CN1019989C - Method for improving performance of corrosion inhibitors in industrial colling waters - Google Patents
Method for improving performance of corrosion inhibitors in industrial colling waters Download PDFInfo
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- CN1019989C CN1019989C CN87102313A CN87102313A CN1019989C CN 1019989 C CN1019989 C CN 1019989C CN 87102313 A CN87102313 A CN 87102313A CN 87102313 A CN87102313 A CN 87102313A CN 1019989 C CN1019989 C CN 1019989C
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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
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
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Abstract
A composition and the use of the composition for inhibiting corrosion in industrial cooling waters which contain hardness and have a pH of at least 8, which composition comprises a water-soluble organic phosphonate capable of inhibiting corrosion in an aqueous alkaline environment and a co- or terpolymer of acrylic acid and certain substituted acrylamides such as t-butyl acrylamide.
Description
The present invention is that a kind of pH of preventing is at least 8 industry cooling hard water corroding method, this method compositions for use comprise can inhibition in aqueous alkaline environment water-soluble organic phosphonate and the multipolymer or the terpolymer of the acrylamide (as the tert-butyl acrylamide) of vinylformic acid and some replacement.
" phosphonate " this term refers to and contains one or more-PO
3H
2The organic substance and the salt thereof of base.Comprise 1-hydroxyl-1 for the useful especially phosphonate of the present invention, 1-ethane di 2 ethylhexyl phosphonic acid (HEDP), 2-phosphinylidyne butane-1,2,4-tricarboxylic acid (PBTC), amino-trimethylene phosphonic (AMP) and their salt.The concentration of the polymkeric substance of enumerating, phosphonate and composition, consumption and (or) scope all refers to effective constituent.
Corrosion be burning become separately ion and (or) take place during insoluble salt.For example, the corrosion of metallic iron be exactly iron change into+2 or+soluble iron or the insoluble ferric oxide and the ironic hydroxide of 3 oxidation state.Corrosion also has dual nature, and it shows that some metallic surface is removed on the one hand, owing to generating insoluble salt deposit accumulation is arranged again on the other hand.Lose metal the structural integrity of device is reduced, can between water system and job stream, leak at last.
The corrosion of known iron in oxygenated water caused by following paired electrochemical process:
Prevent that metal from being to form protective barrier layer in the metallic surface by oxygenated water corrosive typical method.This blocking layer prevention oxygen contacts with the metallic surface and makes burning.The effect that a kind of chemical additive will play inhibiter will be convenient to make this process to take place, and make the blocking layer that generates oxygen flow not and can keep.By just accomplishing this point with the interaction of negative electrode or anodic half-cell reaction.
Inhibiter can make the Fe of gained with 1 interaction of anodic reaction
+ 2Generate not oxygen flow blocking layer, prevent further corrosion.Realize this point, should comprise some compositions like this in the corrosion inhibitor compound: can direct and Fe
+ 2React and make its sedimentary composition; Can promote Fe
+ 2Be oxidized to the Fe of typical indissoluble
+ 3The composition of compound; Or help to generate insoluble Fe
+ 3The composition of compound.
The other method that inhibiter works is to make oxygen in corrosion cathodic reduction.The half-cell that oxygen is reduced in the corrosion process is represented in reaction 2.The product of this reaction is hydroxyl (OH
-) ion.Owing to there is hydroxyl to generate, being subjected to oxygen is that the pH of metallic surface of corrosive nature of media is generally much higher than surrounding medium.Chemical compound lot solubleness under the high situation of pH value reduces.These compounds can be at the corrosion cathode deposition, if sedimentary form is an oxygen flow and be nonconducting not, these compounds just play the effect of effective corrosion inhibitors.
Inhibiter is to work by creating a kind of environment that can make corrosion process cause inhibitory reaction in the metallic surface.Composite corrosion inhibitor is acted on effectively, and the component of composition should not precipitate under the porous medium condition.Had a large amount of in the document about prevent the narration of this sedimentary inhibiter effectively by dynamic inhibition.Wherein an example is a United States Patent (USP) the 3rd, 880, and No. 765, this patent has been introduced the method that prevents precipitation of calcium carbonate with polymkeric substance.
United States Patent (USP) the 4th, 303 has been narrated for No. 568 inorganic phosphate and phosphonate has been used the corrosion that causes with the control oxygenated water with critical inhibiter (threshold inhibitor).United States Patent (USP) the 4th, 443 has further been studied this method No. 340, and it points out having the composition that only contains inorganic phosphate and polymer-type inhibiter under the situation of dissolved iron also can work well.
For reaching the purpose of inhibition, should adopt inhibiter to change the chemical property of medium again.United States Patent (USP) the 4th, 547, a kind of corrosion inhibition method of introducing for No. 540 are to rely under the condition of high pH and high basicity to operate.Because this method needn't adopt inorganic phosphate, the product of gained more meets the requirements from the viewpoint to the influence of environment.
The present invention describes the polymkeric substance contain a series of uniquenesses, phosphonate and for the fragrant pyrroles's who selects for use phosphonate inhibition compound.Adopt these polymkeric substance to improve the performance of inhibiter widely.
United States Patent (USP) the 4th, 566 has been discussed the problem of multipolymer of the present invention as scale inhibitor for No. 973.General these compounds are the multipolymers that contain tertiary butyl acrylamide unit and other comonomer.We find that these compounds are effective phosphonic acids calcium inhibiter, and can be used as the active principle of the corrosion inhibitor compound that contains phosphonate.
The present invention is that a kind of phosphonate inhibiter that improves is at least the method for the performance in 8 the hard water system at pH, and the 5～50ppm that promptly batches in this hard water system comprises the composition of following material:
I, a kind of can inhibition in aqueous alkaline environment water-soluble organic phosphonate and
II, a kind of water-soluble non-crosslinked unregulated polymer, the consisting of of this polymkeric substance contains the acrylamide that 50～90 parts of (weight) vinylformic acid and 10～50 parts (weight) replace in per 100 parts of (weight) polymerization single polymerization monomers, the weight-average molecular weight of described polymkeric substance is about 1,000～50,000, the chemical formulation below the definition of the polymerized unit of the acrylamide of vinylformic acid and replacement is available:
M is about 10～700 in the formula, and n is about 0.1～350, limited by molecular weight,
R and R
1Respectively be selected from hydrogen and methyl;
X is selected from hydrogen, sodium, potassium, calcium, ammonium and magnesium part;
R
2And R
3Respectively be selected from hydrogen and contain the substituting group of 1～8 carbon atom altogether and not substituting group, wherein R
2(or) R
3On the replacement base system be selected from alkyl, aryl and ketone group, its condition is R
2(or) R
3Not hydrogen;
The weight ratio of polymkeric substance and phosphonate is 0.2/1～2/1 in the composition.
In general, any water-soluble phosphine hydrochlorate that can play corrosion inhibition in alkaline system all can be used for the present invention.Can be referring to United States Patent (USP) the 4th, 303, No. 568, this patent has been enumerated many representational phosphonates, and its disclosed content is quoted from this.
The organic phospho acid compound is that those have C, that is:
Compound in above-mentioned scope generally belongs to one of three types of following general formula:
R is for containing the low alkyl group of 1～6 carbon atom approximately, as methyl, ethyl, butyl, propyl group, sec.-propyl, amyl group, isopentyl and hexyl in the formula; The low alkyl group that contains the replacement of 1～6 carbon atom is as hydroxyl and the amino alkyl that replaces; Monocyclic aryl is as phenyl, benzene etc.; (as hydroxyl, the amino replacement) monocyclic aromatics that replaces, the aromatic substance (as benzylphosphonic acid) that low alkyl group replaces; M is a water-soluble cationic, as sodium, potassium, amine, lithium etc. or hydrogen.
The object lesson of the compound that this chemical formula is included has:
Methyl-phosphorous acid
CH
3PO
3H
2
Ethylphosphonic acid
CH
3CH
2PO
3H
2
2-hydroxyethyl phosphonic acids
The 2-ciliatine
The sec.-propyl phosphonic acids
Phosphenylic acid
C
6H
5-PO
3H
2
Benzylphosphonic acid
C
6H
5CH
2PO
3H
2
R in the formula
1Be alkylidene group that contains 1～12 carbon atom approximately or the alkylidene group that contains the replacement of 1～12 carbon atom approximately, as the alkylidene group that hydroxyl, amino etc. replace, the definition of M is the same.
Included concrete typical compound and the chemical formula thereof of above-mentioned chemical formula is as follows:
Methylenediphosphonate (MDP)
H
2O
3P-CH
2-PO
3H
2
Ethylidene diphosphonic acid
H
2O
3P-CH（CH
3）PO
3H
2
Isopropylidenediphosphonic acid
（CH
3）
2C（PO
3H
2）
2
The 1-hydroxyl, ethylidene diphosphonic acid (HEDP)
The hexa-methylene di 2 ethylhexyl phosphonic acid
H
2O
3P-CH
2（CH
2）
4CH
2-PO
3H
2
The trimethylene di 2 ethylhexyl phosphonic acid
H
2O
3P-（CH
2）
3-PO
3H
2
The decamethylene di 2 ethylhexyl phosphonic acid
H
2O
3P-（CH
2）
10-PO
3H
2
The 1-hydroxyl, the propylidene di 2 ethylhexyl phosphonic acid
H
2O
3PC（OH）CH
2（CH
3）PO
3H
2
1,6-dihydroxyl, 1,6-dimethyl, hexa-methylene di 2 ethylhexyl phosphonic acid
H
2O
3PC（CH
3）（OH）（CH
2）
4C（CH
3）（OH）PO
3H
2
Dihydroxyl, the diethyl ethylidene diphosphonic acid
H
2O
3PC（OH）（C
2H
5）C（OH）（C
2H
5）PO
3H
2
R in the formula
2For containing the low-grade alkylidene of 1～4 carbon atom approximately, or the low-grade alkylidene that replaces of amino or hydroxyl; R
3Be [R
2-PO
3M
2] H, OH, amino, the amino of replacement contains the alkyl of 1～6 carbon atom, and the alkyl that contains the replacement of 1～6 carbon atom is (as OH, NH
2Replace), the monocyclic aryl of monocyclic aryl and replacement is (as OH, NH
2Replace); R
4Be R
3Or with the group of following chemical formulation:
R in the formula
5And R
6Respectively be hydrogen, contain the low alkyl group of 1～6 carbon atom approximately, the low alkyl group of replacement is (as OH, NH
2Replace), hydrogen, hydroxyl, amino, the amino of replacement, the monocyclic aryl of monocyclic aryl and replacement (as OH and amino the replacement); R
7Be R
5, R
6Or R
2-PO
3M
2Base (R
2Definition the same); N is the number among 1～about 15; Y is the number among about 1～about 14; The definition of M is the same.
The typical compound that above-mentioned chemical formula is included or its chemical formula are as follows:
Nitrilo-three (methylene phosphonic acid)
N（CH
2PO
3H
2）
3
Imino--two (methylene phosphonic acid)
NH（CH
2PO
3H
2）
2
Normal-butyl-amino-two (methyl-phosphorous acid)
C
4H
9N（CH
2PO
3H
2）
2
Decyl-amino-two (methyl-phosphorous acid)
C
10H
21N（CH
2PO
3H
2）
2
Trisodium-pentadecyl-amino-dimethyl phosphine hydrochlorate
C
15H
31N（CH
2PO
3HNa）（CH
2PO
3Na
2）
Normal-butyl-amino-two (ethylphosphonic acid)
C
4H
9N（CH
2CH
2PO
3H
2）
2
Four sodium-normal-butyl-amino-two (phosphonic salt)
C
4H
9N（CH
2PO
3Na
2）
2
Three ammoniums-tetradecyl-amino-two (phosphonic salt)
C
14H
29N（CH
2PO
3（NH
4）
2）CH
2PO
3HNH
4
Phenyl-amino-two (methyl-phosphorous acid)
C
6H
5N（CH
2PO
3H
2）
2
4-hydroxyl-phenyl-amino-two (methyl-phosphorous acid)
HOC
6H
4N（CH
2PO
3H
2）
2
Phenyl propyl amino-two (methyl-phosphorous acid)
C
6H
5（CH
2）
3N（CH
2PO
3H
2）
2
Four sodium phenylethyl amino-two (methyl-phosphorous acid)
C
6H
5（CH
2）
2N（CH
2PO
3Na
2）
2
Ethylene diamine four (methyl-phosphorous acid)
（H
2O
3PCH
2）
2N（CH
2）
2N（CH
2PO
3H
2）
2
Trimethylene diamines four (methyl-phosphorous acid)
（H
2O
3PCH
2）
2N（CH
2）
3N（CH
2PO
3H
2）
2
Heptamethylene diamines four (methyl-phosphorous acid)
（H
2O
3PCH
2）
2N（CH
2）
7N（CH
2PO
3H
2）
2
Decamethylene diamine four (methyl-phosphorous acid)
（H
2O
3PCH
2）
2N（CH
2）
10N（CH
2PO
3H
2）
2
Ten tetramethylene-diamines four (methyl-phosphorous acid)
（H
2O
3PCH
2）
2N（CH
2）
14N（CH
2PO
3H
2）
2
Ethylene diamine three (methyl-phosphorous acid)
（H
2O
3PCH
2）
2N（CH
2）
2NHCH
2PO
3H
2
Ethylene diamine two (methyl-phosphorous acid)
H
2O
3PCH
2）
2NH（CH
2）
2NHCH
2PO
3H
2
N-hexylamine two (methyl-phosphorous acid)
C
6H
13N（CH
2PO
3H
2）
2
Diethylenetriamine five (methyl-phosphorous acid)
（H
2O
3PCH
2）
2N（CH
2）
2N（CH
2PO
3H
2）-
（CH
2）
2N（CH
2PO
3H
2）
2
Thanomin two (methyl-phosphorous acid)
HO（CH
2）
2N（CH
2PO
3H
2）
2
N-hexyl-amino (isopropylidene phosphonic acids) methyl-phosphorous acid
C
6H
13N（C（CH
3）
2PO
3H
2）（CH
2PO
3H
2）
Trishydroxymethyl, methylamine two (methyl-phosphorous acid)
（HOCH
2）
3CN（CH
2PO
3H
2）
2
Triethylenetetramine (TETA) six (methyl-phosphorous acid)
（H
2O
3PCH
2）
2N（CH
2）
2N（CH
2PO
3H
2）（CH
2）
2N-
（CH
2PO
3H
2）（CH
2）
2N（CH
2PO
3H
2）
2
Monoethanolamine, diethylenetriamine three (methyl-phosphorous acid)
HOCH
2CH
2N（CH
2PO
3H
2）（CH
2）
2NH（CH
2）
2N-
（CH
2PO
3H
2）
2
Chlorethylidene amine two (methyl-phosphorous acid)
ClCH
2CH
2N（（CH
2PO（OH）
2）
2
Enumerate above-claimed cpd and only be in order to reach illustrational purpose, and be not all to list the compound that is applicable to the scope of the invention.
Best phosphonate is following two kinds of compounds
A.2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid and
B.1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid.
Though these phosphonates all can use with one or more polymkeric substance separately, the better effects if during mixture (as the mixture of A and B) of use phosphonate.The weight ratio of A and B is 0.5/1～4/1 when mixing use, is 0.5/1～2/1 preferably, is preferably about 0.67/1.
Except that phosphonate, also can adopt additive, as tolytriazole.Tolytriazole is effective for the corrosion that alleviates copper.
Water-soluble non-crosslinked random copolymers is at United States Patent (USP) the 4th, 566, detailed narration arranged in No. 973, and the patentee is to being specifically described as follows that it is done:
Be applicable to that the multipolymer here is to contain the vinylformic acid that the structural formula below useful represents and the unitary unregulated polymer of acrylamide polymerization of replacement:
M and n are about the number in 0.1～700 scope in the formula, and m is in 10～700 scopes, and n is limited by molecular weight in 0.1～350 scope; R and R
1Respectively be selected from hydrogen and methyl; X is a hydrogen, basic metal, alkaline-earth metal or ammonium, particularly hydrogen, sodium, potassium, calcium, ammonium and magnesium; R
2And R
3Respectively be selected from hydrogen, contain the alkyl of 1～8 carbon atom or the alkyl of replacement altogether, its condition is R
2And R
3Can not all be hydrogen, but one of them (R
2Or R
3) can be hydrogen.R
2And R
3Substituting group on the base comprises alkyl, aryl and ketone group, but in the concrete scheme of preferentially selecting for use R
2And R
3Respectively be selected from alkyl that contains 1～8 carbon atom and the alkyl (containing a ketone substituting group) that contains the replacement of 1～8 carbon atom.R
2And R
3Object lesson comprise the tertiary butyl, sec.-propyl, isobutyl-, methyl, 2-(2,4,4-tri-methyl-amyl) and 2-(2-methyl-4-oxygen amyl group).
The vinylformic acid that is applicable to this purpose generally is meant the single unsaturated monocarboxylic acid that contains 3～4 carbon atoms.The object lesson of this acid comprises vinylformic acid and methacrylic acid, preferably vinylformic acid.The acrylamide of said replacement here is meant that generally the sort of its nitrogen-atoms is contained the acrylamide that alkyl replaced of 1～8 carbon atom.
Other comonomer as long as it brings injurious effects can for desired performance, also can use with the acrylamide of vinylformic acid and replacement.The example of this class comonomer comprises acrylate and methacrylic ester, acrylamide and Methacrylamide, vinyl cyanide, vinyl ester etc.
Acrylic acid units in the comonomer can be acid form or neutral form, in and form in, the hydrogen of carboxyl is replaced by basic metal, alkaline-earth metal or ammonium cation, it depends on neutralization medium.Generally, comonomer can neutralize with highly basic such as sodium hydroxide, and at this moment the hydrogen on the carboxyl of acrylic acid units is replaced by sodium.When making neutralizing agent with amine, hydrogen is replaced by ammonium.That useful comonomer comprises is unneutralized, part neutral and neutral three classes fully.
It is the random copolymers of non-crosslinked basically that the monomer polymerization result generates, and its molecular weight can be regulated with try and error method.Preferably can obtain the multipolymer of high yield, promptly productive rate be comonomer weight about 50～99%.
The polymkeric substance of the above-mentioned type is modification so also, promptly introduces the trimerization monomer of the non-ionic or cationic polar group that contains groups such as being selected from amido, lower alkyl esters and maleic acid salt in its structure, and its weight can reach 30%.
Can be used for polymerization and acrylamide is arranged, methyl acrylate or ethyl ester, MALEIC ANHYDRIDE with the monomeric preferably example that generates ter-polymers.The example of other adoptable polar monomer has vinylacetate, vinyl cyanide, various vinyl ketones, vinyl ether etc.Following compounds can be used as these monomeric examples: vinyl pyrrolidone, methylvinylether, methacrylonitrile, vinyl carbinol, methyl methacrylate, μ-diethylaminoethyl-methacrylic ester, vinyl trimethylacetic acid ester, methyl isobutyrate, cyclohexyl methacrylate, vinyl laurate, stearic acid vinyl ester, N-vinyl imide, the N-vinyl lactam, glycol ether-dimethacrylate, diallyl maleate, allyl methacrylate(AMA), Phthalic acid, diallyl ester, diallyl adipate etc.
That the weight-average molecular weight of the polymkeric substance that generates can be is about 1,000～and about 50,000, preferably be about 2,000～30,000, make reference material with the known polystyrene of molecular weight and record with the aqueous gel permeation chromatography.
The acid number that records the multipolymer of generation with general KOH volumetry is 310～about 740, be equivalent to the monomeric unit that contains the COOH base of 40～about 95% weight fraction.Preferably polymkeric substance contains 50%(weight) above free carboxy and acid number be in 390～about 700 scope.
Described the 1st～No. 12 polymer composition of following Table A for preferentially selecting for use.
The Table A polymeric material
Polymer composition numbering M.W. forms (mole %)
1????（9300）????AA/t-BAm（88∶12）
2????（1200）????AA/t-BAm（88∶12）
3????（17700）????AA/t-BAm（88∶12）
4????（25900）????AA/t-BAm（88∶12）
5????（8900）????AA/EA/t-BAm（86∶8∶6）
6????（9400）????AA/Am/t-BAm（84∶11∶5）＊
7????（8200）????AA/MAA/t-BAm（68∶19∶13
8????（13300）＊????AA/MAA/t-BAm（68∶19∶13
9????（14300）＊????AA/MAA/t-BAm（68∶19∶13
10????（15700）＊????AA/MAA/t-BAm（68∶19∶13
11????（15600）????AA/MAA/t-BAm（68∶19∶13
12????（23000）????AA/MAA/t-BAm（68∶19∶13
Weight-average molecular weight is M.W. or Mw.
* weight-average molecular weight system is that elutriant is measured with the aqueous gel permeation chromatography with tetrahydrofuran (THF) (THF).
The 1st～No. 4 polymer composition is the not neutralized copolymer of vinylformic acid and tertiary butyl acrylamide (t-BAm).No. 5 polymer composition, No. 6 polymer composition and the 7th～No. 12 polymer composition all are terpolymers, contain ethyl propenoate (EA), acrylamide (Am) and methacrylic acid (MAA) additional monomer unit respectively.
A distinguishing feature of these polymkeric substance is to have the tert-butyl acrylamide unit.This sterically hindered hydrophobic acrylamido has fabulous resistance to hydrolysis, thereby this unit makes polymkeric substance have excellent characteristic.
The multipolymer of being made up of vinylformic acid and tert-butyl acrylamide contains 50～90%(weight) vinylformic acid and 10～50%(weight) the tert-butyl acrylamide.Be preferably and contain vinylformic acid 70～90%(weight), contain tert-butyl acrylamide 10～30%(weight).Preferably contain vinylformic acid 80～90%(weight), contain tert-butyl acrylamide 10～20%(weight).
The weight percentage compositing range of terpolymer is as follows:
A. vinylformic acid 40～90, are preferably 40～80, and preferably 60～80.
B. methacrylic acid 5～30, are preferably 10～30, and preferably 10～20.
C. the tert-butyl acrylamide 5～50, are preferably 10～30, and preferably 10～20.
The batching consumption of water system will make the weight of aforementioned component I and II occupy the 5～50ppm of imitating composition, is preferably 8～40ppm, preferably 15～30ppm.
Consumption capping when beginning to add these components helps the control corrosion and begins to form protective membrane.Consumption can reduce after the about week, reduces to till the maintenance consumption of the best always.The system that handles is industrial circulating water and acyclic water coolant, and this water makes its pH reach 8 at least owing to its natural character or through pH regulator.The pH of system should be in 8～9.5 scope, in 8.5～9.2 the scope of being everlasting.The characteristics of these systems are to contain the calcium ion of 10ppm at least, and can produce corrosive nature to ferrous metal and the non-ferrous metal that is in contact with it.
The following examples are representative formulas of this programme effect.
Embodiment 1
14 gram softening waters can be added in glass or the stainless steel vessel, under agitation add the aqueous solution of following material successively:
7 gram 1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid [60%(weight)],
12 gram 2-phosphonic acids acyl group butane-1,2, the 4-tricarboxylic acid [50%(weight)],
15.3 gram vinylformic acid/tert-butyl acrylamide copolymer [49%(weight)].
Mixture put in the ice bath cools off, then under vigorous stirring with about 22 gram 50%(weight) aqueous sodium hydroxide solution slowly adds makes the mixture alkalization in the solution.The temperature of solution remains on below 130 °F when adding alkali.With 4.7 gram 50%(weight) the tolytriazole sodium solution pH is transferred to 13.The softening water that adds capacity at last is to obtain 100 gram products.Remove cooling bath and stirred solution when its temperature reaches room temperature till.
Aforesaid method is done simple change just can make composition change at an easy rate.For example, if reduce the consumption of polymkeric substance and sodium hydroxide and increase last amount of water, will obtain to contain the composition of rudimentary polymkeric substance effective constituent.On the other hand, polymkeric substance and inhibiter also can add respectively.
In laboratory test, rigid positively charged ion and basicity M CaCO
3Or concentration circulation (cycles of concentratian) expression.Fe
+ nRow are made Fe, and the inhibiter of listing (monomeric or polymkeric substance) is meant effective constituent.In the sedimental analysis of heat exchanger, all components is all listed the chemical element of compound or the weight percentage of its sour form.
Heat " beaker " test with standard comes, the performance of evaluation phosphonate inhibiter (table B).Adopt the calcium and the inhibiter liquid storage of phosphonic acids calcium inhibition test.Prepare Bayer PBS-AM and Dequest 2010 liquid storages (1000ppm effective constituent) in addition.St.Louis, the Dequest-2010 that the Monsanto company of Missouri makes is a hydroxyl ethylidene 1,1-di 2 ethylhexyl phosphonic acid (HEDP) (referring to United States Patent (USP) the 3rd, 959, No. 168).PBS-AM is the 2-phosphinylidyne butane-1,2 of Bayer company, the tricarboxylic trade mark of 4-.400 ml distilled waters are added in the beaker of the strap clamp cover that keeps 60 ± 2 ℃ when beginning to test.The adding liquid storage makes in 500 milliliters of experimental liquids that obtain at last and contains 360ppmCa
+ 2, 10ppm inhibiter, 5.6ppm Dequest and 8ppmPBS-AM.With aqueous sodium hydroxide solution pH is transferred to 9.2 then.
The pH that wanted the manual shift sample in the 1st hour every 15 minutes once regulated once every 1 hour later on.4 hours test period is enough to make these precipitin reaction stabilizations.A part that preferably makes every kind of testing liquid is by rhodia/nitrocellulose millipore filter (HA type, 0.45 micron).Get the filtered sample of five equilibrium and not filtered sample carry out spectrophotometric analysis to measure the total content of phosphonate.In order to study the influence of granular size, other gets a sample and makes it by 0.10 micron millipore filter (VC type).The inhibition percentage is determined by following formula:
Inhibition percentage=([filtering-blank])/([unfiltered-blank]) * 100
The corrosion inhibition of table B phosphonic acids calcium
10ppm polymkeric substance effective constituent
5.6ppmDeqnest 2010 and 8ppm Bayer PBS-AM(effective constituent)
360ppm Ca（CaCO
3）
140 °F/pH9.2/4 hour
Polymer composition numbering M.W.H
2O corrosion inhibition rate %
Strainer size (micron)
0.45????0.10
1????（9300）????82%????26
5????（8900）????74????24
6????（9400）????8????13
11????（15600）????98????58
Versa????TL-4????（19000）????95????26
In phosphonic acids calcium corrosion inhibition test, studied the funtcional relationship of polymer performance and deposit seeds size, the results are shown among the table B.
Phosphonic acids calcium " inhibition " process promptly is particulate to be increased be reduced to a minimum.Make the dirt grain keep very little size and quality, this finally is a key factor of determining polymer performance.The strainer that adopts the mean size in hole to be respectively 0.10 micron and 0.45 micron can be observed the difference of polymer performance at an easy rate.The over-all properties of o.11 polymer composition (MW=15,600) is best, and it is unique polymkeric substance that still has good corrosion inhibition when adopting 0.10 micron filter.The low-molecular weight copolymer of Versa TL-4(sulfonated phenylethylene and maleic acid) and No. 1, No. 5 polymer composition with 0.45 micron filter the time, have good corrosion inhibition, but its performance reduces rapidly when the strainer aperture drops to 0.10 micron.Particularly the o.11 polymer composition on testing table test and intercooling tower test in all have best over-all properties.
The test of intercooling tower is a kind of dynamic testing of simulating a lot of characteristics of industrial circulating cooling water system.Total test method D.T.Reed and R.Nass " the small-scale short-term method of evaluation treatment of cooling water-whether be worth? " one literary composition (" the 36th international water conference year can write down ", Pittsburgh, Pennsylvania, Nov.4-6,1975).
Table C has listed total operational condition.
Table C
Intercooling tower test operation condition
Pipe numbering metal */thermal load (British thermal unit (Btu)/square feet-hour)
8 MS/15, the 000(top)
7????SS/15，000
6????MS/12，400
5????Adm/5，000
4????MS/5，000
3????SS/12，400
2????Adm/12，400
1 SS/12, the 400(bottom)
Make up water: synthetic #3**
The requirement cycle: 4
50L/125 of tank volume/temperature * * *
Retention time index 24 hours
Flow velocity 2gpm
pH????9.2
Product-high-content 200ppm
Product-maintenance dose 100ppm
Test period 14 days
* MS=mild steel Adm=admiraltymetal SS=306 stainless steel
It is 90ppm Ca that the synthetic #3 of * contains total ion concentration
+ 2, 50ppm Mg
+ 2, 90ppm Cl
-, 50ppm vitriol, 110ppm Na
+With 110～120ppm " M " basicity (CaCO
3)
* * return water temperature exceeds 10 °F.
As show shown in the D, the 1st, 3,5,6,7 and No. 11 polymer composition be according to embodiment 1 preparation and be used for VTL-4 in the direct substitution high pH standard recipe.Use according to the preparation of the method for embodiment 1 but contain (120/pH13) show that polymkeric substance did not have hydrolysis in 3 months of the long-term stability tests that some prescriptions of the 1st, 6 or No. 11 polymer composition carry out.PCT deposition/corrosion rate is listed among the following table D.
Table D
The heat exchanger tube test-results
Polymer deposition (milligram/day) corrosion (mpy)
(ppm effective constituent) MS Adm SS MS Adm SS
Blank-no polymkeric substance * 148 8-8.8 0.6-
No. 1 polymer composition 72 10 42 2.8 0.45 0.0
（7.5）
No. 3 polymer composition 30 2 37 1.3 0.0-0.1
（7.5）
No. 5 polymer composition 76 15 49 2.9 0.35 0.0
（7.5）
No. 6 polymer composition 101 26 72 3.1 0.20 0.1
（7.5）
No. 7 polymer composition 57 10 94 1.3 0.05 0.0
（7.5）
O.11 polymer composition 21 3 15 1.3 0.25 0.1
（7.5）
O.11 polymer composition 2.9 0.04 0.0
（5）＊＊
Versa????TL-4????54????7????27????2.8????0.2????0.0
（7.5）
* blank test is to carry out under return water temperature is 110 situation.The severe degree that reduces the blank test condition is necessary, and this is owing to meeting fouling under higher temperature is too much.
The mean value of twice test of *
Find that it is desirable adding the small amount of toluene triazole in some cases.
The chemical dictionary of Hackh (the 4th edition, the 91st page, referring to benzotriazole) tolytriazole is described, tolytriazole can be used as the inhibiter on the copper and copper alloy surface that contacts with water, and the amount that is used for this system during use is 1～20ppm(weight).
Claims (3)
1, a kind of phosphonate inhibiter that improves is at least the method for the performance in 8 the hard water system at pH, and the feature of this method is the composition that comprises following material of 5～50ppm of batching in this hard water system,
I, a kind of can inhibition in aqueous alkaline environment water-soluble organic phosphonate and
II, a kind of water-soluble non-crosslinked unregulated polymer, the consisting of of this polymkeric substance contains the acrylamide that 50～90 parts of (weight) vinylformic acid and 10～50 parts (weight) replace in per 100 parts of (weight) polymerization single polymerization monomers, the weight-average molecular weight of described polymkeric substance is about 1,000～50,000, the chemical formulation below the definition of the polymerized unit of the acrylamide of vinylformic acid and replacement is available:
M is about 10～700 in the formula, and n is about 0.1～350, limited by molecular weight,
R and R
1Respectively be selected from hydrogen and methyl;
X is selected from hydrogen, sodium, potassium, calcium, ammonium and magnesium part;
R
2And R
3Respectively be selected from hydrogen and contain the substituting group of 1～8 carbon atom altogether and not substituting group, wherein R
2(or) R
3On the replacement base system be selected from alkyl, aryl and ketone group, its condition is R
2(or) R
3Not hydrogen,
The weight ratio of polymkeric substance and phosphonate is 0.2/1～2/1 in the composition.
2, the described method of claim 1, wherein the consumption of phosphonate comprises 2-phosphinylidyne butane-1,2,4-tricarboxylic acid and 1-hydroxyl ethane-1, the ratio of 1-di 2 ethylhexyl phosphonic acid is 0.5/1～4/1.
3, the described method of claim 1, the described composition of the 8～30ppm that batches in the wherein said water system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84441586A | 1986-03-26 | 1986-03-26 | |
| US844415 | 1986-03-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87102313A CN87102313A (en) | 1988-02-24 |
| CN1019989C true CN1019989C (en) | 1993-03-03 |
Family
ID=25292665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87102313A Expired - Fee Related CN1019989C (en) | 1986-03-26 | 1987-03-25 | Method for improving performance of corrosion inhibitors in industrial colling waters |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0238728B1 (en) |
| JP (1) | JPS62270786A (en) |
| CN (1) | CN1019989C (en) |
| AT (1) | ATE56051T1 (en) |
| AU (1) | AU593082B2 (en) |
| BR (1) | BR8701331A (en) |
| CA (1) | CA1329474C (en) |
| DE (1) | DE3673809D1 (en) |
| DK (1) | DK169709B1 (en) |
| ES (1) | ES2016796B3 (en) |
| FI (1) | FI871242A (en) |
| GR (1) | GR3001105T3 (en) |
| MX (1) | MX173411B (en) |
| PT (1) | PT84551B (en) |
| TR (1) | TR24741A (en) |
| ZA (1) | ZA872236B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034738C (en) * | 1993-03-27 | 1997-04-30 | 云浮硫铁矿企业集团公司 | Protective agent composition |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4717542A (en) * | 1987-01-23 | 1988-01-05 | W. R. Grace & Co. | Inhibiting corrosion of iron base metals |
| WO1989007633A1 (en) * | 1988-02-18 | 1989-08-24 | John Kenneth Bethune | Absorbent polymer compositions |
| GB9505675D0 (en) * | 1995-03-21 | 1995-05-10 | Diversey Corp | Cleaning compositions |
| WO2006096477A1 (en) * | 2005-03-04 | 2006-09-14 | The Procter & Gamble Company | Automatic dishwashing composition with corrosion inhibitors |
| CN101368091B (en) * | 2007-08-16 | 2012-01-11 | 中国石油天然气集团公司 | Oil well cement retarder |
| CN101560022B (en) * | 2009-05-26 | 2011-05-11 | 西安协力动力科技有限公司 | Compound corrosion and scale inhibitor |
| US10351453B2 (en) | 2016-04-14 | 2019-07-16 | Nch Corporation | Composition and method for inhibiting corrosion |
| US11085118B2 (en) | 2016-04-14 | 2021-08-10 | Nch Corporation | Composition and method for inhibiting corrosion and scale |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1208827A (en) * | 1968-02-23 | 1970-10-14 | Grace W R & Co | Composition and process for inhibiting scaling and/or corrosion in cooling water systems and for stabilizing phosphate solutions |
| DE2333353C2 (en) * | 1973-06-30 | 1983-05-19 | Bayer Ag, 5090 Leverkusen | Process for preventing corrosion in water-bearing systems and anti-corrosion agents for carrying out the process |
| US4317744A (en) * | 1979-04-25 | 1982-03-02 | Drew Chemical Corporation | Corrosion inhibitor |
| GB2124607B (en) * | 1982-07-16 | 1986-02-05 | Katayama Chemical Works Co | Scale-inhibiting agent |
| US4566973A (en) * | 1984-08-06 | 1986-01-28 | The B. F. Goodrich Company | Scale inhibition in water systems |
| GB2168359B (en) * | 1984-11-08 | 1988-05-05 | Grace W R & Co | A method of inhibiting corrosion in aqueous systems |
| US4650591A (en) * | 1985-08-29 | 1987-03-17 | Calgon Corporation | Acrylic acid/2-acrylamido-2-methylpropylsulfonic acid/2-acrylamido-2-methylpropyl phosphonic acid polymers as scale and corrosion inhibitors |
| US4752443A (en) * | 1986-05-09 | 1988-06-21 | Nalco Chemical Company | Cooling water corrosion inhibition method |
-
1986
- 1986-12-30 EP EP86118127A patent/EP0238728B1/en not_active Expired - Lifetime
- 1986-12-30 DE DE8686118127T patent/DE3673809D1/en not_active Expired - Fee Related
- 1986-12-30 ES ES86118127T patent/ES2016796B3/en not_active Expired - Lifetime
- 1986-12-30 AT AT86118127T patent/ATE56051T1/en not_active IP Right Cessation
-
1987
- 1987-02-10 CA CA000529357A patent/CA1329474C/en not_active Expired - Fee Related
- 1987-03-20 FI FI871242A patent/FI871242A/en not_active Application Discontinuation
- 1987-03-20 JP JP62067764A patent/JPS62270786A/en active Granted
- 1987-03-24 PT PT84551A patent/PT84551B/en not_active IP Right Cessation
- 1987-03-24 TR TR87/0194A patent/TR24741A/en unknown
- 1987-03-24 BR BR8701331A patent/BR8701331A/en not_active IP Right Cessation
- 1987-03-24 MX MX005678A patent/MX173411B/en unknown
- 1987-03-25 CN CN87102313A patent/CN1019989C/en not_active Expired - Fee Related
- 1987-03-25 AU AU70632/87A patent/AU593082B2/en not_active Ceased
- 1987-03-25 DK DK150787A patent/DK169709B1/en not_active IP Right Cessation
- 1987-03-26 ZA ZA872236A patent/ZA872236B/en unknown
-
1990
- 1990-11-26 GR GR90400963T patent/GR3001105T3/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034738C (en) * | 1993-03-27 | 1997-04-30 | 云浮硫铁矿企业集团公司 | Protective agent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0146593B2 (en) | 1989-10-09 |
| DK150787A (en) | 1987-09-27 |
| BR8701331A (en) | 1988-01-05 |
| MX173411B (en) | 1994-03-02 |
| PT84551B (en) | 1989-11-10 |
| FI871242A0 (en) | 1987-03-20 |
| DK150787D0 (en) | 1987-03-25 |
| GR3001105T3 (en) | 1992-05-12 |
| CA1329474C (en) | 1994-05-17 |
| TR24741A (en) | 1992-03-06 |
| ES2016796B3 (en) | 1990-12-01 |
| DK169709B1 (en) | 1995-01-16 |
| ATE56051T1 (en) | 1990-09-15 |
| AU593082B2 (en) | 1990-02-01 |
| AU7063287A (en) | 1987-10-01 |
| EP0238728B1 (en) | 1990-08-29 |
| FI871242A (en) | 1987-09-27 |
| CN87102313A (en) | 1988-02-24 |
| ZA872236B (en) | 1987-11-25 |
| EP0238728A1 (en) | 1987-09-30 |
| PT84551A (en) | 1987-04-01 |
| DE3673809D1 (en) | 1990-10-04 |
| JPS62270786A (en) | 1987-11-25 |
| MX5678A (en) | 1993-09-01 |
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