CN1426681A - Composite bactericide containing dialkyl quaternary ammonium salt and its application - Google Patents

Composite bactericide containing dialkyl quaternary ammonium salt and its application Download PDF

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Publication number
CN1426681A
CN1426681A CN 01144335 CN01144335A CN1426681A CN 1426681 A CN1426681 A CN 1426681A CN 01144335 CN01144335 CN 01144335 CN 01144335 A CN01144335 A CN 01144335A CN 1426681 A CN1426681 A CN 1426681A
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quaternary ammonium
ammonium salt
dialkyl quaternary
bactericide
compound disinfectant
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CN1186980C (en
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郦和生
张春原
郭红卫
樊大勇
张伟
王岽
王骄凌
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
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Abstract

A composite disinfectant containing dialkyl quaternary ammonium salt for disinfecting the circulated cooling water contains at least one dialkyl quaternary ammonium salt disinfectant and at least one non-oxide disinfectant chosen from frequency used quaternary ammonium salt, isothiazolinone, glutaraldehyde, and bithiocyanomethane.

Description

A kind of compound disinfectant and application thereof that contains dialkyl quaternary ammonium salt
Technical field
The present invention relates to a kind of compound disinfectant and application thereof that contains dialkyl quaternary ammonium salt, more particularly, the present invention relates to a kind of the contain compound disinfectant of dialkyl quaternary ammonium salt and the application in recirculating cooling water system thereof.
Technical background
The control of bacterium and algae in the recirculating cooling water system is controlled by adding bactericide usually.Bactericide commonly used is divided into two big class, i.e. oxidized form and non-oxidative bactericides.Oxidative bactericide comprises that chlorine, sodium dichloro cyanurate (are called for short Puritabs, sym-closene (abbreviation strong chlorine oil), active bromine etc.; Non-oxidative bactericide comprises dodecyl benzyl dimethyl ammonium chloride (be called for short " 1227 "), dodecyl dimethyl benzyl ammonium bromide (bromogeramine), myristyl dimethyl benzyl ammonium chloride (being called for short " 1427 "), tetradecyl dimethyl benzyl ammonium, isothiazolinone, glutaraldehyde, dithiocyano-methane etc.These several series bactericidal agents often only have a kind of function, and it is better to peel off effect as the foundry loam of " 1227 ", " 1427 ", bromogeramine, but the sterilization duration is not long, are difficult to control effectively the microorganism harm in the recirculated cooling water; Dithiocyano-methane is then responsive to the pH value of water, and toxicity is big, and range of application is subjected to certain limitation.Simultaneously, what these several series bactericidal agents had has used when China's introducing seventies large chemical fertilizer device is taken to circulating water treatment, and newer has also used about 10 years as isothiazolinone, glutaraldehyde bactericide etc., and update speed is slow.Microorganism is owing to exist environmental suitability, and promptly the genetic material along with the variation microorganism self of environment also changes thereupon, thereby is adapted to new environment.Be embodied in the microorganisms pesticide resistance in recirculating cooling water system, promptly microorganism has certain adaptability to bactericide commonly used, and the working concentration of common fungicide is continued to increase.
Bactericide composite is to solve the microorganism pesticide resistance and make medicament have a kind of effective ways of multifunctionality (refer to peel off, instantaneous sterilization effect and sterilization longer duration function).Compositely be generally composite between the non-oxidative bactericide, seldom use oxidized form and non-oxidative bactericide composite.Principle of compound be two kinds or various sterilization agent composite after, the bactericidal property of compound disinfectant is better than each bactericide and acts on sum separately.Requirement decreases on cost, and collaborative or complementary effect are arranged on performance.
Summary of the invention
The inventor discovers: to recirculating cooling water system, particularly the recirculating cooling water system of material from leakage is arranged, utilize bactericide commonly used to be difficult to control the growth of bacterium, often form zoogloea easily.To such system, the dialkyl quaternary ammonium salt bactericide has bactericidal effect preferably, but its cost of material is higher, its product cost is just high, thereby make its use cost height, the present invention utilizes dialkyl quaternary ammonium salt bactericide and composite pesticide resistance and the dialkyl quaternary ammonium salt use cost high problem of bacterium to common fungicide that solved dexterously of non-oxidative bactericide commonly used.Following table has been listed the price of various bactericide:
The price of table 1 bactericide
Bactericide Price (ten thousand yuan/ton)
Isothiazolinone (1.5%) ????1.0
????1227(46%) ????1.2
Glutaraldehyde (25%) ????1.4
Dialkyl quaternary ammonium salt (60%) ????2.6
The purpose of this invention is to provide a kind of compound disinfectant that contains the dialkyl quaternary ammonium salt class, it is low that this compound disinfectant has good sterilization algae removal effect and use cost, solved the pesticide resistance of bacterium to common fungicide simultaneously.
Another object of the present invention is that the compound disinfectant that will contain the dialkyl quaternary ammonium salt class is used for recirculating cooling water system.
The present invention relates to a kind of compound disinfectant that contains dialkyl quaternary ammonium salt, comprise at least a dialkyl quaternary ammonium salt bactericide and at least a non-oxidative bactericide, the general formula of described dialkyl quaternary ammonium salt is R 1(R 3) 2NR 2X, wherein R 1With R 2Difference, R 1Be dodecyl, myristyl or cetyl, R 2Be octyl or decyl, R 3For carbon number is the alkyl of 1-4, X is a chlorine or bromine, and described non-oxidative bactericide is quaternary ammonium salt commonly used, isothiazolinone, glutaraldehyde, the dithiocyano-methane that is different from above-mentioned dialkyl quaternary ammonium salt.
Quaternary ammonium salt commonly used of the present invention is dodecyl benzyl dimethyl ammonium chloride, myristyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, tetradecyl dimethyl benzyl ammonium.
The preferred R of dialkyl quaternary ammonium salt of the present invention 1Be dodecyl, R 2Be decyl, R 3For carbon number is the alkyl of 1-4, X is a chlorine or bromine; R 1Be myristyl, R 2Be octyl group, R 3For carbon number is the alkyl of 1-4, X is a chlorine or bromine; R 1Be myristyl, R 2Be decyl, R 3For carbon number is the alkyl of 1-4, X is a chlorine or bromine; R 1Be cetyl, R 2Be octyl group, R 3For carbon number is the alkyl of 1-4, X is a chlorine or bromine.
R of the present invention 3Be preferably methyl; Described X is preferably bromine.
Dialkyl quaternary ammonium salt of the present invention is most preferably: dodecyl dimethyl decyl ammonium bromide, myristyl dimethyl octyl group ammonium bromide, myristyl dimethyl decyl ammonium bromide and hexadecyldimethyl benzyl ammonium octyl group ammonium bromide.
Dialkyl quaternary ammonium salt of the present invention can make with conventional method, as tertiary amine, bromo-hydrocarbons and water being added temperature reaction in the reactor simultaneously, obtains dialkyl quaternary ammonium salt; Perhaps tertiary amine (or halogenated hydrocarbons) and water are put into reaction vessel, heat up, drip halogenated hydrocarbons (or tertiary amine) again, reaction obtains dialkyl quaternary ammonium salt.Its raw material proportioning, reaction temperature and reaction time can change in very wide scope, and the mole proportioning of preferred feedstock is: tertiary amine/bromo-hydrocarbons=(1.7~0.8)/1; Reaction temperature is 40~105 ℃; Reaction time is 2~12 hours.
Dialkyl quaternary ammonium salt bactericide of the present invention and non-oxidative bactericide compound proportion commonly used can change in very wide scope, and the weight ratio of preferred dialkyl quaternary ammonium salt bactericide and non-oxidative bactericide is 1: 20~200: 1.Dialkyl quaternary ammonium salt bactericide and quaternary ammonium salt bactericide compound proportion commonly used are 1: 20~15: 1 (weight ratio) preferably; Dialkyl quaternary ammonium salt bactericide and glutaraldehyde compound proportion are 1: 20~15: 1 (weight ratio) preferably; Dialkyl quaternary ammonium salt bactericide and isothiazolinone compound proportion are 5: 1~150: 1 (weight ratio) preferably; Dialkyl quaternary ammonium salt bactericide and two kinds of composite weight ratios of non-oxidative bactericide are 1: 20~15: 1 preferably.Those of ordinary skills are easy to determine that by testing it has the compound proportion of synergy.
The effective total concentration of compound disinfectant in recirculated cooling water that contains the dialkyl quaternary ammonium salt class of the present invention is 2~50mg/L.
Available conventional method prepares the compound disinfectant that contains the dialkyl quaternary ammonium salt class of the present invention, the reinforced order of each component is unimportant, for example dialkyl quaternary ammonium salt bactericide and non-oxidative bactericide and water can be mixed in predetermined ratio, can make the required compound disinfectant that contains the dialkyl quaternary ammonium salt class.Also can earlier dialkyl quaternary ammonium salt be made the aqueous solution, and then non-oxidative bactericide directly added wherein or non-oxidative bactericide made the aqueous solution after mix with it.
The present invention is by composite with at least a dialkyl quaternary ammonium salt bactericide and at least a other common fungicide, and utilize the sterilization mechanism and the sterilization idiocratic of different bactericide, be re-dubbed a kind of good peeling off effect but also have good instantaneous sterilization and the compound disinfectant of sterilization longer duration that not only had, thereby reach the purpose of microorganism in the control recirculated cooling water, simultaneously, reduced the use cost of dialkyl quaternary ammonium salt.
Compound disinfectant of the present invention, be applicable to the control of recirculating cooling water system bacterium and algae, be specially adapted to material from leakage and (leak oil as distillation system, the control of microorganisms of system space division system gas leakage etc.), also be applicable to simultaneously the control of microorganism when sewage is back to recirculating cooling water system after secondary biochemical treatment, thereby solve the foundry loam deposition problems that causes by microorganism.
Embodiment
The following examples will help to illustrate the present invention, but not limit to its scope.
Resulting quaternary ammonium salt adopts the assay method (tetraphenylboron sodium method) of active quantities in the professional standard HG/T 2230-90 of the People's Republic of China (PRC) dodecyl benzyl dimethyl ammonium chloride to measure among the following embodiment, and the molecular weight that just molecular weight of dodecyl benzyl dimethyl ammonium chloride is changed to corresponding quaternary ammonium salt when calculating gets final product.
Embodiment 1
In being housed, four neck flasks of agitator, reflux condenser and thermometer add 0.25mol 14 tertiary amines, 0.25mol n-octane bromide and 75mL water, be warming up to 90 ℃, keep 90~100 ℃ of reactions of temperature 6h, get myristyl dimethyl octyl group bromize ammonium solution 178 grams, gained solution homogeneous, stable, transparent, not stratified, wherein the content of myristyl dimethyl octyl group ammonium bromide is 60.53%, and the yield of myristyl dimethyl octyl group ammonium bromide is 99.3%.
Embodiment 2
In being housed, four neck flasks of agitator, reflux condenser and thermometer add 0.25mol 16 tertiary amines, 0.25mol n-octane bromide and 68mL water, be warming up to 90 ℃, keep 90~100 ℃ of reactions of temperature 4h, get hexadecyldimethyl benzyl ammonium octyl group bromize ammonium solution 177 grams, gained solution homogeneous, stable, transparent, not stratified, wherein the content of hexadecyldimethyl benzyl ammonium octyl group ammonium bromide is 64.11%, and the yield of hexadecyldimethyl benzyl ammonium octyl group ammonium bromide is 99.1%.Embodiment 3
In being housed, four neck flasks of agitator, reflux condenser and thermometer add 0.25mol 14 tertiary amines, 0.25mol bromo n-decane and 75mL water, be warming up to 90 ℃, keep 90~100 ℃ of reactions of temperature 8h, get myristyl dimethyl decyl bromize ammonium solution 184 grams, gained solution homogeneous, stable, transparent, not stratified, wherein the content of myristyl dimethyl decyl ammonium bromide is 61.92%, and the yield of myristyl dimethyl decyl ammonium bromide is 99.5%.
Embodiment 4
In being housed, four neck flasks of agitator, reflux condenser and thermometer add 0.25mol 12 tertiary amines, 0.25mol bromo n-decane and 70mL water, be warming up to 90 ℃, keep 90~100 ℃ of reactions of temperature 10h, get dodecyl dimethyl decyl bromize ammonium solution 174 grams, gained solution homogeneous, stable, transparent, not stratified, wherein the content of dodecyl dimethyl decyl ammonium bromide is 61.92%, and the yield of dodecyl dimethyl decyl ammonium bromide is 99.3%.
Embodiment 5
The water that adds 0.25mol 14 tertiary amines and 90ml in the four-hole boiling flask that agitator, reflux condenser, constant pressure funnel and thermometer are housed, heating is also stirred.Be warming up to 60 ℃, in bottle, slowly drip the 0.25mol n-octane bromide, slowly heat up in the dropping process.Treat that n-octane bromide dropwises, continue to be warming up to 90 ℃, keep 90~100 ℃ of reactions of temperature 3h, get myristyl dimethyl octyl group bromize ammonium solution 193 grams, gained solution homogeneous, stable, transparent, not stratified, wherein the content of myristyl dimethyl octyl group ammonium bromide is 55.77%, and the yield of myristyl dimethyl octyl group ammonium bromide is 99.2%.
Embodiment 6
Add 0.25mol 16 tertiary amines and 70ml water in the four-hole boiling flask that agitator, reflux condenser, constant pressure funnel and thermometer are housed, heating is also stirred.Be warming up to 60 ℃, in bottle, slowly drip the 0.25mol n-octane bromide, slowly heat up in the dropping process.Treat that n-octane bromide dropwises, continue to be warming up to 90 ℃, keep 90~100 ℃ of reactions of temperature 5h, get hexadecyldimethyl benzyl ammonium octyl group bromize ammonium solution 178 grams, gained solution homogeneous, stable, transparent, not stratified, wherein the content of hexadecyldimethyl benzyl ammonium octyl group ammonium bromide is 63.68%, and the yield of hexadecyldimethyl benzyl ammonium octyl group ammonium bromide is 99.0%.
Embodiment 7
Add 0.25mol 14 tertiary amines and 75ml water in the four-hole boiling flask that agitator, reflux condenser, constant pressure funnel and thermometer are housed, heating is also stirred.Be warming up to 60 ℃, in bottle, slowly drip 0.25mol bromo n-decane, slowly heat up in the dropping process.Treat that the bromo n-decane dropwises, continue to be warming up to 90 ℃, keep 90~100 ℃ of reactions of temperature 7h, get myristyl dimethyl decyl bromize ammonium solution 183 grams, gained solution homogeneous, stable, transparent, not stratified, wherein the content of myristyl dimethyl decyl ammonium bromide is 62.07%, and the yield of myristyl dimethyl decyl ammonium bromide is 99.2%.
Embodiment 8
Add 0.25mol 12 tertiary amines and 80ml water in the four-hole boiling flask that agitator, reflux condenser, constant pressure funnel and thermometer are housed, heating is also stirred.Be warming up to 60 ℃, in bottle, slowly drip 0.25mol bromo n-decane, slowly heat up in the dropping process.Treat that the bromo n-decane dropwises, continue to be warming up to 90 ℃, keep 90~100 ℃ of reactions of temperature 9h, get dodecyl dimethyl decyl bromize ammonium solution 184 grams, gained solution homogeneous, stable, transparent, not stratified, wherein the content of dodecyl dimethyl decyl ammonium bromide is 58.44%, and the yield of dodecyl dimethyl decyl ammonium bromide is 99.1%.
The compound method of the compound disinfectant of following embodiment is: with after water mixes by a certain percentage, stirring obtains with the aqueous solution of several bactericide.Example 9
The aqueous solution of the myristyl dimethyl octyl group ammonium bromide that water, embodiment 1 are obtained (being called for short new) with " 1227 " aqueous solution composite after, carry out the bactericidal property test, compound proportion, concentration of sterilant and bactericidal effect see Table 2.Its bactericidal property assessment method (following embodiment also uses same assessment method) is as follows:
Directly get the oil plant cycle water of material from leakage (oil leaks), add certain density bactericide, place 30 ℃ of incubators,, make blank sample simultaneously, calculate sterilizing rate in certain hour monitoring bacterial population.
Figure A0114433500091
To the bacterial classification of separate sources, the bactericidal property difference of its bactericide especially to containing zoogleic bacterial classification, often will descend many with the bactericidal property of the bactericide of concentration.
The composite back in table 2 myristyl dimethyl octyl group ammonium bromide and " 1227 " bactericidal property
Proportioning (weight ratio) is new: " 1227 " Effective total concentration (mg/L) Sterilizing rate (%)
????1h ????24h ????48h ????72h
????1∶18 ????5 ????/ ????77.1 ????/ ????/
????15 ????73.1 ????99.9 ????99.9 ????99.9
????3∶14 ????5 ????/ ????56.3 ????45.0 ????/
????15 ????65.4 ????99.9 ????99.9 ????99.9
????1∶3 ????5 ????/ ????35.4 ????7.1 ????/
????15 ????23.1 ????99.9 ????80.7 ????/
????1∶2 ????5 ????/ ????/ ????/ ????/
????15 ????/ ????99.6 ????69.3 ????/
????3∶4 ????5 ????/ ????/ ????/ ????/
????15 ????/ ????99.6 ????46.4 ????/
????7∶6 ????5 ????/ ????75.0 ????14.3 ????/
????15 ????/ ????99.9 ????99.0 ????/
????2∶1 ????5 ????/ ????64.6 ????/ ????/
????15 ????15.4 ????99.9 ????99.9 ????99.9
????10∶3 ????5 ????/ ????99.5 ????82.1 ????/
????15 ????99.2 ????99.9 ????99.9 ????99.9
Annotate: starter bacteria number: 1.3 * 10 5Individual/ml, "/" expression does not have bactericidal effect, down together; Weight ratio is the weight ratio of active ingredient, down together.
After the result shows that myristyl dimethyl octyl group ammonium bromide quaternary ammonium salt bactericide and " 1227 " are composite, its sterilization feature difference of different ratios, there are two collaborative districts, be the high and ratio of ratio when hanging down synergy better, when being 15mg/L, valid density not only has the instantaneous sterilization effect, and the advantage of sterilization longer duration.Example 10
The aqueous solution of the myristyl dimethyl octyl group ammonium bromide that water, embodiment 1 are obtained (being called for short new) carries out bactericidal property after (being called for short different), the aqueous solution was composite with isothiazolinone to be tested, and compound proportion and bactericidal effect see Table 3.
Table 3 isothiazolinone and the composite result of myristyl dimethyl octyl group ammonium bromide
Proportioning (weight ratio) is new: different Effective total concentration (mg/L) Sterilizing rate (%)
????1h ????24h ????48h ????72h
????67∶1 ????5 ????/ ????98.3 ????31.4 ????/
????15 ????99.7 ????99.9 ????99.9 ????99.9
????34∶1 ????5 ????/ ????96.5 ????72.9 ????/
????15 ????99.8 ????99.9 ????99.9 ????99.9
Annotate: starter bacteria number: 1.3 * 10 5Individual/ml example 11
Carry out bactericidal property after the aqueous solution of the myristyl dimethyl octyl group ammonium bromide that water, embodiment 1 are obtained (being called for short new) and the isothiazolinone aqueous solution (being called for short different) and " 1227 " aqueous solution are composite and test, compound proportion and bactericidal effect see Table 4.
Bactericidal effect during three kinds of composite reagents of table 4
Proportioning (weight ratio) is new: " 1227 ": different Effective total concentration (mg/L) Sterilizing rate (%)
????1h ????24h ????48h ????72h
????10∶40∶1 ????15 ????99.9 ????99.9 ????87.9 ????/
????12∶48∶1 ????15 ????99.0 ????99.9 ????90.0 ????/
????18∶72∶1 ????15 ????99.8 ????99.9 ????98.9 ????/
????36∶144∶1 ????15 ????99.9 ????99.9 ????90.3 ????/
????21∶49∶1 ????15 ????99.9 ????99.9 ????99.1 ????85.5
????27∶63∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.8
????36∶84∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
????48∶72∶1 ????15 ????99.9 ????99.9 ????99.9 ????66.7
????36∶63∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
????48∶84∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
????35∶56∶1 ????15 ????99.9 ????99.9 ????99.9 ????98.6
Starter bacteria number: 1.3 * 10 5Individual/ml.
Example 12
The aqueous solution of the myristyl dimethyl octyl group ammonium bromide that water, embodiment 1 are obtained (being called for short new) carries out bactericidal property with glutaraldehyde water solution after composite to be tested, and compound proportion and bactericidal effect see Table 5.
The composite effect of table 5 myristyl dimethyl octyl group ammonium bromide and glutaraldehyde
Proportioning (weight ratio) is new: glutaraldehyde Effective total concentration (mg/L) Sterilizing rate (%)
????1h ????24h ????48h ????72h
????2∶3 ????5 ????75.1 ????87.1 ????73.2 ????56.3
????15 ????83.1 ????99.9 ????99.9 ????99.9
????1∶1 ????5 ????84.7 ????89.2 ????73.2 ????68.2
????15 ????90.2 ????99.9 ????99.8 ????99.9
????3∶2 ????5 ????79.2 ????90.1 ????84.2 ????71.4
????15 ????92.3 ????99.9 ????99.9 ????99.8
????4∶1 ????5 ????92.3 ????94.5 ????91.5 ????89.2
????15 ????99.9 ????99.9 ????99.9 ????99.9
????6∶1 ????5 ????99.9 ????99.5 ????98.3 ????94.2
????15 ????99.9 ????99.9 ????99.9 ????99.9
Starter bacteria number: 5.3 * 10 5Individual/ml.Example 13
The aqueous solution of the myristyl dimethyl octyl group ammonium bromide that water, embodiment 1 are obtained (being called for short new) and glutaraldehyde water solution and isothiazolinone are carried out bactericidal property after (being called for short different), the aqueous solution was composite and are tested, and compound proportion and bactericidal effect see Table 6.
Bactericidal effect when table 6 three is composite
Proportioning is new: glutaraldehyde: different Effective total concentration (mg/L) Sterilizing rate (%)
????1h ????24h ????48h ????72h
????20∶40∶1 ????15 ????99.8 ????99.9 ????88.9 ????84.2
????24∶48∶1 ????15 ????99.5 ????99.9 ????95.3 ????94.9
????36∶72∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
????72∶144∶1 ????15 ????99.9 ????99.9 ????99.3 ????98.4
????42∶49∶1 ????15 ????99.9 ????99.9 ????99.1 ????89.5
????54∶63∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.8
????72∶84∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
????96∶72∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
????72∶63∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
????96∶84∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
????70∶56∶1 ????15 ????99.9 ????99.9 ????99.9 ????98.9
Starter bacteria number: 1.3 * 10 5Individual/ml.
Embodiment 14
Carry out the bactericidal property test after the aqueous solution of the hexadecyldimethyl benzyl ammonium octyl group ammonium bromide (being called for short new 1) that water, embodiment 2 are obtained and isothiazolinone (the being called for short different) aqueous solution and " 1227 " aqueous solution are composite, compound proportion and bactericidal effect see Table 7.
Bactericidal effect when table 7 three is composite
Proportioning (weight ratio) new 1: " 1227 ": different Effective total concentration (mg/L) Sterilizing rate (%)
????1h ????24h ????48h ????72h
??10∶40∶1 ????15 ????99.9 ????99.9 ????90.1 ????78.3
??12∶48∶1 ????15 ????99.9 ????99.9 ????98.5 ????74.3
??18∶72∶1 ????15 ????99.1 ????99.9 ????99.9 ????99.0
??36∶144∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.1
??21∶49∶1 ????15 ????98.9 ????99.9 ????99.4 ????79.7
??27∶63∶1 ????15 ????99.4 ????99.9 ????99.9 ????90.3
??36∶84∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.5
??48∶72∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
??36∶63∶1 ????15 ????99.5 ????99.9 ????99.9 ????94.8
??48∶84∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
??35∶56∶1 ????15 ????99.7 ????99.9 ????99.9 ????98.5
Starter bacteria number: 7.3 * 10 5Individual/ml.
Embodiment 15
Carry out the bactericidal property test after the aqueous solution of the myristyl dimethyl decyl ammonium bromide (being called for short new 2) that water, embodiment 3 are obtained and isothiazolinone (the being called for short different) aqueous solution and " 1227 " aqueous solution are composite, compound proportion and bactericidal effect see Table 8.
Bactericidal effect when table 8 three is composite
Proportioning (weight ratio) new 2: " 1227 ": different Effective total concentration (mg/L) Sterilizing rate (%)
????1h ????24h ????48h ????72h
????10∶40∶1 ????15 ????98.5 ????99.9 ????95.2 ????81.5
????18∶72∶1 ????15 ????99.7 ????99.9 ????99.9 ????89.3
????36∶144∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
????21∶49∶1 ????15 ????99.9 ????99.9 ????99.9 ????89.5
????27∶63∶1 ????15 ????99.9 ????99.9 ????99.9 ????94.6
????36∶84∶1 ????15 ????99.8 ????99.9 ????99.9 ????98.2
????48∶72∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.9
????35∶56∶1 ????15 ????99.9 ????99.9 ????99.9 ????99.5
Starter bacteria number: 5.2 * 10 6Individual/ml.Example 16
The aqueous solution of the dodecyl dimethyl decyl ammonium bromide (being called for short new 3) that water, embodiment 4 are obtained and isothiazolinone were carried out the bactericidal property test after (being called for short different), the aqueous solution was composite, and compound proportion and bactericidal effect see Table 9.
The composite effect of table 9 dodecyl dimethyl decyl ammonium bromide and isothiazolinone
Proportioning new 3: different Effective total concentration (mg/L) Sterilizing rate (%)
????1h ????24h ????48h ????72h
????10∶1 ????5 ????65.9 ????80.3 ????63.5 ????/
????15 ????91.2 ????99.9 ????99.9 ????99.9
????15∶1 ????5 ????70.8 ????85.4 ????78.2 ????50.3
????15 ????94.5 ????99.9 ????99.8 ????99.9
????67∶1 ????5 ????95.6 ????98.4 ????94.1 ????85.6
????15 ????99.9 ????99.9 ????99.9 ????99.9
????100∶1 ????5 ????99.9 ????99.9 ????99.3 ????95.7
????15 ????99.9 ????99.9 ????99.9 ????99.9
Annotate: starter bacteria number: 4.9 * 10 6Individual/ml.Comparative Examples 1
Carry out the bactericidal property test with common fungicide 1227, isothiazolinone, glutaraldehyde and dialkyl quaternary ammonium salt bactericide, bactericidal effect sees Table 10.
Table 10 bactericide is to the bactericidal effect of oil plant cycle water
Bactericide Valid density (mg/L) Sterilizing rate (%)
????1h ????24h ????48h ????72h
1227 ????10 ????55.9 ????/ ????/ ????/
????30 ????81.2 ????/ ????/ ????/
Isothiazolinone ????0.15 ????/ ????55.4 ????/ ????/
????0.45 ????/ ????65.8 ????/ ????/
Glutaraldehyde ????10 ????21.5 ????/ ????/ ????/
????30 ????/ ????/ ????/ ????/
Myristyl dimethyl octyl group ammonium bromide ????10 ????65.7 ????85.9 ????71.3 ????/
????30 ????78.4 ????99.8 ????99.9 ????99.9
Myristyl dimethyl decyl ammonium bromide ????10 ????34.5 ????65.0 ????/ ????/
????30 ????98.7 ????99.9 ????99.9 ????99.4
Dodecyl dimethyl decyl ammonium bromide ????10 ????86.4 ????89.5 ????/ ????/
????30 ????99.9 ????99.9 ????99.9 ????99.9
Hexadecyldimethyl benzyl ammonium octyl group ammonium bromide ????10 ????62.3 ????79.5 ????34.2 ????/
????30 ????95.8 ????99.9 ????98.7 ????90.4
Starter bacteria number: 2.9 * 10 6Individual/ml.

Claims (10)

1, a kind of compound disinfectant that contains dialkyl quaternary ammonium salt comprises at least a dialkyl quaternary ammonium salt bactericide and at least a non-oxidative bactericide, and the general formula of described dialkyl quaternary ammonium salt is R 1(R 3) 2NR 2X, wherein R 1With R 2Difference, R 1Be dodecyl, myristyl or cetyl, R 2Be octyl or decyl, R 3For carbon number is the alkyl of 1-4, X is a chlorine or bromine, and described non-oxidative bactericide is quaternary ammonium salt commonly used, isothiazolinone, glutaraldehyde, the dithiocyano-methane that is different from above-mentioned dialkyl quaternary ammonium salt.
2, compound disinfectant according to claim 1 is characterized in that described quaternary ammonium salt commonly used is dodecyl benzyl dimethyl ammonium chloride, myristyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide or tetradecyl dimethyl benzyl ammonium.
3,, it is characterized in that the R of described dialkyl quaternary ammonium salt according to each described compound disinfectant of claim 1-2 1Be dodecyl, R 2Be decyl.
4,, it is characterized in that the R of described dialkyl quaternary ammonium salt according to each described compound disinfectant of claim 1-2 1Be myristyl, R 2Be octyl group.
5,, it is characterized in that the R of described dialkyl quaternary ammonium salt according to each described compound disinfectant of claim 1-2 1Be myristyl, R 2Be decyl.
6,, it is characterized in that the R of described dialkyl quaternary ammonium salt according to each described compound disinfectant of claim 1-2 1Be cetyl, R 2Be octyl group.
7,, it is characterized in that the R of described dialkyl quaternary ammonium salt according to each described compound disinfectant of claim 1-6 3Be methyl.
8, according to each described compound disinfectant of claim 1-7, the X that it is characterized in that described dialkyl quaternary ammonium salt is a bromine.
9, according to each described compound disinfectant of claim 1-8, the weight ratio that it is characterized in that described dialkyl quaternary ammonium salt bactericide and non-oxidative bactericide is 1: 20~200: 1.
10, each described compound disinfectant of claim 1-9 is applicable to the control of recirculating cooling water system bacterium and algae, is specially adapted to the material from leakage system and through bacterium and the algae control of the reusing sewage after the secondary biochemical treatment during in recirculated cooling water.
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