CN101928075A - Closed-type circulating cooling water system inhibiter and preparation method thereof - Google Patents
Closed-type circulating cooling water system inhibiter and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a closed-type circulating cooling water system inhibiter and a preparation method thereof. The inhibiter comprises the following components in percentage by weight: 1-5% of molybdate, 5-20% of alkyl alkanol amine, 1-3% of deoxidant, 0.5-1.5% of copper protective agent and the balance of water. The preparation method comprises the following steps: (1) adding the deoxidant into a proper quantity of water at normal temperature, stirring until the deoxidant is completely dissolved; (2) adding the molybdate, the copper protective agent and the alkyl alkanol amine into the completely-dissolved solution, and stirring until solution is even and transparent. The inhibiter of the invention dose not contain phosphorus, silicon or zinc, is suitable for various water qualities and has strong high temperature resistant capability; and at the temperature of 70 DEG C, carbon steel, red copper and brass test specimens still shine within 72 hours.
Description
Technical field
The present invention relates to a kind of recirculating cooling water system inhibiter, particularly a kind of closed-type circulating cooling water system inhibiter.
Background technology
In human water, water coolant accounts for about 70% of industrial water consumption, and recirculating cooling water system has worked to save a large amount of process waters.Closed-type circulating cooling water system is a kind of of recirculating cooling water system.The characteristics of this system are: what cause less than evaporation is concentrated, and amount of makeup water is few, generally all uses de-mineralized water or softening water water as a supplement; Working condition is relatively harsher, than higher, can reach 60～70 ℃ such as operating temperature; Whole cooling water system material is formed complicated, comprise cast iron, cast aluminium, carbon steel, copper alloy etc., and the overwhelming majority is a connection state.The main generation produces the oxygen uptake corrosion with dissolved oxygen in the closed-type circulating cooling water system in the cathodic depolarization effect.There is uniform corrosion in the material relatively poor relatively to solidity to corrosions such as cast iron, carbon steels.
At the corrosion present situation of cooling water system, directly anti-corrosion measure is exactly to add the inhibiter that can significantly suppress multiple metallic corrosion in the water coolant.Cooling water system inhibiter from initial chromic salt, poly-phosphate to organic phosphonate; From high phosphorus, metallic low-phosphorous, the all-organic formula of filling a prescription, demonstrate water treatment corrosion inhibitors and just develop towards directions such as many kinds, high-level efficiency, hypotoxicities.In recent years, along with the raising of global environment consciousness, the body eutrophication that the introducing of elements such as the toxic action of inhibiter, corrosion mitigating effect, phosphorus, nitrogen is caused and the aspects such as incompatibility of oxidisability biocide have been proposed new requirement.According to the strategy of sustainable development, advance Green Chemistry, research and develop functional, cheap, nontoxic, harmless, free of contamination Chrome-free, no zinc, low-phosphorous and even non-phosphate inhibitor is the developing direction of water treatment corrosion inhibitors.Tang Jun etc. have summarized the present situation and the greenization progress of recirculating cooling water system inhibiter in 2004 the 6th phases " Treatment of Industrial Water ".At present, during the without phosphorus prescription of domestic environment-friendly type is used or be that comprehensive rust inhibition is bad, or be that the high-temperature corrosion resistance performance is bad, therefore almost there is not the precedent of successful Application.
Summary of the invention
In view of this, in order to overcome the deficiencies in the prior art, the invention provides a kind of not phosphorous, not siliceous, not zinciferous closed-type circulating cooling water system inhibiter, this closed-type circulating cooling water system inhibiter is efficient, nontoxic, stable, applied widely.
A kind of closed-type circulating cooling water system inhibiter provided by the invention, by weight percentage, it contains following component:
Molybdate 1%～5%, alkyl alcoholamine 5%～20%,
Oxygen scavenger 1%～3%, copper protective agent 0.5%～1.5%, surplus is a water.
Further, described molybdate be Sodium orthomolybdate, ammonium molybdate, potassium molybdate wherein any one, two or three.
Further, described alkyl alcoholamine is trolamine, Yi Bingchunan wherein any one or two kinds.
Further, described oxygen scavenger is the oximes material.
Further, described oximes material be DMKO, ethylidenehydroxylamine, methyl ethyl ketoxime wherein any one, two or three.
Further, described copper protective agent is benzotriazole, mercaptobenzothiazole wherein any one or two kinds.
Further, the mass ratio of described molybdate and alkyl alcoholamine is 1: 5～1: 10.
The present invention also provides the preparation method of described closed-type circulating cooling water system inhibiter; its step comprises: (1) down adds in the water of described amount in normal temperature described oxygen scavenger; be stirred to dissolving fully; (2) described molybdate, copper protective agent and alkyl alcoholamine are added in the described consoluet solution again; be stirred to the solution transparent and homogeneous, promptly.
Molybdenum corrosion inhibitor such as molybdate etc. have good corrosion mitigating effect, with the compound use suppressible point erosion of other medicament, thermostability height, do not generate advantage such as calcium molybdate precipitation with calcium ion.The inhibition process of molybdate is MoO
4 2-With Fe
2+At first form the non-protective title complex, then Fe
2+Be oxidized to Fe by the dissolved oxygen in the water again
3+, Fe at this moment
2+Molybdate complexes changes into the molybdic acid high ferro and covers the metallic surface, forms protective membrane, produces certain corrosion inhibition.
The alkyl alcoholamine inhibiter is the adsorptive type organic inhibitor, it is adsorbed on the gap location of passive film, make film become fine and close and complete, improved corrosion inhibition rate, but after the content of alkyl alcoholamine is increased to certain value, the effect of its absorption and repair membrane integrity promptly reaches a definite value, increases concentration again, and corrosion inhibition rate changes not remarkable.Therefore, its maximum consumption is 20% in the present invention, and better with the mass ratio of molybdate effect in 1: 5～1: 10 scope.
The existence of oxygen in water; it is a big factor that causes equipment corrosion; prove through lot of experiments and industrial application; oxime compounds not only has good deoxygenation processing performance as oxygen scavenger; and the material surface of heat power equipment had the effect of passivation corrosionproof protection, also have the harmless characteristics of low toxicity.
Part copper and copper alloy material are arranged in the recirculated water equipment; copper protective agent benzotriazole among the present invention, mercaptobenzothiazole mainly rely on and copper surface on active copper atom or cupric ion produce a kind of chemisorption; thereby or and then the sequestering action that takes place form one deck densification and firm protective, make copper material equipment obtain excellent protection.
Several compositions have good synergy among the present invention, and this invention inhibiter heat-resisting ability is strengthened, and under 70 ℃, carbon steel, red copper, brass test piece 72h internal surface keep light.Inhibiter provided by the invention is compared with currently available products, has the following advantages:
1. not phosphorous, not siliceous, do not contain zinc or other poisonous and harmful heavy metallics.
2. heat-resisting ability is strong, and is under 70 ℃ temperature, still bright in carbon steel, red copper, the brass test piece 72h.
3. be suitable for multiple water quality.Not only be adapted at using in deionized water, the softening water, and, in multiple water quality, carbon steel, copper alloy, stainless corrosion rate all are lower than the GB50050-2007 specified standards to being that the circulating cooling system equipment of heat-eliminating medium has long-acting rust inhibition equally with the tap water.
Embodiment
Further illustrate the present invention in the following embodiments, this does not limit the scope of the invention.
Embodiment 1
A kind of closed-type circulating cooling water system inhibiter, composed of the following components, Sodium orthomolybdate 1%, ammonium molybdate 2%, trolamine 15%, DMKO 2%, benzotriazole 1.2%, surplus is a water.
The preparation method of above-mentioned inhibiter is: (1) down adds in the water of described amount in normal temperature described DMKO, be stirred to dissolving fully, (2) more described Sodium orthomolybdate and ammonium molybdate, benzotriazole and trolamine are added in the described consoluet solution, be stirred to the solution transparent and homogeneous, promptly.
Embodiment 2
A kind of closed-type circulating cooling water system inhibiter, composed of the following components, Sodium orthomolybdate 1.5%, potassium molybdate 0.5%, trolamine 10%, Yi Bingchunan 2%, ethylidenehydroxylamine 3%, mercaptobenzothiazole 1.0%, surplus is a water.
The preparation method of above-mentioned inhibiter is: (1) down adds in the water of described amount in normal temperature described ethylidenehydroxylamine, be stirred to dissolving fully, (2) more described Sodium orthomolybdate and potassium molybdate, mercaptobenzothiazole, Yi Bingchunan and trolamine are added in the described consoluet solution, be stirred to the solution transparent and homogeneous, promptly.
Embodiment 3
A kind of closed-type circulating cooling water system inhibiter, composed of the following components, potassium molybdate 1%, ammonium molybdate 1%, trolamine 12%, DMKO 1.5%, ethylidenehydroxylamine 0.5%, methyl ethyl ketoxime 0.5%, benzotriazole 1.5%, surplus is a water.
The preparation method of above-mentioned inhibiter is: (1) down adds in the water of described amount in normal temperature described DMKO, ethylidenehydroxylamine and methyl ethyl ketoxime, be stirred to dissolving fully, (2) more described potassium molybdate and ammonium molybdate, benzotriazole and trolamine are added in the described consoluet solution, be stirred to the solution transparent and homogeneous, promptly.
Embodiment 4
A kind of closed-type circulating cooling water system inhibiter, composed of the following components, Sodium orthomolybdate 2.5%, trolamine 13%, DMKO 2%, benzotriazole 0.6%, mercaptobenzothiazole 0.4%, surplus is a water.
The preparation method of above-mentioned inhibiter is: (1) down adds in the water of described amount in normal temperature described DMKO, be stirred to dissolving fully, (2) described Sodium orthomolybdate, benzotriazole, mercaptobenzothiazole and trolamine are added in the described consoluet solution again, be stirred to the solution transparent and homogeneous, promptly.
Embodiment 5
A kind of closed-type circulating cooling water system inhibiter, composed of the following components, Sodium orthomolybdate 2%, ammonium molybdate 0.5%, Yi Bingchunan 14%, DMKO 2.5%, ethylidenehydroxylamine 0.5%, benzotriazole 1.0%, surplus is a water.
The preparation method of above-mentioned inhibiter is: (1) down adds in the water of described amount in normal temperature described DMKO and ethylidenehydroxylamine, be stirred to dissolving fully, (2) more described Sodium orthomolybdate and ammonium molybdate, benzotriazole and Yi Bingchunan are added in the described consoluet solution, be stirred to the solution transparent and homogeneous, promptly.
Embodiment 6
A kind of closed-type circulating cooling water system inhibiter, composed of the following components, Sodium orthomolybdate 3.5%, trolamine 10%, Yi Bingchunan 5%, DMKO 3%, methyl ethyl ketoxime 0.5%, benzotriazole 0.4%, mercaptobenzothiazole 0.6%, surplus is a water.
The preparation method of above-mentioned inhibiter is: (1) down adds in the water of described amount in normal temperature described DMKO and methyl ethyl ketoxime, be stirred to dissolving fully, (2) described Sodium orthomolybdate, benzotriazole, mercaptobenzothiazole, Yi Bingchunan and trolamine are added in the described consoluet solution again, be stirred to the solution transparent and homogeneous, promptly.
Embodiment 7
A kind of closed-type circulating cooling water system inhibiter, composed of the following components, Sodium orthomolybdate 2%, potassium molybdate 2%, trolamine 20%, DMKO 3%, benzotriazole 0.7%, mercaptobenzothiazole 0.7%, surplus is a water.
The preparation method of above-mentioned inhibiter is: (1) down adds in the water of described amount in normal temperature described DMKO, be stirred to dissolving fully, (2) more described Sodium orthomolybdate and potassium molybdate, benzotriazole and trolamine are added in the described consoluet solution, be stirred to the solution transparent and homogeneous, promptly.
The test example:
Its performance is tested by following way in product of making by above-mentioned 7 embodiment and commercially available prod (general Bei Di company, TW-1802 refrigerated water inhibiter), and test result sees Table 1,
1. test condition:
Instrument and equipment: RCC-I I spin etching tester, analytical balance (0.1mg)
Probe temperature: 70 ± 1 ℃
Test duration: hanging into temperature from sample is that 70 ± 1 ℃ test solution is counted, and soaks through 72 hours and finishes.
Test water: deionized water, softening water, tap water
2. use test piece:
Recirculated cooling water handle standard test piece 1. cast iron, 2. the 20# carbon steel, 3. red copper, 4. brass with filter paper antirust grease to be wiped examination clean, in acetone and dehydrated alcohol, wash respectively then with absorbent cotton, place on the clean filter paper, blot with filter paper, place more than the moisture eliminator 4h, weigh (being accurate to 0.1mg), it is standby to put into moisture eliminator.
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 dries up, and weighs (being accurate to 0.1mg) after 24 hours in the anticorrosion moisture eliminator, calculates erosion rate.
Medicament total concentration: 500mg/L
Table 1 test result
From last table, find out, the 0.075mm/a of regulation during inhibiter of the present invention requires well below the GB50050-2007 Code for design of industrial recirculating cooling water treatment the corrosion of Carbon Steel rate, the 0.005mm/a of regulation during the corrosion rate of copper alloy required well below the GB50050-2007 Code for design of industrial recirculating cooling water treatment, and compare with commercially available inhibiter, effect is more obvious.And this test carries out under 70 ± 1 ℃ condition, and product performance are stable, illustrate that heat-resisting ability is better than general product suitable under 40 ℃ of conditions.
Claims (8)
1. a closed-type circulating cooling water system inhibiter is characterized in that, by weight percentage, it contains following component:
Molybdate 1%～5%, alkyl alcoholamine 5%～20%,
Oxygen scavenger 1%～3%, copper protective agent 0.5%～1.5%, surplus is a water.
2. according to the described closed-type circulating cooling water system inhibiter of claim 1, it is characterized in that, described molybdate be Sodium orthomolybdate, ammonium molybdate, potassium molybdate wherein any one, two or three.
3. according to the described closed-type circulating cooling water system inhibiter of claim 1, it is characterized in that described alkyl alcoholamine is trolamine, Yi Bingchunan wherein any one or two kinds.
4. according to the described closed-type circulating cooling water system inhibiter of claim 1, it is characterized in that described oxygen scavenger is the oximes material.
5. according to the described closed-type circulating cooling water system inhibiter of claim 4, it is characterized in that, described oximes material be DMKO, ethylidenehydroxylamine, methyl ethyl ketoxime wherein any one, two or three.
6. according to the described closed-type circulating cooling water system inhibiter of claim 1, it is characterized in that described copper protective agent is benzotriazole, mercaptobenzothiazole wherein any one or two kinds.
7. according to the described closed-type circulating cooling water system inhibiter of claim 1, it is characterized in that the mass ratio of described molybdate and alkyl alcoholamine is 1: 5～1: 10.
8. according to the preparation method of the described closed-type circulating cooling water system inhibiter of claim 1; it is characterized in that; its step comprises: (1) down adds in the water of described amount in normal temperature described oxygen scavenger; be stirred to dissolving fully; (2) described molybdate, copper protective agent and alkyl alcoholamine are added in the described consoluet solution again; be stirred to the solution transparent and homogeneous, promptly get described closed-type circulating cooling water system inhibiter.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508570A (en) * | 2012-06-25 | 2014-01-15 | 上海思曼泰化工科技有限公司 | Environmental protection and high efficiency corrosion inhibitor for inhibiting salt water corrosion on carbon steel, preparation method and use method thereof |
| CN104773845A (en) * | 2014-01-15 | 2015-07-15 | 东莞新科技术研究开发有限公司 | Corrosion inhibitor for recirculated cooling water |
| CN105417737A (en) * | 2015-12-29 | 2016-03-23 | 山东英联化学科技有限公司 | Composite corrosion inhibitor used for soft water closed circulating water |
| CN106167305A (en) * | 2015-11-25 | 2016-11-30 | 天津市奔晟新材料科技开发有限公司 | The neutralizing amine protective agent of boiler and condensate system |
| CN106676509A (en) * | 2017-02-23 | 2017-05-17 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | Corrosion inhibition pretreatment filming agent and preparing method and application |
| CN107605436A (en) * | 2017-10-18 | 2018-01-19 | 武汉三江航天远方科技有限公司 | It is applicable the suppression oxygen corrosion devices and methods therefor of oxygen-enriched combustion-supporting heavy oil wells injection thermal recovery technology |
| CN108425118A (en) * | 2018-03-21 | 2018-08-21 | 西安理工大学 | A kind of quaternary built vapour phase inhibitor and preparation method thereof for carbon steel and brass |
| CN109019884A (en) * | 2018-09-29 | 2018-12-18 | 河北卓能电力科技有限公司 | A kind of compound slow corrosion dirt dispersion agent and its application |
| CN109652809A (en) * | 2019-01-15 | 2019-04-19 | 北京化工大学 | A kind of hybrid corrosion inhibitor in the water base coolant liquid of ethylene glycol |
| CN110819992A (en) * | 2019-11-27 | 2020-02-21 | 济南鼎隆化工科技有限公司 | Environment-friendly organic metal corrosion inhibitor and preparation method and application thereof |
| CN113061894A (en) * | 2021-03-02 | 2021-07-02 | 福建宁德核电有限公司 | Corrosion inhibitor and preparation method thereof, and corrosion inhibition method of closed cooling water system |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508570A (en) * | 2012-06-25 | 2014-01-15 | 上海思曼泰化工科技有限公司 | Environmental protection and high efficiency corrosion inhibitor for inhibiting salt water corrosion on carbon steel, preparation method and use method thereof |
| CN104773845A (en) * | 2014-01-15 | 2015-07-15 | 东莞新科技术研究开发有限公司 | Corrosion inhibitor for recirculated cooling water |
| CN106167305A (en) * | 2015-11-25 | 2016-11-30 | 天津市奔晟新材料科技开发有限公司 | The neutralizing amine protective agent of boiler and condensate system |
| CN105417737A (en) * | 2015-12-29 | 2016-03-23 | 山东英联化学科技有限公司 | Composite corrosion inhibitor used for soft water closed circulating water |
| CN106676509A (en) * | 2017-02-23 | 2017-05-17 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | Corrosion inhibition pretreatment filming agent and preparing method and application |
| CN107605436A (en) * | 2017-10-18 | 2018-01-19 | 武汉三江航天远方科技有限公司 | It is applicable the suppression oxygen corrosion devices and methods therefor of oxygen-enriched combustion-supporting heavy oil wells injection thermal recovery technology |
| CN108425118A (en) * | 2018-03-21 | 2018-08-21 | 西安理工大学 | A kind of quaternary built vapour phase inhibitor and preparation method thereof for carbon steel and brass |
| CN108425118B (en) * | 2018-03-21 | 2019-12-24 | 西安理工大学 | Quaternary compound vapor phase corrosion inhibitor for carbon steel and brass and preparation method thereof |
| CN109019884A (en) * | 2018-09-29 | 2018-12-18 | 河北卓能电力科技有限公司 | A kind of compound slow corrosion dirt dispersion agent and its application |
| CN109652809A (en) * | 2019-01-15 | 2019-04-19 | 北京化工大学 | A kind of hybrid corrosion inhibitor in the water base coolant liquid of ethylene glycol |
| CN110819992A (en) * | 2019-11-27 | 2020-02-21 | 济南鼎隆化工科技有限公司 | Environment-friendly organic metal corrosion inhibitor and preparation method and application thereof |
| CN113061894A (en) * | 2021-03-02 | 2021-07-02 | 福建宁德核电有限公司 | Corrosion inhibitor and preparation method thereof, and corrosion inhibition method of closed cooling water system |
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