CN104694937B - A kind of micro- alkalization transitional period heat exchanger electrochemistry induction filming method of recirculated cooling water - Google Patents
A kind of micro- alkalization transitional period heat exchanger electrochemistry induction filming method of recirculated cooling water Download PDFInfo
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- CN104694937B CN104694937B CN201510099788.0A CN201510099788A CN104694937B CN 104694937 B CN104694937 B CN 104694937B CN 201510099788 A CN201510099788 A CN 201510099788A CN 104694937 B CN104694937 B CN 104694937B
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Abstract
A kind of micro- alkalization transitional period heat exchanger electrochemistry induction filming method of recirculated cooling water.First, by recirculating cooling water system heat exchanger and more active metal --- spelter is connected, galvanic cell is formed, recirculated water pH is adjusted to 2 ~ 4, the metal ion content in recirculated water is monitored in running, after about 2 ~ 3 days, when its ascendant trend slows down, cleaning is completed.For brassiness heat exchanger, system is adjusted to alkalescence, adds oxidant, one layer of Cu can be formed on its surface after certain time2O passivating films, after removing cathodic protection, gradate as stable CuO passivating films, hereafter, brass corrosion speed<0.005mm/a.It is first disposable to add Fe for carbon steel matter heat exchanger2+, after circulating certain time, solution is adjusted to alkalescence, adds oxidant, certain time recession removes cathodic protection, and its surface forms the iron oxide passivating film of densification, corrosion rate<0.01mm/a, local corrosion is prevented, complete the micro- alkalization transition stage of recirculated cooling water.
Description
Technical field
The present invention relates to the micro- quenched transition stage of alkalization of recirculated cooling water, the Chemical cleaning of heat exchanging device metal and corrosion are controlled
Method processed, it is combined especially with cathodic protection and oxidant passivation, brass and carbon steel surface is produced uniform passivation film
Method.
Background technology
It is existing to be related to recirculating cooling water system heat exchanger Chemical cleaning and pre- membrane technology, it is to be realized using corrosion inhibiting and descaling agent
Both metal surface dirt had been removed, the dual purpose of erosion of the acid medium to metallic matrix when reducing cleaning again.The technology is divided into
Two classes, one kind are to clean offline, and one kind is on-line cleaning.Both principles are identical, that is, add dilute strong acid or have the weak acid of complexing,
And corrosion inhibiting and descaling agent is added, medicament circulates certain time in system, and one layer of organic film is adhered on the new surface after cleaning, afterwards
Running in only need to supplement medicament, appropriate repairing is carried out to organic film.But when both drug concentration and circulation
Between it is otherwise varied, clean carried out during shutdown offline, medicament is denseer, and processing time is shorter, can complete within 1 ~ 2 day, clean
Cheng Hou, cleaning fluid need to update.Then adding consistency is relatively low for on-line cleaning, and processing time lasts about 15 ~ 20 days, after the completion of cleaning,
Cleaning fluid progressively discharges with concentrated water.This cleaning method is subsequently handled more appropriate using method for dosing medicine.
And the micro- alkalization process of recirculated cooling water is then processing cycle cooling water replenishment, the knot such as calcium therein, magnesium ion is removed
Incrustation ion, go to denitrogenate, the nutrient such as phosphorus, and the chlorion for promoting corrosion and sulfate ion are converted into the carbonate of alkalescence
Ion or bicarbonate ion, recirculated cooling water is quenched to alkalescence scope（pH=8.0~9.0）, do not add separately in recirculated water
Under conditions of medicine, realize that the microorganisms such as antiscale, anticorrosion and anti-algae multiply, while realize zero-emission.Traditional chemistry is clear
Wash with after the processing of pre- membrane process, what is formed in metal surface is organic film, and when micro- alkalization is quenched, the film on surface will constantly take off
Fall, new film is difficult to be formed, and incomplete film will result in microelectrode, accelerates local corrosion.Therefore, the pre- membrane process of tradition is uncomfortable
With the operation of micro- alkalization process, it is necessary to develop a kind of new cleaning prefilming method.
The micro- alkalization service requirement heat exchanger metal surface of recirculated cooling water forms one layer of fine and close passivating film, its main component
For the oxide of metal in itself, and Chemical cleaning and oxide film forming are conflicting.To solve the above problems, the present invention utilizes the moon
When Chemical cleaning is alleviated in pole guard method, pickling medium that metallic matrix is subject to is corroded, and metal surface is kept after cleaning
It is clean.For more inert brass heat exchanger, medium is adjusted to alkalescence after cleaning, and adds oxidant, first will be sacrificial
Domestic animal anode surface is progressively passivated, then the copper ion slowly discharged is deposited on into its surface, forms dense oxidation film, removes sacrifice sun
Pole, the pre- film of inorganic oxide of brass surfaces is realized, completes micro- alkalization process transition.For more active simple steel heat exchanger,
Because its surface ion is active, it is easier to that local corrosion occurs, so as to form galvanic cell.Therefore, before using zinc anode protection
Put, add Fe2+Ion, the irony film of one layer of external source, then slowly closing anode and negative electrode are formed on its surface first, realizes table
Face densification film forming, complete micro- alkalization transition.Chemical cleaning and pre- film are carried out in this way, realize micro- alkalization process smooth transition
Method, have not yet to see report.
The content of the invention
The purpose of the present invention is：A kind of system heat exchanger electricity for realizing the micro- quenched smooth transition of alkalization of recirculated cooling water is provided
Chemical induction equilibrium film build method, in particular for the metallic recuperator surface clean and balanced film forming of brass and carbon steel material.
The object of the present invention is achieved like this：
A kind of micro- alkalization transitional period heat exchanger electrochemistry induction filming method of recirculated cooling water：First, made using metallic zinc
For sacrificial anode, galvanic cell is formed with heat exchanger metal, in cycle chemistry cleaning process, protection heat exchanger matrix exempts from acidity
Dielectric corrosion；After brass heat exchanger system cleans, water quality is adjusted to alkalescence, adds oxidant, makes its surface form Cu2O
Protective layer, after removing cathodic protection, oxide skin(coating) gradates the CuO protective layers to stablize, and completes micro- alkalization transition；Or carbon
After steel heat exchanger system cleans, FeSO need to be added4, in the presence of galvanic cell, Fe2+Ionic adsorption in matrix surface, and
It is reduced, electroplates last layer film, cover uneven spot corrosion area, then water quality is adjusted to alkalescence, adds oxidant, slowly aoxidize shape
Into the iron oxide diaphragm of densification, micro- alkalization transition is completed.
Preferably, after simple steel heat exchanger cleaning, FeSO is added4When, between a, pH maintain 2 ~ 4, conditioning agent
From HCl or H2SO4； b、Fe2+Ion is provided by following one or more combination, including FeSO4With Fe (NO3)2；c、
Fe2+After ion addition system, content in system is between the mmol/L of 1mmol/L ~ 10.
Preferably, when recirculating cooling water system alkalizes, basifier NaOH, Na2CO3、NaHCO3With Ca (OH)2In one
Kind or several combinations.
Preferably, when recirculating cooling water system adds oxidant, a, oxidant are hydrogen peroxide；B, oxidant concentration is
10mmol/L~200mmol/L ；C, circulation time is 2 ~ 12h to oxidant in systems.）
It is characteristic of the invention that：
1st, traditional corrosion inhibiting and descaling agent is replaced using cathode protecting process, in Process of Chemical Cleaning, guarantee can be removed and changed
The dirt on hot device surface, thermal resistance is reduced, improve heat transfer efficiency, and can protection metallic matrix, prevent from perforating, surface after Chemical cleaning
Cleanliness without any pollution；
2nd, using the galvanic cell of cathodic protection, in acid condition, the uniform metal of last layer is plated on active metal surface
Film, prevent because surface has a pitting or dirt, form galvanic cell, local accelerated corrosion occurs during passivation, is follow-up oxidant
Passivation creates favorable conditions；
3rd, hydrogen peroxide etc. can be selected in the passivator after pre- film, and it is a kind of chemical agent of clean environment firendly, after oxidation reaction
Water is generated, therefore, passivating solution is not required to discharge, and will not cause great lot of water resources waste and environmental pollution, is more beneficial for realizing online
Cleaning and transition；
4th, the improvement to conventional method is the method achieve, reduces the application of corrosion inhibiting and descaling agent, while is advantageous to promote
The popularization and application of the micro- alkalization process of recirculated cooling water of more energy-conserving and environment-protective industrially, will produce bigger social benefit and
Economic benefit.
Embodiment
The present invention is described in further detail with reference to specific embodiment, but protection scope of the present invention is not limited in
This.
Embodiment 1
The old system during new construction system or overhaul for brass material heat exchanger, takes offline chemical cleaning side
Method.Immersed from 500mm × 500mm × 10mm zine plates or aluminium sheet as sacrificial anode in recirculated cooling water, use 12mm2Blister copper is led
Anode is connected by line with heat exchanger both ends, forms galvanic cell.It is 1 to reuse hydrochloric acid, sulfuric acid or select one and Proportion of Citric Acid:
1 solution adjusts recirculated water to acidity, pH=2 ~ 4, circular flow 24h, and 2h once determines Cu in cleaning process2+Content, and examine
PH is surveyed, if pH has risen, supplements acid solution in time.Concentration changes with time curve is drawn, curve rises to peak, stops
Pickling.
Add NaOH, Na2CO3、NaHCO3With Ca (OH)2One of which or several combinations are made into carbonate buffer solution, will
Recirculated water pH is adjusted to 8 ~ 9, is added hydrogen peroxide as oxidant, is made H in recirculated water2O2Concentration is 10mmol/L ~ 200mmol/
L, after running 2 ~ 12h, brass surfaces form the red Cu of light2O passivating films.
Zine plate or aluminium sheet are removed, brass surfaces oxide-film gradates the CuO films for black under Effect of Dissolved Oxygen, steady
Under fixed alkalescence condition of water quality, film realizes self-renewing and dynamic equilibrium, protects matrix metal, reduces corrosion rate.
Embodiment 2
For the old system during the new construction system of carbon steel material heat exchanger or overhaul, take using method in example 1
Carry out offline chemical cleaning.
After cleaning, FeSO is added4、Fe(NO3)2Or FeCl2In a kind of ferrous salt, make Fe in recirculated water2+Ion contains
Measure as 1mmol/L ~ 10mmol/L, Fe2+Ion, to movable cathode, is adsorbed in heat exchanger surface under galvanic cell electric field action, and
Iron atom is reduced into, the pre- film with discrete phase same material is formed, surface smut or pitting is effectively covered, alkali can be prevented
Local accelerated corrosion occurs under property oxidation environment.
The step identical with example 1 is recycled to be alkalized and be passivated, final carbon steel crosses the oxidation that water surface forms densification
Iron film, and self-renewing and mending-leakage are realized in stable alkaline buffer solution, the corrosion rate of carbon steel is controlled in standard model
In enclosing.
Embodiment 3
For the old system that need to be run without interruption, in-site chemical cleaning method is taken.Using the cathodic protection side in example 1
Case, strong acid and citric acid 1:1 proportioning dosing, system pH is adjusted to 3 ~ 4, and monitors metal ion and pH in recirculated water daily, fitted
Shi Tianjia cleanings acid, runs about 15 days, completes in-site chemical cleaning.
For copper heat exchanger, then directly the pre- film of oxide is obtained, completes micro- alkalization using the alkalization oxidation of the method for example 1
Transition.For carbon steel matter heat exchanger, then the pre- film of ferrous absorbing and reducing is first carried out using example 2, then aoxidize using being alkalized in example 1
Method obtains the pre- film of oxide, completes transition.
Claims (4)
- A kind of 1. micro- alkalization transitional period heat exchanger electrochemistry induction filming method of recirculated cooling water：First, using metallic zinc as Sacrificial anode, galvanic cell is formed with heat exchanger metal, in cycle chemistry cleaning process, protection heat exchanger matrix exempts from acid Jie Matter is corroded；After brass heat exchanger system cleans, water quality is adjusted to alkalescence, adds oxidant, makes its surface form Cu2O is protected Sheath, after removing cathodic protection, oxide skin(coating) gradates the CuO protective layers to stablize, and completes micro- alkalization transition；Or carbon steel After heat exchanger system cleans, FeSO need to be added4, in the presence of galvanic cell, Fe2+Ionic adsorption in matrix surface, and by Reduction, last layer film is electroplated, cover uneven spot corrosion area, then water quality is adjusted to alkalescence, add oxidant, slowly oxidation is formed Fine and close iron oxide diaphragm, completes micro- alkalization transition.
- 2. a kind of micro- alkalization transitional period heat exchanger electrochemistry induction filming method of recirculated cooling water according to claim 1, Characterized in that, after simple steel heat exchanger cleans, FeSO is added4When, between a, pH maintain 2 ~ 4, conditioning agent is selected HCl or H2SO4； b、Fe2+Ion is provided by following one or more combination, including FeSO4With Fe (NO3)2；c、Fe2+From After sub- addition system, content in system is between the mmol/L of 1mmol/L ~ 10.
- 3. a kind of micro- alkalization transitional period heat exchanger electrochemistry induction filming method of recirculated cooling water according to claim 1, Characterized in that, when recirculating cooling water system alkalizes, basifier NaOH, Na2CO3、NaHCO3With Ca (OH)2In one kind or Several combinations.
- 4. a kind of micro- alkalization transitional period heat exchanger electrochemistry induction filming method of recirculated cooling water according to claim 1, Characterized in that, when recirculating cooling water system adds oxidant, a, oxidant are hydrogen peroxide；B, oxidant concentration is 10mmol/L ~200mmol/L ；C, circulation time is 2 ~ 12h to oxidant in systems.
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| CN104949571B (en) * | 2015-06-17 | 2018-06-26 | 彭伟 | The online precise chemical structure cleaning method and device of a kind of tubular heat exchanger zero-emission |
| CN108823588B (en) * | 2018-06-05 | 2020-06-23 | 青岛科技大学 | Ag modified Cu2O nanobelt/foam copper composite electrode and preparation method thereof |
| CN112938919B (en) * | 2021-01-27 | 2022-07-15 | 华中科技大学 | Treatment method of waste etching liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3479268A (en) * | 1966-08-01 | 1969-11-18 | Gen Electric | Method of applying a binder to electro phoretically deposited porous matrix |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3479268A (en) * | 1966-08-01 | 1969-11-18 | Gen Electric | Method of applying a binder to electro phoretically deposited porous matrix |
Non-Patent Citations (1)
| Title |
|---|
| 循环冷却水软化微碱化协同防垢防腐防污研究;曾惠明;《中国博士论文全文数据库工程科技Ⅰ辑》;20130915(第09期);第B015-8页 * |
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Effective date of registration: 20220223 Address after: 324200 No. 6, Zhensheng Road, Qingshi Town, Changshan County, Quzhou City, Zhejiang Province Patentee after: ZHEJIANG CHANGSHAN LISHENG NEW MATERIAL CO.,LTD. Patentee after: Lv Liang Address before: 324000 North China Road No. 78, Quzhou, Quzhou, Zhejiang Patentee before: QUZHOU University Patentee before: Lv Liang |
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