CN110357278A - A kind of alkaline corrosion inhibitor and its preparation method and application - Google Patents
A kind of alkaline corrosion inhibitor and its preparation method and application Download PDFInfo
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- CN110357278A CN110357278A CN201910655221.5A CN201910655221A CN110357278A CN 110357278 A CN110357278 A CN 110357278A CN 201910655221 A CN201910655221 A CN 201910655221A CN 110357278 A CN110357278 A CN 110357278A
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- corrosion
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
- C02F5/125—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen combined with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
- C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a kind of alkaline corrosion inhibitors, suitable for low-hardness water closed-cycle system, the corrosion inhibiter ingredient is in terms of quality %, including hydroxy ethylene diphosphonic acid sodium salt: 4 ~ 12, poly-aspartate derivant: 5 ~ 15, sodium nitrite: 15 ~ 25, dispersing agent: 3 ~ 5 and the low-hardness water of surplus compound.This corrosion inhibiter pH is alkalinity, synergistic by compounding, and the 3% ~ 5% of dosage when the dosage of nitrite is used alone for it, effectively changing influences caused by environment when sodium nitrite is used alone, and medicament corrosion mitigating effect is good, and dosage is low；Suitable for low-hardness water closed-cycle system, it is capable of the corrosion mitigating effect of effective guarantee heat exchanger, pipeline and equipment, extends service life.
Description
Technical field
The present invention relates to a kind of alkaline corrosion inhibitors and its preparation method and application.
Background technique
Water resource is irreplaceable natural resources, and China's shortage of water resources, water resource of per capita is world average level
A quarter, belong to serious water shortage country.Therefore just become current to reasonable utilization, exploitation and the water conservation of water resource to protect
Water resource is protected, realizes the link of sustainable development of socio-economy most critical.
Steel industry is with water rich and influential family, the blast furnace furnace wall of iron and steel enterprise, continuous cast mold, steel-making oxygen rifle and oxygen generation system etc.
Workshop section's equipment thermic load is high, and recirculated cooling water is easy fouling or corrosion, so that the service life of product quality and equipment is influenced, institute
To have obtained increasingly extensive application using low-hardness water closed cycle in the production of these departments.
Low-hardness water closed-cycle system, hardness is very low in water, in operational process, heat exchanger surface form scale can
Energy property is greatly lowered, and avoids heat exchanger surface scale formation, and due to not having dirty layer to protect, corrosion is aggravated；In addition sealing and circulating
Water oxygen is not easy to be precipitated, and has aggravated the oxygen concentration polarization corrosion of dissolved oxygen.So the corrosion of low-hardness water closed circuit circulatory system
It is more serious for opposite open type circulatory system, dedicated corrosion inhibiter must be added in operational process, just can guarantee heat exchange equipment not
It is corroded.
Enclosed Type Circulating Cooling Water System requirement cooling water quality is good, rate of water make-up is small, in order to improve the effect of corrosion control,
It adjusts the pH of Enclosed Type Circulating Cooling Water System and is run using the effect of excellent effect soft corrosion inhibiter is lower, it in this way can be steel
The corrosion rate of iron substantially reduces, and reaches state specified standards.
Delayed using series of phosphate with oxidisability is added currently, the common corrosion inhibition method of low-hardness water closed-cycle system has
Lose two methods of agent.
Common oxidisability corrosion inhibitor formula mainly has chromate series corrosion inhibiter, silicate corrosion inhibitor, molybdate corrosion inhibiter
With nitrite series corrosion inhibiter.
Chromate series corrosion inhibiter is the corrosion inhibiter more early applied, and corrosion mitigating effect is excellent, but has toxicity, and pollutes ring
Border is rarely employed.
Silicate corrosion inhibitor has nontoxicity, free of contamination feature, but dosage is big, to water quality requirement height, is also easy to produce spot corrosion,
Controlling bad can also generate silicate scale.
Molybdate series corrosion inhibiter, economic cost is excessively high, and in market under the premise of keen competition, unit is rarely employed.
Nitrite series corrosion inhibiter, due to cheap, film forming is fast, and inhibition is good, individually or based on sodium nitrite
For corrosion inhibitor formula actual use amount in the mg/L of 500 mg/L ~ 1000, dosing is big.If the usage amount by sodium nitrite is big
Big reduction and other corrosion inhibiter compounding, corrosion mitigating effect are up to state standards, and are a kind of good methods.
Summary of the invention
It is good that the object of the present invention is to provide a kind of corrosion inhibitions, low-hardness water alkaline corrosion inhibitor at low cost and its preparation side
Method, the corrosion inhibiter are capable of the inhibition effect of effective guarantee heat exchanger, pipeline and equipment mainly for circulating low-hardness water closed system
Fruit extends service life.
The present invention adopts the following technical scheme:
A kind of alkaline corrosion inhibitor, which is characterized in that it includes the component of following parts by weight: hydroxy ethylene diphosphonic acid sodium salt 4 ~ 12
Part, 10 ~ 15 parts of poly-aspartate derivant, 15 ~ 25 parts of sodium nitrite, 3 ~ 5 parts of dispersing agent and soft water supply 100 parts.
Preferably comprising the component of following parts by weight: 8 parts of hydroxy ethylene diphosphonic acid sodium salt, poly-aspartate are derivative
15 parts of object, 25 parts of sodium nitrite, 4 parts of dispersing agent and soft water supply 100 parts.
Further, contain carboxylic acid group and sulfonic group poly-aspartate while the poly-aspartate derivant is modified
Derivative is synthesized using aspartic acid thermal polycondensation product polysuccinimide (PSI) and 2-aminoethanesulfonic acid, aspartic acid
A kind of poly-aspartate derivant PASP-SEA-ASP, pH be alkalinity.
Further, the hydroxy ethylene diphosphonic acid sodium salt is four sodium of hydroxy ethylene diphosphonic acid, pH 12.
Further, the dispersing agent is sodium lignin sulfonate.
A kind of preparation method of above-mentioned alkaline corrosion inhibitor, which is characterized in that sodium nitrite and dispersing agent are first dissolved in soft water
Middle stirring 5 minutes, solid matter are added poly-aspartate derivant stirring, are eventually adding hydroxy ethylene diphosphine after being completely dissolved
Acid sodium-salt stirs evenly.
A kind of application of above-mentioned alkaline corrosion inhibitor in low-hardness water closed-cycle system.It is slow that the alkalinity is added in water per ton
80 ~ 100 grams of agent of erosion.
Poly-aspartate is the novel water treatment agent of one kind of early 1990s exploitation, not phosphorous, is a kind of from original
Expect the preparation process biodegradable environmental type water treatment agent harmless to environment and human body to final products, poly- asparagus fern
Propylhomoserin (PASP) is a kind of polyaminoacid with carboxylic acid side chain, it can biodegrade and chelate and dispersion performance, but
Its corrosion inhibition is not so good as organic phosphine corrosion inhibiter, in order to improve the corrosion mitigating effect of poly-aspartate, on the basis of poly-aspartate
On, different proportion functional group sulfonic group and carboxylic acid group are introduced into the molecule of poly-aspartate, has synthesized a kind of while having contained carboxylic
Acidic group and sulfonic poly-aspartate derivant, pH are alkalinity, and corrosion inhibition increases compared with poly-aspartate, and belonging to can
Degradable chemical.Since poly-aspartate graft copolymer is by the biggish carboxyl of electronegativity, carbonyl, hydroxyl and the pole-NH-
Property group and the nonpolar base of carbon, hydrogen atom composition constitute, the polar group in these groups is adsorbed in metal surface, changes
The activation energy of metal ionization process can be improved in the structure of the electric double layer of change；And non-polar group is oriented far from metal surface
Arrangement forms one layer of hydrophobic film, becomes the barrier of corrosion reaction substance diffusion, is suppressed corrosion reaction,
Hydroxy ethylene diphosphonic acid sodium salt is tetrasodium salt, belongs to organic phospho acid salt anti-incrustation corrosion inhibitor, has strong basicity, in water
There is good complexing power to iron ion, copper ion, calcium ion etc., good corrosion inhibition is still played at 250 DEG C, in high pH
Under it is still very stable, facile hydrolysis and decomposition, not cheap, it is generally the case that it is used in compounding with other corrosion inhibiter, they it
Between there is synergy, to improve corrosion inhibition.
Sodium lignin sulfonate is a kind of natural polymers, has strong basicity, and have very strong dispersibility, is fitted
Disperse in an aqueous medium in by solid.It can guarantee the uniformity of corrosion inhibition film well.
Sodium nitrite belongs to positive polarity corrosion inhibiter, and matal deactivator can constitute protection in the metal anode part being corroded
Property oxidant film, for carbon steel material, it can form one layer of fine and close gamma-iron oxide film in steel surface, make surface passivation,
Resist corrosion of metal.And the suction-operated of the oxidant film of sodium nitrite formation on the metal surface is stronger.
The beneficial effects of the present invention are: the present invention mutually coordinates in line with type oxide film corrosion inhibiter, adsorbed film type corrosion inhibiter
Principle, alkaline corrosion inhibitor are suitable for soft sealing and circulating water system, have stronger chemisorption in metal surface, slow down
Anode and cathode reaction, alleviates the corrosion of low-hardness water system material, and corrosion mitigating effect is all good, performance is good, and effective time is long,
Optimal rate of corrosion is 0.028 mm/a, hence it is evident that less than the Circulating Water Corrosion standard of national regulation, corrosion inhibition rate reaches 97% or more.It should
The dissolubility of corrosion inhibiter in water is high, usage amount is smaller, and economic cost is low, is a kind of low-hardness water alkalinity with development prospect
Corrosion inhibiter.
Specific embodiment
The present invention is further described below with reference to specific case study on implementation.
A kind of alkaline corrosion inhibitor, the corrosion inhibiter are prepared by following methods,
First it is stirred sodium nitrite and dispersing agent sodium lignin sulfonate are soluble in water 5 minutes, after solid matter is completely dissolved
It is added while being stirred containing carboxylic acid group and sulfonic group poly-aspartate derivant, be eventually adding the stirring of four sodium of hydroxy ethylene diphosphonic acid
Uniformly.
Corrosion test uses measurement-rotary hanging plate method of water treatment agent corrosion inhibition, and the method is the People's Republic of China (PRC)
Standard GB/T/T18175-2000, instrument are ZJ type immersion corrosion experiment view, test water: ion exchange resin softened water；
Test temperature: 60 DEG C；Rotation speed: 80r/min；Test period: 72h；Lacing film is carbon steel lacing film.
1 softened water quality situation of table
。
2 orthogonal test factor of table and level
。
3 orthogonal test designs table L9(3 of table4) and experimental result
。
Range analysis is carried out to above-mentioned data, can obtain formula A3B1C3D2, the corrosion mitigating effect of medicament is preferable, at this time carbon steel
Corrosion rate be 0.035mm/a, the far smaller than corrosion rate 0.075mm/a of national regulation, corrosion inhibition rate 97.33%.It is per ton
It is 80 ~ 100 grams that alkaline corrosion inhibitor dosage, which is added, in water, and cost is computed less than 0.5 yuan, is far below other class low-hardness water inhibitions
Agent.Simultaneously as can be seen that in terms of corrosion inhibition, sodium nitrite is primary influence factor, is secondly hydroxy ethylene diphosphonic acid
Four sodium and contain carboxylic acid group and sulfonic group poly-aspartate derivant.
Embodiment 1
2800m3Blast furnace cooling stave, hot-blast valve and tuyere small sleeve use low-hardness water closed-cycle system, and water used is ion friendship
Change resin softened water, the corrosion inhibiter of addition is alkaline corrosion inhibitor of the invention, be formulated as sodium nitrite 20ppm, containing carboxylic acid group and
10 ppm of sulfonic group poly-aspartate derivant, four sodium of hydroxy ethylene diphosphonic acid, 10 ppm, dispersing agent 4ppm.Blast furnace is in 2010
Year goes into operation, and blast furnace soft water closed circulation system iron ion content is gradually lowered to 1mg/l hereinafter, reaching by 6-8 mg/l after dosing
Professional standard.6 groups of lacing films are hung with during operation in pipeline, from the lacing film of taking-up, surface without apparent corrosion phenomenon,
Almost the same with reset condition, surface is photochromic in metal, and lacing film corrosion rate complies fully between 0.031 ~ 0.065mm/a
The regulation of GB 50050-2017 Code for design of industrial recirculating cooling water treatment.
Embodiment 2
120 tons of converter oxygen gun closed-cycle systems, low-hardness water are the reverse osmosis produced water of dynamics factory's production, come 30 degree of left sides of coolant-temperature gage
The right side, 40 degree of return water temperature or so, cooling equipment uses plate heat exchanger, and medicament used is alkaline corrosion inhibitor of the invention, formula
For sodium nitrite 25ppm, contain carboxylic acid group and sulfonic group poly-aspartate derivant 10ppm, four sodium 12 of hydroxy ethylene diphosphonic acid
Ppm, dispersing agent 3ppm.This formula has been applied for many years in the closed oxygen rifle circulatory system of converter, the content of iron in circulating ion
0.2 ~ 0.8mg/l, 4 ~ 8NTU of turbidity, system run all right have four groups of lacing film in circulation, and seclected time is 6 months and 9
A month, shown through monitoring result, lacing film any surface finish, no spot corrosion, Non-scale and foundry loam, lacing film corrosion rate be 0.032 ~
Between 0.056mm/a, the regulation of GB 50050-2017 Code for design of industrial recirculating cooling water treatment is complied fully with.
Embodiment 3
Continuous cast mold soft water cooling water system is low-hardness water closed-cycle system, and moisturizing used is ion exchange resin
Softened water is formulated using being alkaline corrosion inhibitor of the invention as sodium nitrite 25ppm, carboxylic acid group and sulfonic group poly-aspartate
12 ppm of derivative, four sodium of hydroxy ethylene diphosphonic acid, 8 ppm, dispersing agent 4ppm.Production run is being just after circulation dosing
Often, iron ion content is less than 1mg/l in water, belongs to normal range (NR), and carbon steel lacing film surface is still bright, heavy without oxides such as iron rust
Product, rate of corrosion comply fully with GB 50050-2017 industrial circulating cooling water processing design rule between 0.028 ~ 0.061mm/a
The regulation of model.
Comparative example 1
Continuous cast mold soft water cooling water system is low-hardness water closed-cycle system, and moisturizing used is ion exchange resin
Softened water uses the formula of corrosion inhibiter for carboxylic acid group and sulfonic group poly-aspartate derivant 15ppm, hydroxy ethylene diphosphonic acid
Four sodium, 8 ppm, dispersing agent 4ppm.Production run is normal after circulation dosing, iron ion content 2.5mg/l or so in water,
There is corrosion phenomenon on carbon steel lacing film surface, and rate of corrosion is between 0.080-0.102mm/a, beyond GB 50050-2017 industry
The regulation of Design of Circulation Cooling Water Treatment specification, by experiments have shown that, lack one such medicament sodium nitrite, corrosion mitigating effect
It is greatly affected.
Comparative example 2
Continuous cast mold soft water cooling water system is low-hardness water closed-cycle system, and moisturizing used is ion exchange resin
Softened water is formulated using being alkaline corrosion inhibitor of the invention as sodium nitrite 25ppm, 10 ppm of poly-aspartate, hydroxyl Asia second
8 ppm of base di 2 ethylhexyl phosphonic acid, dispersing agent 4ppm.Production run is normal after circulation dosing, and iron ion content 1.0 in water ~
There is corrosion phenomenon on 2.0mg/l, carbon steel lacing film surface, have the oxides such as iron rust deposition, rate of corrosion 0.085-0.121mm/a it
Between, the regulation beyond GB 50050-2017 Code for design of industrial recirculating cooling water treatment, it is seen that gather carboxylic acid group and sulfonic group
Aspartame is changed to poly-aspartate, four sodium of hydroxy ethylene diphosphonic acid is changed to hydroxy ethylene diphosphonic acid, dosage phase
Corrosion mitigating effect is bad in the case where.
Practical application proves that soft alkaline corrosion inhibitor of the invention is suitable for the low-hardness water circulatory system, and dosage is low,
At low cost, corrosion mitigating effect is good, and water temperature has a wide range of application, and can guarantee that using effect complies fully with GB50050-2017 industry and follows
The regulation of ring cold water process design specification.The corrosion inhibiter has the characteristics that high-performance, dosage are small, low-cost, and application is worth to push away
Extensively.
Certainly, the above is only one embodiment of the present invention, it should be pointed out that the common skill of the art
For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
It belongs within the scope of protection of the claims of the present invention.
Claims (7)
1. a kind of alkaline corrosion inhibitor, which is characterized in that it includes the component of following parts by weight: hydroxy ethylene diphosphonic acid sodium salt 4 ~
12 parts, 5 ~ 15 parts of poly-aspartate derivant, 15 ~ 25 parts of sodium nitrite, 3 ~ 5 parts of dispersing agent and soft water supply 100 parts.
2. alkaline corrosion inhibitor according to claim 1, which is characterized in that the poly-aspartate derivant is the same of modification
Shi Hanyou carboxylic acid group and sulfonic poly-aspartate derivant.
3. alkaline corrosion inhibitor according to claim 1, which is characterized in that the pH of the poly-aspartate derivant is alkali
Property.
4. alkaline corrosion inhibitor according to claim 1, which is characterized in that the hydroxy ethylene diphosphonic acid sodium salt is hydroxyl
Four sodium of ethylidene diphosphonic acid.
5. alkaline corrosion inhibitor according to claim 1, which is characterized in that the dispersing agent is sodium lignin sulfonate.
6. a kind of preparation method of any one of such as claim 1 ~ 5 alkaline corrosion inhibitor, which is characterized in that first by sodium nitrite
It is dissolved in soft water and stirring 5 minutes with dispersing agent, poly-aspartate derivant, which is added, after being completely dissolved in solid matter continues to stir, most
Hydroxy ethylene diphosphonic acid sodium salt is added afterwards, stirs evenly.
7. a kind of application of claim 1 ~ 5 alkaline corrosion inhibitor in low-hardness water closed-cycle system.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113470872A (en) * | 2021-06-25 | 2021-10-01 | 广西桂潮电缆投资有限公司 | Anti-corrosion cable for mine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113470872A (en) * | 2021-06-25 | 2021-10-01 | 广西桂潮电缆投资有限公司 | Anti-corrosion cable for mine |
| CN113470872B (en) * | 2021-06-25 | 2022-11-15 | 广西桂潮电缆投资有限公司 | Anti-corrosion cable for mine |
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Application publication date: 20191022 |