CN1338437A - Process for suppressing corrosion of cyclic cooling water - Google Patents
Process for suppressing corrosion of cyclic cooling water Download PDFInfo
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- CN1338437A CN1338437A CN 00121541 CN00121541A CN1338437A CN 1338437 A CN1338437 A CN 1338437A CN 00121541 CN00121541 CN 00121541 CN 00121541 A CN00121541 A CN 00121541A CN 1338437 A CN1338437 A CN 1338437A
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- salicylaldoxime
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Abstract
A process for suppressing the corrosion of cyclic cooling water features that a corrosion inhibitor containing C1-C5 alkylcarboxylic acid substituted salicylaldehyde oxime and optional one or more of acyl substituted sodium sarcosinate, alkyl substituted succinimide, and acrylic copolymer, imorganic zinc salt and molydbate. Its advantages include less dosage of inhibitor, high effect, low cost and no phosphorus pollution.
Description
The present invention relates to suppress the corrosive method of recirculated water.
It is a lot of that recirculating cooling water system produces the corrosive factor, has from airborne oxygen and recirculated cooling water to concentrate that dissolved salts concentration such as causing chlorion increases and the galvanic corrosion that causes; Have because the microbiological corrosion that microbial reproduction causes; Also have because the underdeposit corrosion that fouling causes etc.
The inhibiter kind that is used for the recirculated cooling water processing has a lot, and early stage chromic salt, nitrite ban use of because the toxicity of self reaches the pollution to environment.Inorganic salts inhibiter such as molybdate, silicate, borate, tungstate and vanadate exploitations early, environmental sound, but because using dosage height separately, must with the composite use of other inhibiter.
What the recirculated cooling water inhibiter was the most frequently used at present is that phosphorus (phosphine) is prescription, because corrosion mitigating effect is good, cheap, is used widely.But, in recent years because body eutrophication is serious, and phosphorus is as the nutrition source of microorganism, and its negative impact to environment also is familiar with by people gradually, to the low phosphatization of water conditioner or not have the cry of phosphatization also more and more higher.
Organic inhibitors such as organic amine, acid amides carboxylic-acid, hydroxycarboxylic acid or organic carboxyl acid class play corrosion inhibition because of it is adsorbable in the metallic surface.Hydroxyoxime is owing to contain carbon-to-nitrogen double bon, and contains the Sauerstoffatom that lone-pair electron can be provided, and therefore very strong complexing and adsorption are arranged in the metallic surface.
Add a small amount of salicylaldoxime in the US 5264155 report water treatment prescriptions, have the effect of anti-sulfide, can play the effect of anti-oxidant type sterilant; The hydroxyl oxime that US 4725320 report chain alkyls replace is applied to the metallic surface and can prevents corrosion.But, the poor stability of salicylaldoxime in water, very easily hydrolysis variable color, and the hydroxyl oxime that alkyl replaces poorly soluble in water is unfavorable in the metallic surface film forming.
The object of the present invention is to provide and a kind ofly can effectively suppress the corrosive method of recirculated water, the required inhibiter dosage of this method is little, and corrosion mitigating effect is good, and cost is low, and without phosphorus pollution.
The method of inhibition corrosion of cyclic cooling water provided by the invention comprises: add in circulating water system and contain C
1～C
5, preferred C
1～C
3The inhibiter of the salicylaldoxime that alkyl carboxylic acid replaces.
The salicylaldoxime using dosage that said alkyl carboxylic acid replaces is 5～500mg/L, preferred 10～100mg/L.
Can also contain in amber uncle imide, acrylic copolymer, inorganic zinc salt and the molybdate that the sodium sarcosinate, alkyl of acyl substituted replace one or more in the said inhibiter.
The sodium sarcosinate that replaces of the sodium sarcosinate that replaces of the preferred lauroyl of the sodium sarcosinate of said acyl substituted and oleoyl wherein, using dosage is 5～50mg/L, preferred 10～20mg/L.
The preferred C of amber uncle's imide that said alkyl replaces
8～C
14The amber uncle imide that alkyl replaces, using dosage is 10～10mg/L, preferred 20～50mg/L.
Said acrylic copolymer is selected from vinylformic acid/2-acrylamido-2-methyl propane sulfonic acid multipolymer, vinylformic acid/maleic acid, vinylformic acid/toxilic acid/2-acrylamido-2-methyl propane sulfonic acid multipolymer, vinylformic acid/3 acrylic acid ester-2-hydroxy-propanesulfonic acid multipolymer, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/3 acrylic acid ester-2-hydroxy-propanesulfonic acid multipolymer and vinylformic acid/allyl group phosphonic acid copolymer.The using dosage of acrylic copolymer is 10～100mg/L, preferred 20～50mg/L.
Said zinc salt can be selected zinc chloride or zinc sulfate for use, and using dosage is 0.5～10mg/L, preferred 2～4mg/L.
Said molybdate is the soluble molybdenum hydrochlorate, can select Sodium orthomolybdate, ammonium molybdate or potassium molybdate etc. for use, and using dosage is 2～20mg/L, preferred 5～10mg/L.
The corrosive method of inhibition recirculated water provided by the invention has adopted the inhibiter of the salicylaldoxime that contains carboxylic acid-substituted, has better stability and corrosion inhibition than salicylaldoxime.If salicylaldoxime and acid amides, carboxylic-acid organic inhibitor or the compound use of inorganic inhibitors such as zinc salt, molybdate with carboxylic acid-substituted can further improve corrosion mitigating effect and reduce the total consumption of inhibiter.
Further specify characteristics of the present invention below by embodiment.
Embodiment 1
Present embodiment is the preparation of the salicylaldoxime of acetic acid substituted.
Salicylaldoxime 27g mixes with methyl chloroacetate 22g, makees solvent with DMF200g, adds salt of wormwood 50g, reaction is 24 hours under 35 ℃ of conditions, steams DMF after the filtration, hydro-oxidation sodium 10g, in 45 ℃ of following hydrolysis 24 hours, get the red-brown aqueous solution, add hydrochloric acid solution is transferred to neutrality, use extracted with diethyl ether, get organic phase, after twice of saturated sodium-chloride water solution washing, get organic phase, use the Calcium Chloride Powder Anhydrous drying, filter, steam ether, get the salicylaldoxime of product acetic acid substituted, code name is SYSS.
Embodiment 2
The salicylaldoxime carboxylic acid-substituted thing of embodiment 1 preparation is made inhibiter, carry out the corrosion coupon experiment, the results are shown in Table 1.With salicylaldoxime as a comparison.
Test specimen: test piece is the 20# carbon steel, area 0.28dm
2
Experiment condition: 55 ℃ of temperature, 48 hours time
Water quality: deionized water, pH5～6
Table 1
| Medicament | Concentration, mg/l | Erosion rate, mdd |
| Salicylaldoxime | ????100 | ????103.4 |
| ????SYSS | ????100 | ????33.7 |
Annotate: mdd represents milligram/decimetre
2. day (mg/dm
2.d)
As can be seen from Table 1, the corrosion inhibition of salicylaldoxime is starkly lower than salicylaldoxime carboxylic acid-substituted thing, and this is because the stability of salicylaldoxime in water not as containing substituent aldoxime, rises in experiment later stage erosion rate.
Embodiment 3
Present embodiment is the corrosion coupon experiment of salicylaldoxime carboxylic acid-substituted thing and sodium N-lauroyl sarcosinate (LS) compound prescription, the results are shown in Table 2.
Test specimen: test piece is the 20# carbon steel, area 0.28dm
2
Experiment condition: 55 ℃ of temperature, 48 hours time
Water quality: deionized water, pH5～6
Table 2
The sodium sarcosinate of acyl substituted is a kind of inhibiter that can be used for recirculating cooling water system preferably, but because the using dosage height costs an arm and a leg, its application is restricted.As can be seen from Table 2, the compound use of the sodium sarcosinate of salicylaldoxime carboxylic acid-substituted thing and acyl substituted can reduce the using dosage of medicament greatly, improves corrosion mitigating effect.
| Medicament | Concentration, mg/l | Erosion rate, mdd |
| ???LS | ????50 | ????20.7 |
| ???SYSS＋LS | ????20＋10 | ????12.7 |
Embodiment 4
Present embodiment is the corrosion coupon experiment of salicylaldoxime carboxylic acid-substituted thing and dodecyl amber uncle imide (DS) compound prescription, the results are shown in Table 3.
Test specimen: test piece is the 20# carbon steel, area 0.28dm
2
Experiment condition: 55 ℃ of temperature, 48 hours time
Water quality: the hard 20mg/l of calcium, total alkalinity 30mg/l pH7～8
Table 3
| Medicament | Concentration, mg/l | Erosion rate, mdd |
| ???DS | ????100 | ????97.5 |
| ???SYSS＋DS | ????20＋50 | ????22.4 |
The amber uncle imide that alkyl replaces can be used as a kind of non-phosphate inhibitor and is used for circulating water system, but the using dosage height, corrosion mitigating effect is not very desirable.As can be seen from Table 3, with the using dosage of salicylaldoxime carboxylic acid-substituted thing compound use can reduction medicament, improve corrosion mitigating effect.
Embodiment 5
Present embodiment is the corrosion coupon experiment of the sodium sarcosinate and the acrylic copolymer compound prescription of salicylaldoxime carboxylic acid-substituted thing and alkyl replacement.The results are shown in Table 4.Wherein the sodium sarcosinate of acyl substituted is sodium N-lauroyl sarcosinate (LS), and acrylic copolymer is vinylformic acid and 2-acrylamido-2-methyl propane sulfonic acid multipolymer (AA).
Test specimen: test piece is the 20# carbon steel, area 0.28dm
2
Experiment condition: 55 ℃ of temperature, 48 hours time
Water quality: the hard 20mg/l of calcium, total alkalinity 30mg/l, pH7～8
Table 4
| Medicament | Concentration, mg/l | Erosion rate, mdd |
| ????SYSS＋LS | ????20＋10 | ????47.2 |
| ????SYSS＋LS＋AA | ????20＋10＋20 | ????42.3 |
Acrylic copolymer is commonly used for dirt dispersion agent in recirculated cooling water, be a kind of main component of water treatment prescription, with the compound use of above-mentioned non-phosphate inhibitor, can further reduce corrosion inhibition rate.
Embodiment 6
Present embodiment is the corrosion coupon experiment of salicylaldoxime carboxylic acid-substituted thing and inorganic zinc salt compound prescription
Test specimen: test piece is the 20# carbon steel, area 0.28dm
2
Experiment condition: 55 ℃ of temperature, 48 hours time
Water quality: deionized water, pH5～6
Table 5
| Medicament | Concentration, mg/l | Erosion rate, mdd |
| ????SYSS | ????100 | ????33.7 |
| ????SYSS＋Zn 2+ | ????100＋2 | ????17.8 |
As can be seen from Table 5, the compound use of salicylaldoxime carboxylic acid-substituted thing and inorganic zinc salt can reduce erosion rate.
Embodiment 7
Present embodiment is the corrosion coupon experiment of salicylaldoxime carboxylic acid-substituted thing and Sodium orthomolybdate compound prescription, the results are shown in Table 6.
Test specimen: test piece is the 20# carbon steel, area 0.28dm
2
Experiment condition: 55 ℃ of temperature, 48 hours time
Water quality: deionized water, pH5～6
Table 6
| Medicament | Concentration mg/l | Erosion rate mdd |
| ????SYSS | ????100 | ????33.7 |
| ????SYSS＋MoO 4 2- | ????100＋5 | ????21.4 |
As can be seen from Table 6, the compound use of salicylaldoxime carboxylic acid-substituted thing and molybdate can reduce erosion rate.
Claims (10)
1. a method that suppresses corrosion of cyclic cooling water comprises: add in circulating water system and contain C
1～C
5The inhibiter of the salicylaldoxime that alkyl carboxylic acid replaces.
2. in accordance with the method for claim 1, it is characterized in that, in circulating water system, add and contain C
1～C
3The inhibiter of the salicylaldoxime that alkyl carboxylic acid replaces.
3. in accordance with the method for claim 1, it is characterized in that the salicylaldoxime using dosage that said alkyl carboxylic acid replaces is 5～500mg/L.
4. in accordance with the method for claim 3, it is characterized in that the salicylaldoxime using dosage that said alkyl carboxylic acid replaces is 10～100mg/L.
5. in accordance with the method for claim 1, it is characterized in that, can also contain in amber uncle imide, acrylic copolymer, inorganic zinc salt and the molybdate that the sodium sarcosinate, alkyl of acyl substituted replace one or more in the said inhibiter.
6. in accordance with the method for claim 1, it is characterized in that wherein the sodium sarcosinate of said acyl substituted is the sodium sarcosinate of lauroyl replacement and the sodium sarcosinate that oleoyl replaces, using dosage is 5～50mg/L.
7. in accordance with the method for claim 1, it is characterized in that the amber uncle imide that said alkyl replaces is selected from C
8～C
14The amber uncle imide that alkyl replaces, using dosage is 10～100mg/L.
8. in accordance with the method for claim 1, it is characterized in that, said acrylic copolymer is selected from vinylformic acid/2-acrylamido-2-methyl propane sulfonic acid multipolymer, vinylformic acid/maleic acid, vinylformic acid/toxilic acid/2-acrylamido-2-methyl propane sulfonic acid multipolymer, vinylformic acid/3 acrylic acid ester-2-hydroxy-propanesulfonic acid multipolymer, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/3 acrylic acid ester-2-hydroxy-propanesulfonic acid multipolymer and vinylformic acid/allyl group phosphonic acid copolymer, the using dosage of acrylic copolymer is 10～100mg/L.
9. in accordance with the method for claim 1, it is characterized in that said zinc salt is selected from zinc chloride and zinc sulfate, using dosage is 0.5～10mg/L.
10. in accordance with the method for claim 1, it is characterized in that said molybdate is selected from Sodium orthomolybdate, potassium molybdate etc. or ammonium molybdate, using dosage is 2～20mg/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00121541 CN1132791C (en) | 2000-08-11 | 2000-08-11 | Process for suppressing corrosion of cyclic cooling water |
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|---|---|---|---|
| CN 00121541 CN1132791C (en) | 2000-08-11 | 2000-08-11 | Process for suppressing corrosion of cyclic cooling water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451598A (en) * | 2010-10-27 | 2012-05-16 | 中国石油化工股份有限公司 | Composite corrosion inhibitor for carbon dioxide removing system and application thereof |
| CN114057304A (en) * | 2020-08-05 | 2022-02-18 | 中国石油化工股份有限公司 | Composition for phosphorus-free pre-filming, method for pre-filming circulating cooling water system by using composition and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928075B (en) * | 2010-08-30 | 2011-12-21 | 蓝星环境工程有限公司 | Closed-type circulating cooling water system inhibiter and preparation method thereof |
-
2000
- 2000-08-11 CN CN 00121541 patent/CN1132791C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451598A (en) * | 2010-10-27 | 2012-05-16 | 中国石油化工股份有限公司 | Composite corrosion inhibitor for carbon dioxide removing system and application thereof |
| CN102451598B (en) * | 2010-10-27 | 2015-01-14 | 中国石油化工股份有限公司 | Composite corrosion inhibitor for carbon dioxide removing system and application thereof |
| CN114057304A (en) * | 2020-08-05 | 2022-02-18 | 中国石油化工股份有限公司 | Composition for phosphorus-free pre-filming, method for pre-filming circulating cooling water system by using composition and application |
| CN114057304B (en) * | 2020-08-05 | 2023-02-28 | 中国石油化工股份有限公司 | Composition for phosphorus-free pre-filming, method for pre-filming circulating cooling water system by using composition and application |
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