CN103787516A - Composite corrosion and scale inhibitor, and its application in circulating cooling water treatment - Google Patents
Composite corrosion and scale inhibitor, and its application in circulating cooling water treatment Download PDFInfo
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- CN103787516A CN103787516A CN201210430513.7A CN201210430513A CN103787516A CN 103787516 A CN103787516 A CN 103787516A CN 201210430513 A CN201210430513 A CN 201210430513A CN 103787516 A CN103787516 A CN 103787516A
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Abstract
The invention discloses a composite corrosion and scale inhibitor, and its application in circulating cooling water treatment. The composite corrosion and scale inhibitor contains oxalic acid and/or oxalate, a sulfonic group-containing copolymer, a scale inhibition additive and a zinc salt, the scale inhibition additive is at least one of organic phosphonic acid, phosphorus-free polycarboxylic acid and phosphorus-free polyacid anhydride, and a weight ratio of oxalic acid and/or oxalate to the sulfonic group-containing copolymer to the scale inhibition additive to the zinc salt by zinc ion is 10-30:2.5-5.5:2-12:1. The composite corrosion and scale inhibitor contains no phosphorus or has a low concentration of total phosphorus, is environmentally-friendly, and is especially suitable for circulating water with the sum of the total alkalinity and the total hardness of above 100mg. The above zinc salt formula containing oxalic acid and/or oxalate realize excellent scale and corrosion inhibition effects.
Description
Technical field
The present invention relates to a kind of composite slow-corrosion scale resistor and the application in circulating cooling water treatment thereof.
Background technology
Inhibition, scale inhibition and microbiological manipulation are the large problems of circulating water treatment to be solved three, and microbiological manipulation realizes by adding sterilant, and inhibition and scale inhibition are realized by adding composite scale-inhibiting corrosion inhibitor.
For low hard, low buck matter, use nature pH value operation process, and the solution of water treatment formula emphasis is inhibition problem, generally adopt the formula of phosphoric acid salt+organic phospho acid+co-polymer of sulfonate+zinc salt.
For hard, the high-alkali water quality of height, a kind for the treatment of process is adjust pH technique, and the etching problem of emphasis resolution system, by adding H
2sO
4the pH value of carrying out controlled circulation water, reduce the basicity in recirculated water, increase inhibiter in formula and the consumption of dispersion agent simultaneously, and then prevent scaling, it is general that what adopt is the formula of organic phospho acid+co-polymer of sulfonate+zinc salt; Another is adjust pH technique not, and what mainly solve is scale inhibition problem, generally adopts organic phospho acid+multipolymer+add depending on particular case formula of zinc salt.
For the water quality of medium hardness, moderate alkalinity, conventionally adopt pH value naturally to move formula, system pH value can reach 9.0, generally adopts that organic phosphonate+containing carboxylic acid group polymer's formula, emphasis solves the problem of scale inhibition, and requires to move under certain cycles of concentration.
Above-mentioned several formula, can solve different problems for different water quality, but all has a higher problem of total phosphorus concentration, strict along with national environmental standard, and phosphorus discharge is restricted day by day, and low-phosphorous or without phosphorus formula becomes a kind of trend.At present increasing people, in the exploitation of paying close attention to the environmentally friendly inhibiter such as molybdate, tungstate, does not still also report as the research of inhibiter this respect oxalic acid.
CN102011129A discloses a kind of corrosion inhibitor, is mainly used in corrosion inhibition in cold rolled sheet continuous pickling technique.Its each component is hexamethylenetetramine, vinyl-amine, thanomin, alkynol alcoxylates, oxalic acid, additive and water.Inhibiter in this invention is restrainer, is not suitable for the daily use of recirculated cooling water, and the object of adding oxalic acid in this invention is mainly to accelerate rust cleaning.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the circulating water treatment method of the corrosion-mitigation scale-inhibition component that a kind of use is not phosphorous or total phosphorus concentration is lower is provided.
To achieve these goals, the invention provides a kind of composite slow-corrosion scale resistor and the application in circulating cooling water treatment thereof, it is characterized in that, this composite slow-corrosion scale resistor contains oxalic acid and/or oxalate, contains sulfonic group multipolymer, scale inhibition additive and zinc salt, described scale inhibition additive is at least one in organic phospho acid, without phosphorus poly carboxylic acid and without phosphorus poly-acid anhydrides, described oxalic acid and/or oxalate, be 10-30:2.5-5.5:2-12:1 containing the weight ratio of sulfonic group multipolymer, scale inhibition additive and zinc salt, wherein the weight of zinc salt is by zine ion.
By technique scheme, composite slow-corrosion scale resistor of the present invention is not phosphorous or total phosphorus concentration is lower, more friendly to environment, is specially adapted to total alkalinity and the recirculated water of total hardness sum more than 100mg/L.The present inventor finds, oxalate can with water in calcium ion form calcium oxalate precipitation, form one deck precipitation membrane in metallic surface, there is good synergistic slow corrosion effect with zinc salt is composite, and composite slow-corrosion scale resistor of the present invention also has Zn in good scale-inhibiting properties and stable water
2+the performance of concentration.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of composite slow-corrosion scale resistor, it is characterized in that, this composite slow-corrosion scale resistor contains oxalic acid and/or oxalate, contains sulfonic group multipolymer, scale inhibition additive and zinc salt, described scale inhibition additive is at least one in organic phospho acid, without phosphorus poly carboxylic acid and without phosphorus poly-acid anhydrides, described oxalic acid and/or oxalate, be 10-30:2.5-5.5:2-12:1 containing the weight ratio of sulfonic group multipolymer, scale inhibition additive and zinc salt, be preferably 15-25:3.5-5:4-9:1, wherein the weight of zinc salt is by zine ion.
In the present invention, described oxalate can be various water miscible oxalate, and for example solubleness in water (under recirculated cooling water treatment temp) is greater than the oxalate of 1g/100g water.Under preferable case, described oxalate is selected from least one in sodium oxalate, potassium oxalate, sodium bioxalate and potassium binoxalate.
In the present invention, described can be the conventional multipolymer using in various this areas of a mainly dissemination containing sulfonic group multipolymer, and can be for containing sulfonic copolymer and/or containing sulfonic terpolymer.Under preferable case, the described sulfonic group multipolymer that contains is selected from toxilic acid and Styrene Sulfonic Acid Copolymer, maleic anhydride and Styrene Sulfonic Acid Copolymer, vinylformic acid and Styrene Sulfonic Acid Copolymer, acrylate and Styrene Sulfonic Acid Copolymer, toxilic acid and allyl sulphonic acid multipolymer, maleic anhydride and allyl sulphonic acid multipolymer, vinylformic acid and allyl sulphonic acid multipolymer, vinylformic acid and vinyl sulfonic acid multipolymer, vinylformic acid and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer, vinylformic acid and acrylamide and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer, vinylformic acid and acrylate and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer, vinylformic acid and toxilic acid and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer, at least one in vinylformic acid and 2-acrylamido-2-methylpropanephosphonic acid and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer.
More preferably, described acrylate is vinylformic acid C
1-8ester, for example vinylformic acid C
1-8alkyl ester and/or vinylformic acid C
1-8hydroxy alkyl ester.
Most preferably, described acrylate is at least one in methyl acrylate, ethyl propenoate and Propylene glycol monoacrylate.
In the present invention, described organic phospho acid refers to the compound that phosphate group is directly connected with carbon atom, can be the conventional various type of organophosphonic acides materials that are conducive to scale inhibition and inhibition that use in this area, but be preferably 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, 2-phosphonate group-1, 2, 4-butane tricarboxylate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycine two methylenephosphonic acids, L-glutamic acid two methylenephosphonic acids, thionamic acid two methylenephosphonic acids, at least one in taurine two methylenephosphonic acids and polyether-based polyamino methylene phosphonic acid.
In the present invention, described without phosphorus poly carboxylic acid and/or without phosphorus have-COOH of poly-acid anhydrides structure maybe can be hydrolyzed the polymkeric substance of generation-COOH, can be the conventional without phosphorus poly carboxylic acid for the preparation of corrosion inhibiting and descaling agent and/or the without phosphorus poly-acid anhydrides of selecting in this area, but be preferably at least one in poly aspartic acid, poly-epoxy succinic acid, polyacrylic acid and hydrolytic polymaleic anhydride.
In the present invention, described zinc salt can be the zinc salt of any solubility, as long as can produce Zn after being added in recirculated water
2+.Under preferable case, described zinc salt is zinc sulfate and/or zinc chloride.
The present invention also provides the application of above-mentioned composite slow-corrosion scale resistor in circulating cooling water treatment.
Can adopt conventional method to prepare composite slow-corrosion scale resistor of the present invention.And in the time that reality is used, after each component of composite slow-corrosion scale resistor of the present invention can being mixed according to above-mentioned weight ratio, add in recirculated cooling water, also can add respectively.Add respectively fashionablely, the reinforced order of each component is not particularly limited.Each component can also be mixed according to certain ratio with water, each component fully be dissolved, and then add in recirculated cooling water.
The working concentration of composite slow-corrosion scale resistor of the present invention in the time that reality is used is preferably 30-80mg/L recirculated cooling water, more preferably 40-65mg/L recirculated cooling water.
Composite slow-corrosion scale resistor of the present invention is specially adapted in the processing of medium hardness that calcium hardness and total alkalinity sum are 100-300mg/L, moderate alkalinity water quality (adopting nature pH value technique).Composite slow-corrosion scale resistor of the present invention is also specially adapted in processing that calcium hardness and total alkalinity sum are more than 300mg/L high rigidity, high alkalinity water quality (adopting acid adding adjust pH technique).
For microbial growth in controlled circulation water, method of the present invention can also comprise sterilant is added into the step in recirculated water, described sterilant can from said components simultaneously or add when different, and the kind of the sterilant using and amount can be all those skilled in the art's various conventional selection, therefore do not repeat them here.
Composite slow-corrosion scale resistor of the present invention has good corrosion inhibition and good resistance CaCO
3dirt performance, is applicable to the processing of recirculated cooling water.
Below will describe the present invention by embodiment, following examples, for the present invention is described, are not only limitation of the present invention.
In following examples, the water quality of testing former water is as shown in table 1, will test former water 1 and concentrate 5 times as test water 1, will test former water 2 and concentrate 3 times as test water 2, wherein Ca
2+, total alkalinity and total hardness be all with CaCO
3meter, Ca
2+represent calcium hardness, the measuring method of each parameter is as follows:
Ca
2+: reference standard GB/T 6910-2006;
Total alkalinity: reference standard GB/T 15451-2006;
Total hardness: reference standard GB/T 6909-2008;
Cl
-: reference standard GB/T 15453-2008;
SO
4 2-: reference standard GB/T 14642-2009;
PH value: reference standard GB/T 6920-1986;
Specific conductivity: reference standard GB/T 6908-2008;
Total molten solid: reference standard GB/T 14415-2007;
Zn
2+：GB/T10656-2008
Table 1
| Water quality | Ca 2+ | Total alkalinity | Total hardness | Cl - | SO 4 2- | pH | Specific conductivity | Total molten solid |
| Former water 1 | 102 | 152 | 179 | 15 | 37 | 7.8 | 213 | 318 |
| Former water 2 | 245 | 365 | 323 | 71 | 106 | 7.6 | 998 | 713 |
Scale inhibition performance is defined as the scale inhibition efficiency of corrosion inhibiting and descaling agent, and the calculation formula of scale inhibition performance is:
Scale inhibition performance=(C-C
0)/(nC
1-C
0) × 100%, wherein,
C: remain Ca in cooling rear water
2+concentration (mg/L)
C
0: the Ca of blank sample
2+concentration (mg/L)
C
1: the Ca in former water
2+concentration (mg/L)
N: cycles of concentration
Average corrosion rate is defined as the inhibition efficiency of corrosion inhibiting and descaling agent, and the calculation formula of average corrosion rate (F) is: F=(C × △ W)/(A × T × ρ), wherein,
C: computational constant, take mm/a(millimeter/year) during as unit, C=8.76 × 10
7
△ W: the corrosion weight loss (g) of test specimen
A: the area (cm of test specimen
2)
T: corrosion test time (h)
ρ: the density (kg/m of material for test
3)
Steady zinc rate is defined as corrosion inhibiting and descaling agent stablize the ability of zinc salt, and steady zinc rate is higher, illustrates that the stability of zinc salt in recirculated water is better, and surely the calculation formula of zinc rate is:
Steady zinc rate=(C-C
0)/(C
1-C
0) × 100%
C: actual measurement Zn
2+concentration (mg/L)
C
0: the Zn of blank sample
2+concentration (mg/L)
C
1: the Zn in former water
2+concentration (mg/L)
Embodiment 1
L-glutamic acid two methylenephosphonic acids that take 18.0g oxalic acid, 6.6g Zinc Sulphate Heptahydrate, 15.0g active matter content and be the maleic anhydride of 30 % by weight and Styrene Sulfonic Acid Copolymer (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/30 of maleic anhydride and styrene sulfonic acid), 16.0g active matter content and be 50 % by weight are dissolved into and in 42.7g water, are made into corrosion-mitigation scale-inhibition medicament.
In test water 1, add with the medicament preparing, the concentration that makes corrosion inhibiting and descaling agent is 35mg/L test water.
Embodiment 2
(Limiting Viscosity is 0.072dl/g 30 ℃ time to take 20.0g sodium oxalate, 3.15g Zinc Chloride Anhydrous, 20.0g active matter content and be the vinylformic acid of 30 % by weight and Styrene Sulfonic Acid Copolymer, weight ratio=70/30 of vinylformic acid and styrene sulfonic acid), 33.3g active matter content is that the polyacrylic acid (Limiting Viscosity is 0.072dl/g 30 ℃ time, and weight-average molecular weight is 3000) of 30 % by weight is dissolved into and in 23.55g water, is made into corrosion-mitigation scale-inhibition medicament.
With the medicament preparing to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, the concentration that makes corrosion inhibiting and descaling agent is 40mg/L test water.
Embodiment 3
Taking 25.0g potassium oxalate, 6.6g Zinc Sulphate Heptahydrate, 23.3g active matter content and be the ethyl propenoate of 30 % by weight and Styrene Sulfonic Acid Copolymer (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/30 of ethyl propenoate and styrene sulfonic acid), 18.0g active matter content and be 50 % by weight 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid is dissolved into and in 27.1g water, is made into corrosion-mitigation scale-inhibition medicament.
With the medicament preparing to test water 1 and 2(sulfuric acid adjust pH 7.8-8.2) in add, the concentration that makes corrosion inhibiting and descaling agent is 45mg/L test water.
Embodiment 4
Taking 30.0g sodium bioxalate, 4.2g Zinc Chloride Anhydrous, 26.7g active matter content and be the maleic anhydride of 30 % by weight and allyl sulphonic acid multipolymer (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/30 of maleic anhydride and allyl sulphonic acid), 12.0g active matter content and be 50 % by weight Amino Trimethylene Phosphonic Acid is dissolved into and in 27.1g water, is made into corrosion-mitigation scale-inhibition medicament.
With the medicament preparing to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, the concentration that makes corrosion inhibiting and descaling agent is 45mg/L test water.
Embodiment 5
Thionamic acid two methylenephosphonic acids that take 35.0g potassium binoxalate, 4.2g Zinc Chloride Anhydrous, 30.0g active matter content and be the vinylformic acid of 30 % by weight and allyl sulphonic acid multipolymer (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/30 of vinylformic acid and allyl sulphonic acid), 10.0g active matter content and be 50 % by weight are dissolved into and in 20.8g water, are made into corrosion-mitigation scale-inhibition medicament.
In test water 1, add with the medicament preparing, the concentration that makes corrosion inhibiting and descaling agent is 50mg/L test water.
Embodiment 6
The hydrolytic polymaleic anhydride (weight-average molecular weight is 1000) that takes 40.0g oxalic acid, 8.8g Zinc Sulphate Heptahydrate, 26.7g active matter content and be the vinylformic acid of 30 % by weight and vinyl sulfonic acid (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/30 of vinylformic acid and vinyl sulfonic acid) multipolymer, 24.0g active matter content and be 50 % by weight is dissolved into and in 100.5g water, is made into corrosion-mitigation scale-inhibition medicament.
With the medicament preparing to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, the concentration that makes corrosion inhibiting and descaling agent is 65mg/L test water.
Embodiment 7
Taking 33.6g sodium oxalate, 2.5g Zinc Chloride Anhydrous, 20.0g active matter content is vinylformic acid and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer (AA/AMPS of 30 % by weight, 30 ℃ time, Limiting Viscosity is 0.072dl/g, weight ratio=70/30 of AA and AMPS), 35.0g active matter content is that the poly aspartic acid (weight-average molecular weight is 3000) of 40 % by weight is dissolved into and in 108.9g water, is made into corrosion-mitigation scale-inhibition medicament.
In test water 1, add with the medicament preparing, the concentration that makes corrosion inhibiting and descaling agent is 50mg/L test water.
Embodiment 8
Taking 30.0g oxalic acid, 10.1g Zinc Sulphate Heptahydrate, 26.7g active matter content is vinylformic acid and acrylamide and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer (AA/AM/AMPS of 30 % by weight, 30 ℃ time, Limiting Viscosity is 0.072dl/g, weight ratio=70/15/15 of AA, AM and AMPS), 20.0g active matter content is that the poly-epoxy succinic acid (weight-average molecular weight is 1000) of 40 % by weight is dissolved into and in 113.2g water, is made into corrosion-mitigation scale-inhibition medicament.
With the medicament preparing respectively to test water 1 and 2(sulfuric acid adjust pH 7.8-8.2) in add, the concentration that makes corrosion inhibiting and descaling agent is 50mg/L test water.
Embodiment 9
Glycine two methylenephosphonic acids that take 45.0g potassium oxalate, 6.6g Zinc Sulphate Heptahydrate, 20.0g active matter content and be the vinylformic acid of 30 % by weight and methyl acrylate and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/15/15 of AA, methyl acrylate and AMPS), 8.0g active matter content and be 50 % by weight are dissolved into and in 20.4g water, are made into corrosion-mitigation scale-inhibition medicament.
In test water 1, add with the medicament preparing, the concentration that makes corrosion inhibiting and descaling agent is 55mg/L test water.
Embodiment 10
Take 25.0g sodium bioxalate, 8.8g Zinc Sulphate Heptahydrate, 23.3g active matter content and be the vinylformic acid of 30 % by weight and vinyl sulfonic acid multipolymer (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/30 of vinylformic acid and vinyl sulfonic acid), 16.0g active matter content and be 50 % by weight two phosphono and sulfonics are dissolved into and are made into corrosion-mitigation scale-inhibition medicament in 26.9g water.
With the medicament preparing to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, the concentration that makes corrosion inhibiting and descaling agent is 55mg/L test water.
Embodiment 11
The ethylene diamine tetra methylene phosphonic acid that takes 35.0g oxalic acid, 3.15g Zinc Chloride Anhydrous, 16.7g active matter content and be the vinylformic acid of 30 % by weight and toxilic acid and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/15/15 of AA, toxilic acid and AMPS), 12.0g active matter content and be 50 % by weight is dissolved into and in 33.15g water, is made into corrosion-mitigation scale-inhibition medicament.
In test water 1, add with the medicament preparing, the concentration that makes corrosion inhibiting and descaling agent is 50mg/L test water.
Embodiment 12
Taurine two methylenephosphonic acids that take 30.0g oxalic acid, 5.3g Zinc Sulphate Heptahydrate, 20.0g active matter content and be the vinylformic acid of 30 % by weight and Styrene Sulfonic Acid Copolymer (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/30 of vinylformic acid and styrene sulfonic acid), 12.0g active matter content and be 50 % by weight are dissolved into and in 32.7g water, are made into corrosion-mitigation scale-inhibition medicament.
In test water 1, add with the medicament preparing, the concentration that makes corrosion inhibiting and descaling agent is 45mg/L test water.
Embodiment 13
The hydroxyethylidene diphosphonic acid guanidine-acetic acid that takes 35.0g sodium oxalate, 4.8g Zinc Sulphate Heptahydrate, 26.7g active matter content and be the toxilic acid of 30 % by weight and Styrene Sulfonic Acid Copolymer (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/30 of toxilic acid and styrene sulfonic acid), 14.0g active matter content and be 50 % by weight is dissolved into and in 19.5g water, is made into corrosion-mitigation scale-inhibition medicament.
With the medicament preparing to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, the concentration that makes corrosion inhibiting and descaling agent is 60mg/L test water.
Embodiment 14
(Limiting Viscosity is 0.072dl/g 30 ℃ time to take 30.0g sodium oxalate, 6.6g Zinc Sulphate Heptahydrate, 23.3g active matter content and be the toxilic acid of 30 % by weight and Styrene Sulfonic Acid Copolymer, weight ratio=70/30 of toxilic acid and styrene sulfonic acid), 12.0g active matter content is that the diethylene triamine pentamethylene phosphonic of 50 % by weight, the polyacrylic acid that 20.0g active matter content is 30 % by weight (Limiting Viscosity is 0.072dl/g 30 ℃ time, and weight-average molecular weight is 3000) are dissolved into and in 108.1g water, are made into corrosion-mitigation scale-inhibition medicament.
With the medicament preparing to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, the concentration that makes corrosion inhibiting and descaling agent is 50mg/L test water.
Embodiment 15
Taking 20.0g sodium oxalate, 6.6g Zinc Sulphate Heptahydrate, 20.0g active matter content and be the methyl acrylate of 30 % by weight and Styrene Sulfonic Acid Copolymer (Limiting Viscosity is 0.072dl/g 30 ℃ time, weight ratio=70/30 of methyl acrylate and styrene sulfonic acid), 13.0g active matter content and be the polyether-based polyamino methylene phosphonic acid of 50 % by weight, poly-epoxy succinic acid (weight-average molecular weight is 1000) that 17.5g active matter content is 40 % by weight is dissolved into and in 22.9g water, is made into corrosion-mitigation scale-inhibition medicament.
In test water 1, add with the medicament preparing, the concentration that makes corrosion inhibiting and descaling agent is 75mg/L test water.
Embodiment 16
(Limiting Viscosity is 0.072dl/g 30 ℃ time to take 30.0g oxalic acid, 8.8g Zinc Sulphate Heptahydrate, 26.7g active matter content and be the vinylformic acid of 30 % by weight and acrylamide and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer, weight ratio=70/15/15 of AA/AM/AMPS), 8.0g active matter content is 2-phosphonate group-1 of 50 % by weight, 2,4-butane tricarboxylate, 20.0g poly aspartic acid (weight-average molecular weight is 3000) are dissolved into and in 106.5g water, are made into corrosion-mitigation scale-inhibition medicament.
With the medicament preparing respectively to test water 1 and 2(sulfuric acid adjust pH 7.8-8.2) in add, the concentration that makes corrosion inhibiting and descaling agent is 55mg/L test water.
Comparative example 1
Add corrosion-mitigation scale-inhibition medicament according to the mode of embodiment 16, different, in the time of preparation corrosion-mitigation scale-inhibition medicament, do not add oxalic acid.
Comparative example 2
Add corrosion-mitigation scale-inhibition medicament according to the mode of embodiment 16, different, the amount of the oxalic acid taking in the time of preparation corrosion-mitigation scale-inhibition medicament is 18g.
The evaluation of anticorrosion-antiscaling property
With the NaOH of 10 % by weight and/or the H of 5% weight
2sO
4the pH value of the test water that has added medicament in each embodiment is adjusted to 7.8-8.2, then in 80 ± 1 ℃ of waters bath with thermostatic control, adopts volumetric flask method to leave standstill 10h, in sampling analysis water, remain Ca after cooling
2+concentration, make blank sample simultaneously, and calculate scale inhibition performance.
The test piece of 20# qualitative carbon steel is fixed on lacing film instrument, puts into test water that each embodiment added medicament (with the NaOH of 10 % by weight and/or the H of 5% weight
2sO
4regulating pH value is 7.8-8.0) in, steady temperature is 45 ± 1 ℃, and keeping rotating speed is 75rpm rotation 72h, and before and after record test, the weight of test piece, calculates average corrosion rate (F).For test water 2, in whole experimentation, to keep pH value within the scope of 7.8-8.2.
Get distilled water preparation Ca
2+concentration is 250mg/L, and basicity is 250mg/L and Zn
2+for the test water of 5mg/L, add the medicament of the consumption adding by embodiment, in 80 ± 1 ℃ of waters bath with thermostatic control, leave standstill 10h, in sampling analysis water, remain Zn
2+concentration, make blank sample simultaneously, and calculate steady zinc rate.
Evaluation result is as shown in table 2:
Table 2
Data declaration in table 3, composite scale-inhibiting corrosion inhibitor good combination property of the present invention, it has good resistance CaCO
3dirt function, also has Zn in satisfactory stability water
2+ability and corrosion inhibition, be applicable to the processing of recirculated cooling water.
Especially, embodiment 16 is compared and can be found out with the result of comparative example 2, the composite slow-corrosion scale resistor of the amount of use oxalic acid and/or oxalate in limited range of the present invention can obtain more excellent scale inhibitor effect.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a composite slow-corrosion scale resistor, it is characterized in that, this composite slow-corrosion scale resistor contains oxalic acid and/or oxalate, contains sulfonic group multipolymer, scale inhibition additive and zinc salt, described scale inhibition additive is at least one in organic phospho acid, without phosphorus poly carboxylic acid and without phosphorus poly-acid anhydrides, described oxalic acid and/or oxalate, be 10-30:2.5-5.5:2-12:1 containing the weight ratio of sulfonic group multipolymer, scale inhibition additive and zinc salt, wherein the weight of zinc salt is by zine ion.
2. composite slow-corrosion scale resistor according to claim 1, wherein, described oxalate is selected from least one in sodium oxalate, potassium oxalate, sodium bioxalate and potassium binoxalate.
3. composite slow-corrosion scale resistor according to claim 1 and 2, wherein, the described sulfonic group multipolymer that contains is selected from toxilic acid and Styrene Sulfonic Acid Copolymer, maleic anhydride and Styrene Sulfonic Acid Copolymer, vinylformic acid and Styrene Sulfonic Acid Copolymer, acrylate and Styrene Sulfonic Acid Copolymer, toxilic acid and allyl sulphonic acid multipolymer, maleic anhydride and allyl sulphonic acid multipolymer, vinylformic acid and allyl sulphonic acid multipolymer, vinylformic acid and vinyl sulfonic acid multipolymer, vinylformic acid and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer, vinylformic acid and acrylamide and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer, vinylformic acid and acrylate and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer, vinylformic acid and toxilic acid and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer, at least one in vinylformic acid and 2-acrylamido-2-methylpropanephosphonic acid and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer.
4. composite slow-corrosion scale resistor according to claim 3, wherein, described acrylate is vinylformic acid C
1-8ester.
5. according to the composite slow-corrosion scale resistor described in claim 3 or 4, wherein, described acrylate is selected from least one in methyl acrylate, ethyl propenoate and Propylene glycol monoacrylate.
6. composite slow-corrosion scale resistor according to claim 1, wherein, described organic phospho acid is selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, 2-phosphonate group-1,2,4-butane tricarboxylate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, at least one in two phosphono and sulfonics, glycine two methylenephosphonic acids, L-glutamic acid two methylenephosphonic acids, thionamic acid two methylenephosphonic acids, taurine two methylenephosphonic acids and polyether-based polyamino methylene phosphonic acid.
7. composite slow-corrosion scale resistor according to claim 1, wherein, without phosphorus poly carboxylic acid and/or without phosphorus poly-acid anhydrides are selected from least one in poly aspartic acid, poly-epoxy succinic acid, polyacrylic acid and hydrolytic polymaleic anhydride.
8. composite slow-corrosion scale resistor according to claim 1, wherein, described zinc salt is zinc sulfate and/or zinc chloride.
9. the application of the composite slow-corrosion scale resistor described in any one in circulating cooling water treatment in claim 1-8.
10. application according to claim 9, wherein, the working concentration of described composite slow-corrosion scale resistor is 30-80mg/L recirculated cooling water.
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| CN104276678A (en) * | 2014-10-20 | 2015-01-14 | 山东华亚环保科技有限公司 | Corrosion and scale inhibitor for circulating cooling water |
| CN105366823A (en) * | 2014-08-29 | 2016-03-02 | 中国石油化工股份有限公司 | Non-phosphorus corrosion and scale inhibitor composition, non-phosphorus corrosion and scale inhibitor, application of non-phosphorus corrosion and scale inhibitor and application of copolymer to corrosion inhibition |
| CN105366822A (en) * | 2014-08-29 | 2016-03-02 | 中国石油化工股份有限公司 | Low-phosphorous corrosion and scale inhibitor composition, low-phosphorous corrosion and scale inhibitor and application thereof |
| CN106186377A (en) * | 2016-07-30 | 2016-12-07 | 山东胜伟园林科技有限公司 | The application in salt discharge hidden pipe of a kind of antisludging agent containing hydrolytic polymaleic anhydride |
| CN107324513A (en) * | 2017-07-24 | 2017-11-07 | 江苏中浩远达环境工程有限公司 | Corrosion inhibiting and descaling agent |
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| CN105366823A (en) * | 2014-08-29 | 2016-03-02 | 中国石油化工股份有限公司 | Non-phosphorus corrosion and scale inhibitor composition, non-phosphorus corrosion and scale inhibitor, application of non-phosphorus corrosion and scale inhibitor and application of copolymer to corrosion inhibition |
| CN105366822A (en) * | 2014-08-29 | 2016-03-02 | 中国石油化工股份有限公司 | Low-phosphorous corrosion and scale inhibitor composition, low-phosphorous corrosion and scale inhibitor and application thereof |
| CN105366822B (en) * | 2014-08-29 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of low-phosphorus corrosion and scale inhibitor composition and low-phosphorus corrosion and scale inhibitor and its application |
| CN105366823B (en) * | 2014-08-29 | 2018-05-18 | 中国石油化工股份有限公司 | Phosphate-free corrosion inhibition antisludging agent composition and phosphate-free corrosion inhibition antisludging agent and its application and application of the copolymer in inhibition |
| CN104276678A (en) * | 2014-10-20 | 2015-01-14 | 山东华亚环保科技有限公司 | Corrosion and scale inhibitor for circulating cooling water |
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| CN107324513A (en) * | 2017-07-24 | 2017-11-07 | 江苏中浩远达环境工程有限公司 | Corrosion inhibiting and descaling agent |
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| CN109835989A (en) * | 2019-04-02 | 2019-06-04 | 常州工程职业技术学院 | A kind of recirculated cooling water composite scale inhibitor and preparation method thereof |
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| CN114105325B (en) * | 2021-09-17 | 2023-09-05 | 自然资源部天津海水淡化与综合利用研究所 | Scale and corrosion inhibitor suitable for seawater desalination water to be used as make-up water of circulating cooling system and application thereof |
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