CN101027429A - Pitting corrosion inhibitor for metal and method of inhibition - Google Patents
Pitting corrosion inhibitor for metal and method of inhibition Download PDFInfo
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- CN101027429A CN101027429A CNA2005800193268A CN200580019326A CN101027429A CN 101027429 A CN101027429 A CN 101027429A CN A2005800193268 A CNA2005800193268 A CN A2005800193268A CN 200580019326 A CN200580019326 A CN 200580019326A CN 101027429 A CN101027429 A CN 101027429A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
Abstract
A pitting corrosion inhibitor for metal comprising (A) a sulfonated copolymer obtained by copolymerizing a sulfonated conjugated diene represented by the general formula [1] with a carboxylated unsaturated compound represented by the general formula [2] at a mole ratio of 1 : 0.1 to 1 : 20, (B) a copolymer having hydrophobic groups which is obtained by copolymerizing maleic acid with an alkene of 4 to 10 carbon atoms at a mole ratio of 1 : 0.8 to 1 : 1.3, and (C) an azole; and a method of inhibiting pitting corrosion of metal by adding the pitting corrosion inhibitor to an aqueous system in an amount of 1 to 100 mg/L in terms of the sum of the component (A), (B) and (C), wherein at least one of R<1> to R<6> is -SO3X and at least one of R<7> to R<10> is -(CH2)mCOOM. Use of the pitting corrosion inhibitor makes it possible to prolong effectively the duration of life of a unit having a carbon steel member in a water-contacting part in an open cooling water circulation system.
Description
Technical field
The present invention relates to pitting corrosion inhibitor for metal and pitting inhibition method.More particularly, the present invention relates in the open loop cooling water system, can under the situation of not using heavy metallic salts such as phosphorus compound and zinc salt, suppress the generation of carbon steel pitting, effectively pitting corrosion inhibitor for metal and the pitting inhibition method that prolongs equipment lives such as heat exchanger.
Background technology
Corrosion of metal not only can produce dirt, also is one of significant trouble that takes place in the cooling water system simultaneously.Corrosion can cause not only that the shortened equipment life, heat-exchanger pipeline of cooling water system are communicated with and the direct fault of leakage, pollution etc. that goods take place, also can be owing to indirect fault such as thermo-efficiency declines that heat exchanger takes place adhering to of corrosion product, pump pressure rising.And having an accident in high temperature, high top pressure operation also can relate to fatal accident probably.If be dissolved in the indissoluble salt in the water coolant owing to concentrate as incrusted deposit on heat-transfer surface, or adhere to mud in system owing to microorganism breed, then mostly meeting in dirt settling bottom generation local corrosion.When general corrosion takes place in the metallic surface in being in corrosive environment, be easy to according to corrosion prediction device lifetime, and also be easy to game, but be local corrosion mostly in real system, the wherein pitting that in most cases produces, its corrosion partial depth ratio open width is big.Like this, in order to produce incrustation scale and corrosion in the anti-water-stopping system, various means have been found out.
For example, in water systems such as boiler, heat exchanger, condenser, pipe arrangement,, proposed to contain the water conditioner (patent documentation 1) of conjugated diolefine sulfonated bodies or its polymkeric substance or multipolymer as the water conditioner that uses in order to prevent to produce incrustation scale.In addition, as not phosphorous, can not produce polyvalent metal ion and insoluble salt, incrustation scale and pollution prevent that effect is good, its effect can long term maintenance, metallic corrosion simultaneously suppresses the also good water conditioner of effect, has proposed to contain the water conditioner (patent documentation 2) by conjugated diolefine sulfonic acid or its salt, (methyl) vinylformic acid or its salt and (methyl) vinylformic acid 2-hydroxy methacrylate or (methyl) acrylamide-2-methyl alkyl sulfonic acid or its salt synthetic 3 group categories multipolymers.
In addition, all do not use and can effectively prevent the anti-corrosion method of metallic material corrosion in the cooling water system, proposed that M basicity is AmgCaCO in water coolant as Phosphorus reagent and zinc class reagent
3/ L, calcium hardness are BmgCaCO
3/ L, silica concentration are CmgSiO
2/ L, magnesium hardness are DmgCaCO
3/ L, bright lattice rel (ラ Application ジ エ リ ア) index are that E, hydrogen ion exponent are pH, when water temperature is t ℃, regulate satisfied (1) 2.4logA+logB 〉=6.4 and C 〉=50, (2) logC+logD+2pH+8.51logt 〉=33, the perhaps water quality of (3) logB+logC 〉=3.4 and E 〉=1.5 is added the anti-corrosion method (patent documentation 3) of water-soluble anionic polymer.In addition, as not causing problem of environmental pollution, can effectively preventing the inhibition method of the corrosion of metal that contacts with water, SiO in water has been proposed in the open loop cooling water system
2Concentration is [SiO
2] (mgSiO
2/ L), calcium hardness is [CaH] (mgCaCO
3/ L) time, regulate water quality so that more than the bright lattice rel index to 1.5, and [SiO
2] * [CaH] 〉=2000, then, add weight-average molecular weight and be the method (patent documentation 4) of multipolymer of toxilic acid, maleic anhydride or their water-soluble salt and the iso-butylene of 1000-20000.
According to these schemes, the effect that can obtain to prevent incrustation scale and even suppress metallic corrosion, but pitting is suppressed to obtain the special efficacy effect.Utilize the anti-corrosion method of toxilic acid-isobutylene copolymers and calcium hardness, silica concentration, on water quality, be subjected to more restriction, and the imperfect situation of pitting effect can occur suppressing.For the saturation index of lime carbonate and the relation of corrosion tendency/fouling tendency, J.W.Ryzner has carried out reporting (non-patent literature 1).Stability (リ ズ Na one) index is that the water quality more than 6 has corrosion tendency, and the water quality of stability index less than 6 has the tendency of fouling.But the water quality average corrosion rate that has fouling tendency usually is less, but the situation of the local corrosion of pitting can occur causing, can not lengthen the life of a machine fully.
[patent documentation 1] Japan special permission No. 2625914 communique (page 1)
[patent documentation 2] Japanese kokai publication hei 9-248555 communique (2-3 page or leaf)
[patent documentation 3] TOHKEMY 2004-107782 communique (2-3 page or leaf)
[patent documentation 4] Japan special fair 4-33868 communique (1-2 page or leaf)
[non-patent literature 1] J.AWWA36472 (1944)
The present invention is to provide a kind of in the open loop cooling water system, can be under the situation of not using heavy metallic salts such as phosphorus compound and zinc salt, suppress the generation of carbon steel pitting, the pitting corrosion inhibitor for metal and the pitting inhibition method that effectively prolong the equipment life that heat exchanger etc. contacts with water are that purpose is made.
Summary of the invention
Present inventors have carried out particular study in order to address the above problem, found that, by in water system, adding the multipolymer and (C) reagent of azole compounds that contains (A) conjugated diolefine sulfonated bodies and multipolymer, (B) toxilic acid and alkene with unsaturated compound of carboxyl, can suppress the generation of pitting effectively, finish the present invention based on this discovery.
That is, the invention provides
(1), a kind of pitting corrosion inhibitor for metal, it is characterized in that containing: (A) the conjugated diolefine sulfonated bodies of representing with respect to 1 mole of general formula [1], the unsaturated compound with carboxyl of copolymerization 0.1-20 mole general formula [2] expression contain the sulfonic group multipolymer, (B) with respect to 1 mole of toxilic acid, copolymerization 0.8-1.3 mole carbonatoms be 4-10 alkene contain the hydrophobic group multipolymer, and (C) azole compounds
(in its formula, R
1～R
6For hydrogen atom, carbonatoms be the alkyl of 1-8, aryl that carbonatoms is 6-20 or-SO
3X, wherein X is hydrogen atom, alkali metal atom, alkaline-earth metal atom, ammonium ion or amino, R
1～R
6At least one of them is-SO
3X),
(in its formula, R
7～R
10At least one of them is-(CH
2)
mCOOM, remaining is that hydrogen or carbonatoms are the alkyl of 1-8, m is 0-8, M is hydrogen atom, basic metal, alkaline-earth metal atom, ammonium ion or amino);
(2), (1) described pitting corrosion inhibitor for metal, wherein contain the sulfonic group multipolymer with respect to 1 weight part (A), contain 0.05-8 weight part (B) and contain hydrophobic group multipolymer and 0.005-0.1 weight part (C) azole compounds; With
(3), a kind of method that suppresses the metal pitting, it is characterized in that: with (A) contain sulfonic group multipolymer, (B) contain the hydrophobic group multipolymer and (C) azole compounds close quantifier, in water system, add (1) or (2) described pitting corrosion inhibitor for metal of 1-100mg/L.
In addition, as the preferred mode of the present invention, can enumerate
(4), (1) or (2) described pitting corrosion inhibitor for metal, wherein azole compounds is a triazole species; With
(5), (4) described pitting corrosion inhibitor for metal, wherein triazole is benzotriazole or tolyl-triazole.
Description of drawings
Fig. 1 is a used flushing test plant system drawing among the embodiment.Among the figure, mark 1 expression water tank, 2 expression pumps, 3 expression carbon steel pipes, 4 expression carbon steel pipes, 5 expression copper pipes, 6 expression corrosometers.
Embodiment
Pitting corrosion inhibitor for metal of the present invention contains: (A) the conjugated diolefine sulfonated bodies of representing with respect to 1 mole of general formula [1], the unsaturated compound with carboxyl of copolymerization 0.1-20 mole general formula [2] expression contain the sulfonic group multipolymer, (B) with respect to 1 mole of toxilic acid, copolymerization 0.8-1.3 mole carbonatoms be 4-10 alkene contain the hydrophobic group multipolymer, and (C) azole compounds
In its formula of [1], R
1～R
6For hydrogen atom, carbonatoms be the alkyl of 1-8, aryl that carbonatoms is 6-20 or-SO
3X, wherein X is hydrogen atom, alkali metal atom, alkaline-earth metal atom, ammonium ion or amino, R
1～R
6At least one of them is-SO
3X,
In its formula of [2], R
7～R
10At least one of them is-(CH
2)
mCOOM, remaining is that hydrogen or carbonatoms are the alkyl of 1-8, and m is 0-8, and M is hydrogen atom, basic metal, alkaline-earth metal atom, ammonium ion or amino.
Conjugated diolefine sulfonated bodies as general formula [1] expression, can enumerate the sulfonic acid and an alkali metal salt thereof of conjugated diolefine, alkaline earth salt, ammonium salt or amine salt etc., as its concrete compound, can enumerate for example 2-methyl isophthalic acid, 3-divinyl-1-sulfonic acid, the 2-methyl isophthalic acid, 3-divinyl-3-sulfonic acid, the 2-methyl isophthalic acid, 3-divinyl-4-sulfonic acid, 1,3-pentadiene-1-sulfonic acid, 1,3-pentadiene-2-sulfonic acid, 1,3-pentadiene-3-sulfonic acid, 1,3-pentadiene-4-sulfonic acid, 2,3-dimethylbutadiene-1-sulfonic acid, the 2-methyl isophthalic acid, 3-pentadiene-4-sulfonic acid, the 3-methyl isophthalic acid, 3-pentadiene-1-sulfonic acid, the 2-methyl isophthalic acid, 3-divinyl-1, the 3-disulfonic acid, the 2-methyl isophthalic acid, 3-divinyl-1, the 4-disulfonic acid, the 2-methyl isophthalic acid, 3-divinyl-1-sodium sulfonate (isoprene sodium sulfonate), the 2-methyl isophthalic acid, 3-divinyl-1-potassium sulfonate, the 2-methyl isophthalic acid, 3-divinyl-1-ammonium sulphonate etc., wherein preferred 2-methyl isophthalic acid, 3-divinyl-1-sodium sulfonate (isoprene sodium sulfonate), the 2-methyl isophthalic acid, 3-divinyl-1-potassium sulfonate, the 2-methyl isophthalic acid, 3-divinyl-1-ammonium sulphonate.
Unsaturated compound as general formula [2] expression with carboxyl, for example, can enumerate vinylformic acid, methacrylic acid, Ba Dousuan, iso-crotonic acid, vinylacetic acid, angelicic acid, tiglic acid, toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, methylfumaric acid, equisetic acid etc.
In the present invention, (A) containing the sulfonic group multipolymer is the conjugated diolefine sulfonated bodies of representing with respect to 1 mole of general formula [1], the multipolymer of the unsaturated compound with carboxyl of copolymerization 0.1-20 mole general formula [2] expression, more preferably with respect to the compound of 1 mole of general formula [1] expression, the multipolymer of the compound of copolymer-1 .5-12 mole general formula [2] expression.With respect to the compound of 1 mole of general formula [1] expression,, when perhaps surpassing 20 moles, all there is the danger that can not fully show the effect that suppresses pitting when 0.1 mole of the quantity not sufficient of the compound of general formula [2] expression.(A) weight-average molecular weight that contains the sulfonic group multipolymer is preferably 3000-15000, more preferably 5000-12000.In addition, in the present invention, the molecular weight of polymkeric substance is by the gel permeation chromatography under the following condition, the weight-average molecular weight of trying to achieve through the conversion of polyoxyethylene glycol standard model.
Use post: ト one ソ one TSK-Gel G 3000PWXL and G4000PWXL
Elutriant: the 0.2mole/L-NaCl aqueous solution
Detector: RI
Separation condition: 40 ℃ of column temperatures, elutriant flow 0.6mL/min
Sample: 0.4%200 μ L
PEG standard model: the PEG reference material that GL サ イ エ Application ス society produces (molecular weight is 100-tens thousand of 10 kinds).
The preparation method that used among the present invention (A) contained the sulfonic group multipolymer has no particular limits, for example, can the unsaturated compound with carboxyl that the conjugated diolefine sulfonated bodies and the general formula [2] of general formula [1] expression are represented is water-soluble, adopt radical polymerization initiator to carry out aqueous solution polymerization.
In the present invention, contain sulfonic multipolymer, can adopt on the basis of the unsaturated compound that the conjugated diolefine sulfonated bodies of general general formula [1] expression and general formula [2] are represented further the multipolymer of monomer copolymerization with other with carboxyl as (A).
As the used carbonatoms of the present invention is the alkene of 4-10, for example, can enumerate 1-butylene, iso-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 4-methyl isophthalic acid-hexene, 5-methyl isophthalic acid-hexene, 1-octene, 5-methyl isophthalic acid-heptene, 1-nonene, 1-decene etc.
In the present invention, (B) containing the hydrophobic group multipolymer is with respect to 1 mole of toxilic acid, copolymerization 0.8-1.3 mole carbonatoms is the multipolymer of the alkene of 4-10, and more preferably with respect to 1 mole of toxilic acid, copolymerization 0.95-1.1 mole carbonatoms is the multipolymer of the alkene of 4-10.With respect to 1 mole of toxilic acid, when 0.8 mole of the quantity not sufficient of alkene, perhaps surpass 1.3 moles, all there is the danger that can not fully show the effect that suppresses pitting.(B) weight-average molecular weight that contains the hydrophobic group multipolymer is preferably 4000-50000, more preferably 5000-35000.
The preparation method who the present invention used (B) is contained the hydrophobic group multipolymer has no particular limits, for example, maleic anhydride and alkene can there be solvent or in the presence of organic solvent, adopt radical polymerization initiator to carry out polymerization, gained maleic anhydride/olefin copolymer is being hydrolyzed and is making.
In the present invention, contain the hydrophobic group multipolymer as (B), except toxilic acid and carbonatoms are the alkene of 4-10, can also be with other monomeric multipolymer of further copolymerization.
(C) azole compounds that the present invention is used is to have to contain heteroatomic pentacyclic aromatics more than 2, and is that at least one is the compound of nitrogen-atoms in the heteroatoms.As azole compounds, can enumerate pyrazoles, imidazoles, 1,2,3-triazole, 1,2,4-triazole, tetrazolium, azoles, different azoles, thiazole, isothiazole, diazole, thiadiazoles, indazole, benzoglyoxaline, benzotriazole, benzoxazol, benzisoxa azoles, benzothiazole, tolyl-triazole etc.Wherein can preferably use benzotriazole and tolyl-triazole.
Pitting corrosion inhibitor for metal of the present invention, (A) contains the sulfonic group multipolymer with respect to 1 weight part, preferably contains 0.05-8 weight part (B) and contains the hydrophobic group multipolymer, more preferably contains the 0.1-4 weight part, further preferably contains the 0.25-1.5 weight part.When containing the sulfonic group multipolymer with respect to 1 weight part (A), (B) contain quantity not sufficient 0.05 weight part of hydrophobic group multipolymer, when perhaps surpassing 8 weight parts, all there is the danger that can not fully show the effect that suppresses pitting.
Pitting corrosion inhibitor for metal of the present invention, (A) contains the sulfonic group multipolymer with respect to 1 weight part, preferably contains 0.005-0.1 weight part (C) azole compounds, more preferably contains the 0.007-0.07 weight part.If (A) contains the sulfonic group multipolymer with respect to 1 weight part, then there is the danger that can not fully show the effect that suppresses pitting in (C) quantity not sufficient 0.005 weight part of azole compounds.(A) contains the sulfonic group multipolymer with respect to 1 weight part, (C) amount of azole compounds is can show sufficient pitting below 0.1 weight part to suppress effect, usually contain the sulfonic group multipolymer with respect to 1 weight part (A), needn't contain (C) azole compounds that surpasses 0.1 weight part.
Formulation to pitting corrosion inhibitor for metal of the present invention has no particular limits, for example, can be to contain (A) to contain sulfonic group multipolymer, (B) and contain the hydrophobic group multipolymer and (C) one-pack type of azole compounds, also can be that (A) contains sulfonic group multipolymer, (B) and contain hydrophobic group multipolymer and (C) any 2 kinds of two-component-types with other a kind of combination in the azole compounds, perhaps, can also be that (A) contains sulfonic group multipolymer, (B) and contain hydrophobic group multipolymer and (C) three component types that add respectively of azole compounds.Wherein therefore one-pack type can preferably use owing to can simplify the reagent injection device and also can make the interpolation concentration ratio keep certain.When making one-pack type,, can add acids such as alkali hydroxide, mineral acid, organic acid in order to make the pitting corrosion inhibitor stabilization.In addition, in order to improve anticorrosion ability, can also be in pitting corrosion inhibitor of the present invention sanitass such as mixed phosphate, polyphosphate, phosphonic acids, zinc salt, aluminate, molybdate, perhaps, also these sanitass can be added in water systems.
In metal pitting inhibition method of the present invention, with (A) contain sulfonic group multipolymer, (B) contain the hydrophobic group multipolymer and (C) azole compounds close quantifier, in water system, add 1-100mg/L, more preferably 10-70mg/L, further preferred 15-50mg/L pitting corrosion inhibitor for metal of the present invention.Contain the hydrophobic group multipolymer and (C) the not enough 1mg/L of total addition of azole compounds if (A) contain sulfonic group multipolymer, (B), have the metal pitting to suppress the danger that effect can not fully be found.If (A) contain sulfonic group multipolymer, (B) contain the hydrophobic group multipolymer and (C) the total addition of azole compounds surpass 100mg/L, then form anticorrosion overlay film and become slowly, metal ion and polymer formation title complex exist to take place and the danger of obstacle such as painted by the mating reaction that contains the sulfonic group multipolymer.
In the present invention, (A) containing the sulfonic group multipolymer can occur owing to mating reaction hinders the situation that anticorrosion overlay film forms copper product with the mixture that (B) contains the hydrophobic group multipolymer.If raise owing to copper product corrosion makes copper ion concentration total in the water in the system, then can be on the Ferrious material surface galvanic deposit dissolved cupric ion and promote corrosion.In the present invention, by adding (C) azole compounds,, thereby can infer the pitting that can suppress metal in the water system effectively because it can promote the formation of the anticorrosion overlay film of copper.
According to pitting corrosion inhibitor for metal of the present invention and pitting inhibition method, can make the pitting degree of depth during certain reduce 30-65%.Because the advance rate of the pitting degree of depth is rule of thumb proportional with 1/3 power of time, so at t equipment life (moon), equipment metal thickness d (mm), during 1 month initial stage between the pitting degree of depth k (mm), t=d
3/ k
3Relational expression set up, can prolong 3-20 doubly according to life-span of present device.
Embodiment
Below, enumerate embodiment the present invention is described more specifically, but the present invention is not subjected to these embodiment to carry out any qualification.
In addition, in embodiment and comparative example, adopt following polymers (all being sodium salt).
(A) contain the sulfonic group multipolymer
Polymkeric substance D: isoprene sulfonic acid/acrylic copolymer, mol ratio 20: 80, weight-average molecular weight are 7500.
Polymkeric substance E: isoprene sulfonic acid/acrylic copolymer, mol ratio 10: 90, weight-average molecular weight 9000.
Polymkeric substance G: isoprene sulfonic acid/acrylic copolymer, mol ratio 10: 90, weight-average molecular weight 23000.
Polymkeric substance H: isoprene sulfonic acid/vinylformic acid/2-hydroxyethyl methacrylate multipolymer, mol ratio 20: 65: 15, weight-average molecular weight 6500.
(B) contain the hydrophobic group multipolymer
Polymer A: toxilic acid/isobutylene copolymers, mol ratio 50: 50, weight-average molecular weight 14000.
Polymer B: toxilic acid/1-hexene copolymer, mol ratio 45: 55, weight-average molecular weight 20000.
Polymkeric substance C: toxilic acid/1-pentene copolymer, mol ratio 53: 47, weight-average molecular weight 6500.
(D) other polymkeric substance
Polymkeric substance F: polymaleic acid, weight-average molecular weight 600.
Polymkeric substance I: toxilic acid/2-acrylamide-2-methyl propane sulfonic acid multipolymer, mol ratio 80: 20, weight-average molecular weight 2000.
In addition, adopt the flushing test device shown in Fig. 1, carry out pitting and suppress effect assessment.From water capacity is the water tank 1 of 52L, carries test water by pump 2, is after 0.5m/s passes through carbon steel pipe 3, carbon steel pipe 4 and copper pipe 5, after corrosometer 6 is circulated in the water tank with the flow velocity.634mL/h supplies with pH in water tank be 8.8, and M basicity is 300mgCaCO
3/ L, calcium hardness are 300mgCaCO
3/ L, silica concentration are 100mgSiO
2/ L test water, superfluous water comes out through water tank overflow.The residence time of test water is 82 hours.The temperature regulation to 30 of test water ℃ carries air to carry out aeration by the ventpipe of water tank bottom with 10L/min.After continuous water flowing during 30 days, measure the maximum pitting degree of depth (mm/30 day) of carbon steel pipe 3.And, adopt anti-polarization method to measure the corrosion speed (mdd=mgdm of carbon steel and copper by corrosometer
-2My god
-1), once a day, calculate 30 days mean value.
Embodiment 1
In test water, add (A) polymkeric substance D to 32mg/L, (B) polymer A to 8mg/L and (C) benzotriazole test to 1mg/L.The maximum pitting degree of depth of carbon steel is 0.21mm/30 day, and corrosion of Carbon Steel speed is 3.2mdd, and the corrosion speed of copper is 0.9mdd.
In test water, add (A) polymkeric substance D to 24mg/L, (B) polymer A to 16mg/L and (C) benzotriazole test to 1mg/L.
Embodiment 3
In test water, add (A) polymkeric substance D to 20mg/L, (B) polymer A to 20mg/L and (C) benzotriazole test to 0.5mg/L and tolyl-triazole to 0.5mg/L.
Embodiment 4～10
In test water, add (A) shown in the table 1 contain sulfonic group multipolymer, (B) contain the hydrophobic group multipolymer and (C) azole compounds test.
Comparative example 1
In test water, add (B) polymer A to 40mg/L and (C) benzotriazole test to 0.05mg/L.The maximum pitting degree of depth of carbon steel is 0.30mm/30 day, and corrosion of Carbon Steel speed is 3.6mdd, and the corrosion speed of copper is 1.6mdd.
Comparative example 2～8
Compound shown in the interpolation table 1 is tested in test water.
Embodiment 1～10 and comparative example 1～8 the results are shown in table 1.
Table 1
| Polymkeric substance (mg/L) | Azole (mg/L) | The maximum pitting degree of depth (mm/30 day) | Corrosion speed (mdd) | |||||||||||
| A | B | C | D | E | F | G | H | I | Benzotriazole | Tolyl-triazole | Carbon steel | Copper | ||
| Embodiment 1 | 8 | - | - | 32 | - | - | - | - | - | 1 | - | 0.21 | 3.2 | 0.9 |
| Embodiment 2 | 16 | - | - | 24 | - | - | - | - | - | 1 | - | 0.17 | 1.9 | 0.8 |
| Embodiment 3 | 20 | - | - | 20 | - | - | - | - | - | 0.5 | 0.5 | 0.20 | 1.7 | 0.9 |
| Embodiment 4 | 24 | - | - | 16 | - | - | - | - | - | 0.5 | 0.5 | 0.23 | 1.3 | 0.9 |
| Embodiment 5 | 32 | - | - | 8 | - | - | - | - | - | 0.5 | - | 0.26 | 3.5 | 0.8 |
| Embodiment 6 | - | 20 | - | 20 | - | - | - | - | - | 0.5 | - | 0.26 | 1.3 | 0.9 |
| Embodiment 7 | 20 | - | - | - | 20 | - | - | - | - | 0.5 | - | 0.25 | 3.6 | 0.8 |
| Embodiment 8 | 5 | - | - | 10 | - | - | - | - | - | 0.25 | 0.25 | 0.25 | 1.7 | 0.7 |
| Embodiment 9 | - | 4 | - | 36 | - | - | - | - | - | 0.25 | 0.25 | 0.24 | 3.8 | 0.9 |
| Embodiment 10 | - | - | 10 | - | 10 | - | - | - | - | 0.1 | - | 0.27 | 2.5 | 0.7 |
| Comparative example 1 | 40 | - | - | - | - | - | - | - | - | 0.05 | - | 0.30 | 3.6 | 1.6 |
| Comparative example 2 | - | - | - | 40 | - | - | - | - | - | - | - | 0.35 | 5.6 | 2.0 |
| Comparative example 3 | - | 20 | 20 | - | - | - | - | - | - | - | - | 0.37 | 4.4 | 1.7 |
| Comparative example 4 | 20 | - | - | - | - | 20 | - | - | - | - | 0.05 | 0.32 | 3.4 | 1.8 |
| Comparative example 5 | - | 16 | - | - | - | - | 24 | - | - | - | - | 0.34 | 4.8 | 2.1 |
| Comparative example 6 | - | 20 | - | - | - | - | - | 20 | - | - | - | 0.35 | 3.5 | 1.9 |
| Comparative example 7 | 8 | - | - | - | - | - | - | - | 32 | - | - | 0.48 | 6.2 | 2.2 |
| Comparative example 8 | - | 24 | - | - | - | - | - | - | - | - | - | 0.36 | 4.8 | 1.5 |
As can be seen from Table 1, in the embodiment 1～10 that in test water, adds (A) isoprene sulfonic acid and the multipolymer of acrylic acid multipolymer, (B) toxilic acid and alkene and (C) benzotriazole or benzotriazole and tolyl-triazole, the maximum pitting degree of depth of carbon steel is 0.17-0.27mm/30 day, finds that pitting suppresses effect.And corrosion of Carbon Steel speed is 1.3-3.8mdd, and the corrosion speed of copper is 0.7-0.9mdd, and the corrosion of carbon steel and copper all is inhibited.
By contrast, adding (B) toxilic acid/isobutylene copolymers and (C) comparative example 1 of benzotriazole, only add the comparative example 2 of (A) isoprene sulfonic acid/acrylic copolymer, only add the comparative example 3 of (B) toxilic acid/olefin copolymer, add (D) polymaleic acid, (B) toxilic acid/isobutylene copolymers and (C) comparative example 4 of tolyl-triazole, add (A) isoprene sulfonic acid/acrylic copolymer and (B) comparative example 5 of toxilic acid/1-hexene copolymer, add (A) isoprene sulfonic acid/vinylformic acid/2-hydroxyethyl methacrylate multipolymer and (B) comparative example 6 of toxilic acid/1-hexene copolymer, add (D) toxilic acid/2-acrylamide-2-methyl propane sulfonic acid multipolymer and (B) comparative example 7 of toxilic acid/isobutylene copolymers, only add in the comparative example 8 of (B) toxilic acid/1-hexene copolymer, the maximum pitting degree of depth of carbon steel is 0.30-0.48mm/30 day, does not show pitting substantially and suppresses effect.And corrosion of Carbon Steel speed is 3.4-6.2mdd, and the corrosion speed of copper is 1.5-2.2mdd, to the corrosion inhibition effect of copper a little less than.Think that copper is corroded in the system that does not add azole compounds, the galvanic deposit of dissolved cupric ion has been quickened corrosion of Carbon Steel on steel surface.
Industrial applicibility
Method according to pitting corrosion inhibitor for metal of the present invention and inhibition pitting, in the open loop cooling water system, can be in the situation of not using the heavy metallic salts such as phosphorus compound and zinc salt, suppress the generation of carbon steel pitting, effectively prolong the life-span of the equipment that heat exchanger etc. contacts with water.
Claims (3)
1. pitting corrosion inhibitor for metal, it is characterized in that containing: (A) the conjugated diolefine sulfonated bodies of representing with respect to 1 mole of general formula [1], the unsaturated compound with carboxyl of copolymerization 0.1-20 mole general formula [2] expression contain the sulfonic group multipolymer, (B) with respect to 1 mole of toxilic acid, copolymerization 0.8-1.3 mole carbonatoms be 4-10 alkene contain the hydrophobic group multipolymer, and (C) azole compounds
In its formula, R
1～R
6For hydrogen atom, carbonatoms be the alkyl of 1-8, aryl that carbonatoms is 6-20 or-SO
3X, wherein X is hydrogen atom, alkali metal atom, alkaline-earth metal atom, ammonium ion or amino, R
1～R
6At least one of them is-SO
3X,
In its formula, R
7～R
10At least one of them is-(CH
2)
mCOOM, remaining is that hydrogen or carbonatoms are the alkyl of 1-8, and m is 0-8, and M is hydrogen atom, basic metal, alkaline-earth metal atom, ammonium ion or amino.
2. the described pitting corrosion inhibitor for metal of claim 1 wherein contains the sulfonic group multipolymer with respect to 1 weight part (A), contains 0.05-8 weight part (B) and contains hydrophobic group multipolymer and 0.005-0.1 weight part (C) azole compounds.
3. method that suppresses the metal pitting, it is characterized in that: with (A) contain sulfonic group multipolymer, (B) contain the hydrophobic group multipolymer and (C) azole compounds close quantifier, in water system, add claim 1 or the 2 described pitting corrosion inhibitor for metal of 1-100mg/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP179537/2004 | 2004-06-17 | ||
| JP2004179537 | 2004-06-17 |
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|---|---|
| CN101027429A true CN101027429A (en) | 2007-08-29 |
| CN100585008C CN100585008C (en) | 2010-01-27 |
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|---|---|
| JP (1) | JP4641027B2 (en) |
| CN (1) | CN100585008C (en) |
| TW (1) | TWI359209B (en) |
| WO (1) | WO2005123981A1 (en) |
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|---|---|---|---|---|
| JP5789916B2 (en) * | 2010-03-31 | 2015-10-07 | 栗田工業株式会社 | Pitting corrosion inhibitor and pitting corrosion suppression method |
| US10087530B2 (en) | 2013-03-04 | 2018-10-02 | Schlumberger Technology Corporation | Corrosion inhibition |
| GB2529723B (en) | 2014-09-01 | 2017-04-05 | Schlumberger Holdings | A method of corrosion inhibition of metal |
| CN105039995B (en) * | 2015-07-09 | 2017-08-29 | 潍坊友容实业有限公司 | A kind of special anti-incrustation corrosion inhibitor of salt-soda soil salt discharge hidden pipe and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5392349A (en) * | 1977-01-25 | 1978-08-14 | Organo Kk | Metal anticorrosive |
| JPS6270586A (en) * | 1985-09-25 | 1987-04-01 | Kurita Water Ind Ltd | Method for inhibiting corrosion of metal |
| JP2625914B2 (en) * | 1988-06-29 | 1997-07-02 | 日本合成ゴム株式会社 | Water treatment agent |
| JP3375798B2 (en) * | 1995-08-21 | 2003-02-10 | 栗田工業株式会社 | Aqueous iron dispersant |
-
2005
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| TWI359209B (en) | 2012-03-01 |
| CN100585008C (en) | 2010-01-27 |
| JP4641027B2 (en) | 2011-03-02 |
| TW200600611A (en) | 2006-01-01 |
| WO2005123981A1 (en) | 2005-12-29 |
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