CN103030223A - Treatment process of circulating cooling water with leaked ammonia nitrogen - Google Patents

Treatment process of circulating cooling water with leaked ammonia nitrogen Download PDF

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Publication number
CN103030223A
CN103030223A CN2011102920086A CN201110292008A CN103030223A CN 103030223 A CN103030223 A CN 103030223A CN 2011102920086 A CN2011102920086 A CN 2011102920086A CN 201110292008 A CN201110292008 A CN 201110292008A CN 103030223 A CN103030223 A CN 103030223A
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acid
test
water
ammonia nitrogen
multipolymer
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华炜
楼琼慧
周学勤
傅迎春
郦和生
李春丽
秦会敏
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention relates to a treatment method of circulating water with leaked ammonia nitrogen, which comprises the following steps: a) controlling the pH value of the circulating water to 7.5-9.0; b) adding a scale and corrosion inhibitor which comprises the following components: A) at least one phosphorus-free corrosion inhibitor, wherein the phosphorus-free corrosion inhibitor is vanadate and/or a natural high-molecular polymer, B) at least one scale inhibiting dispersant which is at least one phosphorus-free polymer with a carboxylic group, and C) a zinc salt; c) adding at least one bromine-containing bactericide; and d ) adding at least one polyoxyethylene nonionic surfactant, wherein a natural macromolecular compound is selected from tannic acid and lignin natural macromolecular compounds. The invention controls the problems of corrosion, scaling, and bacterial growth in the circulating water system with leaked ammonia nitrogen by methods of adjusting the pH value of the circulating water, and combining with the phosphorus-free scale and corrosion inhibitor and the non-chlorine bactericide.

Description

A kind for the treatment of process of circulating cooling water that leaks ammonia nitrogen
Technical field
The present invention relates to a kind for the treatment of process of circulating cooling water that contains ammonia nitrogen, more particularly the present invention relates to the treatment process of circulating cooling water that production equipment leaks, has ammonia nitrogen to enter.
Background technology
Usually the used crude oil of refinery contains nitrogenous compound, can produce the streams that contains ammonia nitrogen in the process of former oil refining, in a single day device leaks, and this streams has formed the recirculated cooling water that contains ammonia nitrogen with regard to having entered inevitably recirculating cooling water system.Ammonia nitrogen enters major control index p H value, the NO that circulating water system will make recirculated water 2 -, NO 3 -, chemical oxygen demand (COD) etc. analyzes the data severe overweight, cause that by ammonia chain-react causes circulating cooling water quality to worsen, cause heat-exchange equipment heavy corrosion, fouling, a large amount of bacterium algae propagation, make circulating water quality unstable, reduced heat-exchange equipment heat-exchange capacity, cause whole plant energy consumption to rise.To solve the problems such as inhibition, scale inhibition and the microorganism of recirculating cooling water system and foundry loam control in the operational process.
Chinese patent application CN1417139A discloses the reusing sewage of high ammonia-nitrogen content in the method for recirculated cooling water, this technique adding alkali, supercarbonate, carbonate increase the fouling factor in the water, and control corrosion and scaling and bacterial growth in the reusing sewage process with anti-incrustation corrosion inhibitor, the symphyogenetic method of sterilant.All different from water quality of the present invention, anti-incrustation corrosion inhibitor and sterilant.
Chinese patent application CN1491907A discloses a kind of composite scale-inhibiting corrosion inhibitor and has been back to application in the recirculated cooling water containing ammonia-nitrogen sewage, be characterized at the reusing sewage that contains ammonia nitrogen during in recirculated cooling water, add acid and control pH value to 6.5~8.5 in the water, and and anti-incrustation corrosion inhibitor, the symphyogenetic method of sterilant control corrosion and scaling in the reusing sewage process and the problem of bacterial growth, all different from water quality of the present invention, treatment process, anti-incrustation corrosion inhibitor and sterilant.
Summary of the invention
The treatment process of circulating cooling water that the object of the present invention is to provide a kind of production equipment generation ammonia nitrogen to leak, namely method of the present invention is applicable to contain in the recirculated cooling water processing of the recirculating cooling water system of ammonia nitrogen.
To achieve the above object of the invention, the invention provides a kind of leakage ammonia nitrogen circulating water treatment method, it may further comprise the steps: a) the pH value of controlled circulation water is between 7.5-9.0; B) add anti-incrustation corrosion inhibitor, described anti-incrustation corrosion inhibitor comprises following component: A) at least a non-phosphate inhibitor, described non-phosphate inhibitor are water-soluble vanadate and/or natural polymers; B) at least a dirt dispersion agent, described dirt dispersion agent are at least a without phosphorus polymkeric substance that contains the carboxylic acid group, C) zinc salt; C) add at least a brominated sterilant; D) add at least a Determination of Polyoxyethylene Non-ionic Surfactants, wherein natural high moleculer eompound is selected from Weibull and lignin natural high moleculer eompound.
When containing ammonia nitrogen in the recirculated cooling water, ammonia nitrogen form with ammonia in cooling tower is overflowed system, can cause the pH value of system to reduce, as the energy derive of nitrifier, the ammonia nitrogen in the recirculated water exceeds standard and will cause the nitrifier raised growth, and the pH value of system also can further reduce, complex reaction can occur in ammonia nitrogen and copper, larger to copper interchanger infection, ammonia nitrogen also can with recirculated water in oxidative bactericide reaction, a large amount of consumption of sterilant can make that microbial growth is difficult to control in the system.The present invention is by regulating the pH value of recirculated cooling water, and controls corrosion and scaling and bacterial growth problem in the recirculating cooling water system that contains ammonia nitrogen with non-phosphorus scale and corrosion inhibitor, brominated sterilant and the symphyogenetic method of nonionogenic tenside.
Water quality is not simultaneously, adjusting meeting to the pH value is slightly different, recirculated water, pH value for moisturizing calcium hardness>250mg/L are adjusted to 7.5~8.0, recirculated water, pH value for moisturizing calcium hardness 100mg/L~250mg/L are adjusted to 8.0~8.5, are adjusted to 8.5~9.0 for recirculated water, the pH value of moisturizing calcium hardness<100mg/L.The present invention preferably regulates the pH value of recirculated water with alkaline matter, described alkaline matter is preferably at least a in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, the saleratus.
Lignin natural polymers of the present invention is selected from xylogen, sodium lignosulfonate and calcium lignin sulphonate; Described vanadate is selected from ortho-vanadate or metavanadate; Described vanadate is preferably from 12 water sodium orthovanadates and ortho-vanadic acid potassium, and metavanadate is preferably from two water sodium metavanadates, anhydrous sodium metavanadate and potassium metavanadate.
The carboxylic acid group's of containing of the present invention without phosphorus polymkeric substance is selected from homopolymer, copolymer and terpolymer are preferably from poly aspartic acid, poly-epoxy succinic acid, polyacrylic acid, polymaleic anhydride, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/Styrene Sulfonic Acid Copolymer, vinylformic acid/Styrene Sulfonic Acid Copolymer, acrylate/Styrene Sulfonic Acid Copolymer, toxilic acid (acid anhydride)/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, acrylic acid/acrylamide/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, vinylformic acid/toxilic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer and vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer; Wherein said acrylate is preferably from vinylformic acid C 1-8Ester is more preferably from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate.
Zinc salt in the anti-incrustation corrosion inhibitor of the present invention is selected from zinc sulfate, zinc chloride and zinc carbonate, preferably sulfuric acid zinc and zinc chloride.
Effective concentration with respect to pending each component of aqueous solution total amount is: the working concentration of vanadate is 20-50mg/L among the component A, and the working concentration of natural polymers is 100-200mg/L, and the concentration of B component is 2-20mg/L, and the concentration of component C is with Zn 2+Count 0.5-3.0mg/L.
Sterilant of the present invention is that brominated sterilant is selected from hypobromous acid and salt, organo bromine microbicide and bromine chloride, and wherein hypobromite is preferably from sodium hypobromite and hypobromous acid calcium; Preferably from 2,2-, two bromo-3-time aminopropan acid amides and 1-bromo-3-chloro-5, the 5-dimethyl is for glycolylurea for organo bromine microbicide.
It is to add 1 time in every 2-3 days that brominated sterilant of the present invention adds frequency, is 5-20 mg/L with respect to pending aqueous solution total amount effective concentration.
Determination of Polyoxyethylene Non-ionic Surfactants of the present invention is selected from long-chain fat polyoxyethylenated alcohol and alkylphenol polyoxyethylene; The preferred self-drifting of described long-chain fat polyoxyethylenated alcohol is Compound, R wherein 3Be C 12~C 18Alkyl, n be 8-40 natural number, be preferably 8-35; Object lesson has paregal O-8(C 12~C 18Aliphatic alcohol polyethenoxy (8) ether), paregal O-10(C 12~C 18Aliphatic alcohol polyethenoxy (10) ether), paregal O-15(C 12~C 18Aliphatic alcohol polyethenoxy (15) ether), paregal O-20(C 12~C 18Aliphatic alcohol polyethenoxy (20) ether), paregal O-30(C 12~C 18Aliphatic alcohol polyethenoxy (30) ether).The preferred self-drifting of described alkylphenol polyoxyethylene is
Figure 563615DEST_PATH_IMAGE002
Compound, R wherein 4Be C 8~C 12Alkyl, be preferably C 8, C 9, C 12Alkyl, n is 3~30 natural number, more preferably from octyl phenol polyoxy ethene (10~20) ether, Nonyl pheno (10~20) ether and dodecyl phenol polyethenoxy (10~20) ether; Concrete example has op-3(sim alkylphenol polyoxyethylene (3) ether), op-6(sim alkylphenol polyoxyethylene (6) ether), op-10(sim alkylphenol polyoxyethylene (10) ether), op-20(sim alkylphenol polyoxyethylene (20) ether), op-30(sim alkylphenol polyoxyethylene (30) ether), NP-4(nonyl phenol polyethenoxy (4) ether), NP-6(nonyl phenol polyethenoxy (6) ether), NP-10(nonyl phenol polyethenoxy (10) ether), NP-21(nonyl phenol polyethenoxy (21) ether), NP-30(nonyl phenol polyethenoxy (30) ether).
Nonionogenic tenside of the present invention adds frequency for adding 2-4 time per month, is 20-50 mg/L with respect to pending aqueous solution total amount effective concentration.
B of the present invention) going on foot described anti-incrustation corrosion inhibitor can add in the mode of single dose, also can be mixed with first composite scale-inhibiting corrosion inhibitor, composite scale-inhibiting corrosion inhibitor is once added in the recirculated water again, preferably carries out in the latter's mode.Available ordinary method prepares non-phosphorus scale and corrosion inhibitor of the present invention, and the reinforced order of each component is unimportant, for example component A, B, C and water can be mixed in predetermined ratio, can make required non-phosphorus scale and corrosion inhibitor.In the preparation process of non-phosphorus scale and corrosion inhibitor, also can add a small amount of acid (such as dilute sulphuric acid, dense or dilute hydrochloric acid etc.), promoting the dissolving of zinc salt, non-phosphate inhibitor etc., with the uniform solution of the composite scale-inhibiting corrosion inhibitor that needing to obtain as early as possible concentration.
The addition step of leakage ammonia nitrogen circulating water treatment process of the present invention can be successively by a), b) and c) carry out, also can carry out a)-c) step by other arbitrary orders, can also carry out simultaneously these three steps, preferably successively by step a), b) and c) carry out.
Characteristics of the present invention are the water quality that is fit under the various stiffness conditions, and use range is wide, and anti-incrustation corrosion inhibitor is without phosphorus medicament, has reduced the nutrition source of bacterial growth, adopt nonionogenic tenside more to be conducive to the performance of the scale effect of Scale inhibitors.
Method of the present invention is applicable to the circulating cooling water treatment that production equipment leaks the recirculating cooling water system of ammonia nitrogen, and its ammonia nitrogen concentration generally is no more than 20mg/L.
Embodiment
The following examples will help to illustrate the present invention, but not limit to its scope.
Used paregal O-8, paregal O-10, paregal O-15, paregal O-20, paregal O-30 is the production of Shanghai Kai Meisite water technology company limited among the following embodiment; Used op-3, op-6, op-10, op-20, op-30, NP-4, NP-6, NP-10, NP-21, NP-30 are sea, Zibo outstanding chemical industry company limited and produce.
The used test raw water quality of following embodiment and Comparative Examples sees Table 1.
Table 1 test raw water quality
? Ca 2+ Total alkalinity Cl - SO 4 2- pH
Test former water 1 75 100 90 150 7.4
Test former water 2 158 198 116 349 7.6
Test former water 3 265 287 142 639 7.8
Annotate: pH is without unit, and specific conductivity is μ s/cm, and its counit is mg/l, Ca 2+, total alkalinity, total hardness be all with CaCO 3Meter, lower same.
The Reliable Evaluating Methods of Their Performance of the composite scale-inhibiting corrosion inhibitor that following embodiment is prepared is as follows:
Corrosion inhibitionWith 20 #The carbon steel test piece is fixed on the lacing film instrument, puts into the test water that is added with the scale inhibitor agent concentration that adds by embodiment and (the former water 1 of table 1 test is replenished Ca 2+Numerical value when being 5 times to its cycles of concentration, as test water 1, control pH value is 8.5~9.0 in the process of the test; To test former water 2 and replenish Ca 2+Numerical value when being 5 times to its cycles of concentration, as test water 2, control pH value is 8.0~8.5 in the process of the test 5; To test former water 3 and replenish Ca 2+Numerical value when being 3 times to its cycles of concentration, as test water 3, control pH value is 7.5~8.0 in the process of the test), 40 ± 1 ℃ of steady temperatures keep rotating speed 75r/min rotation 72h, and the weight of test piece is calculated average corrosion rate before and after the record test.
The average corrosion rate calculation formula is:
F=(C×△W)/(A×T×ρ)
C: computational constant, during take mm/a as unit, C=8.76 * 10 7
△ W: the corrosion weight loss of test specimen (g)
A: the area (cm of test specimen 2)
T: corrosion test time (h)
ρ: the density (kg/m of material for test 3).
Resistance calcium carbonate scale performanceGet test water and (the former water 1 of test in the table 1 is replenished Ca 2+Numerical value when being 5 times to its cycles of concentration, as test water 1, control pH value is 8.5~9.0 in the process of the test; To test former water 2 and replenish Ca 2+Numerical value when being 5 times to its cycles of concentration, as test water 2, control pH value is 8.0~8.5 in the process of the test; To test former water 3 and replenish Ca 2+Numerical value when being 5 times to its cycles of concentration, as test water 3, control pH value is 7.5~8.0 in the process of the test) add volumetric flask, then add required certain density anti-incrustation corrosion inhibitor, in 80 ± 1 ℃ of waters bath with thermostatic control, leave standstill 10h, remain Ca in the sampling analysis water after cooling 2+Concentration, make simultaneously blank sample, and calculate scale inhibition performance.
The scale inhibition performance calculation formula is: scale inhibition performance=(C-C 0)/(C 1-C 0) * 100%
C: the rear Ca of test solution test that adds water conditioner 2+Concentration (mg/L)
C 0: with the Ca after the blank test solution test of water conditioner 2+Concentration (mg/L)
C 1: Ca in the test solution that configures before the test 2+Concentration (mg/L).
The mensuration of heterotrophic bacterium:Get the test water sample, in sterilisable chamber, adopt 10 times of dilution technologies of former water, the test water sample is diluted to suitable multiple, and the water sample of corresponding extension rate is inoculated in the culture dish.Then aseptic culture medium is poured in the culture dish, mix with water sample, cultivate 72 ± 4h etc. being inverted in the incubator that is placed on 29 ± 1 ℃ after the culture medium solidifying.After the cultivation, take out culture dish, select those culture dish with 30-300 bacterium colony to count, colony number be multiply by the heterotrophic bacterium number that corresponding dilution training number is this water sample.
Adhere to the mensuration of speed:Test tube is positioned in the bypass of interchanger, takes out test tube after the off-test, clean the test tube outer wall after, constant temperature drying takes by weighing the heavy (W of band bur test tube 1).Then clean the inboard wall of test tube bur, dry, take by weighing the heavy (W of test tube 2), calculate and adhere to speed F '.
F’=7.2×10 5×(W 1-W 2)/(A×t)
A: the area (cm of test specimen 2)
T: corrosion test time (h).
When measuring scale-inhibiting properties, following embodiment and Comparative Examples are used all adjust pHs not of any test water quality; When measuring corrosion inhibition, following embodiment and Comparative Examples need adjust pH.
Embodiment 1
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 66.4g 12 water sodium orthovanadates and 12.5g solid content and be 40% poly aspartic acid (molecular weight 3000), be dissolved in the 166.7g water, then 10 of the dilute sulphuric acids volume ratio that adds 4.4g Zinc vitriol and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 1, add the 10mg/L ammonia nitrogen when inhibition and antisludging test, then add the phosphate-free corrosion inhibition antisludging agent for preparing, make sodium orthovanadate in the water, poly aspartic acid, Zn 2+Effective concentration be respectively 30mg/L, 5mg/L, 1mg/L, then add paregal O-8 25mg/L, regulate with 4%NaOH at last and the pH of stabilizing solution is 8.7 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 2
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 180.0g xylogen and 20.0g solid content and be 40% poly-epoxy succinic acid (molecular weight 1000), be dissolved in the 46.8g water, then 10 of the dilute sulphuric acids volume ratio that adds 3.2g Zinc Chloride Anhydrous and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 1, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make xylogen in the water, poly-epoxy succinic acid, Zn 2+Effective concentration be respectively 180mg/L, 8mg/L, 1.5mg/L, then add paregal O-10 35mg/L, regulate with 4%NaOH at last and the pH of stabilizing solution is 8.7 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 3
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 31.6g two water sodium metavanadates and 33.3g solid content and be 30% polyacrylic acid (molecular weight 3000), be dissolved in the 178.5g water, then 10 of the dilute sulphuric acids volume ratio that adds 6.6g Zinc vitriol and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 2, add the 10mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make sodium metavanadate in the water, polyacrylic acid, Zn 2+Effective concentration be respectively 25mg/L, 10mg/L, 1.5mg/L, then add paregal O-15 30mg/L, regulate with 4% yellow soda ash at last and the pH of stabilizing solution is 8.2 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 4
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 120.0g sodium lignosulfonate and 30.0g solid content and be 50% polymaleic anhydride (molecular weight 1000), be dissolved in the 55.6g water, then 10 of the dilute sulphuric acids volume ratio that adds 4.4g Zinc vitriol and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 2, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make sodium lignosulfonate in the water, polymaleic anhydride, Zn 2+Effective concentration be respectively 120mg/L, 15mg/L, 1.0mg/L, then add paregal O-20 40mg/L, regulate with 4% salt of wormwood at last and the pH of stabilizing solution is 8.2 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 5
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 150.0g Weibull and 33.3g solid content and be 30% vinylformic acid/(mass ratio of vinylformic acid and Propylene glycol monoacrylate is 7:3 to the Propylene glycol monoacrylate multipolymer in the multipolymer, Limiting Viscosity in the time of 30 ℃ is 0.069dl/g), be dissolved in the 57.9g water, then 10 of the dilute sulphuric acids volume ratio that adds 8.8g Zinc vitriol and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 3, add the 10mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make Weibull in the water, vinylformic acid/Propylene glycol monoacrylate multipolymer, Zn 2+Effective concentration be respectively 150mg/L, 10mg/L, 2.0mg/L, then add paregal O-30 30mg/L, regulate with 4% yellow soda ash at last and the pH of stabilizing solution is 7.8 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 6
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing the anhydrous sodium metavanadate of 35.0g and 60.0g solid content and be 30% vinylformic acid/Propylene glycol monoacrylate/(mass ratio of vinylformic acid, Propylene glycol monoacrylate and methyl acrylate is 3:1:1 to methyl acrylate copolymer in the multipolymer, Limiting Viscosity in the time of 30 ℃ is 0.071dl/g), be dissolved in the 149.7g water, then 10 of the dilute sulphuric acids volume ratio that adds 5.3g Zinc Chloride Anhydrous and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 3, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make sodium metavanadate in the water, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, Zn 2+Effective concentration be respectively 35mg/L, 18mg/L, 2.5mg/L, then add op-3 45mg/L, regulate with 4% sodium bicarbonate at last and the pH of stabilizing solution is 7.8 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 7
The preparation of phosphate-free corrosion inhibition antisludging agent: (mass ratio of toxilic acid and styrene sulfonic acid is 7:3 in the multipolymer to take by weighing 88.5g 12 water sodium orthovanadates and 26.7g solid content and be toxilic acid/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.072dl/g), be dissolved in the 130.6g water, then 10 of the dilute sulphuric acids volume ratio that adds 4.2g Zinc Chloride Anhydrous and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 1, add the 20mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make sodium orthovanadate in the water, toxilic acid/Styrene Sulfonic Acid Copolymer, Zn 2+Effective concentration be respectively 40mg/L, 8mg/L, 2.0mg/L, then add op-6 35mg/L, regulate with 4% potassium hydroxide at last and the pH of stabilizing solution is 8.7 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 8
The preparation of phosphate-free corrosion inhibition antisludging agent: (mass ratio of vinylformic acid and styrene sulfonic acid is 7:3 in the multipolymer to take by weighing 140.0g calcium lignin sulphonate and 40.0g solid content and be vinylformic acid/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.072dl/g), be dissolved in the 64.7g water, then 10 of the dilute sulphuric acids volume ratio that adds 5.3g Zinc Chloride Anhydrous and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 1, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make calcium lignin sulphonate in the water, vinylformic acid/Styrene Sulfonic Acid Copolymer, Zn 2+Effective concentration be respectively 140mg/L, 12mg/L, 2.5mg/L, then add op-10 40mg/L, regulate with 4% yellow soda ash at last and the pH of stabilizing solution is 8.7 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 9
The preparation of phosphate-free corrosion inhibition antisludging agent: (mass ratio of methyl acrylate and styrene sulfonic acid is 7:3 in the multipolymer to take by weighing 130.0g sodium lignosulfonate and 33.3g solid content and be methyl acrylate/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.074dl/g), be dissolved in the 83.5g water, then 10 of the dilute sulphuric acids volume ratio that adds 3.2g Zinc Chloride Anhydrous and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 2, add the 20mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make sodium lignosulfonate in the water, methyl acrylate/Styrene Sulfonic Acid Copolymer, Zn 2+Effective concentration be respectively 130mg/L, 10mg/L, 1.5mg/L, then add op-20 45mg/L, regulate with 4% yellow soda ash at last and the pH of stabilizing solution is 8.2 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 10
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 120.0g Weibull and 40.0g solid content and be 30% maleic anhydride/(mass ratio of maleic anhydride and allyl sulphonic acid is 7:3 to the allyl sulphonic acid multipolymer in the multipolymer, Limiting Viscosity in the time of 30 ℃ is 0.069dl/g), be dissolved in the 81.2g water, then 10 of the dilute sulphuric acids volume ratio that adds 8.8g Zinc vitriol and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 2, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make Weibull in the water, maleic anhydride/allyl sulphonic acid multipolymer, Zn 2+Effective concentration be respectively 120mg/L, 12mg/L, 2.0mg/L, then add op-30 35mg/L, regulate with 4% yellow soda ash at last and the pH of stabilizing solution is 8.2 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 11
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 45.0g ortho-vanadic acid potassium and 40.0g solid content and be 30% vinylformic acid/(mass ratio of vinylformic acid and allyl sulphonic acid is 7:3 to the allyl sulphonic acid multipolymer in the multipolymer, Limiting Viscosity in the time of 30 ℃ is 0.069dl/g), be dissolved in the 158.4g water, then 10 of the dilute sulphuric acids volume ratio that adds 6.6g Zinc vitriol and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 3, add the 20mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make water Central Plains potassium vanadate, vinylformic acid/allyl sulphonic acid multipolymer, Zn 2+Effective concentration be respectively 45mg/L, 12mg/L, 1.5mg/L, then add NP-4 40mg/L, regulate with 4% saleratus at last and the pH of stabilizing solution is 7.6 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 12
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 44.2g two water sodium metavanadates and 50.0g solid content and be 30% vinylformic acid/(mass ratio of vinylformic acid and vinyl sulfonic acid is 8:2 to the vinyl sulfonic acid multipolymer in the multipolymer, Limiting Viscosity in the time of 30 ℃ is 0.067dl/g), be dissolved in the 151.6g water, then 10 of the dilute sulphuric acids volume ratio that adds 4.2g Zinc Chloride Anhydrous and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 3, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make sodium metavanadate in the water, vinylformic acid/vinyl sulfonic acid multipolymer, Zn 2+Effective concentration be respectively 35mg/L, 15mg/L, 2.0mg/L, then add NP-6 35mg/L, regulate with 4% saleratus at last and the pH of stabilizing solution is 7.6 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 13
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 160.0g Weibull and 33.3.0g solid content and be 30% vinylformic acid/(mass ratio of vinylformic acid and 2-methyl in the multipolymer-2'-acrylamido propane sulfonic acid is 7:3 to 2-methyl-2'-acrylamido propane sulfonic acid multipolymer, Limiting Viscosity in the time of 30 ℃ is 0.069dl/g), be dissolved in the 45.7g water, then 10 of the dilute sulphuric acids volume ratio that adds 11.0g Zinc vitriol and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 1, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make Weibull in the water, vinylformic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, Zn 2+Effective concentration be respectively 160mg/L, 10mg/L, 2.5mg/L, then add NP-10 40mg/L, regulate with 4% sodium hydroxide at last and the pH of stabilizing solution is 8.7 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 14
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 150.0g calcium lignin sulphonate and 33.3.0g solid content and be 30% acrylic acid/acrylamide/(mass ratio of vinylformic acid, acrylamide and 2-methyl-2'-acrylamido propane sulfonic acid is 3:1:1 to 2-methyl-2'-acrylamido propane sulfonic acid multipolymer in the multipolymer, Limiting Viscosity in the time of 30 ℃ is 0.071dl/g), be dissolved in the 63.5g water, then 10 of the dilute sulphuric acids volume ratio that adds 3.2g Zinc Chloride Anhydrous and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 2, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make calcium lignin sulphonate in the water, acrylic acid/acrylamide/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, Zn 2+Effective concentration be respectively 150mg/L, 10mg/L, 1.5mg/L, then add NP-21 35mg/L, regulate with 4% yellow soda ash sodium at last and the pH of stabilizing solution is 8.2 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 15
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing 25.0g potassium metavanadate, 110.0g xylogen and 40.0g solid content and be 30% vinylformic acid/methyl acrylate/(mass ratio of vinylformic acid, methyl acrylate and 2-methyl-2'-acrylamido propane sulfonic acid is 3:1:1 to 2-methyl-2'-acrylamido propane sulfonic acid multipolymer in the multipolymer, Limiting Viscosity in the time of 30 ℃ is 0.065dl/g), be dissolved in the 75.0g water, then 10 of the dilute sulphuric acids volume ratio that adds the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 2, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make the effective concentration of potassium metavanadate in the water, xylogen, vinylformic acid/methyl acrylate/2-methyl-2'-acrylamido propane sulfonic acid multipolymer be respectively 25mg/L, 110mg/L, 12mg/L, then add NP-30 35mg/L, regulating also with 4% yellow soda ash sodium at last, the pH of stabilizing solution is 7.6 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 16
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing the anhydrous sodium metavanadate of 30.0g, 120.0g Weibull and 33.3g solid content and be 30% vinylformic acid/toxilic acid/(mass ratio of vinylformic acid, toxilic acid and 2-methyl-2'-acrylamido propane sulfonic acid is 3:1:1 to 2-methyl-2'-acrylamido propane sulfonic acid multipolymer in the multipolymer, Limiting Viscosity in the time of 30 ℃ is 0.075dl/g), be dissolved in the 66.7g water, then 10 of the dilute sulphuric acids volume ratio that adds the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 1, add the 10mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make the effective concentration of sodium metavanadate in the water, Weibull, vinylformic acid/toxilic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer be respectively 30mg/L, 120mg/L, 10mg/L, then add 15mg/L paregal O-8,15mg/L op-10, regulating also with 4% yellow soda ash sodium at last, the pH of stabilizing solution is 8.7 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Embodiment 17
The preparation of phosphate-free corrosion inhibition antisludging agent: take by weighing the 150.0g sodium lignosulfonate, be 30% vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer (vinylformic acid in the multipolymer 20.0g solid content is 30% polyacrylic acid (molecular weight 3000) and 20.0g solid content, the mass ratio of 2-acrylamido-2-methylpropanephosphonic acid and 2-methyl-2'-acrylamido propane sulfonic acid is 3:1:1, Limiting Viscosity in the time of 30 ℃ is 0.073dl/g), be dissolved in the 56.8g water, then 10 of the dilute sulphuric acids volume ratio that adds 3.2g Zinc vitriol and the 1:3(vitriol oil and water), fully dissolving, shake up, namely obtain the 250g liquid medicine of required preparation.
In test water 2, add the 10mg/L ammonia nitrogen when inhibition and antisludging test, then add phosphate-free corrosion inhibition antisludging agent, make sodium lignosulfonate in the water, polyacrylic acid, vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, Zn 2+Effective concentration be respectively 150mg/L, 6mg/L, 6mg/L, 1.5mg/L, then add 15mg/L op-20,10mg/LNP-21, regulate with 4% yellow soda ash sodium at last and the pH of stabilizing solution is 8.2 ± 0.2.Surveyed an ammonia nitrogen in per 4 hours during corrosion inhibition test, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Comparative Examples 1
Test is not except adding paregal O-8, and test conditions and testing sequence are with embodiment 1, and test-results sees Table 2.
Comparative Examples 2
Test is not except adding the op-20, and test conditions and testing sequence are with embodiment 9, and test-results sees Table 2.
Comparative Examples 3
Test is not except adding the NP-4, and test conditions and testing sequence are with embodiment 11, and test-results sees Table 2.
Comparative Examples 4
Test is except adjust pH not, and test conditions and testing sequence are with embodiment 7, and test-results sees Table 2.
Comparative Examples 5
Test is except adjust pH not, and test conditions and testing sequence are with embodiment 3, and test-results sees Table 2.
Comparative Examples 6
Test is except adjust pH not, and test conditions and testing sequence are with embodiment 12, and test-results sees Table 2.
The scale inhibitor effect of table 2 anti-incrustation corrosion inhibitor
Embodiment Experimental water Resistance calcium carbonate scale rate (%) Corrosion of carbon steel speed (mm/a)
Embodiment 1 1 97.7 0.029
Embodiment 2 1 98.2 0.031
Embodiment 3 2 98.0 0.022
Embodiment 4 2 98.3 0.023
Embodiment 5 3 95.8 0.031
Embodiment 6 3 96.2 0.032
Embodiment 7 1 98.2 0.029
Embodiment 8 1 98.6 0.030
Embodiment 9 2 97.8 0.023
Embodiment 10 2 98.0 0.022
Embodiment 11 3 95.7 0.031
Embodiment 12 3 96.0 0.030
Embodiment 13 1 98.3 0.029
Embodiment 14 2 97.9 0.022
Embodiment 15 3 96.2 0.029
Embodiment 16 1 98.6 0.030
Embodiment 17 2 98.3 0.022
Comparative Examples 1 1 94.5 0.032
Comparative Examples 2 2 95.3 0.025
Comparative Examples 3 3 93.5 0.034
Comparative Examples 4 1 98.5 0.142
Comparative Examples 5 2 95.2 0.117
Comparative Examples 6 3 91.6 0.122
Data by above-described embodiment and Comparative Examples can be found out: when adopting method of the present invention to process the various water quality of oil product leakage, the adding of tensio-active agent does not affect inhibition and the resistance calcium carbonate scale performance of anti-incrustation corrosion inhibitor.
For simulated field, carried out dynamic analog test.The dynamic analog test method is undertaken by the chemical industry standard HG/T2160-91 of the People's Republic of China (PRC), and embodiment 18-is dynamic analog test.
Embodiment 18
The control parameter is as follows:
Test water quality: former water 1
Cycles of concentration: 5.0 ± 0.2
PH value: 8.7 ± 0.2
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
The temperature difference: 10 ℃
Days running: 15 days.
The A tower: phosphate-free corrosion inhibition antisludging agent adopts medicament and the concentration among the embodiment 1, and paregal O-8 25mg/L added ammonia nitrogen one time in per 4 hours, and keeping the ammonia-nitrogen content in the water is 15 mg/L, adds each sodium bromate in per three days, and adding concentration is 15mg/L.Test-results sees Table 3, table 4.
The B tower: except not adding paregal O-8, all the other parameters are with the A tower.Test-results sees Table 3, table 4.
The C tower: except not regulating the pH value, all the other parameters are with the A tower.Test-results sees Table 3, table 4.
Embodiment 19
The control parameter is as follows:
Test water quality: former water 2
Cycles of concentration: 5.0 ± 0.2
PH value: 8.2 ± 0.2
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
The temperature difference: 10 ℃
Days running: 15 days
The A tower: phosphate-free corrosion inhibition antisludging agent adopts medicament and the concentration among the embodiment 9, adds op-20 45mg/L, adds one time ammonia nitrogen in per 4 hours, keeping the ammonia-nitrogen content in the water is 20 mg/L, added one time 2 in per three days, 2-two bromo-3-time aminopropan acid amides, adding concentration is 18mg/L.Test-results sees Table 3, table 4.
The B tower: phosphate-free corrosion inhibition antisludging agent adopts medicament and the concentration among the embodiment 14, adds NP-21 35mg/L, adds ammonia nitrogen one time in per 4 hours, and keeping the ammonia-nitrogen content in the water is 15 mg/L, adds each calcium bromate in per three days, and adding concentration is 15mg/L.Test-results sees Table 3, table 4.
Embodiment 20
The control parameter is as follows:
Test water quality: former water 3
Cycles of concentration: 5.0 ± 0.2
PH value: 7.8 ± 0.2
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
The temperature difference: 10 ℃
Days running: 15 days.
The A tower: phosphate-free corrosion inhibition antisludging agent adopts medicament and the concentration among the embodiment 11, adds NP-4 40mg/L, adds ammonia nitrogen one time in per 4 hours, and keeping the ammonia-nitrogen content in the water is 20 mg/L, adds bromine chloride one time in per three days, and adding concentration is 15mg/L.Test-results sees Table 3, table 4.
The B tower: phosphate-free corrosion inhibition antisludging agent adopts medicament and the concentration among the embodiment 15, adds NP-30 35mg/L, adds one time ammonia nitrogen in per 4 hours, keeping the ammonia-nitrogen content in the water is 15 mg/L, added 1-bromo-3-chloro-5 in per three days one time, the 5-dimethyl is for glycolylurea, and adding concentration is 10mg/L.Test-results sees Table 3, table 4.
Table 3 dynamic analog test test tube is * as a result
Figure 2011102920086100002DEST_PATH_IMAGE003
Table 4 heterotrophic bacterium monitoring result
Figure 462563DEST_PATH_IMAGE004
Regulation among the standard GB/T 50050-2007 " Code for design of industrial recirculating cooling water treatment ", the corrosion speed of the carbon steel tube wall of open type system is less than or equal to 0.125mm/a; The corrosion speed of " the small-sized experimental analogic method of testing laboratory " regulation carbon steel is " fine " level at 0-0.028mm/a in " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment, 0.028-0.056mm/a between be " good " level, 0.056-0.070mm/a for " can allow " level; Adhesion speed is " fine " level at 0-6mcm, is " good " level at 6-15mcm, is " can allow " level at 15-20mcm.Heterotrophic bacterium is controlled at 10 5Below be qualified.
This shows that use in the recirculated water that circulating water treatment prescription of the present invention is applied to ammonia nitrogen leak, erosion rate all is lower than 0.056mm/a, reach China Petrochemical Industry's " good level " standard, adhere to speed and all be lower than between 6-15mcm, reach " good level " standard, heterotrophic bacterium is all less than 1.0 * 10 5In the span of control.

Claims (10)

1. one kind leaks ammonia nitrogen circulating water treatment method, and it may further comprise the steps: a) the pH value of controlled circulation water is between 7.5-9.0; B) add anti-incrustation corrosion inhibitor, described anti-incrustation corrosion inhibitor comprises following component: A) at least a non-phosphate inhibitor, described non-phosphate inhibitor are water-soluble vanadate and/or natural polymers; B) at least a dirt dispersion agent, described dirt dispersion agent are at least a without phosphorus polymkeric substance that contains the carboxylic acid group, C) zinc salt; C) add at least a brominated sterilant; D) add at least a Determination of Polyoxyethylene Non-ionic Surfactants, wherein natural high moleculer eompound is selected from Weibull and lignin natural high moleculer eompound; Preferably recirculated water, the pH value for moisturizing calcium hardness>250mg/L is adjusted to 7.5~8.0, recirculated water, pH value for moisturizing calcium hardness 100mg/L~250mg/L are adjusted to 8.0~8.5, are adjusted to 8.5~9.0 for recirculated water, the pH value of moisturizing calcium hardness<100mg/L.
2. circulating water treatment method according to claim 1 is characterized in that regulating with alkaline matter that the pH value of recirculated water, described alkaline matter are preferably at least a in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, the saleratus.
3. circulating water treatment method according to claim 1 and 2 is characterized in that described lignin natural polymers is selected from xylogen, sodium lignosulfonate and calcium lignin sulphonate; Described vanadate is ortho-vanadate or metavanadate; Described vanadate is preferably from 12 water sodium orthovanadates, ortho-vanadic acid potassium, and metavanadate is preferably from two water sodium metavanadates, anhydrous sodium metavanadate and potassium metavanadate.
4. each described circulating water treatment method according to claim 1-3, it is characterized in that the without phosphorus polymkeric substance that contains the carboxylic acid group is selected from homopolymer, copolymer and terpolymer are preferably from poly aspartic acid, poly-epoxy succinic acid, polyacrylic acid, polymaleic anhydride, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/Styrene Sulfonic Acid Copolymer, vinylformic acid/Styrene Sulfonic Acid Copolymer, acrylate/Styrene Sulfonic Acid Copolymer, toxilic acid (acid anhydride)/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, acrylic acid/acrylamide/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, vinylformic acid/toxilic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer and vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer; Wherein said acrylate is preferably from vinylformic acid C 1-8Ester is more preferably from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate.
5. each described circulating water treatment method is characterized in that described zinc salt is zinc sulfate or zinc chloride according to claim 1-4.
6. described circulating water treatment method is characterized in that described sterilant is brominated sterilant according to claim 1-5, is selected from hypobromous acid and salt thereof, organo bromine microbicide and bromine chloride, and wherein hypobromite is preferably from sodium hypobromite and hypobromous acid calcium; Preferably from 2,2-, two bromo-3-time aminopropan acid amides and 1-bromo-3-chloro-5, the 5-dimethyl is for glycolylurea for organo bromine microbicide.
7. each described circulating water treatment method is characterized in that described Determination of Polyoxyethylene Non-ionic Surfactants is selected from long-chain fat polyoxyethylenated alcohol and alkylphenol polyoxyethylene according to claim 1-6; The preferred self-drifting of described long-chain fat polyoxyethylenated alcohol is
Figure 2011102920086100001DEST_PATH_IMAGE001
Compound, R wherein 3Be C 12~C 18Alkyl, n be 8-40 natural number, be preferably 8-35; The preferred self-drifting of described alkylphenol polyoxyethylene is
Figure 46953DEST_PATH_IMAGE002
Compound, R wherein 4Be C 8~C 12Alkyl, be preferably C 8, C 9, C 12Alkyl, n is 3~30 natural number, more preferably from octyl phenol polyoxy ethene (10~20) ether, Nonyl pheno (10~20) ether and dodecyl phenol polyethenoxy (10~20) ether.
8. each described circulating water treatment method according to claim 1-7, it is characterized in that with respect to the effective concentration of pending each component of aqueous solution total amount being: the working concentration of vanadate is 20-50mg/L among the component A, the working concentration of natural polymers is 100-200mg/L, the concentration of B component is 2-20mg/L, and the concentration of component C is with Zn 2+Count 0.5-3.0mg/L.
9. each described circulating water treatment method according to claim 1-8 is characterized in that it is to add 1 time in every 2-3 days that brominated sterilant of the present invention adds frequency, is 5-20 mg/L with respect to pending aqueous solution total amount effective concentration.
10. each described circulating water treatment method is characterized in that nonionogenic tenside of the present invention is 20-50 mg/L with respect to pending aqueous solution total amount effective concentration according to claim 1-9.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104710023A (en) * 2015-02-15 2015-06-17 中国海洋石油总公司 Preparation method of non-phosphorus environment-friendly dirt dispersion agent special for seawater circulating cooling water
CN104817194A (en) * 2015-05-08 2015-08-05 山东应天节能环保科技有限公司 Corrosion and scale inhibitor specially used for circulating water system in oxygen production plant and preparation method thereof
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CN107746118A (en) * 2017-09-26 2018-03-02 浙江海洋大学 A kind of water treatment agent and preparation method thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1338435A (en) * 2000-08-11 2002-03-06 中国石油化工股份有限公司 Process for treating cyclic cooling water
CN1491907A (en) * 2002-10-23 2004-04-28 中国石油化工股份有限公司北京燕山分 Composite scale resistant corrosion inhibitor and its use in reusing ammonia-nitrogen containing waste water in circulating cooling water
CN1785853A (en) * 2004-12-10 2006-06-14 中国石化北京燕化石油化工股份有限公司 Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application in water treatment
CN1789159A (en) * 2005-12-05 2006-06-21 赵清顺 Sterilization inhibitor for circulated cooling water treatment
CN101066811A (en) * 2007-06-15 2007-11-07 武汉金坡化工科技有限公司 No-phosphate corrosion and scale inhibitor and its application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1338435A (en) * 2000-08-11 2002-03-06 中国石油化工股份有限公司 Process for treating cyclic cooling water
CN1491907A (en) * 2002-10-23 2004-04-28 中国石油化工股份有限公司北京燕山分 Composite scale resistant corrosion inhibitor and its use in reusing ammonia-nitrogen containing waste water in circulating cooling water
CN1785853A (en) * 2004-12-10 2006-06-14 中国石化北京燕化石油化工股份有限公司 Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application in water treatment
CN1789159A (en) * 2005-12-05 2006-06-21 赵清顺 Sterilization inhibitor for circulated cooling water treatment
CN101066811A (en) * 2007-06-15 2007-11-07 武汉金坡化工科技有限公司 No-phosphate corrosion and scale inhibitor and its application

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN104891680A (en) * 2015-05-08 2015-09-09 山东应天节能环保科技有限公司 Non-phosphorus corrosion and scale inhibitor and preparation method thereof
CN105036362A (en) * 2015-06-30 2015-11-11 苏州佑君环境科技有限公司 Low-phosphorous and environmental friendly antisludging agent and preparation method of antisludging agent
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Application publication date: 20130410