CN100441526C - Long effective environmental protection type corrosion inhibitor for inclosed recirculated cooling water - Google Patents

Long effective environmental protection type corrosion inhibitor for inclosed recirculated cooling water Download PDF

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Publication number
CN100441526C
CN100441526C CNB2006101244738A CN200610124473A CN100441526C CN 100441526 C CN100441526 C CN 100441526C CN B2006101244738 A CNB2006101244738 A CN B2006101244738A CN 200610124473 A CN200610124473 A CN 200610124473A CN 100441526 C CN100441526 C CN 100441526C
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acid
corrosion inhibitor
cooling water
recirculated cooling
sodium
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CN1915866A (en
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陈勇
刘建容
张万灵
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Wuhan Iron and Steel Group Corp
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Wuhan Iron and Steel Group Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

This invention discloses an environmentally friendly long-effective corrosion inhibitor for sealed circulation cooling water system, which is composed of: molybdate or tungstate 10-20 wt.%, a mixture of C4-12 monocarboxylic acid and polycarboxylic acid 60-70 wt.%, complexing organic carboxylate 0-3 wt.%, polymer 0.05-3 wt.%, benzotriazola 0.005-1 wt.%, Zn salt 0.005-1 wt.%, and NaOH 10-15 wt.%. The corrosion inhibitor does not contain nitrate, nitrite, chromate, inorganic and organic phosphate, borate and silicate, thus is environmentally friendly. Besides, the corrosion inhibitor has such advantages as low dosage, high profit, and long and good effect on heat-conductive metals such as normal carbon steel, red copper and brass.

Description

Corrosion inhibitor for inclosed recirculated cooling water
Technical field
The present invention relates to a kind of long effective environmental protection type corrosion inhibitor for inclosed recirculated cooling water.
Background technology
A large amount of high temperature services that use in the metallurgy industry, as blast furnace, steel melting furnace, crystallizer etc., great majority adopt closed soft water circulation cooling at present, owing under hot conditions, contact for a long time with soft water, the pipeline of cooling system causes leakage because of corrosion, therefore need to add anticorrosion corrosion inhibitor, etch-proof requirement is primary in the soft water cooling system.
At present, the inhibiter kind that the domestic overwhelming majority's enterprise uses remains based on inorganic phosphate, organophosphate, and the borate of use, silicate are also arranged, and What is more is still using nitrate, nitrite and chromic salt.Nitrate, nitrite and chromic salt product have bigger toxicity and very strong system cancer power to human body, and environmental pollution is very big, have forbidden that in the world the material that contains mentioned component uses as inhibiter, and strict regulation is carried out in the discharging of this type of material.Inorganic phosphate and organic phosphonate corrosion inhibition are higher, and price is more cheap, but the discharging of phosphorus can cause the eutrophication in local waters, and environment is had bigger pollution, and the developed countries such as the U.S., European Union, Japan etc. all begin restriction and uses this series products.The current inhibiter of water coolant in the world is to developing the nontoxic environment amenable direction of human body, domesticly also must develop product that therefore must the development compliance with environmental protection requirements towards this direction.
Summary of the invention
Technical problem to be solved by this invention is: the corrosion inhibitor for inclosed recirculated cooling water that a kind of compliance with environmental protection requirements is provided.This inhibiter does not contain the material to environment and human body harmful, belongs to green product; Consumption is few simultaneously, and drug effect is long, meets the economy requirement.
The technical solution adopted for the present invention to solve the technical problems is: by mass percentage, the component of this inhibiter comprises molybdate or tungstate 10～20%, organic carboxyl acid 60～70%, ethylenediamine tetraacetic acid (EDTA) 2.45%, organic polymer 2.45～3%, benzotriazole 0.05～1%, zinc salt 0.05～1%, sodium hydroxide 10～15%; Organic carboxyl acid is one or more organic carboxyl acids that contain 4～12 carbon atoms, and organic polymer is polyacrylic acid and/or polymaleic acid.The preparation method of this inhibiter is: earlier organic carboxyl acid is mixed with tungstate or molybdate, mix with ethylenediamine tetraacetic acid (EDTA) and organic polymer, add benzotriazole, zinc salt and sodium hydroxide then, get final product.
Inhibiter provided by the invention is compared with currently available products, has following major advantage:
Do not comprise the material to environment and human body harmful such as nitrate, nitrite, chromic salt, inorganic phosphate, organic phosphonate, borate, silicate, belong to green product; This product usage quantity is few simultaneously, the drug effect height, and duration of efficacy is long, and economic performance is good.This product has fabulous corrosion-resisting function to thermal conductive metallic material commonly used such as plain carbon stool, red copper, brass.
Embodiment
Long effective environmental protection type blast furnace corrosion inhibitor for inclosed recirculated cooling water provided by the invention, by mass percentage, its component comprises: molybdate or tungstate 10～20%, organic carboxyl acid 60～70%, ethylenediamine tetraacetic acid (EDTA) 2.45%, organic polymer 2.45～3%, benzotriazole 0.05～1%, zinc salt 0.05～1%, sodium hydroxide 10～15%; Organic carboxyl acid is one or more organic carboxyl acids that contain 4～12 carbon atoms, and organic polymer is polyacrylic acid and/or polymaleic acid.
Inhibiter of the present invention is made by following method:
Earlier organic carboxyl acid is mixed with tungstate or molybdate, mix with ethylenediamine tetraacetic acid (EDTA) and organic polymer again, add benzotriazole, zinc salt and sodium hydroxide then, get final product.
Above-mentioned tungstate can be selected a kind of in sodium wolframate, ammonium tungstate, the potassium wolframate for use, or several.
Above-mentioned monobasic that contains 4～12 carbon atoms and polynary organic carboxyl acid mixture, can select a kind of in phenylformic acid, tartrate, citric acid, toxilic acid, gluconic acid, caproic acid, hexanodioic acid, enanthic acid, sad, isocaprylic acid, suberic acid, n-nonanoic acid, nonane diacid, capric acid, sebacic acid, the lauric acid or the composition of multiple carboxylic acid or sodium salt for use.
Above-mentioned zinc salt can be selected a kind of in zinc sulfate, the zinc chloride or two kinds of compositions for use.
Above-mentioned organic polymer can be selected a kind of in polyacrylic acid, the polymaleic acid or two kinds of mixtures for use.
Enumerate several formulation examples below, so that the invention will be further described.
Prescription 1: Sodium orthomolybdate 1.0g, Sodium Benzoate 2.0g, tartrate 2.0g, Sodium octoate 0.5g, trisodium citrate 2.0g, sebacic acid 0.5g, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.245g, polyacrylic acid 0.245g, benzotriazole 0.005g, zinc sulfate 0.005g, sodium hydroxide 1.5g.
Prescription 2: Sodium orthomolybdate 1.5g, Sodium Benzoate 1.0g, tartrate 2.5g, Sodium octoate 0.5g, trisodium citrate 2.0g, sebacic acid 0.5g, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.245g, polyacrylic acid 0.245g, benzotriazole 0.005g, zinc sulfate 0.005g, sodium hydroxide 1.5g.
Prescription 3: Sodium orthomolybdate 2.0g, Sodium Benzoate 1.0g, tartrate 2.0g, Sodium octoate 0.5g, trisodium citrate 2.0g, sebacic acid 0.5g, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.245g, polyacrylic acid 0.245g, benzotriazole 0.005g, zinc sulfate 0.005g, sodium hydroxide 1.5g.
Prescription 4: Sodium orthomolybdate 0.5g, sodium wolframate 0.5g, Sodium Benzoate 2.0g, tartrate, 2.0g, Sodium n-caproate 0.5g, trisodium citrate 2.0g, sebacic acid 0.5g, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.245g, polyacrylic acid 0.245g, zinc sulfate 0.005g, benzotriazole 0.005g, sodium hydroxide 1.5g.
Prescription 5: Sodium orthomolybdate 0.75g, sodium wolframate 0.75g, Sodium Benzoate 1.0g, tartrate, 1.5g, Sodium n-caproate 0.5g, trisodium citrate 2.5g, sebacic acid 1.0g, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.245g, polyacrylic acid 0.245g, zinc sulfate 0.005g, benzotriazole 0.005g, sodium hydroxide 1.5g.
Prescription 6: Sodium orthomolybdate 1.0g, sodium wolframate 1.0g, Sodium Benzoate 1.0g, tartrate, 1.5g, Sodium n-caproate 0.5g, trisodium citrate 2.5g, sebacic acid 0.5g, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.245g, polyacrylic acid 0.245g, zinc sulfate 0.005g, benzotriazole 0.005g, sodium hydroxide 1.5g.
Prescription 7: sodium wolframate 1.0g, Sodium Benzoate 2.0g, tartrate, 1.0g, Sunmorl N 60S 0.5g, trisodium citrate 2.5g, sebacic acid 0.5g, lauric acid 0.5g, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.245g, polymaleic acid 0.245g, zinc sulfate 0.005g, benzotriazole 0.005g, sodium hydroxide 1.5g.
Prescription 8: sodium wolframate 1.5g, Sodium Benzoate 1.5g, tartrate, 1.0g, Sunmorl N 60S 0.5g, trisodium citrate 2.5g, sebacic acid 0.5g, lauric acid 0.5g, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.245g, polymaleic acid 0.245g, zinc sulfate 0.005g, benzotriazole 0.005g, sodium hydroxide 1.5g.
Prescription 9: sodium wolframate 2.0g, Sodium Benzoate 1.0g, tartrate, 1.0g, Sunmorl N 60S 0.5g, trisodium citrate 3.0g, hexanodioic acid 0.5g, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.245g, polymaleic acid 0.245g, zinc sulfate 0.005g, benzotriazole 0.005g, sodium hydroxide 1.5g.
The product that above-mentioned prescription is made is tested by following testing method, and test result sees Table 1.
1. test condition:
Instrument and equipment: RCC-II spin etching tester, analytical balance (0.1mg).
Probe temperature: 50 ± 1 ℃
Test duration: hanging temperature from sample is to count 50 ± 1 ℃ the test solution, soaks through 72 hours and finishes.
Test water: corrosion neutral water (Cl -, SO 4 2-, HCO 3 -Each 100ppm)
2. use test piece: corrosion rotary hanging plate standard test specimen No. 20 carbon steels, brass, (I type 50mm * 25mm * 2mm, surface-area are 28cm to red copper 2), then that surface cleaning is clean, use soaked in absolute ethyl alcohol, cold wind dries up, weigh (being accurate to 0.1mg), it is standby to put into moisture eliminator.
3. aftertreatment: after 72 hours finish, take out test piece, with brush flush away corrosion product, clean with pickle solution in case of necessity, soak with raw spirit then, hair dryer cold wind dries up, and puts into moisture eliminator (being accurate to 0.1mg) calculating erosion rate of weighing after 24 hours.
Above-mentioned 9 assembly sides are dissolved in the 20L corrosion neutral water, and the medicament total concentration is 500mg/L.
Table 1 test result
Figure C20061012447300051

Claims (4)

1. corrosion inhibitor for inclosed recirculated cooling water is characterized in that:
By the quality proportioning, the component of this inhibiter comprises: molybdate or tungstate 10～20%, organic carboxyl acid 60～70%, ethylenediamine tetraacetic acid (EDTA) 2.45%, organic polymer 2.45～3%, benzotriazole 0.05～1%, zinc salt 0.05～1%, sodium hydroxide 10～15%; Organic carboxyl acid is one or more organic carboxyl acids that contain 4～12 carbon atoms, and organic polymer is polyacrylic acid and/or polymaleic acid,
This inhibiter is made by following method: earlier organic carboxyl acid is mixed with tungstate or molybdate, mix with ethylenediamine tetraacetic acid (EDTA) and organic polymer, add benzotriazole, zinc salt and sodium hydroxide then, get final product.
2. corrosion inhibitor for inclosed recirculated cooling water according to claim 1 is characterized in that: tungstate is a kind of in sodium wolframate, ammonium tungstate, the potassium wolframate, or several.
3. corrosion inhibitor for inclosed recirculated cooling water according to claim 1, it is characterized in that: organic carboxyl acid is a kind of in phenylformic acid, tartrate, citric acid, toxilic acid, gluconic acid, caproic acid, hexanodioic acid, enanthic acid, sad, isocaprylic acid, suberic acid, n-nonanoic acid, nonane diacid, capric acid, sebacic acid, the lauric acid, or multiple carboxylic acid or sodium salt.
4. corrosion inhibitor for inclosed recirculated cooling water according to claim 1 is characterized in that: zinc salt is a kind of in zinc sulfate, the zinc chloride, or two kinds.
CNB2006101244738A 2006-09-07 2006-09-07 Long effective environmental protection type corrosion inhibitor for inclosed recirculated cooling water Expired - Fee Related CN100441526C (en)

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CN102408162B (en) * 2010-09-21 2013-06-19 中国石油化工股份有限公司 Phosphorus-free corrosion and scale inhibitor used for industrial circulation cooling water
CN102452724B (en) * 2010-10-20 2014-01-29 中国石油化工股份有限公司 Composite corrosion and scale inhibitor and its application in water treatment
CN102557276A (en) * 2010-12-17 2012-07-11 上海洗霸科技股份有限公司 Composite water treatment agent of closed type circulating water system
CN102730847B (en) * 2011-04-02 2014-11-12 中国石油化工股份有限公司 Non-phosphorus composite anti- incrustation corrosion inhibiter and its application in water treatment
CN103570153B (en) * 2012-07-24 2015-10-07 中国石油化工股份有限公司 A kind of Treated sewage reusing is in the method for recirculating cooling water system
CN103938213B (en) * 2014-04-24 2017-09-05 姬光河 A kind of antirust solution
CN104310607A (en) * 2014-10-22 2015-01-28 山东华亚环保科技有限公司 Compound corrosion inhibitor used for boiler water
CN104773844B (en) * 2015-04-24 2017-01-25 北京京诚科林环保科技有限公司 Corrosion inhibitor for air-tight circulating cooling water system as well as preparation method and application thereof
CN104893838B (en) * 2015-05-26 2017-11-03 广州立白企业集团有限公司 A kind of domestic air conditioning cleaning aerosol combination and preparation method thereof
CN105018940A (en) * 2015-07-06 2015-11-04 安徽省蓝天能源环保科技有限公司 Bactericidal water soluble copper corrosion inhibitor
CN106336022A (en) * 2016-10-09 2017-01-18 广西大学 Corrosion and scale inhibitor for inhibiting deposition of alkaline earth metal undissolved salt in water
CN109837546B (en) * 2017-11-24 2021-06-08 北京蓝星清洗有限公司 Ammonium persulfate corrosion inhibitor used in production oil pipeline of offshore oil field and application thereof
CN110055541A (en) * 2019-05-08 2019-07-26 北京欧源化工环保科技有限公司 A kind of water circulation system protective agent and its preparation process
CN111875071A (en) * 2020-06-22 2020-11-03 北京新叶能源科技有限公司 Boiler water regulating agent and preparation method thereof

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