CN102633372A - Phosphate-free copper alloy composite corrosion inhibitor for seawater circulating cooling water, and preparation and using methods of phosphate-free copper alloy composite corrosion inhibitor - Google Patents
Phosphate-free copper alloy composite corrosion inhibitor for seawater circulating cooling water, and preparation and using methods of phosphate-free copper alloy composite corrosion inhibitor Download PDFInfo
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Abstract
本发明公开了一种海水循环冷却水无磷铜合金复合缓蚀剂及其制备和使用方法，包括预膜剂和正常运行缓蚀剂，所述预膜剂为有机唑类化合物，所述缓蚀剂由有机唑类化合物和无机盐组成。针对海水循环冷却工艺特点和系统经济运行要求，提出先采用高浓度的有机唑类多元预膜剂处理，再转入低浓度复配的正常运行缓蚀剂处理冷却海水的一种工艺，实现缓蚀剂高浓度快速成膜，低浓度维持运行修膜的目的，在浓缩倍数1.8～2.2间，控制铜合金腐蚀速率小于0.003mm/a。本发明的缓蚀剂产品原料来源广泛，溶解性良好，性价比高，低毒，环保型无磷，不污染海洋环境；与海水阻垢分散剂、菌藻抑制剂配伍性好。The invention discloses a phosphorus-free copper alloy composite corrosion inhibitor for seawater circulating cooling water and its preparation and use method, comprising a pre-film agent and a normal operation corrosion inhibitor, the pre-film agent is an organic azole compound, the inhibitor The etching agent is composed of organic azole compounds and inorganic salts. According to the characteristics of the seawater circulation cooling process and the requirements of the economical operation of the system, it is proposed to use a high-concentration organic azole multi-component pre-coating agent to treat the cooling seawater first, and then transfer to a low-concentration compound normal operation corrosion inhibitor to treat the cooling seawater. The high concentration of etchant quickly forms a film, and the purpose of maintaining and repairing the film at a low concentration is to control the corrosion rate of copper alloy to less than 0.003mm/a when the concentration ratio is between 1.8 and 2.2. The corrosion inhibitor product of the invention has a wide range of raw materials, good solubility, high cost performance, low toxicity, environmental protection, phosphorus-free, and does not pollute the marine environment; it has good compatibility with seawater scale inhibitors and dispersants and bacteria and algae inhibitors.
Description
Technical field
The present invention relates to the industrial circulating cooling water processing technology field, more particularly, relating to a kind of circularly-cooling sea water does not have phosphor copper composite corrosion inhibitor and preparation and method of use.
Background technology
Seawater circulation cooling is as an environmental protective, water saving technology; There is huge potential application demand in high water consumption industries such as electric power, chemical industry, petrochemical industry, iron and steel; The development and use seawater replaces fresh water as industrial circulating cooling water, is to alleviate China coastal cities and regional Freshwater resources are in short supply, one of important channel of the protection marine eco-environment.
In Freshwater resources today in short supply day by day, direct seawater utilization has obtained the common concern of various circles of society.Increasing Coastal Power Plant and chemical enterprise adopt the alternative fresh water of seawater to make industrial water coolant and are applied in the production.Copper alloy is widely used in the condenser (or heat exchanger) of cooling system because of its good heat conduction and machinability; Yet because the complicacy of seawater component and the variety of infection factor; More serious corrosion can take place in copper alloy in seawer system, thereby influences its thermal conductivity and work-ing life.About seawer system or the research of seawater circulating cooling system copper alloy inhibiter; Abroad be U.S. Exxon company report the earliest; System's cycles of concentration is controlled at 1.5～2.0; Admiraltymetal corrosion control index reaches 0.03mm/a (An Innovative Approach to Controlling Salt Water Cooling Tower System Problems [J] .Materials performance, 1978,17 (12): 16-22).Domestic in seawater or simulated seawater (salt medium) copper inhibitor research very active.More about simulated seawater copper inhibitor research report in salt solution and synthetic sea water, copper inhibitor research report is less in seawater and circulation refrigerated sea water.For example: " preparation method of composite corrosion inhibitor for copper nickel alloy in the seawater " (Chinese publication CN1880505A; 2005) the phosphorous compound prescription of being made up of benzoglyoxaline 15%～35%, zinc sulfate 1%～2%, Sodium orthomolybdate 35%～60%, water glass 7%～15%, Sunmorl N 60S 7%～14%, Sodium hexametaphosphate 99 2%～4%, Starso 2%～4% is provided; Under the 300mg/L working concentration; Corrosion inhibition rate to B10 surpasses 90%; The corrosion inhibition rate of B30 is surpassed 85%, but its test conditions leaves standstill in the seawater at normal temperature, be applicable to airtight or leave standstill the anticorrosion of system's copper alloy; Incompatible at open type seawater circulating cooling system, beyond affordability especially economically." seawater is as the treatment process of recirculated cooling water " (Chinese granted patent CN11275878C; 2006) the seawater water treatment method of being made up of inhibiter, Scale inhibitors, biocide is provided; Wherein the inhibiter dosage is 40mg/L～50mg/L; Form phosphorous compound prescription by Sodium orthomolybdate 10%～20%, Sunmorl N 60S 12%～20%, Sodium Benzoate 5%～10%, zinc sulfate 10%～20%, zinc chloride 5%～10%, trisodium citrate 8%～15%, thionamic acid 4%～8%, Sodium hexametaphosphate 99 4%～8%, sodium sulfate 5%～10, phenylpropyl alcohol triazole 4%～10%; At the seawater cycles of concentration is 1.5～2.0; The erosion rate of control admiraltymetal is less than 0.009mm/a; Corrosion inhibition rate is on the low side, and the inhibition index does not reach the technical requirements less than 0.005mm/a of " circularly-cooling sea water Treatment Design standard " (GB/T 23248-2009) regulation, and cost of water treatment is also higher.
Analyze from the finding relevant report; About achievement in research and practical application also have certain gap; Still be faced with some problem demanding prompt solutions aspect technology, economy, the environmental protection: (1) experiment condition can not fine simulated seawater circulating cooling system operation condition (temperature, flow velocity, concentration rate etc.), and the flexibility of achievement in research in the cooled with seawater system does not have cogency; (2) the neutralization technology index has much room for improvement, some composite corrosion inhibitors of developing, and corrosion mitigating effect is on the low side, and control corrosion of copper alloy speed does not reach the technical requirements of circularly-cooling sea water Treatment Design regulation and stipulation; (3) cost of water treatment is higher, and agent of inhibiter list or compound prescription consumption in seawater is big, and like the huge height of Sodium orthomolybdate unit price, and working concentration is higher, has improved cost of water treatment greatly.And the M.L. in the existing industrial colling of some composite corrosion inhibitor ton cost of water treatment of preresearch estimates is up to several times and even tens times, and use cost is very expensive, does not have the practicality and the market competitiveness at the seawater circulating cooling system; (4) discharge water will be limited by environmental protection, for a long time, is prone to cause phosphorus (phosphine) corrosion inhibitor of body eutrophication to occupy the main flow of water conditioner; In recent years; Receive the restriction of country, local sewage drainage standard and sea environment-friendly, started the cry of " limit phosphorus ", " taboo phosphorus " in the treatment of cooling water field once more, some phosphorous water conditioners lose the competitive edge in market gradually; Be faced with the situation that is eliminated, no phosphatization water technology has become the focus that industry is paid close attention to.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; Provide a kind of circularly-cooling sea water not have phosphor copper composite corrosion inhibitor and preparation and method of use; To solve the etching problem of copper alloy in the seawater circulating cooling system; To the needs of current seawater recirculation refrigerating technology development and marine eco-environment protection, design research and development new copper alloy corrosion inhibitor of sea water around performance, environment and economic three general objectives.
The object of the invention is achieved through following technical proposals:
A kind of circularly-cooling sea water does not have the phosphor copper composite corrosion inhibitor, forms by the prefilming agent of pretreatment stage use and the inhibiter of normal operating phase use, wherein:
Said prefilming agent is organic azole compounds, one or both of benzotriazole, mercapto benzothiazole, TTA or tetrahydroglyoxaline for example, and consumption is 100mg/L～200mg/L, mainly utilizes its adsorption precipitation effect;
Said inhibiter is made up of organic azole compounds and inorganic salt; Wherein: said organic azole compounds is one or both of benzotriazole, mercapto benzothiazole, TTA or tetrahydroglyoxaline; Consumption is 3mg/L～9mg/L, mainly utilizes its adsorption precipitation effect
Said inorganic salt are rare-earth salts, zinc salt or molybdate, mainly utilize its cathode deposition effect, and consumption is 2mg/L～20mg/L:
Said rare-earth salts is the inorganic acid salt or the organic acid salt of REE; Be specially hydrochloride, nitrate salt or acetate; For example Lanthanum trichloride, Lanthanum trinitrate, lanthanum acetate, zirconium nitrate, Cerium II Chloride, cerous nitrate, cerous acetate, Yttrium trichloride, Yttrium trinitrate or acetic acid yttrium mainly utilize REE to react;
Said zinc salt is zinc sulfate, zinc chloride or Zinc Gluconate, with Zn
2+The meter consumption mainly is to utilize zine ion to react
Said molybdate is molybdic acid an alkali metal salt or molybdic acid alkaline earth salt, and for example Sodium orthomolybdate, Potassium orthomolybdate, magnesium molybdate or ammonium molybdate mainly are to utilize its oxidation-resistance.
Each component content is preferably following:
The consumption of organic azole compounds is 150mg/L～200mg/L in the said prefilming agent.
The consumption of organic azole compounds is 3mg/L～6mg/L in the said inhibiter.
The consumption of inorganic salt is 2～15mg/L in the said inhibiter.
When preparing composite corrosion inhibitor of the present invention; Benzotriazole water or organic solvent (like ethanol) dissolving; Tetrahydroglyoxaline dissolves with organic solvent (like Virahol); Mercapto benzothiazole, TTA are with alkali lye (like sodium hydroxide) dissolving, and other inorganic salt get final product with solvent (deionized water or tap water) preparation.
Carry out constant volume after utilizing solvent (deionized water, tap water, organic alcohol or alkali lye) directly to dissolve respective substance, get final product (stirring capable of using or heating come accelerate dissolution) to reach finite concentration; Calculate its usage quantity according to seawater usage quantity and the strength of solution (organism and inorganic salt) prepared then; With solution of having prepared and sea water mixing, so that each component in the final seawater reaches the concentration requirement of inhibiter under prefilming agent and the normal operation respectively.
Composite corrosion inhibitor of the present invention is selected without phosphorus raw material for use, and selecting organic azole, inorganic salt compound for use is raw material, and collaborative organic azole inhibiter adsorption precipitation film, inorganic salt cathode deposition membranous type binding mode are realized to the corrosion inhibition of copper alloy in seawater.
In use; At first (step 1) will prepare be used for the prefilming agent that pretreatment stage uses (can be earlier according to the working concentration of the amount of seawater, prefilming agent and set of dispense than the consumption that calculates each component and be mixed with solution) be added to seawater or additional seawater (to reach the concentration requirement of prefilming agent in the invention); Then under the normal temperature (20 ℃～30 ℃), dynamically under the condition of (lacing film rotating speed 80r/min～120r/min or start recycle pump); Move 24h at least continuously; Preferred 24h～48h is to form preservative protective film at copper alloy surface fast; (step 2) changes in the normal inhibition seawater behind the film in advance; Be about to the inhibiter that the normal operating phase of preparation uses (can be according to the seawater amount or possess the water yield, concentration rate, seawater rate of water make-up or blowdown flow rate, the set of dispense of normally moving inhibiter working concentration and inhibiter is than basic dosage that calculates each component and usual amounts just; Take by weighing and be mixed with solution again) be added to (to reach the concentration requirement of inhibiter in the invention) in seawater or the cooling system, keep the operation of inhibiter lower concentration to realize reparation to protective membrane.
A kind of circularly-cooling sea water of the present invention does not have the phosphor copper composite corrosion inhibitor; Comprise prefilming agent and normal operation inhibiter; To seawater circulation process for cooling characteristics and systematic economy operating requirement, propose to adopt earlier the polynary prefilming agent of organic azole of high density to handle, change a kind of technology that the composite normal operation inhibiter of lower concentration is handled refrigerated sea water again over to; Realize inhibiter high density fast filming; Lower concentration is kept the purpose that film is repaiied in operation, and 1.8～2.2 of cycles of concentration, control corrosion of copper alloy speed is less than 0.003mm/a; Technical performance index reaches the 0.005mm/a standard technique requirement that " circularly-cooling sea water Treatment Design standard " (GB/T23248-2009) stipulated, technico-economical comparison can reach the domestic seawater circulation cooling demonstration project level of at present having moved.Corrosion inhibitor product raw material sources of the present invention are extensive, favorable solubility, and cost performance is high, low toxicity, environment-friendly type is without phosphorus, not pollution of marine environment; Good with seawater dirt dispersion agent, bacterium algae suppressor factor compatibleness, be a kind of efficient, economic non-phosphate environment-friendly type seawater water conditioner, have broad application prospects.
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.The seawater that uses is taken from Tanggu, Tianjin seawater cleaning factory, water-quality guideline: pH value 7.31, specific conductivity 3.99 * 10
4μ s/cm, basicity 123mg/L, turbidity＜10mg/L, Ca
2+380mg/L, Mg
2+1162mg/L, SO
4 2-2478mg/L, Cl
-17403mg/L.
Electrochemical test method adopts weak polarization measuring technology commonly used, the corrosion condition and the inhibiter film forming situation of monitoring aluminum brass working electrode.
The corrosion weight loss method is according to " mensuration of water conditioner corrosion inhibition-rotary hanging plate method " GB/T 18175-2000 standard; Material is aluminum brass (HAl77-2A), admiraltymetal (HSn62, HSn70) test piece or test ring; Experiment condition is: behind the preparatory film 24h of normal temperature (20 ℃) dynamic (rotating speed 80r/min); Change in 50 ℃ ± 1 ℃ the normal inhibition seawater, move 120 hours continuously.
Dynamic analog test is to utilize power system seawater circulation cooling dynamic simulation tester to carry out, and experiment condition is: quantity of circulating water 1000L/h, velocity in pipes 0.6m/s, possess water yield 450L, cycles of concentration 1.8～2.2, Balance of nature pH value, 45 ℃ of recirculated water leaving water temperature(LWT)s, 6 ℃～10 ℃ of the cooling tower Inlet and outlet water temperature difference, test and use material to be brass (HAl77-2A, HSn62, HSn70) test tube and test piece, 18 days test periods.
Without the situation of carrying out inhibition under the preparatory film disposition:
1. without film processing in advance, directly in seawater, add benzotriazole 1mg/L, mercapto benzothiazole 6mg/L, zinc chloride (Zn
2+Meter) 5mg/L, under normal temperature (20 ℃) static conditions, aluminum brass electrode film forming 1h, measurement of polarization resistance are 8266 Ω cm
2, erosion rate 0.04106mm/a, corrosion inhibition rate 34.51%.
2. without film processing in advance, directly in seawater, add benzotriazole 2mg/L, mercapto benzothiazole 6mg/L, zinc sulfate (Zn
2+Meter) 5mg/L, under normal temperature (20 ℃) static conditions, aluminum brass electrode film forming 1h, measurement of polarization resistance are 10483 Ω cm
2, erosion rate 0.02885mm/a, corrosion inhibition rate 54%.
3. without film processing in advance, directly in seawater, add benzotriazole 3mg/L, mercapto benzothiazole 2mg/L, Zinc Gluconate (Zn
2+Meter) 4mg/L, under normal temperature (20 ℃) static conditions, aluminum brass electrode film forming 1h, measurement of polarization resistance are 10138 Ω cm
2, erosion rate 0.03232mm/a, corrosion inhibition rate 48.45%.
Embodiment 1
By the corrosion weight loss test; In seawater, add benzotriazole 50mg/L, mercapto benzothiazole 50mg/L, with the aluminum brass test piece carry out preparatory film handle (under 20 ℃ of normal temperature, dynamically be lacing film rotating speed 80r/min; Move 24h continuously); Change benzotriazole 2mg/L again over to, mercapto benzothiazole 6mg/L, zinc sulfate (Zn
2+Meter) moves in the seawater of 2mg/L, measure erosion rate 0.00150mm/a.
Embodiment 2
By the corrosion weight loss test; In seawater, add benzotriazole 50mg/L, mercapto benzothiazole 50mg/L, with the aluminum brass test piece carry out preparatory film handle (under 20 ℃ of normal temperature, dynamically be lacing film rotating speed 120r/min; Move 48h continuously); Change benzotriazole 3mg/L again over to, mercapto benzothiazole 2mg/L, zinc chloride (Zn
2+Meter) moves in the seawater of 4mg/L, measure erosion rate 0.00125mm/a.
Embodiment 3
By the corrosion weight loss test, in seawater, add benzotriazole 50mg/L, mercapto benzothiazole 100mg/L; With the aluminum brass test piece carry out preparatory film handle (under 20 ℃ of normal temperature, dynamically be lacing film rotating speed 100r/min; Move 35h continuously), change benzotriazole 2mg/L again over to, mercapto benzothiazole 6mg/L; Move in the seawater of Zinc Gluconate 5mg/L, measure erosion rate 0.00146mm/a.
Embodiment 4
By the corrosion weight loss test, in seawater, add benzotriazole 80mg/L, mercapto benzothiazole 100mg/L; With the aluminum brass test piece carry out preparatory film handle (under 20 ℃ of normal temperature, dynamically be lacing film rotating speed 80r/min; Move 24h continuously), change benzotriazole 3mg/L again over to, mercapto benzothiazole 3mg/L; Move in the seawater of Lanthanum trinitrate 5mg/L, measure erosion rate 0.00143mm/a.
Embodiment 5
By the corrosion weight loss test, in seawater, add benzotriazole 50mg/L, mercapto benzothiazole 150mg/L; With the aluminum brass test piece carry out preparatory film handle (under 20 ℃ of normal temperature, dynamically be lacing film rotating speed 80r/min; Move 48h continuously), change benzotriazole 3mg/L again over to, mercapto benzothiazole 6mg/L; Move in the seawater of Sodium orthomolybdate 15mg/L, measure erosion rate 0.00074mm/a.
Embodiment 6
By the corrosion weight loss test, in seawater, add benzotriazole 40mg/L, mercapto benzothiazole 150mg/L; With the aluminum brass test piece carry out preparatory film handle (under 20 ℃ of normal temperature, dynamically be lacing film rotating speed 80r/min; Move 30h continuously), change benzotriazole 3mg/L again over to, mercapto benzothiazole 2mg/L; Move in the seawater of Potassium orthomolybdate 20mg/L, measure erosion rate 0.00090mm/a.
Embodiment 7
By the corrosion weight loss test, in seawater, add TTA 40mg/L, mercapto benzothiazole 80mg/L; With the aluminum brass test piece carry out preparatory film handle (under 20 ℃ of normal temperature, dynamically be lacing film rotating speed 80r/min; Move 30h continuously), change TTA 3mg/L again over to, mercapto benzothiazole 2mg/L; Move in the seawater of Yttrium trichloride 20mg/L, measure erosion rate 0.00115mm/a.
Embodiment 8
By the corrosion weight loss test, in seawater, add benzotriazole 40mg/L, tetrahydroglyoxaline 150mg/L; With the aluminum brass test piece carry out preparatory film handle (under 20 ℃ of normal temperature, dynamically be lacing film rotating speed 80r/min; Move 30h continuously), change benzotriazole 3mg/L again over to, tetrahydroglyoxaline 6mg/L; Move in the seawater of Cerium II Chloride 15mg/L, measure erosion rate 0.00124mm/a.
Embodiment 9
By the corrosion weight loss test, in seawater, add tetrahydroglyoxaline 50mg/L, mercapto benzothiazole 70mg/L; With the aluminum brass test piece carry out preparatory film handle (under 20 ℃ of normal temperature, dynamically be lacing film rotating speed 80r/min; Move 24h continuously), change benzotriazole 3mg/L again over to, mercapto benzothiazole 2mg/L; Move in the seawater of lanthanum acetate 5mg/L, measure erosion rate 0.00108mm/a.
Embodiment 10
By the corrosion weight loss test, in seawater, add tetrahydroglyoxaline 40mg/L, mercapto benzothiazole 150mg/L; With the aluminum brass test piece carry out preparatory film handle (under 20 ℃ of normal temperature, dynamically be lacing film rotating speed 80r/min; Move 30h continuously), change benzotriazole 3mg/L again over to, mercapto benzothiazole 2mg/L; Move in the seawater of ammonium molybdate 15mg/L, measure erosion rate 0.00098mm/a.
Preparatory film processing with identical is handled three kinds of different brass materials with the inhibition scheme of normal operation
In seawater, add benzotriazole 50mg/L, mercapto benzothiazole 150mg/L, under dynamic (80r/min) condition of normal temperature (20 ℃), aluminum brass electrode film forming 24h, weak polarization test polarization resistance is 126.4K Ω cm
2Three kinds of brass are all carried out carrying out benzotriazole 2mg/L again, mercapto benzothiazole 6mg/L, zinc chloride (Zn after preparatory film handles
2+Meter) normally operation in the seawater of 2mg/L, corrosion weight loss result is: the erosion rate of Hsn62, Hsn70, HAl77-2A is respectively 0.00207mm/a, 0.00083mm/a, 0.00118mm/a.
Utilize power system seawater circulation cooling dynamic analog test; Above-mentioned three kinds of different brass materials are handled; Film is handled and is handled said with epimere with normal operation in advance; The erosion rate of corrosion of copper alloy control result: HAl77-2A is less than 0.002mm/a, and the erosion rate of Hsn62 and HSn70 is all less than 0.003mm/a.
Although above the preferred embodiments of the present invention are described; But the present invention is not limited to above-mentioned embodiment, and above-mentioned embodiment only is schematically, is not restrictive; Those of ordinary skill in the art is under enlightenment of the present invention; Not breaking away under the scope situation that aim of the present invention and claim protect, can also make the concrete conversion of a lot of forms, these all belong within protection scope of the present invention.
Claims (9)
1. a circularly-cooling sea water does not have the phosphor copper composite corrosion inhibitor, is made up of the prefilming agent of pretreatment stage use and the inhibiter of normal operating phase use, it is characterized in that, wherein:
Said prefilming agent is organic azole compounds, and consumption is 100mg/L～200mg/L;
Said inhibiter is made up of organic azole compounds and inorganic salt, and wherein: said organic azole compounds is one or both of benzotriazole, mercapto benzothiazole, TTA or tetrahydroglyoxaline, and consumption is 3mg/L～9mg/L
Said inorganic salt are rare-earth salts, zinc salt or molybdate, and consumption is 2mg/L～20mg/L:
Said rare-earth salts is the inorganic acid salt or the organic acid salt of REE, is specially hydrochloride, nitrate salt or acetate;
Said zinc salt is zinc sulfate, zinc chloride or Zinc Gluconate
Said molybdate is molybdic acid an alkali metal salt or molybdic acid alkaline earth salt.
2. a kind of circularly-cooling sea water according to claim 1 does not have the phosphor copper composite corrosion inhibitor; It is characterized in that; In said prefilming agent, said organic azole compounds is one or both of benzotriazole, mercapto benzothiazole, TTA or tetrahydroglyoxaline; In the inhibiter that normal operating phase uses; Said molybdate is Sodium orthomolybdate, Potassium orthomolybdate, magnesium molybdate or ammonium molybdate, and said rare-earth salts is Lanthanum trichloride, Lanthanum trinitrate, lanthanum acetate, zirconium nitrate, Cerium II Chloride, cerous nitrate, cerous acetate, Yttrium trichloride, Yttrium trinitrate or acetic acid yttrium.
3. a kind of circularly-cooling sea water according to claim 1 does not have the phosphor copper composite corrosion inhibitor, it is characterized in that, each component content is preferably following:
The consumption of organic azole compounds is 150mg/L～200mg/L in the said prefilming agent
The consumption of organic azole compounds is 3mg/L～6mg/L in the said inhibiter
The consumption of inorganic salt is 2～15mg/L in the said inhibiter.
4. method for preparing composite corrosion inhibitor as claimed in claim 1; It is characterized in that, benzotriazole water or organic solvent dissolution, tetrahydroglyoxaline is used organic solvent dissolution; Mercapto benzothiazole, TTA dissolve with alkali lye, and other inorganic salt get final product with the solvent preparation; Carry out constant volume after utilizing solvent directly to dissolve respective substance; Get final product to reach finite concentration; Calculate its usage quantity according to seawater usage quantity and the strength of solution prepared then; With solution of having prepared and sea water mixing, so that each component in the final seawater reaches the concentration requirement of inhibiter under prefilming agent and the normal operation respectively.
5. the preparation method of composite corrosion inhibitor according to claim 4; It is characterized in that; The said organic solvent that is used to dissolve benzotriazole is an ethanol; The organic solvent that is used to dissolve tetrahydroglyoxaline is a Virahol, and the alkali lye that is used to dissolve mercapto benzothiazole, TTA is aqueous sodium hydroxide solution; The solvent that is used for dissolve inorganic salts is deionized water or tap water.
6. the preparation method of composite corrosion inhibitor according to claim 4; It is characterized in that; Said inorganic salt are rare-earth salts, zinc salt or molybdate; Said molybdate is Sodium orthomolybdate, Potassium orthomolybdate, magnesium molybdate or ammonium molybdate, and said rare-earth salts is Lanthanum trichloride, Lanthanum trinitrate, lanthanum acetate, zirconium nitrate, Cerium II Chloride, cerous nitrate, cerous acetate, Yttrium trichloride, Yttrium trinitrate or acetic acid yttrium, and said zinc salt is zinc sulfate, zinc chloride or Zinc Gluconate.
7. the method for use of a composite corrosion inhibitor as claimed in claim 1; It is characterized in that in use, at first (prefilming agent that pretreatment stage uses that is used for that will prepare of step 1) is added to seawater or additional seawater; So that each component reaches the concentration requirement of prefilming agent; Then at normal temperatures, under the dynamic condition, move 24h at least continuously, to form preservative protective film fast at copper alloy surface; (step 2) changes in the normal inhibition seawater behind the film in advance; Be about to inhibiter that the normal operating phase of preparation uses and be added in seawater or the cooling system, keep the operation of inhibiter lower concentration to realize reparation to protective membrane so that each component reaches the concentration requirement of inhibiter.
8. the method for use of composite corrosion inhibitor according to claim 7 is characterized in that, in the said step (1), normal temperature is 20 ℃～30 ℃, and said dynamic condition is lacing film rotating speed 80r/min～120r/min or starts recycle pump.
9. the method for use of composite corrosion inhibitor according to claim 7 is characterized in that, in the said step (1), and the preferred 24h～48h of continuous operating time.
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| CN104152909A (en) * | 2014-08-21 | 2014-11-19 | 长沙沃尔金属表面技术有限公司 | Powder alloy casting part aqueous rust preventive and preparing method thereof |
| CN105016489A (en) * | 2014-04-18 | 2015-11-04 | 梁瑛 | Composition used for water systems as well as preparation method and using method thereof |
| CN107055819A (en) * | 2016-11-13 | 2017-08-18 | 滨州学院 | A kind of Green Water Treatment Reagents and its application with corrosion and scale inhibition performance |
| CN110036140A (en) * | 2016-10-04 | 2019-07-19 | 联邦科学和工业研究组织 | Inhibit the method for corrosion |
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| CN119430395A (en) * | 2024-10-29 | 2025-02-14 | 谭明国 | Carbon steel corrosion resistance method for typical water quality in thermal and nuclear power plants |
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| CN103352225A (en) * | 2013-07-22 | 2013-10-16 | 上海电力学院 | Brass corrosion inhibitor and preparation method thereof |
| CN103436888A (en) * | 2013-08-23 | 2013-12-11 | 南京理工大学 | High temperature copper corrosion inhibitor containing benzimidazole and preparation method of high temperature copper corrosion inhibitor |
| CN105016489A (en) * | 2014-04-18 | 2015-11-04 | 梁瑛 | Composition used for water systems as well as preparation method and using method thereof |
| CN104152909A (en) * | 2014-08-21 | 2014-11-19 | 长沙沃尔金属表面技术有限公司 | Powder alloy casting part aqueous rust preventive and preparing method thereof |
| CN110036140A (en) * | 2016-10-04 | 2019-07-19 | 联邦科学和工业研究组织 | Inhibit the method for corrosion |
| CN107055819A (en) * | 2016-11-13 | 2017-08-18 | 滨州学院 | A kind of Green Water Treatment Reagents and its application with corrosion and scale inhibition performance |
| CN107055819B (en) * | 2016-11-13 | 2020-08-21 | 滨州学院 | A green water treatment agent with corrosion and scale inhibition properties and its application |
| CN115094406A (en) * | 2022-06-20 | 2022-09-23 | 邢台旭阳科技有限公司 | Non-phosphorus prefilming agent and its preparation method and application |
| CN115094406B (en) * | 2022-06-20 | 2023-10-20 | 邢台旭阳科技有限公司 | Phosphorus-free prefilming agent and preparation method and application thereof |
| CN119430395A (en) * | 2024-10-29 | 2025-02-14 | 谭明国 | Carbon steel corrosion resistance method for typical water quality in thermal and nuclear power plants |
| CN120082891A (en) * | 2025-04-28 | 2025-06-03 | 山东理工大学 | Method for improving surface corrosion resistance of copper foil by adopting 2-mercaptobenzothiazole-cerium composite corrosion inhibitor |
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