CN103030225A - Treatment process of circulating cooling water with leaked ammonia nitrogen - Google Patents
Treatment process of circulating cooling water with leaked ammonia nitrogen Download PDFInfo
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- CN103030225A CN103030225A CN2011102927564A CN201110292756A CN103030225A CN 103030225 A CN103030225 A CN 103030225A CN 2011102927564 A CN2011102927564 A CN 2011102927564A CN 201110292756 A CN201110292756 A CN 201110292756A CN 103030225 A CN103030225 A CN 103030225A
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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 selected from thiourea and its derivative and a nitrogen-containing heterocyclic compound type adsorption film corrosion inhibitor, 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 sulfonate nonionic surfactant. 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
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, and described non-phosphate inhibitor is for being selected from thiocarbamide and derivative thereof and nitrogen-containing heterocycle compound class absorption membranous type inhibiter; 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 sulfonate type anion surfactant.
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.
The derivative of thiocarbamide of the present invention is selected from methylthiourea, ethyl thiourea, diphenyl thiourea, thiosinamine, tolylthiourea; Nitrogen-containing heterocycle compound is selected from Five-membered Heterocyclic Compounds, hexa-atomic nitrogen-containing heterocycle compound and nitrogenous fused heterocyclic compound; Five-membered Heterocyclic Compounds is preferably from tetrahydroglyoxaline, glyoxal ethyline quinoline, hexa-atomic nitrogen-containing heterocycle compound is preferably from morpholine, piperazine, 2-methylpiperazine, 1,4 lupetazins, nitrogenous fused heterocyclic compound are preferably from benzotriazole, methyl benzotriazazole, mercaptobenzothiazole and urotropine.
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 concentration of component A is 80-200mg/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.
Sulfonate type anion surfactant of the present invention is selected from chain alkyl arylsulphonate, sulfonated alkyl naphathalene; Preferably from C
12～C
18Alkylbenzene sulfonate and carbonatoms are C
4～C
8Double alkyl naphthalene sulfonate; Most preferably from Sodium dodecylbenzene sulfonate, tetradecyl benzene sulfonic acid sodium salt, hexadecyl benzene sulfonic acid sodium salt, 4,8-sodium dibutyl naphthalene sulfonate, two hexyl sodium naphthalene sulfonate, two octyl group sodium naphthalene sulfonate.
Sulfonate type anion surfactant 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 anion surfactant 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.
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; 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), 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 120.0g thiocarbamide and 12.5g solid content and be 40% poly aspartic acid (molecular weight 3000), be dissolved in the 113.1g 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 thiocarbamide in the water, poly aspartic acid, Zn
2+Effective concentration be respectively 120mg/L, 5mg/L, 1mg/L, then add Sodium dodecylbenzene sulfonate 25mg/L, regulate with 4%NaOH at last and the pH of stabilizing solution is 8.7 ± 0.2.Surveyed an ammonia-nitrogen content in per 4 hours in the corrosion inhibition test process, 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 150.0g methylthiourea and 20.0g solid content and be 40% poly-epoxy succinic acid (molecular weight 1000), be dissolved in the 76.8g 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 the phosphate-free corrosion inhibition antisludging agent for preparing, make methylthiourea in the water, poly-epoxy succinic acid, Zn
2+Effective concentration be respectively 150mg/L, 8mg/L, 1.5mg/L, then add 4,8-sodium dibutyl naphthalene sulfonate 35mg/L, regulate with 4%NaOH at last and the pH of stabilizing solution is 8.7 ± 0.2.Surveyed an ammonia-nitrogen content in per 4 hours in the corrosion inhibition test process, 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 140.0g ethyl thiourea and 33.3g solid content and be 30% polyacrylic acid (molecular weight 3000), be dissolved in the 73.4g 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 2, add the 10mg/L ammonia nitrogen when inhibition and antisludging test, then add the phosphate-free corrosion inhibition antisludging agent for preparing, make ethyl thiourea in the water, polyacrylic acid, Zn
2+Effective concentration be respectively 140mg/L, 10mg/L, 1.5mg/L, then add tetradecyl benzene sulfonic acid sodium salt 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 content in per 4 hours in the corrosion inhibition test process, 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 160.0g diphenyl thiourea 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 the phosphate-free corrosion inhibition antisludging agent for preparing, make diphenyl thiourea in the water, polymaleic anhydride, Zn
2+Effective concentration be respectively 160mg/L, 15mg/L, 1.0mg/L, then add two hexyl sodium naphthalene sulfonate 40mg/L, regulating also with 4% salt of wormwood at last, the pH of stabilizing solution is 8.2 ± 0.2.Surveyed an ammonia-nitrogen content in per 4 hours in the corrosion inhibition test process, 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 180.0g thiosinamine 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 30.9g 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 the phosphate-free corrosion inhibition antisludging agent for preparing, make thiosinamine in the water, vinylformic acid/Propylene glycol monoacrylate multipolymer, Zn
2+Effective concentration be respectively 180mg/L, 10mg/L, 2.0mg/L, then add hexadecyl benzene sulfonic acid sodium salt 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 content in per 4 hours in the corrosion inhibition test process, 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 150.0g tolylthiourea 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 34.7g 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 the phosphate-free corrosion inhibition antisludging agent for preparing, make tolylthiourea in the water, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, Zn
2+Effective concentration be respectively 150mg/L, 18mg/L, 2.5mg/L, then add two octyl group sodium naphthalene sulfonate 45mg/L, regulating also with 4% sodium bicarbonate at last, the pH of stabilizing solution is 7.8 ± 0.2.Surveyed an ammonia-nitrogen content in per 4 hours in the corrosion inhibition test process, 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 150.0g urotropine 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 69.1g 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 the phosphate-free corrosion inhibition antisludging agent for preparing, make urotropine in the water, toxilic acid/Styrene Sulfonic Acid Copolymer, Zn
2+Effective concentration be respectively 150mg/L, 8mg/L, 2.0mg/L, then add Sodium dodecylbenzene sulfonate 35mg/L, regulate with 4% potassium hydroxide at last and the pH of stabilizing solution is 8.7 ± 0.2.Surveyed an ammonia-nitrogen content in per 4 hours in the corrosion inhibition test process, 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 160.0g tetrahydroglyoxaline 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 69.1g 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 the phosphate-free corrosion inhibition antisludging agent for preparing, make tetrahydroglyoxaline in the water, vinylformic acid/Styrene Sulfonic Acid Copolymer, Zn
2+Effective concentration be respectively 160mg/L, 12mg/L, 2.5mg/L, then add 4,8-dibutyl sodium sulfonate 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 content in per 4 hours in the corrosion inhibition test process, 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 150.0g2-Methylimidazole quinoline 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 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 20mg/L ammonia nitrogen when inhibition and antisludging test, then add the phosphate-free corrosion inhibition antisludging agent for preparing, make glyoxal ethyline quinoline, methyl acrylate/Styrene Sulfonic Acid Copolymer, Zn in the water
2+Effective concentration be respectively 150mg/L, 10mg/L, 1.5mg/L, then add tetradecyl benzene sulfonic acid sodium salt 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 content in per 4 hours in the corrosion inhibition test process, 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 140.0g morpholine 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 61.2g 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 the phosphate-free corrosion inhibition antisludging agent for preparing, make morpholine in the water, maleic anhydride/allyl sulphonic acid multipolymer, Zn
2+Effective concentration be respectively 140mg/L, 12mg/L, 2.0mg/L, then add Sodium dodecylbenzene sulfonate 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 content in per 4 hours in the corrosion inhibition test process, 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 150.0g piperazine and 40.0g solid content and be 30% acrylic acid/esters/(mass ratio of vinylformic acid, 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 0.069dl/g), be dissolved in the 51.2g 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 3, add the 20mg/L ammonia nitrogen when inhibition and antisludging test, then add the phosphate-free corrosion inhibition antisludging agent for preparing, make piperazine in the water, acrylic acid/esters/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, Zn
2+Effective concentration be respectively 150mg/L, 12mg/L, 2.0mg/L, then add hexadecyl benzene sulfonic acid sodium salt 40mg/L, regulate with 4% saleratus at last and the pH of stabilizing solution is 7.6 ± 0.2.Surveyed an ammonia-nitrogen content in per 4 hours in the corrosion inhibition test process, 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 the 160.0g2-methylpiperazine, 20.0g solid content 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) and the 26.7g solid content 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 40.1g 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 3, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add the phosphate-free corrosion inhibition antisludging agent for preparing, make 2-methylpiperazine in the water, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, Zn
2+Effective concentration be respectively 160mg/L, 6mg/L, 8mg/L, 1.5mg/L, then add two hexyl sodium naphthalene sulfonate 35mg/L, regulating also with 4% saleratus at last, the pH of stabilizing solution is 7.6 ± 0.2.Surveyed an ammonia-nitrogen content in per 4 hours in the corrosion inhibition test process, 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 110.0g benzotriazole 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 103.5g 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 3, add the 15mg/L ammonia nitrogen when inhibition and antisludging test, then add the phosphate-free corrosion inhibition antisludging agent for preparing, make benzotriazole in the water, acrylic acid/acrylamide/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, Zn
2+Effective concentration be respectively 110mg/L, 10mg/L, 1.5mg/L, then add 4,8-sodium dibutyl naphthalene sulfonate 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 content in per 4 hours in the corrosion inhibition test process, 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 the 50.0g methyl benzotriazazole, 70.0g1,4-lupetazin and 33.3g solid content are vinylformic acid/toxilic acid of 30%/2-methyl-2'-acrylamido propane sulfonic acid multipolymer (vinylformic acid in the multipolymer, the mass ratio of toxilic acid and 2-methyl-2'-acrylamido propane sulfonic acid is 3:1:1, Limiting Viscosity in the time of 30 ℃ is 0.075dl/g), be dissolved in the 87.9g 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 1, add the 10mg/L ammonia nitrogen when inhibition and antisludging test, then add the phosphate-free corrosion inhibition antisludging agent for preparing, make methyl benzotriazazole in the water, Isosorbide-5-Nitrae-lupetazin, vinylformic acid/toxilic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, Zn
2+Effective concentration be respectively 50mg/L, 70mg/L, 10mg/L, 2.0mg/L, then add the two octyl group sodium naphthalene sulfonates of 15mg/L hexadecyl benzene sulfonic acid sodium salt, 15mg/L, regulating also with 4% yellow soda ash sodium at last, the pH of stabilizing solution is 8.7 ± 0.2.Surveyed an ammonia-nitrogen content in per 4 hours in the corrosion inhibition test process, 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 the 90.0g mercaptobenzothiazole, 20.0g solid content is that (mass ratio of vinylformic acid and allyl sulphonic acid is 7:3 to 30% vinylformic acid/allyl sulphonic acid multipolymer in the multipolymer, Limiting Viscosity in the time of 30 ℃ is 0.071dl/g) and the 20.0g solid content be 30% vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer (vinylformic acid in the multipolymer, 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 116.8g 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 the phosphate-free corrosion inhibition antisludging agent for preparing, make mercaptobenzothiazole in the water, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, Zn
2+Effective concentration be respectively 90mg/L, 6mg/L, 6mg/L, 1.5mg/L, then add the 35mg/L Sodium dodecylbenzene sulfonate, regulate with 4% yellow soda ash sodium at last and the pH of stabilizing solution is 8.2 ± 0.2.Surveyed an ammonia-nitrogen content in per 4 hours in the corrosion inhibition test process, and additional ammonia nitrogen is to desired concn, test-results sees Table 2.
Comparative Examples 1
Test is not except adding the Sodium dodecylbenzene sulfonate, 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 tetradecyl benzene sulfonic acid sodium salt, and test conditions and testing sequence are with embodiment 9, and test-results sees Table 2.
Comparative Examples 3
Test is not except adding two hexyl sodium naphthalene sulfonates, and test conditions and testing sequence are with embodiment 12, 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 13, 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 | 97.5 | 0.030 |
| Embodiment 2 | 1 | 98.2 | 0.031 |
| Embodiment 3 | 2 | 97.2 | 0.022 |
| Embodiment 4 | 2 | 97.5 | 0.021 |
| Embodiment 5 | 3 | 96.0 | 0.031 |
| Embodiment 6 | 3 | 96.5 | 0.032 |
| Embodiment 7 | 1 | 98.1 | 0.032 |
| Embodiment 8 | 1 | 98.7 | 0.030 |
| Embodiment 9 | 2 | 97.3 | 0.022 |
| Embodiment 10 | 2 | 97.1 | 0.023 |
| Embodiment 11 | 3 | 95.5 | 0.031 |
| Embodiment 12 | 3 | 96.3 | 0.030 |
| Embodiment 13 | 3 | 96.8 | 0.023 |
| Embodiment 14 | 1 | 98.5 | 0.029 |
| Embodiment 15 | 2 | 97.3 | 0.021 |
| Comparative Examples 1 | 1 | 96.5 | 0.032 |
| Comparative Examples 2 | 2 | 96.0 | 0.024 |
| Comparative Examples 3 | 3 | 94.5 | 0.032 |
| Comparative Examples 4 | 1 | 98.3 | 0.142 |
| Comparative Examples 5 | 2 | 94.9 | 0.117 |
| Comparative Examples 6 | 3 | 91.3 | 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 16
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, add Sodium dodecylbenzene sulfonate 25mg/L, added ammonia nitrogen solution one time in per 4 hours, keeping the ammonia-nitrogen content in the water is 15 mg/L, added each sodium bromate in per three days, adding concentration is 15mg/L.Test-results sees Table 3, table 4.
The B tower: except not adding the Sodium dodecylbenzene sulfonate, 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 17
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 tetradecyl benzene sulfonic acid sodium salt 45mg/L, adds one time ammonia nitrogen solution 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 15, add Sodium dodecylbenzene sulfonate 15mg/L, added ammonia nitrogen solution one time in per 4 hours, keeping the ammonia-nitrogen content in the water is 15 mg/L, added each calcium bromate in per three days, adding concentration is 15mg/L.The 1st day and the 8th day test-results see Table 3, table 4.
Embodiment 18
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 13, add 4,8 sodium dibutyl naphthalene sulfonate 35mg/L, added one time ammonia nitrogen solution 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.
The B tower: phosphate-free corrosion inhibition antisludging agent adopts medicament and the concentration among the embodiment 12, adds two hexyl sodium naphthalene sulfonate 35mg/L, adds ammonia nitrogen solution 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.
Table 3 dynamic analog test test tube is * as a result
Table 4 heterotrophic bacterium monitoring result
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 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, and described non-phosphate inhibitor is for being selected from thiocarbamide and derivative thereof and nitrogen-containing heterocycle compound class absorption membranous type inhibiter; 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 sulfonate type anion surfactant; 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 the derivative of described thiocarbamide is selected from methylthiourea, ethyl thiourea, diphenyl thiourea, thiosinamine, tolylthiourea; Nitrogen-containing heterocycle compound is selected from Five-membered Heterocyclic Compounds, hexa-atomic nitrogen-containing heterocycle compound and nitrogenous fused heterocyclic compound; Five-membered Heterocyclic Compounds is preferably from tetrahydroglyoxaline, glyoxal ethyline quinoline, hexa-atomic nitrogen-containing heterocycle compound is preferably from morpholine, piperazine, 2-methylpiperazine, 1,4 lupetazins, nitrogenous fused heterocyclic compound are preferably from benzotriazole, methyl benzotriazazole, mercaptobenzothiazole and urotropine.
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 brominated sterilant is selected from hypobromous acid and salt, organo bromine microbicide and bromine chloride according to claim 1-5, 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 sulfonate type anion surfactant is selected from chain alkyl arylsulphonate, sulfonated alkyl naphathalene according to claim 1-6; Preferably from C
12～C
18Alkylbenzene sulfonate and carbonatoms are C
4～C
8Double alkyl naphthalene sulfonate; Most preferably from Sodium dodecylbenzene sulfonate, tetradecyl benzene sulfonic acid sodium salt, hexadecyl benzene sulfonic acid sodium salt, 4,8-sodium dibutyl naphthalene sulfonate, two hexyl sodium naphthalene sulfonate, two octyl group sodium naphthalene sulfonate.
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 concentration of component A is 80-200mg/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.
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 described brominated sterilant 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 sulfonate type anion surfactant 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 (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896380A (en) * | 2014-04-01 | 2014-07-02 | 安庆丰源化工有限公司 | Fine chemical waste water treating agent for efficiently removing ammonia nitrogen |
| CN104843880A (en) * | 2015-05-13 | 2015-08-19 | 扬州大学 | Compound corrosion inhibitor and application of compound corrosion inhibitor in carbon steel material circulating cooling water system |
| CN106478875A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of copolymer and preparation method and application |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069081A (en) * | 1991-07-30 | 1993-02-17 | 韩允志 | The compound method of pickling slow-corrosive agent for copper heat exchanger |
| CN1085525A (en) * | 1992-10-15 | 1994-04-20 | 聂新宇 | Automatic scale removing agent for water tank of vehicle |
| US5866032A (en) * | 1995-11-01 | 1999-02-02 | Betzdearborn Inc. | Composition for controlling scale formation in aqueous systems |
| 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 |
| CN1715450A (en) * | 2004-06-29 | 2006-01-04 | 上海万森水处理有限公司 | Acid corrosion inhibitor |
| CN101033551A (en) * | 2007-04-16 | 2007-09-12 | 重庆大学 | Acid pickling inhibitor and preparation method thereof |
| CN101608313A (en) * | 2009-07-14 | 2009-12-23 | 南京科盛环保科技有限公司 | A kind of high-efficiency solid pickling inhibitor for many metals |
-
2011
- 2011-09-29 CN CN201110292756.4A patent/CN103030225B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069081A (en) * | 1991-07-30 | 1993-02-17 | 韩允志 | The compound method of pickling slow-corrosive agent for copper heat exchanger |
| CN1085525A (en) * | 1992-10-15 | 1994-04-20 | 聂新宇 | Automatic scale removing agent for water tank of vehicle |
| US5866032A (en) * | 1995-11-01 | 1999-02-02 | Betzdearborn Inc. | Composition for controlling scale formation in aqueous systems |
| 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 |
| CN1715450A (en) * | 2004-06-29 | 2006-01-04 | 上海万森水处理有限公司 | Acid corrosion inhibitor |
| CN101033551A (en) * | 2007-04-16 | 2007-09-12 | 重庆大学 | Acid pickling inhibitor and preparation method thereof |
| CN101608313A (en) * | 2009-07-14 | 2009-12-23 | 南京科盛环保科技有限公司 | A kind of high-efficiency solid pickling inhibitor for many metals |
Non-Patent Citations (1)
| Title |
|---|
| 姜琳，郦和生等: "含氨氮污水回用于循环冷却水的技术", 《工业水处理》 * |
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|---|---|---|---|---|
| CN103896380A (en) * | 2014-04-01 | 2014-07-02 | 安庆丰源化工有限公司 | Fine chemical waste water treating agent for efficiently removing ammonia nitrogen |
| CN103896380B (en) * | 2014-04-01 | 2015-09-16 | 安庆丰源化工有限公司 | A kind of Fine Chemistry Wastewater treatment agent of efficient removal ammonia nitrogen |
| CN104843880A (en) * | 2015-05-13 | 2015-08-19 | 扬州大学 | Compound corrosion inhibitor and application of compound corrosion inhibitor in carbon steel material circulating cooling water system |
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| CN109422353A (en) * | 2017-08-29 | 2019-03-05 | 中国石油化工股份有限公司 | The composition of circulating water cooling treatment containing ammonia nitrogen and its application |
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| CN107381840B (en) * | 2017-09-06 | 2020-10-16 | 钟司雨 | Environment-friendly scale and corrosion inhibitor and preparation method thereof |
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