-tolimidazole
In 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 electric jacket heating, turn on agitator, adds o-phenylenediamine and acetic acid, is warming up to 120-130 DEG C, reacts 10 hours.React complete, cooling reactant liquor, pours reactant liquor in beaker into, drips 10% sodium hydroxide solution, regulates pH to neutral, has a large amount of faint yellow flocculent deposits to occur, continues to drop to pH to alkalescence.Treat that it is cooled to 20～40 DEG C of left and right, suction filtration obtains the thick product of faint yellow mud shape.By crude product heating and melting, after melting, add activated carbon decolorizing, cooling after decolouring, be recrystallized and obtain intermediate (I) with ethanol-water solution.
The fusing point test of intermediate (I) 2-tolimidazole is 175-176 DEG C.
In infrared analysis, the peak at 2920 places is CH
3peak, 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=7.2035～7.2465 in HNMR spectrogram, 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 in the corresponding N-H in δ=10.6719.
(2) preparation of intermediate (II) 1-the first and second ethers-2-tolimidazole
In the there-necked flask of 100mL, add the sodium hydroxide of mass concentration 40%, intermediate (I) 2-tolimidazole 3g, phase transfer catalyst tetrabutyl ammonium bromide 0.05g.Heating reactant liquor to 80-100 DEG C of left and right, is treated that 2-tolimidazole dissolves completely and is added chloromethyl ether, reacts 10 hours.Cooling reactant liquor, point oil-yielding stratum, water layer extracts several times with toluene.The oil reservoir separating 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).
There are 2H δ=5.7473～5.8165, peak of the upper alkyl chain connecting of imidazole ring N 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=0.9805～1.1235,3H δ=2.5416～2.6186,2 upper methyl H peaks 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 DEG C, reaction 8-12 hour.The cooling white depositions that obtains, suction filtration takes out unreacted raw material and solvent, obtains faint yellow head product.The crystal that obtains white plates with acetonitrile recrystallization for three times, suction filtration obtains product.R is selected from octane, dodecane, tridecane, the tetradecane, hexadecane.
In the time that R is dodecane, benzoglioxaline salt
1in HNMR spectrogram, 2H δ=3.2654～3.5783, H peak that are connected with imidazole ring N in dodecyl, adjacent 2H δ=1.5205～1.6015, H peak, C
3～C
112H δ=1.2014～1.3530, upper H peak, 3H δ=0.8945～0.9566.H on 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 taking 100 parts of isothiazolinone as example, non-limiting examples is described below:
1,100 parts of isothiazolinone, 100 parts of glutaraldehydes, 100 parts of 1-the first and second ethers-2-methyl-3-octyl benzoglioxaline salts, 100 parts of the EO/PO polyethers of n=20, stir, and n is the degree of polymerization, lower same.
2,100 parts of isothiazolinone, 100 parts of glutaraldehydes, 150 parts of 1-the first and second ethers-2-methyl-3-dodecyl benzoglioxaline salts, 100 parts of the EO/PO polyethers of n=25, stir.
3,100 parts of isothiazolinone, 150 parts of glutaraldehydes, 120 parts of 1-the first and second ethers-2-methyl-3-tridecyl benzoglioxaline salts, 200 parts of the EO/PO polyethers of n=23, stir.
4,100 parts of isothiazolinone, 120 parts of glutaraldehydes, 100 parts of 1-the first and second ethers-2-methyl-3-cetyl benzoglioxaline salts, 150 parts of the EO/PO polyethers of n=30, stir.
5,100 parts of isothiazolinone, 100 parts of glutaraldehydes, 120 parts of 1-the first and second ethers-2-methyl-3-myristyl benzoglioxaline salts, 200 parts of the EO/PO polyethers of n=20, stir.
6,100 parts of isothiazolinone, 135 parts of glutaraldehydes, 125 parts of 1-the first and second ethers-2-methyl-3-tridecyl benzoglioxaline salts, 180 parts of the EO/PO polyethers of n=30, stir.
(3) the on-the-spot applicable cases of this composite sterilizer algicide
Water composition in You Mou river, Jin Yuan steam power plant production water source, Hefei and certain sewage treatment plant, circulating water system reclaims water, the about 300m of rate of water make-up from engineering industry water, air compressor cooling water and drier cooling water etc.
3/ h.This Circulated water system of thermal power plant is provided with ClO
2generator, generally circulation adopts and adds ClO
2mode carry out sterilization processing, but after unit operation a period of time, on cooling column column and pool wall, produce more foundry loam and algae.Carry out cooling subsidiary engine equipment from air cooler of generators and other employing cycle water 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 85% left and right.And, this factory use 1227 o'clock dosages substantially at 200mg/L(to possess watermeter) left and right, dosage is in 600kg left and right each time.In addition, add at 1227 o'clock, on-the-spot circulation produces a lot of bubbles, easily causes heat exchanger tube vent plug, causes exchange capability of heat to decline, and threatens the safe operation that follows pump.
In conjunction with the current ClO of the on-the-spot recirculating cooling water system of this steam power plant
2loss amount is larger, and system concentration rate is lower, and short feature and the operation present situation of the system time of staying of biocide, in order to ensure good bactericidal effect, improves and implement operation cost performance, adopts composite sterilizer algicide of the present invention to carry out sterilization algae removal.It is lower that composite sterilizer algicide adds front on-the-spot turbidity of circulating water, is 1.82NTU; After composite sterilizing agent algicide adds, turbidity of circulating water is soaring rapidly, tends 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 be greater than all the time turbidity before 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 tower, cause turbidity of circulating water slow decreasing, proved thus the respond well (see figure 1) of peeling off of composite sterilizer algicide.
From sterilizing rate, composite sterilizer algicide added after 1 hour, this thermoelectricity circulation heterotroph number 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 micro organism quantity is still little, 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 are avoided, and compare 1227, still less, dosage only needs 100～150mg/L(to possess watermeter to the dosage of composite sterilizer algicide) left and right, and sterilizing rate and foundry loam, that algae peels off effect is fine, comparing 1227 has obvious superiority.
Claims (1)
1. a composite sterilizer algicide, is characterized in that: be the composition being 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 3:1 mass ratio by CMIT and MIT; Described benzoglioxaline salt is 1-the first and second ethers shown in following chemical formula-2-methyl-3-R base benzimidazole quaternary ammonium salt:
X in formula :-CH
2oCH
2cH
3, R is selected from C
8-C
16the alkyl of carbon.
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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 |
| US9781928B2 (en) * | 2016-02-05 | 2017-10-10 | Dow Global Technologies Llc | Microbicidal composition |
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| 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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| CN1102050A (en) * | 1993-10-30 | 1995-05-03 | 曾志雄 | Quaternary ammonium salt compound disinfectant |
| CN1186980C (en) * | 2001-12-17 | 2005-02-02 | 北京燕山石油化工公司研究院 | Composite bactericide containing dialkyl quaternary ammonium salt and its application |
| CN1224577C (en) * | 2002-12-30 | 2005-10-26 | 中国石油化工股份有限公司北京燕山分公司研究院 | Method for utiliznig sterilizing agent in circular cooling water |
| CN1251592C (en) * | 2003-12-30 | 2006-04-19 | 成都柯邦药业有限公司 | Double long chain quaternary ammonium complex iodine isothiazolinone complex antiseptic for aquatic product |
| CN101422152B (en) * | 2007-11-01 | 2012-08-08 | 中国石油天然气股份有限公司 | Composite biocide |
| CN101423300B (en) * | 2008-11-14 | 2010-06-16 | 安徽省电力科学研究院 | Scale and corrosion inhibitor suitable for reclaimed water reuse system |
| CN102726446A (en) * | 2012-07-11 | 2012-10-17 | 山东天庆科技发展有限公司 | Efficient compound sterilizing agent for circulating water system |
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