CN101066811A - No-phosphate corrosion and scale inhibitor and its application - Google Patents
No-phosphate corrosion and scale inhibitor and its application Download PDFInfo
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- CN101066811A CN101066811A CN 200710052475 CN200710052475A CN101066811A CN 101066811 A CN101066811 A CN 101066811A CN 200710052475 CN200710052475 CN 200710052475 CN 200710052475 A CN200710052475 A CN 200710052475A CN 101066811 A CN101066811 A CN 101066811A
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- phosphate
- corrosion inhibition
- molybdate
- antisludging agent
- free corrosion
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Abstract
The present invention relates to no-phosphate corrosion and scale inhibitor and its application. The no-phosphate corrosion and scale inhibitor consists of polyaspartic acid and/or polyepoxy succinic acid 10-20 wt%, polymaleic anhydride 20-30 wt%, copolymer of acrylic acid and 2-acrylamido-2-methyl propenyl sulfonic acid 15-20 wt%, zinc salt 3-5 wt%, natural organic high molecular compound 5-12 wt%, molybdate 5-8 wt%, and other components 5-20 wt%. It has excellent corrosion retarding performance, high scale inhibiting performance and environment friendship.
Description
Technical field
The present invention relates to the application in a kind of phosphate-free corrosion inhibition antisludging agent and the recirculated cooling water thereof.
Background technology
China's gross amount of water resources occupies the 6th in the world, but the occupancy volume per person only be the world per capita 1/4th, the 88th in the world of row belongs to lack of water country.And limited water resource distributes also very inhomogeneous, and 81% is distributed in the Yangtze valley and areas to the south, and many cities are in the serious water shortage state, in 467 cities, the whole nation, the lack of water city just has 300, serious water shortage have 50, the annual financial loss that causes because of lack of water reaches 2,000 hundred million yuan.China is the water resources anxiety on the one hand, but on the other hand in a large amount of waste precious water resource, China's urban industry on average has only 30%, per ten thousand yuan of industrial production value water withdrawals on average up to 500m with ratio of water recycle
3Water, there is a big difference compared with developed countries.Along with the water resources imbalance between supply and demand is becoming increasingly acute, each enterprise will face high water rate and effluent charge, how to improve the water technology level, water saving, the behave that improve recycling rate of water used by the industries, the minimizing blowdown is not only " merit is in eternal lasting; sharp in the present age " also is the major issue that is related to enterprise's its own existence and development.
The development of organic inhibitor in recent years is very rapid, and comparatively speaking, but their lower concentrations use but thermostability is poor slightly.Classes maximum in the organic inhibitor are organic amines, comprise aliphatic amide and aromatic amine, monoamine, diamine or polyamine and salt thereof.From green concept, should replace or reduce the application of aromatic amine with more aliphatic amide; The phosphorus that the organic amine inhibiter also can replace many inorganic heavy metal inhibiter such as China such as strontium yellow, zinc phosphate, barium borate and silicophosphate to widely apply at present is water conditioner, owing to easily making discharging waters bacterium algae propagation, its eutrophication causes " red tide " public hazards, at present therefore polymkeric substance such as a large amount of polyacrylic acid that use and multipolymer readily biodegradable does not then belong to environmentally friendly water conditioner.
Since the nineties in 20th century, all developed phosphorus-free green anti-incrustation corrosion inhibitor poly aspartic acid (PASP) and poly-epoxy succinic acid (PESA) both at home and abroad with biodegradability, though they possess certain corrosion inhibition, be not good inhibiter, mainly be used as Scale inhibitors.Without phosphorus water treatment corrosion inhibitors of less types, because the defective of various water treatment corrosion inhibitorses self, their application is restricted, except that minority kinds such as molybdate, zinc salt, Sunmorl N 60S at present also with the composite use of phosphorus family corrosion inhibitor, being eliminated basically of other, the example of successful Application seldom.
Without phosphorus organic inhibitor is that everybody relatively pays close attention to and rising and research field competitive power at present, and people try hard to develop out functional, cheap, nontoxic, free of contamination inhibiter new variety.From the data of being grasped, following inhibiter component should be nontoxic, free of contamination sulfur-bearing, nitrogenous, the organic compound and the high molecular polymer that contain complex construction such as oxygen.Oxygen-containing organic compound (derivatives of carboxylic acid, ether, ester, aldehyde, phenol, alcohol etc.) with contain N, the S compound is compared, tempo is faster.
Along with the proposition and the enforcement of the strategy of sustainable development, the notion of Green Chemistry impels people to develop some eco-friendly water conditioners.Phosphate-free corrosion inhibition antisludging agent more and more is subjected to the attention of water treatment field with its excellent inhibition, scale inhibition performance and favorable environment protection, become the research field that has development prospect and competitive power both at home and abroad and 21 century water conditioner developing direction.
Summary of the invention
The object of the present invention is to provide a kind of phosphate-free corrosion inhibition antisludging agent and application thereof, this phosphate-free corrosion inhibition antisludging agent has excellent inhibition, scale inhibition performance and favorable environment protection.
To achieve these goals, technical scheme of the present invention is: a kind of phosphate-free corrosion inhibition antisludging agent, it is characterized in that it is mixed by following raw material: 1) poly aspartic acid is or/and poly-epoxy succinic acid, 2) polymaleic anhydride, 3) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3) zinc salt, 4) natural organic high-molecular, 5) molybdate, 6) other compositions, the shared mass percent of each raw material is:
Poly aspartic acid is or/and poly-epoxy succinic acid 10-20%,
Polymaleic anhydride 20-30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 15-20%,
Zinc salt 3-5%,
Natural organic high-molecular 5-12%,
Molybdate 5-8%,
Other compositions 5-20%;
Wherein, when poly aspartic acid and poly-epoxy succinic acid, be any proportioning between poly aspartic acid and the poly-epoxy succinic acid raw material;
Described other compositions are any one or any one the above mixing in sodium polyacrylate, vinylformic acid-Propylene glycol monoacrylate multipolymer, borate, azole, the organic amine, are any proportioning between the raw material during any one above mixing.
Described zinc salt is zinc chloride or zinc sulfate.
Described natural organic high-molecular is Sunmorl N 60S or lignin derivative.
Described molybdate is potassium molybdate or Sodium orthomolybdate.
Described borate is Sodium Tetraborate or sodium tetraborate.
Described azole is benzotriazole or dredges basic benzene a pair of horses going side by side azoles.
Described organic amine is hexamethylenetetramine, thiocarbamide and carboxylic acid amide.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, it is characterized in that adding in every liter of recirculated cooling water 30-50 milligram phosphate-free corrosion inhibition antisludging agent.
The salient features of no phosphine corrosion inhibiting and descaling agent has following characteristics: 1, the feature of environmental protection.Because of without phosphorus in the medicament and heavy metal ion exist, and LD50＞10.0g/kg, for the nontoxic level of reality, there is not the restriction of any blowdown.2, corrosion inhibition is good.To use inorganic inhibitor Sodium orthomolybdate, zinc salt etc. all be the inhibition component of corrosion inhibition excellence, and the organic inhibitor Sunmorl N 60S, mercaptobenzothiazole, the organic amine molecule that use have N structure R
1,-R
2,-R
3,-CH
2COO
-Deng substituting group the strong electronic action that pushes away is arranged, the lone-pair electron cloud density on the N atom is increased, polarity strengthens, and can enter the empty d track of Fe easilier, thereby makes the molecular chain inhibiter produce good chemisorption on the Fe surface, suppresses the anodic corrosion of Fe.In addition, with Fe or Fe
N+Coordination forms stable five yuan or six-ring chelating membrane, and this film is insoluble in water, and its long-chain Fe metal dorsad, has covered the metallic surface effectively, has hindered entering of corrosive medium, and the metal current potential is shuffled, and has stoped corrosion of metal.Inhibition synergism between each component makes under 30mg/L concentration, to 20
#Carbon steel corrosion inhibition rate＞96%.3, scale-inhibiting properties is good.Owing to there is not Ca
3(PO
4)
2The problem of dirt, the scale inhibition component in the prescription mainly is to the CaCO in the water
3Play effects such as solubilising or lattice distortion, and reach CaCO
3Disperse purpose.
The composite polybasic phosphate-free corrosion inhibition antisludging agent that forms has following beneficial effect or/and poly-epoxy succinic acid is a host with poly aspartic acid in the present invention:
1) avoid because the eutrophication problem of the water quality that the discharging of phosphorus causes alleviates environmental pollution, the present invention has favorable environment protection;
2) can effectively alleviate the bacterial corrosion and the tongue algae growth question of circulating water system, thereby reduce the consumption of circulating water sterilizing algicide, alleviate the secondary pollution that brings behind the disinfection by chlorine; The present invention has excellent inhibition, scale inhibition performance and favorable environment protection;
3) avoid causing circulating water system Ca owing to the degraded of phosphorus
3(PO
4)
2The deposition of dirt, the heat transfer coefficient of raising cold exchange device reduces energy expenditure;
4) to calcium and alkali tolerance height, the Cl of resisting high-concentration
-And SO
4 2-Corrosion, the pH scope of adaptation is wide, provides technical qualification for recirculated water moves, reduces sewage discharge under the high concentration multiple condition;
5) but the high-efficient corrosion inhibitor and the prescription that are back to circulating water system for the exploitation sewage effluent provide new technological approaches.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly aspartic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer (for existing raw material), 3)))), and the shared mass percent of each raw material is:
Poly aspartic acid 10%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 15%,
Zinc salt 5%,
Natural organic high-molecular 12%,
Molybdate 8%,
Other compositions 20%;
Described other compositions are sodium polyacrylate; Described zinc salt is a zinc chloride; Described natural organic high-molecular is a Sunmorl N 60S; Described molybdate is a potassium molybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 30 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 2:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly aspartic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly aspartic acid 20%,
Polymaleic anhydride 20%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 20%,
Zinc salt 5%,
Natural organic high-molecular 10%,
Molybdate 5%,
Other compositions 20%;
Described other compositions are vinylformic acid-Propylene glycol monoacrylate multipolymer; Described zinc salt is a zinc chloride; Described natural organic high-molecular is a Sunmorl N 60S; Described molybdate is a potassium molybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 35 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 3:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly aspartic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly aspartic acid 20%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 20%,
Zinc salt 4%,
Natural organic high-molecular 7%,
Molybdate 6%,
Other compositions 13%;
Described other compositions are borate, and described borate is a potassium borate; Described zinc salt is a zinc sulfate; Described natural organic high-molecular is a lignin derivative; Described molybdate is a Sodium orthomolybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 40 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 4:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly aspartic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly aspartic acid 15%,
Polymaleic anhydride 25%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 17%,
Zinc salt 5%,
Natural organic high-molecular 10%,
Molybdate 8%,
Other compositions 20%;
Described other compositions are azole, and described azole is a benzotriazole; Described zinc salt is a zinc sulfate; Described natural organic high-molecular is a lignin derivative; Described molybdate is a Sodium orthomolybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 45 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 5:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly aspartic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly aspartic acid 20%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 20%,
Zinc salt 4%,
Natural organic high-molecular 6%,
Molybdate 6%,
Other compositions 14%;
Described other compositions are organic amine, and described organic amine is a hexamethylenetetramine; Described zinc salt is a zinc sulfate; Described natural organic high-molecular is a lignin derivative; Described molybdate is a Sodium orthomolybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 50 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 6:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly aspartic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly aspartic acid 20%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 20%,
Zinc salt 3%,
Natural organic high-molecular 5%,
Molybdate 5%,
Other compositions 17%;
Described other compositions are sodium polyacrylate and vinylformic acid-Propylene glycol monoacrylate multipolymer, and the mass percent of sodium polyacrylate, vinylformic acid-Propylene glycol monoacrylate multipolymer respectively accounts for 1/2; Described zinc salt is a zinc chloride; Described natural organic high-molecular is a Sunmorl N 60S; Described molybdate is a Sodium orthomolybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 38 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 7:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly aspartic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly aspartic acid 20%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 20%,
Zinc salt 5%,
Natural organic high-molecular 12%,
Molybdate 8%,
Other compositions 5%;
Described other compositions are borate, azole, organic amine, and the shared mass percent of borate is 1%, the shared mass percent of azole is 2%, the shared mass percent of organic amine is 2%; Described borate is a Sodium Tetraborate, and described azole is for dredging basic benzene a pair of horses going side by side azoles (or claiming to dredge basic benzothiazole), and described organic amine is a thiocarbamide;
Described zinc salt is a zinc chloride; Described natural organic high-molecular is a lignin derivative; Described molybdate is a Sodium orthomolybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 47 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 8:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly-epoxy succinic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly-epoxy succinic acid 10%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 15%,
Zinc salt 5%,
Natural organic high-molecular 12%,
Molybdate 8%,
Other compositions 20%
Described other compositions are sodium polyacrylate; Described zinc salt is a zinc chloride; Described natural organic high-molecular is a Sunmorl N 60S; Described molybdate is a potassium molybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 30 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 9:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly-epoxy succinic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly-epoxy succinic acid 20%,
Polymaleic anhydride 20%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 20%,
Zinc salt 5%,
Natural organic high-molecular 10%,
Molybdate 5%,
Other compositions 20%;
Described other compositions are vinylformic acid-Propylene glycol monoacrylate multipolymer; Described zinc salt is a zinc chloride; Described natural organic high-molecular is a Sunmorl N 60S; Described molybdate is a potassium molybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 35 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 10:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly-epoxy succinic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly-epoxy succinic acid 20%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 20%,
Zinc salt 4%,
Natural organic high-molecular 7%,
Molybdate 6%,
Other compositions 13%;
Described other compositions are borate, and described borate is a potassium borate; Described zinc salt is a zinc sulfate; Described natural organic high-molecular is a lignin derivative; Described molybdate is a Sodium orthomolybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 40 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 11:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly-epoxy succinic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly-epoxy succinic acid 15%,
Polymaleic anhydride 25%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 17%,
Zinc salt 5%,
Natural organic high-molecular 10%,
Molybdate 8%,
Other compositions 20%
Described other compositions are azole, and described azole is a benzotriazole; Described zinc salt is a zinc sulfate; Described natural organic high-molecular is a lignin derivative; Described molybdate is a Sodium orthomolybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 45 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 12:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly-epoxy succinic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly-epoxy succinic acid 15%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 20%,
Zinc salt 4%,
Natural organic high-molecular 6%,
Molybdate 6%,
Other compositions 14%;
Described other compositions are organic amine, and described organic amine is a hexamethylenetetramine; Described zinc salt is a zinc sulfate; Described natural organic high-molecular is a lignin derivative; Described molybdate is a Sodium orthomolybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 50 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 13:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly-epoxy succinic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly-epoxy succinic acid 20%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 20%,
Zinc salt 3%,
Natural organic high-molecular 5%,
Molybdate 5%,
Other compositions 17%;
Described other compositions are sodium polyacrylate and vinylformic acid-Propylene glycol monoacrylate multipolymer, and the mass percent of sodium polyacrylate, vinylformic acid-Propylene glycol monoacrylate multipolymer respectively accounts for 1/2; Described zinc salt is a zinc chloride; Described natural organic high-molecular is a Sunmorl N 60S; Described molybdate is a Sodium orthomolybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 38 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 14:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: other compositions molybdate, 6 natural organic high-molecular, 5 zinc salt, 4 polymaleic anhydride, 3 1) poly-epoxy succinic acid, 2)) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3)))), and the shared mass percent of each raw material is:
Poly-epoxy succinic acid 20%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 15%,
Zinc salt 5%,
Natural organic high-molecular 8%,
Molybdate 8%,
Other compositions 14%;
Described other compositions are borate, azole, organic amine, and the shared mass percent of borate is 3%, the shared mass percent of azole is 2%, the shared mass percent of organic amine is 6%; Described borate is a sodium tetraborate, and described azole is a benzotriazole, and described organic amine is a thiocarbamide;
Described zinc salt is a zinc chloride; Described natural organic high-molecular is a Sunmorl N 60S; Described molybdate is a Sodium orthomolybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 40 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 15:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: 1) poly aspartic acid and poly-epoxy succinic acid, 2) polymaleic anhydride, 3) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3) zinc salt, 4) natural organic high-molecular, 5) molybdate, 6) other compositions, the shared mass percent of each raw material is:
Poly aspartic acid and poly-epoxy succinic acid 10%,
Polymaleic anhydride 30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 15%,
Zinc salt 5%,
Natural organic high-molecular 12%,
Molybdate 8%,
Other compositions 20%
Wherein poly aspartic acid, the shared mass percent of poly-epoxy succinic acid respectively are 5%;
Described other compositions are sodium polyacrylate; Described zinc salt is a zinc chloride; Described natural organic high-molecular is a Sunmorl N 60S; Described molybdate is a potassium molybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 30 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
Embodiment 16:
A kind of phosphate-free corrosion inhibition antisludging agent, it is mixed by following raw material: 1) poly aspartic acid and poly-epoxy succinic acid, 2) polymaleic anhydride, 3) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3) zinc salt, 4) natural organic high-molecular, 5) molybdate, 6) other compositions, the shared mass percent of each raw material is:
Poly aspartic acid and poly-epoxy succinic acid 20%,
Polymaleic anhydride 20%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 20%,
Zinc salt 5%,
Natural organic high-molecular 10%,
Molybdate 5%,
Other compositions 20%;
Wherein poly aspartic acid, the shared mass percent of poly-epoxy succinic acid respectively are 10%;
Described other compositions are vinylformic acid-Propylene glycol monoacrylate multipolymer; Described zinc salt is a zinc chloride; Described natural organic high-molecular is a Sunmorl N 60S; Described molybdate is a potassium molybdate.
Above-mentioned a kind of phosphate-free corrosion inhibition antisludging agent is applied in the recirculated cooling water, adds 35 milligrams of phosphate-free corrosion inhibition antisludging agents in every liter of recirculated cooling water.
1. test portion
1.1 test water quality: the moisturizing of Guizhou Chemical-Ferdtilizer Factory's recirculating cooling water system, water quality analysis sees Table 1.
Table 1 moisturizing data of water quality table
| Project | PH | Specific conductivity | Total hardness (CaCO 3Meter) | Total alkalinity (CaCO 3Meter) | Ca 2+ CCaCO 3Meter) | Mg 2+(CaCO meter) | Cl - |
| Unit | / | μS/cm | mg/l | mg/l | mg/l | mg/l | mg/l |
| Mean value | 7.8 | 230 | 116 | 105 | 94 | 22 | 8.51 |
1.2 static test result
According to the water quality characteristics of Guizhou Chemical-Ferdtilizer Factory, select embodiment 14 (being phosphate-free corrosion inhibition antisludging agent JP-307) for use.In order to verify the feasibility of prescription, further done a series of proof test.
1.2.1 scale-inhibiting properties test-tosca method (GB/T16632-1996)
Test-results such as table 2:
Table 2 static sedimentation method test-results
| The medicament title | Add dose (mg/L) | Scale inhibition performance % |
| JP-307 | 30 | 76.99 |
| 40 | 93.61 | |
| 50 | 99.47 |
1.2.2 corrosion inhibition test-rotary hanging plate method (GB/T18175-2000)
Test-results such as table 3:
Table 3 rotary hanging plate method test-results
| The medicament title | Add dose (mg/L) | Corrosion rate (m/a) | Corrosion inhibition rate % |
| JP-307 | 0 | 1.1043 | - |
| 30 | 0.1630 | 85.24 | |
| 40 | 0.0579 | 94.76 | |
| 50 | 0.0186 | 98.32 |
1.2.3 test data analyzer
From above testing data as can be known, non-phosphorus scale and corrosion inhibitor JP-307 has good scale inhibition and corrosion inhibition.Performance index all can reach the content of relevant regulations among the GB/50050-95, and pharmaceutical quantities tentatively is decided to be 50mg/L.
1.3 dynamic property simplation verification test
For whether further proof test medicament meets on-the-spot operating requirement, make situations such as the more approaching on-the-spot aeration of test effect, heat exchange, the performance verification test below having designed, the i.e. small-sized dynamic testing of simulated field condition.Under the specified criteria of laboratory, with saturated vapor under the normal pressure or hot water heating heat exchanger, significant parameters such as the flow velocity of simulated field, fluidised form, water quality, metal material, heat transfer intensity and cooling water intakeoutfall, after the long run test 10 to 15 days, the recirculated water concentration rate is maintained between 2.5～3.0, check corrosion and fouling situation.
This test adopts the intelligent water conditioning dynamic analog of WT-A type like tester, this machine is by computer system management, by requirement of experiment design data input computer auto-control, automatically print instantaneous fouling resistance and average year fouling resistance value by print system, operator chemically examine water quality on request and regulate and control drug concentration.
1.3.1 testing data
Table 4 dynamic testing data
1.3.2 test-results discussion
By the dynamic analog test result as can be known the JP-307 non-phosphorus scale and corrosion inhibitor have excellent inhibition and scale-inhibiting properties when the 50mg/L, its experimental result is better than the standard index requirement of GB/50050-95, can satisfy the operation needs of recirculating cooling water system, and experimental data trend conforms to front static test data also.
1.4 non-phosphorus scale and corrosion inhibitor JP-307 and Biocidal algae-killing agent Synergism Testing
The daily employing of recirculated water be that the Biocidal algae-killing agent kind is more, select several more typical Biocidal algae-killing agents to do simultaneous test here.Quaternary ammonium salt 1227, isothiazolinone, dioxide peroxide etc. are arranged.Process of the test and result are as follows.
1.4.1 Biocidal algae-killing agent is to the influence test (scale inhibition method fast) of medicament scale-inhibiting properties
Biocidal algae-killing agent adopts quick scale inhibition method to the influence test of medicament scale-inhibiting properties.
1.4.1.1 testing data result:
Table 5 is the antisludging test data results fast
| Sequence number | The medicament title | Drug concentration (mg/L) | Calcium ion steady concentration (mmol/L) |
| 1 | JP-307 | 50 | 5.89 |
| Quaternary ammonium salt | 0 | ||
| 2 | JP-307 | 50 | 5.88 |
| Quaternary ammonium salt | 80 | ||
| 3 | JP-307 | 50 | 5.89 |
| Isothiazolinone | 0 | ||
| 4 | JP-307 | 50 | 5.90 |
| Isothiazolinone | 80 | ||
| 5 | JP-307 | 50 | 5.89 |
| Dioxide peroxide | 0 | ||
| 6 | JP-307 | 50 | 5.87 |
| Dioxide peroxide | 40 |
1.4.1.2 test data analyzer:
Data from last table as can be seen, JP-307 and Biocidal algae-killing agent be used the back scale inhibition effect be not subjected to tangible influence, illustrate that the compatibleness of JP-307 and sterilant is better.
1.4.2 Biocidal algae-killing agent is to the influence test (rotary hanging plate method) of medicament corrosion inhibition
Here several more typical Biocidal algae-killing agent of selecting in the top test of still selecting is done simultaneous test.Quaternary ammonium salt 1227, isothiazolinone, dioxide peroxide etc. are arranged.Test conditions: test temperature: 45 ± 1 ℃; Test period: 144 hours; Adding consistency: anti-incrustation corrosion inhibitor 50mg/L, sterilant 80mg/L; Test piece material: carbon steel; Test piece area: 28.0cm
21.4.2.1 Biocidal algae-killing agent influences test-results such as table 6 to the corrosion inhibition of JP-307 non-phosphorus scale and corrosion inhibitor
Table 6 corrosion inhibition testing data
| Medicament title (mg/L) | Initial weight (g) | Test back weight (g) | Weightlessness (removing the pickling blank) (g) | Erosion rate (mm/a) |
| JP-307(50) | 20.0568 | 20.0553 | 0.0015 | 0.0021 |
| 22.5984 | 22.5971 | 0.0013 | 0.0019 | |
| JP-307 (50) quaternary ammonium salt (80) | 21.6532 | 21.6516 | 0.0016 | 0.0022 |
| 22.0312 | 22.0298 | 0.0014 | 0.0023 | |
| JP-307 (50) isothiazolinone (80) | 20.0856 | 20.0839 | 0.0017 | 0.0025 |
| 22.0015 | 22.0003 | 0.0012 | 0.0018 | |
| JP-307 (50) dioxide peroxide (80) | 20.0568 | 20.0553 | 0.0015 | 0.0021 |
| 22.5984 | 22.5971 | 0.0013 | 0.0019 |
1.4.2.2 test data analyzer:
Data results from last table as can be seen, Biocidal algae-killing agent does not produce very big influence to the corrosion inhibition of anti-incrustation corrosion inhibitor, illustrate that the Biocidal algae-killing agent of using always can be used with anti-incrustation corrosion inhibitor.
1.5 on-the-spot industrial test
With your chemical industry water water quality and the static test result of testing laboratory is foundation, closing the on-the-spot dosing test of two-cycle system and ornithine cycle water system in July, 2006, regulate the correlation parameter of circulating water system, investigate the JP-307 non-phosphorus scale and corrosion inhibitor and use scale inhibitor efficient, parameters such as the daily controlling index of corresponding system, adding consistency are provided for later normal operation simultaneously in circulating water system.
1.5.1 the water quality characteristics of circulating water system
1.5.1.1 close the two-cycle system for field because there is certain leakage in system itself and has other industrial sewage to sneak into recirculated water, recirculated water is slant acidity always, pH is in below 6.5 for a long time, is lower than 6.0 especially during to summer, and circulating water system corrosion situation is serious.
1.5.1.2 the ornithine cycle water system is owing to consider water-saving situation, more than the concentration rate to 4.5 of recirculated water times, pH reaches more than 9.0, and fouling is also very serious.
1.5.2 dosing treatment Countermeasures
1.5.2.1 two-cycle systemic circulation water water quality is abominable at closing, the characteristics of seriously corroded in definite JP-307 non-phosphorus scale and corrosion inhibitor prescription, are mainly considered its corrosion mitigating effect.Strengthen inhibition ingredient, and need add the non-phosphate acidic inhibiter simultaneously and be used.
1.5.2.2 at the serious characteristics of ornithine cycle water system fouling tendency, in design non-phosphorus scale and corrosion inhibitor prescription, emphasis is considered its scale-inhibiting properties.
1.5.3 ornithine cycle water system non-phosphorus scale and corrosion inhibitor JP-307 performance test
1.5.3.1 the tracking monitor of this test in place scale inhibition effect and concentration rate
The basis for estimation of scale inhibition and concentration rate is judged with following experimental formula:
Cl
X-be the chloride ion content in the recirculated water;
Cl
B-be the chloride ion content in the make up water;
Ca
X-be the calcium ion concn in the recirculated water;
Ca
B-be the calcium ion concn in the make up water;
When Δ H=0.2, the K value is high concentration ratio;
During Δ H ≈ 0, the K value is for stablizing concentration rate;
Corresponding carbonate hardness is the limit carbonate hardness during high concentration ratio.
1.5.3.1.1 the concentration rate of ornithine cycle water system and fouling situation see Table 7
Table 7 ornithine cycle water fouling situation data
| Date | Cl - (mg/L) | Ca 2+ (mg/L) | The pH value | K Cl- | ΔH |
| July 5 | 41.36 | 440.86 | 9.1 | 4.86 | 0.17 |
| July 6 | 40.76 | 438.98 | 9.0 | 4.79 | 0.12 |
| July 7 | 39.32 | 429.64 | 8.8 | 4.62 | 0.06 |
| July 8 | 40.34 | 438.04 | 8.9 | 4.74 | 0.08 |
| July 9 | 38.47 | 422.06 | 8.8 | 4.52 | 0.03 |
| July 10 | 42.63 | 454.96 | 9.1 | 5.01 | 0.17 |
| July 11 | 38.89 | 424.88 | 8.7 | 4.57 | 0.05 |
| July 12 | 40.68 | 440.86 | 8.7 | 4.78 | 0.09 |
| July 13 | 40.93 | 441.80 | 8.8 | 4.81 | 0.11 |
| July 14 | 40.85 | 443.68 | 8.6 | 4.80 | 0.08 |
| July 15 | 41.61 | 445.56 | 8.9 | 4.89 | 0.15 |
| July 16 | 41.87 | 449.32 | 9.0 | 4.92 | 0.14 |
| July 17 | 42.21 | 450.26 | 9.1 | 4.96 | 0.17 |
| July 18 | 42.12 | 453.08 | 9.0 | 4.95 | 0.13 |
| July 19 | 42.81 | 454.96 | 9.2 | 5.03 | 0.19 |
| July 20 | 37.44 | 410.78 | 8.4 | 4.40 | 0.03 |
| July 21 | 38.38 | 422.06 | 8.6 | 4.51 | 0.02 |
| July 22 | 38.89 | 425.82 | 8.6 | 4.57 | 0.04 |
| July 23 | 39.66 | 435.22 | 8.8 | 4.66 | 0.03 |
| July 24 | 40.25 | 436.16 | 8.7 | 4.73 | 0.09 |
| July 25 | 41.02 | 443.68 | 8.8 | 4.82 | 0.10 |
| July 26 | 42.63 | 453.08 | 9.1 | 5.01 | 0.19 |
| July 27 | 36.76 | 405.14 | 8.5 | 4.32 | 0.01 |
| July 28 | 38.12 | 419.24 | 8.5 | 4.48 | 0.02 |
| July 29 | 39.57 | 430.52 | 8.7 | 4.65 | 0.07 |
| July 30 | 40.51 | 437.10 | 8.9 | 4.76 | 0.11 |
| August 1 | 42.04 | 451.20 | 9.0 | 4.94 | 0.14 |
| August 2 | 42.55 | 453.08 | 9.0 | 5.00 | 0.18 |
| August 3 | 38.98 | 426.76 | 8.6 | 4.58 | 0.04 |
| August 4 | 39.40 | 428.64 | 8.7 | 4.63 | 0.07 |
| August 5 | 40.93 | 444.62 | 8.7 | 4.81 | 0.08 |
Annotate: go up Ca in the table
2+With CaCO
3Meter.The dose that adds of test in place is discussed dosing 80mg/L meter according to reason.
1.5.3.1.2 test data analyzer
Testing data from last table when the adding dose and be 80mg/L of non-phosphorus scale and corrosion inhibitor JP-307, can be controlled the fouling situation of ornithine cycle water system as can be seen,
1.5.3.2 ornithine cycle water system hanging film scene corrosion inhibition monitoring
The test piece of handling well is hung on on-the-spot return water pipe, circulating water pool and continuous dosing etc. locate, observe the situation of test piece every day, during off-test test piece is analyzed.
1.5.3.2.1 the test in ornithine cycle water system non-phosphorus scale and corrosion inhibitor JP-307 corrosion inhibition testing data July 5 to one month on the 5th August, the test site lacing film the results are shown in Table 8
Table 8 urea system hanging film scene monitoring test result
| Medicament | Test piece number | Test piece initial weight (g) | After the test piece heavy (g) | Average weightless (g) | Erosion rate (mm/a) |
| JP-307 80mg/L | 1182 | 22.1722 | 22.1438 | 0.0284 | 0.0157 |
| 1185 | 21.9475 | 21.9171 | 0.0304 | 0.0168 | |
| 1184 | 22.3225 | 22.2952 | 0.0273 | 0.0151 |
1.5.3.2.2 data analysis
Industrial circulating cooling water system through after the water conditioning, should reach every technical indicator of GB/50050-95 " Treatment of Industrial Water design specifications " defined.
That is: corrosion of carbon steel speed＜0.125mm/a
By above result as can be known, the corrosion inhibition of non-phosphorus scale and corrosion inhibitor JP-307 reaches standard-required.
1.5.4 close the non-phosphorus scale and corrosion inhibitor JP-307 of two-cycle system performance test
Close two-cycle system water quality characteristics as can be known by foregoing, recirculated water is slant acidity always, and pH is in below 6.5 for a long time, is lower than 6.0 especially during to summer, and circulating water system corrosion situation is serious.At this corrodibility water quality, emphasis considers to solve the etching problem of recirculated water.Consider pH under the condition about 6.0, common inhibition ingredient can not effectively be controlled corrosion rate below 0.125mm/a, thus in non-phosphorus scale and corrosion inhibitor JP-307, increased non-phosphate acidic inhibiter composition especially, and strengthened dosage.Closing the test of two-cycle system for field on 15th July 15 to August.
1.5.4.1 close the monitoring of two-cycle system for field lacing film corrosion inhibition
The test piece of handling well is hung on return water pipe, circulating water pool etc. locate, observe the situation of test piece every day, during off-test test piece is analyzed.
1.5.4.1.1 close the non-phosphorus scale and corrosion inhibitor JP-307 of two-cycle system corrosion inhibition testing data
Table 9 closes two-cycle system for field hanging test data
| Medicament | Test piece number | Test piece initial weight (g) | After the test piece heavy (g) | Average weightless (g) | Erosion rate (mm/a) |
| JP-307 120mg/L | 1187 | 20.6153 | 20.4280 | 0.1873 | 0.1037 |
| 1189 | 22.2628 | 22.0663 | 0.1965 | 0.1088 | |
| 1190 | 22.4417 | 22.2336 | 0.2081 | 0.1152 |
1.5.4.1.2 data analysis
From the testing data of table 9 as can be seen, the carbon steel material corrosion mitigating effect under the acid condition of water quality of the involutory two-cycle of non-phosphorus scale and corrosion inhibitor JP-307 system is the requirement that can reach GB/50050-95 " Treatment of Industrial Water design specifications " defined.
Claims (8)
1. phosphate-free corrosion inhibition antisludging agent, it is characterized in that it is mixed by following raw material: 1) poly aspartic acid is or/and poly-epoxy succinic acid, 2) polymaleic anhydride, 3) vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 3) zinc salt, 4) natural organic high-molecular, 5) molybdate, 6) other compositions, the shared mass percent of each raw material is:
Poly aspartic acid is or/and poly-epoxy succinic acid 10-20%,
Polymaleic anhydride 20-30%,
Vinylformic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer 15-20%,
Zinc salt 3-5%,
Natural organic high-molecular 5-12%,
Molybdate 5-8%,
Other compositions 5-20%;
Wherein, when poly aspartic acid and poly-epoxy succinic acid, be any proportioning between poly aspartic acid and the poly-epoxy succinic acid raw material;
Described other compositions are any one or any one the above mixing in sodium polyacrylate, vinylformic acid-Propylene glycol monoacrylate multipolymer, borate, azole, the organic amine, are any proportioning between the raw material during any one above mixing.
2. a kind of phosphate-free corrosion inhibition antisludging agent according to claim 1 is characterized in that: described zinc salt is zinc chloride or zinc sulfate.
3. a kind of phosphate-free corrosion inhibition antisludging agent according to claim 1 is characterized in that: described natural organic high-molecular is Sunmorl N 60S or lignin derivative.
4. a kind of phosphate-free corrosion inhibition antisludging agent according to claim 1 is characterized in that: described molybdate is potassium molybdate or Sodium orthomolybdate.
5. a kind of phosphate-free corrosion inhibition antisludging agent according to claim 1 is characterized in that: described borate is Sodium Tetraborate or sodium tetraborate.
6. a kind of phosphate-free corrosion inhibition antisludging agent according to claim 1 is characterized in that: described azole is benzotriazole or dredges basic benzene a pair of horses going side by side azoles.
7. a kind of phosphate-free corrosion inhibition antisludging agent according to claim 1 is characterized in that: described organic amine is hexamethylenetetramine, thiocarbamide or carboxylic acid amide.
8. a kind of phosphate-free corrosion inhibition antisludging agent as claimed in claim 1 is applied in the recirculated cooling water, it is characterized in that adding in every liter of recirculated cooling water 30-50 milligram phosphate-free corrosion inhibition antisludging agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100524755A CN100509652C (en) | 2007-06-15 | 2007-06-15 | No-phosphate corrosion and scale inhibitor and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100524755A CN100509652C (en) | 2007-06-15 | 2007-06-15 | No-phosphate corrosion and scale inhibitor and application thereof |
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| CN100509652C CN100509652C (en) | 2009-07-08 |
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