CN102187872A - Preparation method of sticky mud inhibitor for water treatment - Google Patents
Preparation method of sticky mud inhibitor for water treatment Download PDFInfo
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- CN102187872A CN102187872A CN2011100655141A CN201110065514A CN102187872A CN 102187872 A CN102187872 A CN 102187872A CN 2011100655141 A CN2011100655141 A CN 2011100655141A CN 201110065514 A CN201110065514 A CN 201110065514A CN 102187872 A CN102187872 A CN 102187872A
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Abstract
The invention relates to a preparation method of a sticky mud inhibitor for water treatment. According to the technical scheme disclosed by the invention, the sticky mud inhibitor is compounded from long-carbon-chain multi-guanidyl polymeric compounds, solvents and auxiliary agents, and the mass content of the sticky mud inhibitor accounts for 10-60% of the total weight; 2) the preparation method comprises the technical steps of: adding long-chain primary amine, diamine, monomeric guanidine and solvents in sequence into a reaction flask provided with a condenser and an ammonia recovery device, wherein the molar ratio of the long-chain primary amine to the diamine to the monomeric guanidine is (0.01-1.2):1:(0.5-2.5); mixing and reacting for 3-8 hours at the temperature of 60-120 DEG C; and then raising the temperature to 140-200 DEG C, and reacting for 4-10 hours while stirring; and finally adding solvents till the required concentration is reached, and thus obtaining the finished product.
Description
Technical field
The invention belongs to water-treatment technology field, relate to the preparation method of a kind of water treatment with the foundry loam inhibitor.
Background technology
In the water treatment of current industrial water, problems such as the bacterium algae grows, biological clay are on the rise, and along with the applying of high concentration ratio technology, make this problem more outstanding.Water fully contacts with air in cooling tower, and it is fully additional that dissolved oxygen in the water is obtained, so the circulation oxygen in water is always saturated.In running, absorbed simultaneously dust, foundry loam, microorganism and spore thereof a large amount of in the air, the system sludge amount increased.Illumination in the cooling tower, preference temperature, sufficient oxygen and nutrient all help bacterium and algae grows, thereby system's foundry loam is increased, and under the deposition, have caused the harm of foundry loam in heat exchanger.Cooling water is in recycling process, and bacterium gathers the formation bacterium colony, and on metallic walls, microorganism not only secreting mucus itself constitutes sediments, and can be attached on the suspended impurity of water and form foundry loam group.Around the foundry loam group and foundry loam group below the concentration cell of formation oxygen, cause serious local corrosion.Microorganism viscosity mud is except quickening underdeposit corrosion, and some bacterium is in metabolic engineering, and the secretion of generation also can directly constitute corrosion.Simultaneously, a large amount of breedings of algae also can make oxygen in water increase, and corrosivity is also just along with increase; Algae death becomes mud and can produce stink and make the water variable color rotten; Algae comes off and also may cause system jams.China exceeds 100 billion because of the direct losses that microbiologic(al) corrosion causes every year, adds that biological clay influences heat exchange and energy consumption of causing etc., and its loss is huger.
How effectively the bacterium algae in the control solution industrial circulating cooling water grows problem, it is one of research emphasis of domestic and international water treatment work scientific research personnel always, develop into today, the comparatively complete bacterium algae control technology and the sterilization algae removal pharmaceutical products of One's name is legion have been formed, add biocide also is industrial circulating cooling water bacterium algae control most convenient, most economical and effective and efficient manner always, and each water treatment user widely uses by the whole world.But along with the raising day by day of environmental protection awareness, harsh more requirement has been proposed existing water treatment sterilization algae removal medicament, require gradually to nothing poison, the development of environmental friendliness aspect.
Exploitation toxicity is low even nontoxic, sterilized removes algae environmental friendliness again, and has the water treatment agent product that foundry loam is extremely efficiently peeled off effect, becomes extremely urgent demand.Correlation technique of the present invention proposes under this background just.
Organic guanidine compound focuses mostly in fields such as cosmetics, beverage, environment disinfected, washing agent now as bactericide, application in water treatment is generally studied less now, existing product only has dodine, hibitane minute quantity product in the Treatment of Industrial Water field application to be arranged, and these products have because of the cost height, have because of poor effect in industrial water conditioning system or former thereby can't use with corrosion inhibiting and descaling agent compatibility difference etc.Characteristics such as and organic guanidine is killed the inhibition effect very efficiently because of having, and possesses environmental friendliness, and low toxicity is nontoxic.Therefore, the exploitation of organic guanidine new product and the application research in water treatment thereof are had very important significance.Be subjected to domestic and international researcher's attention in recent years day by day.
Organic guanidine compound of polymerization such as polyhexamethylene guanide etc., because its distinctive molecular structure, make it have the performance of a lot of excellences, as characteristics such as broad-spectrum high efficacy, low, still, the no pesticide resistance of working concentration, biodegradable, environmental sounds, make it become a very potential class water treatment biocide.Its bactericide mechanism is: because guanidine radicals has very high activity, make polymer become electropositive, easily be electronegative each bacterioid, virus absorption usually, thereby the splitting function that has suppressed bacterial virus, make bacterial virus lose fecundity, and the organic guanidine of polymerization concentrate on a plurality of guanidine radicals with more having strengthened this effect on a part; Simultaneously, owing to be high molecular polymer, the film that polymer forms can stop up the respiration channel of microorganism, and microorganism is choked to death rapidly.But the shortcoming that this series products has is, its surface-active is lower, do not have foundry loam substantially and peel off function, in the industrial circulating cooling water adhere to bacterium, the biological clay effect is faint.
Summary of the invention
Preparation method of the present invention provides a kind of novel water treatment foundry loam inhibitor, it all has the very excellent inhibition effect of killing to heterotroph common in the water treatment, iron bacteria sulfate reducing bacteria and most algae, and has excellent biological clay stripping performance.Novel water treatment foundry loam inhibitor of the present invention; on the method basis of organic diamine compound and monomer guanidine synthesized polymer guanidine; the structure complex method of long carbochain is introduced in employing in molecule; the physics winding effect and the oiliness absorption property of resulting composite have been improved; and degree of depth bactericidal effect; thereby strengthened the surface-active of product medicament greatly; make it possess excellent foundry loam and peel off function; implementation result shows; not only can kill the plankton in the cycle water; the biological clay of also peelable cleaning channels equipment surface is protected line equipment comprehensively completely, and elimination bacterium algae grows the adverse effect to circulation.The foundry loam that is fit to very much industrial circulating cooling water suppresses to remove.
The present invention is the preparation method of a kind of water treatment with the foundry loam inhibitor, it is characterized in that; Adopt following technical scheme:
1) compound composition:
This water treatment is made up of long carbochain polyguanidine base polymerizable compound, solvent, auxiliary agent with the foundry loam inhibitor; Long carbochain polyguanidine base polymerizable compound wherein has the structural formula of following compound (I):
Wherein: m 〉=1
M＝HCl、CH
3COOH、CHOOH、HNO
3、1/2H
2SO
4、1/3H
3PO
4
R
1=CH
3(CH
2)
n, wherein, n=7～17
R
2=H, or CH
3(CH
2)
n, wherein, n=7～17
Wherein, x=2,6,8; Y=0,1,2,3
(I)
Above-mentioned long carbochain polyguanidine base polymerizable compound, be characterized in: described long-chain primary amine is shown in structural formula (II):
CH
3(CH
2)
nNH
2
Wherein, n=9～17
(II)
Above-mentioned long carbochain polyguanidine base polymerizable compound, be characterized in: used diamines is compound shown in structural formula (III), (IV):
Above-mentioned long carbochain polyguanidine base polymerizable compound, be characterized in: used monomer guanidine is guanidine hydrochloride, guanidine sulfate, phosphoguanidine, guanidine acetate;
Above-mentioned long carbochain polyguanidine base polymerizable compound, be characterized in: solvent for use is water, acetone, ethylene glycol, glycerine, 1,2-propane diols, 1, ammediol, N, dinethylformamide, isopropyl alcohol, diethylene glycol (DEG), triethylene glycol, sulfolane etc., its mass content accounts for 10～90% of gross weight;
Above-mentioned long carbochain polyguanidine base polymerizable compound is characterized in: adjuvant used is Macrogol 200, PEG400, Macrogol 600, polysorbate60, Tween 80; Alkylphenol polyoxyethylene: be selected from OP-10, OP-15, OP-20, its auxiliary agent mass content is 1～20%;
Above-mentioned long carbochain polyguanidine base polymerizable compound, be characterized in: used halogenated hydrocarbons is a compound shown in the structural formula (V):
CH
3(CH
2)
aX，
Wherein, a=9～17; X=Cl, Br, I
(V)
Above-mentioned long carbochain polyguanidine base polymerizable compound is characterized in: this water treatment is made up of one or more of the described compound of compound (I) with the foundry loam inhibitor, and its mass content accounts for 10～60% of gross weight;
2) preparation method:
Concrete processing step is as follows:
Method one: in the reaction bulb that condenser and ammonia retracting device are housed, add long-chain primary amine, diamines, monomer guanidine and solvent successively, the mol ratio of long-chain primary amine, diamines, monomer guanidine is 0.01～1.2: 1: 0.5～2.5, behind 60～120 ℃ of stirring reaction 3～8h, be warming up to 140～200 ℃, stirring reaction 4～10h; Add solvent at last and allocate, promptly get product to desired concn;
Method two: in the reaction bulb that condenser and ammonia retracting device are housed, add diamines and solvent, during then in room temperature～120 ℃, in reaction bulb, drip halogenated hydrocarbons, dropwise 30～120 ℃ of insulation reaction 1～5h in back, add the monomer guanidine again, be warmed up to 60～120 ℃ of reaction 2～6h, be warmed up to 140～200 ℃ of reaction 4～10h again; Add solvent at last and allocate, promptly get product to desired concn; Wherein material adds mol ratio and is: halogenated hydrocarbons: diamines: monomer guanidine=0.01～1.2: 1: 0.5～2.5.
According to preparation method of the present invention, it is characterized in that water treatment is decided on the biological clay situation on bacterium in the water and the tube wall with the working concentration of foundry loam inhibitor in water system; The general impact type dosing method that adopts, working concentration is generally 10～100mg/L.
Advantage that the present invention has and good effect: a kind of novel water treatment preparation method of foundry loam inhibitor of the present invention's research and development, it is compared with the conventional sterilization agent, it is compound to have structure, sterilization is efficient, the antibacterial time is long, no pesticide resistance, nontoxic, characteristics such as safe in utilization, and synthesis technique is simple, various metal materials there is not corrosion, environmentally friendly, be applicable to industrial circulating cooling water, to heterotroph in the water (TGB), iron bacteria, sulfate reducing bacteria (SRB) and various algae have and excellent killing effect, and the biological clay in the circulation is had the excellent effect of peeling off.
The water treatment foundry loam inhibitor of the inventive method preparation, employing inserts long carbochain in the organic guanidine compound molecule of the polymerization of routine, make and not only contain a plurality of guanidine radicals structures but also contain long carbon-chain structure in the compound molecule structure, because the guanidine radicals structure has very high activity, make polymer become electropositive, easily be electronegative biological clay usually, each bacterioid is adsorbed, thereby the splitting function that has suppressed bacterial virus, make bacterial virus lose fecundity, the introducing of long carbon-chain structure lipophilic group then can make medicament to thalline, the winding parcel of foundry loam, the infiltration dissolution strengthens greatly, thereby biological clay is peeled off easily, and germicidal efficiency is improved.Therefore, the water treatment of the inventive method exploitation had both had efficient, the antibacterial time length of sterilization of the organic guanidine of polymerization, no pesticide resistance, environmental friendliness, characteristics such as safe in utilization with the foundry loam inhibitor, heterotroph, iron bacteria, sulfate reducing bacteria and various algae in the water are had and excellent killing effect, simultaneously can effectively peel off cleaning to the biological clay in the circulation again, be very suitable for foundry loam cleaning and inhibition in the industrial circulating cooling water.
Embodiment
Embodiment 1
In the 1000ml four-hole boiling flask that mechanical agitation, reflux condensing tube, thermometer and ammonia absorption plant are housed, add dodecyl dimethyl tertiary amine 22.2g (96% respectively, 0.10mol), diethylenetriamine 104.2g (99%, 1.0mol), guanidine hydrochloride 96.8g (1.0mol), ethylene glycol 100g, heat temperature raising to 80 ℃, reaction 4h; Be warming up to 160 ℃ again, continue reaction 5h.Add the allotment of entry and auxiliary agent at last and promptly get the organic guanidine product of certain solid content polymerization.
Embodiment 2
In the 1000ml four-hole boiling flask that mechanical agitation, reflux condensing tube, thermometer and ammonia absorption plant are housed, add myristyl dimethyl tertiary amine 25.1g (96% respectively, 0.10mol), triethylene tetramine 147.5g (99%, 1.0mol), guanidine hydrochloride 96.8g (1.0mol), diethylene glycol (DEG) 100g, heat temperature raising to 80 ℃, reaction 4h; Be warming up to 160 ℃ again, continue reaction 5h.Add the allotment of entry and auxiliary agent at last and promptly get the organic guanidine product of certain solid content polymerization.
Embodiment 3
In the 1000ml four-hole boiling flask that mechanical agitation, reflux condensing tube, thermometer and ammonia absorption plant are housed, add hexadecyldimethyl benzyl ammonium tertiary amine 28.0g (96% respectively, 0.10mol), hexamethylene diamine 117.2g (99%, 1.0mol), guanidine hydrochloride 96.8g (1.0mol), diethylene glycol (DEG) 100g, heat temperature raising to 80 ℃, reaction 4h; Be warming up to 180 ℃ again, continue reaction 8h.Add the allotment of entry and auxiliary agent at last and promptly get the organic guanidine product of certain solid content polymerization.
Embodiment 4
In the 1000ml four-hole boiling flask that mechanical agitation, reflux condensing tube, thermometer and ammonia absorption plant are housed, add dodecyl dimethyl tertiary amine 22.2g (96% respectively, 0.10mol), two propylene triamine 132.3g (99%, 1.0mol), guanidine hydrochloride 96.8g (99%, 1.0mol), sulfolane 50g, heat temperature raising to 70 ℃, reaction 2h; Be warming up to 150 ℃ again, continue reaction 4h.Add the allotment of entry and auxiliary agent at last and promptly get the organic guanidine product of certain solid content polymerization.
Embodiment 5
In the 1000ml four-hole boiling flask that mechanical agitation, reflux condensing tube, thermometer and ammonia absorption plant are housed, and adding diethylenetriamine 104.2g (99%, 1.0mol), ethylene glycol 60g.Be added dropwise under the room temperature then 1-chlorinated dodecane 20.68 (99%, 0.10mol), be warmed up to 50～55 ℃ after finishing, insulation reaction 2h, add again guanidine sulfate 130.8g (99%, 0.6mol), heat temperature raising to 80 ℃, reaction 2h; Be warming up to 160 ℃ again, continue reaction 6h.Add the allotment of entry and auxiliary agent at last and promptly get the organic guanidine product of certain solid content polymerization.
Embodiment 6
In the 1000ml four-hole boiling flask that mechanical agitation, reflux condensing tube, thermometer and ammonia absorption plant are housed, and adding hexamethylene diamine 117.2g (99%, 1.0mol), diethylene glycol (DEG) 100g.Be added dropwise under the room temperature then 1-bromotetradecane 14g (99%, 0.05mol), be warmed up to 80 ℃ after finishing, insulation reaction 2h, add again guanidine hydrochloride 96.8g (99%, 1.0mol), heat temperature raising to 80 ℃, reaction 2h; Be warming up to 180 ℃ again, continue reaction 10h.Add the allotment of entry and auxiliary agent at last and promptly get the organic guanidine product of certain solid content polymerization.
Embodiment 7
In the 500ml four-hole boiling flask that mechanical agitation, reflux condensing tube, thermometer and ammonia absorption plant are housed, and adding ethylenediamine 60g (99%, 1.0mol), sulfolane 30g.Be added dropwise under the room temperature then 1-chlorooctadecane 7.3g (99%, 0.025mol), be warmed up to 80 ℃ after finishing, insulation reaction 2h, add again guanidine hydrochloride 96.8g (99%, 1.0mol), heat temperature raising to 120 ℃, reaction 3h; Be warming up to 180 ℃ again, continue reaction 8h.Add the allotment of entry and auxiliary agent at last and promptly get the organic guanidine product of certain solid content polymerization.
Embodiment 8 bactericidal property evaluations
The method of evaluating performance of bactericide adopts the test bottle method of disappearance dilution method, reference standard is GB/T14643.1-1993 " mucus forms the mensuration plate count of bacterium in the industrial circulating cooling water ", GB/T14643.5-1993 " the mensuration MPN method of sulfate reducing bacteria in the industrial circulating cooling water ", GB/T14643.6-1993 " the mensuration MPN method of iron bacteria in the industrial circulating cooling water ".The SRB bacterial classification is taken from east, Ji oil field extracted water, and bacteria suspension adopts the oil field extracted water preparation of east, Ji, bacterium medicine 2h time of contact, T=50 ℃; TGB and FB bacterial classification be from the big seamless steel tubing mill in Tianjin cycle water, the on-the-spot water preparation of this factory of bacteria suspension, time of contact 4h, T=35 ℃.Table 1 is the sterilization test result:
The bactericidal property evaluation of the novel foundry loam inhibitor of table 1 the present invention relatively
Annotate: the novel glutinous mud inhibitor product (20% effective mass content) that " sticking-1 "-embodiment of the invention 1 is synthesized; The novel glutinous mud inhibitor product (20% effective mass content) that " sticking-2 "-embodiment of the invention 7 is synthesized; The commercially available polyhexamethylene guanidine hydrochloride of GA-(25% effective mass content); The 1227-dodecyl benzyl dimethyl ammonium chloride, 45% effective mass content; Bi-quaternary ammonium salt-biquaternary ammonium salts bactericides product, 40% effective mass content; Isothiazolinone---import industrial goods, 14% effective mass content.
The test of embodiment 9 foundry loam stripping performances
The foundry loam stripping performance of medicament adopts homemade foundry loam evaluating apparatus to test, and its flow process is as follows: (1) adds bacterial classification in culture tank and nutrients carries out the cultivation of bacterium algae; (2) after cultivation is finished, insert the stainless steel testing tube in test box, dynamic circulation makes the stainless steel testing tube grow foundry loam after the regulation requirement, takes out testing tube, and 42 ± 1 ℃ of dry 6h weigh; (3) testing tube after will weighing inserts test box again, adds adhesive mud remover to be measured, and operation 24h takes out testing tube then, and 42 ± 1 ℃ of dry 6h weigh.Whole dynamic control parameter is: pH value=8.0～8.5,32 ± 1 ℃ of temperature, flow velocity 1.0m/h.Test result is shown in Table 2:
The test of the novel foundry loam inhibitor of table 2 the present invention stripping performance relatively
Annotate: the novel glutinous mud inhibitor product (20% effective mass content) that " sticking-1 "-embodiment of the invention 1 is synthesized; The novel glutinous mud inhibitor product (20% effective mass content) that " sticking-2 "-embodiment of the invention 7 is synthesized; The commercially available polyhexamethylene guanidine hydrochloride of GA-(25% effective mass content); The 1227-dodecyl benzyl dimethyl ammonium chloride, 45% effective mass content; Bi-quaternary ammonium salt-biquaternary ammonium salts bactericides product, 40% effective mass content; Isothiazolinone---import industrial goods, 14% effective mass content.
Claims (2)
1. the preparation method of a water treatment usefulness foundry loam inhibitor is characterized in that; Adopt following technical scheme:
1) compound composition:
This water treatment is made up of long carbochain polyguanidine base polymerizable compound, solvent, auxiliary agent with the foundry loam inhibitor; Long carbochain polyguanidine base polymerizable compound wherein has the structural formula of following compound (I):
Wherein: m 〉=1
M＝HCl、CH
3COOH、CHOOH、HNO
3、1/2H
2SO
4、1/3H
3PO
4
R
1=CH
3(CH
2)
n, wherein, n=7～17
R
2=H, or CH
3(CH
2)
n, wherein, n=7～17
Wherein, x=2,6,8; Y=0,1,2,3
(I)
Above-mentioned long carbochain polyguanidine base polymerizable compound, be characterized in: described long-chain primary amine is shown in structural formula (II):
CH
3(CH
2)
nNH
2
Wherein, n=9～17
(II)
Above-mentioned long carbochain polyguanidine base polymerizable compound, be characterized in: used diamines is compound shown in structural formula (III), (IV):
Above-mentioned long carbochain polyguanidine base polymerizable compound, be characterized in: used monomer guanidine is guanidine hydrochloride, guanidine sulfate, phosphoguanidine, guanidine acetate;
Above-mentioned long carbochain polyguanidine base polymerizable compound, be characterized in: solvent for use is water, acetone, ethylene glycol, glycerine, 1,2-propane diols, 1, ammediol, N, dinethylformamide, isopropyl alcohol, diethylene glycol (DEG), triethylene glycol, sulfolane etc., its mass content accounts for 10～90% of gross weight;
Above-mentioned long carbochain polyguanidine base polymerizable compound is characterized in: adjuvant used is Macrogol 200, PEG400, Macrogol 600, polysorbate60, Tween 80; Alkylphenol polyoxyethylene: be selected from OP-10, OP-15, OP-20, its auxiliary agent mass content is 1～20%;
Above-mentioned long carbochain polyguanidine base polymerizable compound, be characterized in: used halogenated hydrocarbons is a compound shown in the structural formula (V):
Wherein, a=9～17; X=Cl, Br, I
(V)
Above-mentioned long carbochain polyguanidine base polymerizable compound is characterized in: this water treatment is made up of one or more of the described compound of compound (I) with the foundry loam inhibitor, and its mass content accounts for 10～60% of gross weight;
2) preparation method:
Concrete processing step is as follows:
Method one: in the reaction bulb that condenser and ammonia retracting device are housed, add long-chain primary amine, diamines, monomer guanidine and solvent successively, the mol ratio of long-chain primary amine, diamines, monomer guanidine is 0.01～1.2: 1: 0.5～2.5, behind 60～120 ℃ of stirring reaction 3～8h, be warming up to 140～200 ℃, stirring reaction 4～10h; Add solvent at last and allocate, promptly get product to desired concn;
Method two: in the reaction bulb that condenser and ammonia retracting device are housed, add diamines and solvent, during then in room temperature～120 ℃, in reaction bulb, drip halogenated hydrocarbons, dropwise 30～120 ℃ of insulation reaction 1～5h in back, add the monomer guanidine again, be warmed up to 60～120 ℃ of reaction 2～6h, be warmed up to 140～200 ℃ of reaction 4～10h again; Add solvent at last and allocate, promptly get product to desired concn; Wherein material adds mol ratio and is: halogenated hydrocarbons: diamines: monomer guanidine=0.01～1.2: 1: 0.5～2.5.
2. according to the described preparation method of claim 1, it is characterized in that water treatment is decided on the biological clay situation on bacterium in the water and the tube wall with the working concentration of foundry loam inhibitor in water system; The general impact type dosing method that adopts, working concentration is generally 10～100mg/L.
Priority Applications (1)
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|---|---|---|---|
| CN2011100655141A CN102187872A (en) | 2011-03-18 | 2011-03-18 | Preparation method of sticky mud inhibitor for water treatment |
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|---|---|---|---|
| CN2011100655141A CN102187872A (en) | 2011-03-18 | 2011-03-18 | Preparation method of sticky mud inhibitor for water treatment |
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| CN102187872A true CN102187872A (en) | 2011-09-21 |
Family
ID=44597396
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103598196A (en) * | 2013-10-25 | 2014-02-26 | 中国海洋石油总公司 | Biological slime stripping agent for water treatment, and preparation method thereof |
| CN106800652A (en) * | 2017-01-26 | 2017-06-06 | 上海富元塑胶科技有限公司 | Guanidine oligomer and preparation method thereof and the application being bonded on polymers for general use strand |
| CN109769850A (en) * | 2018-12-05 | 2019-05-21 | 中海油天津化工研究设计院有限公司 | A kind of seawater direct-current cooling system marine growth inhibitor and preparation method |
| CN110269066A (en) * | 2019-06-25 | 2019-09-24 | 天津市职业大学 | Compound disinfectant and its preparation method and application |
| CN110301437A (en) * | 2019-07-11 | 2019-10-08 | 北京中天兰清环境科技有限公司 | A kind of sterilization synergy remover for circulating water treatment |
| CN113508820A (en) * | 2021-06-29 | 2021-10-19 | 中海油天津化工研究设计院有限公司 | Oil-soluble efficient bactericide and preparation method thereof |
-
2011
- 2011-03-18 CN CN2011100655141A patent/CN102187872A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103598196A (en) * | 2013-10-25 | 2014-02-26 | 中国海洋石油总公司 | Biological slime stripping agent for water treatment, and preparation method thereof |
| CN106800652A (en) * | 2017-01-26 | 2017-06-06 | 上海富元塑胶科技有限公司 | Guanidine oligomer and preparation method thereof and the application being bonded on polymers for general use strand |
| CN109769850A (en) * | 2018-12-05 | 2019-05-21 | 中海油天津化工研究设计院有限公司 | A kind of seawater direct-current cooling system marine growth inhibitor and preparation method |
| CN110269066A (en) * | 2019-06-25 | 2019-09-24 | 天津市职业大学 | Compound disinfectant and its preparation method and application |
| CN110301437A (en) * | 2019-07-11 | 2019-10-08 | 北京中天兰清环境科技有限公司 | A kind of sterilization synergy remover for circulating water treatment |
| CN113508820A (en) * | 2021-06-29 | 2021-10-19 | 中海油天津化工研究设计院有限公司 | Oil-soluble efficient bactericide and preparation method thereof |
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Application publication date: 20110921 |