CN102153212A - Composite corrosion and scale inhibitor containing benzotriazole - Google Patents
Composite corrosion and scale inhibitor containing benzotriazole Download PDFInfo
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- CN102153212A CN102153212A CN 201110087619 CN201110087619A CN102153212A CN 102153212 A CN102153212 A CN 102153212A CN 201110087619 CN201110087619 CN 201110087619 CN 201110087619 A CN201110087619 A CN 201110087619A CN 102153212 A CN102153212 A CN 102153212A
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- benzotriazole
- corrosion
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- scale resistor
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Abstract
The invention discloses a composite corrosion and scale inhibitor containing benzotriazole. The corrosion and scale inhibitor is compounded by a maleic acid compound, an acrylic acid terpolymer, a zinc salt, gluconate, a sulfamate compound and benzotriazole; and the composite corrosion and scale inhibitor containing benzotriazole, which is disclosed by the invention, is widely applied and can be used for corrosion and scale inhibitions of devices made of carbon steel, copper and copper alloys. The composite corrosion and scale inhibitor containing benzotriazole has a full phosphate-free formula so that the treated exterior drainage causes no eutrophication pollution to a water body due to phosphorus, and belongs to an environment friendly product; moreover, the composite corrosion and scale inhibitor has the advantages of no need of prefilming equipment before used, operation availability at a normal temperature, stable treatment effect, annual corrosion rate of lower than 0.0240 mm.a-1 to the carbon steel, calcium carbonate resistance rate of more than 98.2%, and very good corrosion and scale inhibiting effect and economic and environmental benefits.
Description
Technical field
The present invention relates to a kind of without phosphorus, biodegradable efficient and environment-friendly type corrosion inhibiting and descaling agent that is used for the industrial circulating cooling water treatment system, be specially and contain the benzotriazole composite slow-corrosion scale resistor.
Background technology
Because the financial loss that metallic corrosion brings to development and national economy accounts for 1.5～4.2% of national economy total output value, the metallic corrosion problem spreads all over the every field of national economy, from the daily life to the industrial and agricultural production, from the hard-core technology to national defense industry, the place of every use metallic substance, all in various degree have an etching problem.It has brought enormous economic loss to people, has caused catastrophic accident, has expended the valuable energy and resource.For the loss that corrosion is caused drops to bottom line, corrosion research person develops and has developed a lot of anticorrosive measures, and it then is wherein more extensive using the organic inhibition dirty-proof agent, the significant means of effect.
The organic inhibition dirty-proof agent molecule is that the polar group at center and nonpolar group that C, H atom are formed constitute by atoms such as the bigger O of electronegativity, N, S, P usually.Polar group is adsorbed in the metallic surface and changes double electrical layers, has improved the activation energy of metal ionization; And non-polar group forms hydrophobic protective membrane away from the metallic surface, and the two acting in conjunction is suppressed the corrosion of metal effect.Along with the reinforcement of environment and awareness of safety, in the Research on Corrosion Inhibitor exploitation, must consider carrying capacity of environment, this just requires us to design the new and effective corrosion inhibiting and descaling agent that conforms and require, the Synergistic technique of development corrosion inhibiting and descaling agent.In the last few years, triazole class compounds caused people's attention owing to have the specific molecule structure day by day with excellent corrosion and scale inhibition performance.Quraishi and Bentiss carry out systematic research to the multiple-unit triazole compounds and find that triazole class compounds has use temperature wide ranges and eco-friendly characteristics.Therefore, the composite high-efficiency corrosion-mitigation scale-inhibition agent of development 3-triazole compounds has approach very much.
Summary of the invention
The object of the present invention is to provide a kind of benzotriazole composite slow-corrosion scale resistor that contains, be used for industrial circulating cooling water system, improve the process water water-saving rate, reduce blowdown flow rate, overcome the secondary pollution that phosphorous corrosion inhibiting and descaling agent brings environment.
The benzotriazole composite slow-corrosion scale resistor that contains provided by the invention comprises maleinization compound, acrylic terpolymer, zinc salt, gluconate, sulfamic acid compound, benzotriazole and distilled water; This composite slow-corrosion scale resistor is formed mass percent: polymaleic acid salt 20%～25%, acrylic terpolymer 12%～18%, zinc salt 10%～15%, gluconate 15%～20%, sulfamic acid compound 1%～2%, benzotriazole 0.5%～1%, all the other are distilled water.
Wherein, described maleinization compound is selected from a kind of or two above mixtures in styrene maleic acid, dimethyl maleic anhydride, hydrolyzed polymaleic anhydride, the maleic anhydride grafted polyethylene.
Described acrylic terpolymer is selected from vinylformic acid-2-acrylamide-2 methyl propane sulfonic acid, vinylformic acid-CALCIUM ACRYLATE-sulfonate terpolymer, phenylethylene-maleic anhydride-dodecyl acrylate terpolymer, the vinylformic acid-AMPS-Propylene glycol monoacrylate terpolymer mixture of one or two or more kinds.
Described zinc salt is selected from zinc nitrate, zinc sulfate, zinc molybdate, zinc borate, the zinc chloride mixture of one or two or more kinds.
Described gluconate is selected from that Potassium Gluconate, gluconic acid are received, one or two or more kinds mixture in the maltonic acid sodium, maltonic acid potassium, Zinc Gluconate, manganese gluconate.
Described sulfamic acid compound is selected from Ammonium sulfamate, Sodium sulfanilate, the thionamic acid mixture of one or two or more kinds.
The preparation method who contains the benzotriazole composite slow-corrosion scale resistor of the present invention: get each material by described composition mass percent, then with distilled water, maleinization compound, acrylic terpolymer, zinc salt, gluconate, sulfamic acid compound and benzotriazole, add in the container successively by said sequence, stir 1h at normal temperatures, promptly get product.
Optimal technical scheme of the present invention is: a kind of benzotriazole composite slow-corrosion scale resistor that contains, be used for industrial cooling circulating water system, it is characterized in that, this composite slow-corrosion scale resistor is formed mass percent: maleinization compound 20%～25%, vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 12%～18%, zinc nitrate or zinc sulfate 10%～15%, gluconate 15%～20%, thionamic acid 1%～2%, benzotriazole 0.5%～1%, all the other are distilled water, and wherein said maleinization compound is selected from hydrolyzed polymaleic anhydride or styrene maleic acid, and described gluconate is maltonic acid sodium or Potassium Gluconate.
According to above-mentioned optimal technical scheme: described containing in the benzotriazole composite slow-corrosion scale resistor, described polymaleic acid compound is a hydrolyzed polymaleic anhydride, and its mass percent concentration is 21%～23%.
According to above-mentioned optimal technical scheme, described containing in the benzotriazole composite slow-corrosion scale resistor, the mass percent concentration of described vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid is 13%～16%.
According to above-mentioned optimal technical scheme: described containing in the benzotriazole composite slow-corrosion scale resistor, the mass percent concentration of described zinc nitrate or zinc sulfate is 12%～15%.
According to above-mentioned optimal technical scheme: described containing in the benzotriazole composite slow-corrosion scale resistor, the mass percent concentration of described gluconate is 16%～19%.
According to above-mentioned optimal technical scheme: described containing in the benzotriazole composite slow-corrosion scale resistor, the mass percent concentration of described thionamic acid is 1.2～1.8%.
According to above-mentioned optimal technical scheme: the described preparation method who contains the benzotriazole composite slow-corrosion scale resistor, it is characterized in that: get each material by described composition mass percent, then with distilled water, maleinization compound, vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid, zinc nitrate or zinc sulfate, gluconate, thionamic acid and benzotriazole, add in the container successively by said sequence, stir 1h at normal temperatures, promptly get product.
The application that contains the benzotriazole composite slow-corrosion scale resistor of the present invention is applicable to the industrial colling recycle system of carbon steel, copper and copper alloy equipment basicity to be lower than 7.0mmol.L
-1, hardness is lower than 8.0mmol.L
-1, C (Ca
2+) be lower than 400mg.L
-1, C (Cl
-) be lower than 800mg.L
-1, electricity is led at 2400us.cm
-1Following industrial cooling circulating water is directly handled, and adds the benzotriazole composite slow-corrosion scale resistor, and its dosage is 20mg.L
-1～50mg.L
-1
The present invention has following characteristics:
1. the benzotriazole composite slow-corrosion scale resistor that contains of the present invention, it is not phosphorous fully to fill a prescription, and has avoided producing the possibility of calcium phosphate scale, so need not to consider to hinder the performance of calcium phosphate, the body eutrophication that is difficult for causing the discharging because of phosphorus to cause simultaneously belongs to environmentally friendly product.
2. originally contain the benzotriazole composite slow-corrosion scale resistor, benzotriazole is because of containing a delocalized electronics π key in the prescription, strengthened absorption with plane absorption configuration, helped increasing the coverage of corrosion inhibiting and descaling agent, and form multilayer absorption on its surface in the metallic surface to metal.
3. the bulk drug wide material sources that originally contain the benzotriazole composite slow-corrosion scale resistor, and corrosion inhibiting and descaling agent preparation technology is simple, and lower to the equipment input, medicament does not need equipment is carried out pre-film before using.
4. originally contain in the benzotriazole composite slow-corrosion scale resistor, the maltonic acid sodium of selecting for use is polyhydroxy carboxylic acids type inhibiter, to Fe
2+On metal good complexing action is arranged, contain in this composite slow-corrosion scale resistor simultaneously-CONH
2With group such as sulfonic group, under the collaborative and dissemination of these groups, reduced the corrosion current in the system, blocked the galvanic cell effect of metallic surface, reduced the speed that is corroded, played provide protection to the metallic surface.
5. it is applied widely originally to contain the benzotriazole composite slow-corrosion scale resistor, and the inhibition and the scale inhibition that can be used for carbon steel, copper and copper alloy equipment are handled.
Specific embodiments:
Below in conjunction with specific embodiment composition and the effect that contains the benzotriazole composite slow-corrosion scale resistor of the present invention is described further, but the scope that the present invention protected is not limited to the scope of embodiment.
Employed medicine is the conventional medicine in commercially available prod or laboratory among the following embodiment.
Embodiment 1
Preparation contains the benzotriazole composite slow-corrosion scale resistor, get each material by following composition mass percent: hydrolyzed polymaleic anhydride or styrene maleic acid 20%～25%, vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 12%～18%, zinc nitrate or zinc sulfate 10%～15%, maltonic acid sodium or Potassium Gluconate 15%～20%, thionamic acid 1%～2%, benzotriazole 0.5%～1%, all the other are distilled water; Then with distilled water, hydrolyzed polymaleic anhydride or styrene maleic acid, vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid, zinc nitrate or zinc sulfate, maltonic acid sodium or Potassium Gluconate, thionamic acid and benzotriazole, add in the container successively by said sequence, stir 1h at normal temperatures, promptly get product.
Embodiment 2
Preparation 100g contains benzotriazole composite slow-corrosion scale resistor, preparation process: get 50% hydrolyzed polymaleic anhydride 21g, 30% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 16g, Zn (NO
3)
2.6H
2O 14g, maltonic acid sodium 16, thionamic acid 1.8g, benzotriazole 0.5g, all the other are distilled water, join successively in the beaker of clean dried, stir, and promptly get product.
Embodiment 3
Preparation 100g contains benzotriazole composite slow-corrosion scale resistor, preparation process: get 50% hydrolyzed polymaleic anhydride 22g, 30% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 15g, Zn (NO
3)
2.6H
2O 13g, maltonic acid sodium 17g, thionamic acid 1.7g, benzotriazole 0.6g, all the other are distilled water, join successively in the beaker of clean dried, stir, and promptly get product.
Embodiment 4
Preparation 100g contains benzotriazole composite slow-corrosion scale resistor, preparation process: get 50% hydrolyzed polymaleic anhydride 23g, 30% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 14g, Zn (NO
3)
2.6H
2O 12g, maltonic acid sodium 18g, thionamic acid 1.6g, benzotriazole 0.7g, all the other are distilled water, join successively in the beaker of clean dried, stir, and promptly get product.
Embodiment 5
Preparation 100g contains benzotriazole composite slow-corrosion scale resistor, preparation process: get 50% hydrolyzed polymaleic anhydride 21g, 30% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 16g, ZnSO
4.7H
2O 14g, maltonic acid sodium 19g, thionamic acid 1.2g, benzotriazole 0.5g, all the other are distilled water, join successively in the beaker of clean dried, stir, and promptly get product.
Embodiment 6
Preparation 100g contains benzotriazole composite slow-corrosion scale resistor, preparation process: get 50% hydrolyzed polymaleic anhydride 22g, 30% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 13g, ZnSO
4.7H
2O 13g, maltonic acid sodium 16g, thionamic acid 1.5g, benzotriazole 0.6g, all the other are distilled water, join successively in the beaker of clean dried, stir, and promptly get product.
Embodiment 7
Preparation 100g contains benzotriazole composite slow-corrosion scale resistor, preparation process: get 50% hydrolyzed polymaleic anhydride 23g, 30% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 14g, ZnSO
4.7H
2O 12g, maltonic acid sodium 17g, thionamic acid 1.4g, benzotriazole 0.7g, all the other are distilled water, join successively in the beaker of clean dried, stir, and promptly get product.
Embodiment 8
Preparation 100g contains benzotriazole composite slow-corrosion scale resistor, preparation process: get 50% hydrolyzed polymaleic anhydride 21g, 30% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 15g, Zn (NO
3)
2.6H
2O 14g, maltonic acid sodium 18g, thionamic acid 1.3g, benzotriazole 0.5g, all the other are distilled water, join successively in the beaker of clean dried, stir, and promptly get product.
Embodiment 9
Preparation 100g contains benzotriazole composite slow-corrosion scale resistor, preparation process: get 50% hydrolyzed polymaleic anhydride 22g, 30% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 16g, ZnSO
4.7H
2O 13g, maltonic acid sodium 19g, thionamic acid 1.2g, benzotriazole 0.6g, all the other are distilled water, join successively in the beaker of clean dried, stir, and promptly get product.
Embodiment 10
Preparation 100g contains benzotriazole composite slow-corrosion scale resistor, preparation process: get 50% hydrolyzed polymaleic anhydride 23g, 30% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 15g, Zn (NO
3)
2.6H
2O 12g, maltonic acid sodium 18g, thionamic acid 1.3g, benzotriazole 0.7g, all the other are distilled water, join successively in the beaker of clean dried, stir, and promptly get product.
Embodiment 11
The benzotriazole composite slow-corrosion scale resistor effect that contains of embodiment 2-10 preparation is tested
This experimental water is enterprise's recirculated cooling water, adopt the rotary hanging plate weight-loss method to measure the corrosion rate of A3 carbon steel in cooling circulating water, the static-state scale inhibition experiment test is measured its scale inhibition lime carbonate rate, and it adds embodiment 2-10 preparation and contains the benzotriazole composite slow-corrosion scale resistor in water.
The experiment water-quality guideline:
The static-state scale inhibition experiment: experimental temperature is 45 ℃, feeds 0.5Lmin to container bottom simultaneously
-1Nitrogen, cycles of concentration stop when being 6 times the experiment.Resistance lime carbonate rate η
kCalculating formula:
η
k＝(C
2-C
1)/(K×C
0-C
1)×100％
In the formula: C
2Be the Ca that surveys behind the adding medicine
2+Mass concentration, mg.L
-1C
1Ca for the actual measurement of adding medicine not
2+Mass concentration, mg.L
-1C
0Be the initial Ca of adding medicine not
2+Mass concentration, mg.L
-1K is C
2, C
1Cycles of concentration under the condition determination.
The rotary hanging plate corrosion experiment: laboratory apparatus is assembled according to the HG/T2159-91 standard.Experiment condition: 1. constant temperature is 45 ± 1 ℃; 2. rotating speed 75r.min
-13. experimental period 72h.The experiment lacing film adopts HG/T 3523-2008 " water coolant chemical treatment standard corrosion coupon technical qualification " I type test piece, and material is the A3 carbon steel coupon, size 50mm * 25mm * 2mm, test piece area 28cm
2Annual corrosion rate (mma
-1) calculation formula as follows:
K
a＝87600(m
0-m)/sρt
In the formula: K
aBe annual corrosion rate, mm.a
-1m
0Be the quality of test piece before testing, g; M is the quality of experiment back test piece, g; S is the test piece surface-area, cm
2ρ is a test piece density, g.cm
-3T is a test period, h.
Test data of experiment is as shown in the table:
| Embodiment | Added amount of chemical mg.L -1 | Annual corrosion rate mm.a -1 | Resistance lime carbonate rate % |
| Embodiment 2 | 30 | 0.0227 | 98.8％ |
| Embodiment 3 | 30 | 0.0199 | 98.5％ |
| Embodiment 4 | 30 | 0.0213 | 98.3％ |
| Embodiment 5 | 30 | 0.0234 | 99.2％ |
| Embodiment 6 | 30 | 0.0212 | 98.7％ |
| Embodiment 7 | 30 | 00214 | 98.2％ |
| Embodiment 8 | 30 | 0.0224 | 99.3％ |
| Embodiment 9 | 30 | 0.0226 | 98.8％ |
| Embodiment 10 | 30 | 0.0205 | 98.2％ |
| Blank | 0 | 0.5621 | --- |
The result shows, adopt of the present invention contain the benzotriazole composite slow-corrosion scale resistor after annual corrosion rate be lower than 0.0240mm.a
-1, resistance lime carbonate rate reaches more than 98.2%.
Claims (8)
1. one kind contains the benzotriazole composite slow-corrosion scale resistor, be used for industrial cooling circulating water system, it is characterized in that, this composite slow-corrosion scale resistor is formed mass percent: maleinization compound 20%～25%, vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid 12%～18%, zinc nitrate or zinc sulfate 10%～15%, gluconate 15%～20%, thionamic acid 1%～2%, benzotriazole 0.5%～1%, all the other are distilled water, and wherein said maleinization compound is selected from hydrolyzed polymaleic anhydride or styrene maleic acid, and described gluconate is maltonic acid sodium or maltonic acid potassium.
2. the benzotriazole composite slow-corrosion scale resistor that contains according to claim 1 is characterized in that described polymaleic acid compound is a hydrolyzed polymaleic anhydride, and its mass percent concentration is 21%～23%.
3. the benzotriazole composite slow-corrosion scale resistor that contains according to claim 1 is characterized in that, the mass percent concentration of described vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid is 13%～16%.
4. the benzotriazole composite slow-corrosion scale resistor that contains according to claim 1 is characterized in that the mass percent concentration of described zinc nitrate or zinc sulfate is 12%～15%.
5. the benzotriazole composite slow-corrosion scale resistor that contains according to claim 1 is characterized in that the mass percent concentration of described gluconate is 16%～19%.
6. the benzotriazole composite slow-corrosion scale resistor that contains according to claim 1 is characterized in that the mass percent concentration of described thionamic acid is 1.2～1.8%.
7. the described preparation method who contains the benzotriazole composite slow-corrosion scale resistor of claim 1, it is characterized in that: get each material by described composition mass percent, then with distilled water, maleinization compound, vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid, zinc nitrate or zinc sulfate, gluconate, thionamic acid and benzotriazole, add in the container successively by said sequence, stir 1h at normal temperatures, promptly get product.
8. the described application that contains the benzotriazole composite slow-corrosion scale resistor of claim 1 is characterized in that, is applicable to the industrial colling recycle system of carbon steel, copper and copper alloy equipment, and basicity is lower than 7.0mmol.L
-1, hardness is lower than 8.0mmol.L
-1, C (Ca
2+) be lower than 400mg.L
-1, pH=7.5～9.2, C (Cl
-) be lower than 800mg.L
-1, electricity is led at 2400 μ s.cm
-1Following industrial cooling circulating water is directly handled, and benzotriazole composite slow-corrosion scale resistor, dosage are 20mg.L
-1～50mg.L
-1
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104884395A (en) * | 2012-12-28 | 2015-09-02 | 埃科莱布美国股份有限公司 | Corrosion and fouling mitigation using non-phosphorus based additives |
| CN104725563B (en) * | 2013-12-19 | 2017-04-12 | 中国科学院金属研究所 | Corrosion inhibitor gel microsphere with intelligent pH value controlled release function and its preparation method and use |
| CN108251847A (en) * | 2018-01-02 | 2018-07-06 | 佛山科学技术学院 | A kind of compound preservative containing benzotriazole and preparation method thereof |
| US10858585B2 (en) | 2018-01-03 | 2020-12-08 | Ecolab Usa Inc. | Benzotriazole derivatives as corrosion inhibitors |
| CN112794507A (en) * | 2021-01-04 | 2021-05-14 | 苏州清扬水处理工程有限公司 | Circulating water treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108251847A (en) * | 2018-01-02 | 2018-07-06 | 佛山科学技术学院 | A kind of compound preservative containing benzotriazole and preparation method thereof |
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| CN112794507A (en) * | 2021-01-04 | 2021-05-14 | 苏州清扬水处理工程有限公司 | Circulating water treatment method |
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| CN102153212B (en) | 2012-07-04 |
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