CN103787516B - A kind of composite slow-corrosion scale resistor and the application in circulating water cooling treatment thereof - Google Patents
A kind of composite slow-corrosion scale resistor and the application in circulating water cooling treatment thereof Download PDFInfo
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- CN103787516B CN103787516B CN201210430513.7A CN201210430513A CN103787516B CN 103787516 B CN103787516 B CN 103787516B CN 201210430513 A CN201210430513 A CN 201210430513A CN 103787516 B CN103787516 B CN 103787516B
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Abstract
The invention discloses a kind of composite slow-corrosion scale resistor and the application in circulating water cooling treatment thereof, this composite slow-corrosion scale resistor contains oxalic acid and/or oxalate, containing 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 condensing model, 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.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 total hardness sum recirculated water at more than 100mg/L.And the zinc salt formula that the present invention contains oxalic acid and/or oxalate can obtain excellent scale inhibitor effect.
Description
Technical field
The present invention relates to a kind of composite slow-corrosion scale resistor and the application in circulating water cooling 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 is by adding sterilant to realize, and inhibition and scale inhibition then realize by adding composite scale-inhibiting corrosion inhibitor.
For low hard, low buck matter, use natural ph operation process, and the solution of water treatment formula emphasis is inhibition problem, generally adopts the formula of phosphoric acid salt+organic phospho acid+co-polymer of sulfonate+zinc salt.
Hard for height, high-alkali water quality, a kind for the treatment of process is the etching problem of adjust pH technique, emphasis resolution system, namely by adding H
2sO
4the pH value carrying out controlled circulation water, reduce the basicity in recirculated water, increase the consumption of inhibiter in formula and dispersion agent simultaneously, and then prevent scaling, general what adopt is the formula of organic phospho acid+co-polymer of sulfonate+zinc salt; Another is not adjust pH technique, and what mainly solve is scale inhibition problem, generally adopts the formula of organic phospho acid+multipolymer+add depending on particular case zinc salt.
For the water quality of medium hardness, moderate alkalinity, usually adopt pH value naturally to run formula, system pH value can reach 9.0, and generally adopt organic phosphonate+containing the formula of carboxylic acid group polymer, emphasis solves the problem of scale inhibition, and requires to run under certain cycles of concentration.
Above-mentioned several formula, can solve different problems for different water quality, but all there is the 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.Increasing people is in the exploitation paying close attention to the environmentally friendly inhibiter such as molybdate, tungstate at present, but does not also report the research of oxalic acid as inhibiter this respect.
CN102011129A discloses a kind of corrosion inhibitor, and what be mainly used in cold rolled sheet continuous pickling technique is corrosion inhibition.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 mainly accelerates rust cleaning.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of circulating water treatment method using not phosphorous or that total phosphorus concentration is lower corrosion-mitigation scale-inhibition component is provided.
To achieve these goals, the invention provides a kind of composite slow-corrosion scale resistor and the application in circulating water cooling treatment thereof, it is characterized in that, this composite slow-corrosion scale resistor contains oxalic acid and/or oxalate, containing 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 condensing model, 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 total hardness sum recirculated water at more than 100mg/L.The present inventor finds, oxalate can form calcium oxalate precipitation with the calcium ion in water, form one deck precipitation membrane in metallic surface, with zinc salt is composite, there is good synergistic slow corrosion effect, 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 in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of 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, containing 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 condensing model, 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 such as, solubleness (at circulating water cooling treatment temperature) in water 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, the described sulfonic group multipolymer that contains can be the multipolymer that the main various this areas routine playing dissemination uses, and can be 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, such as 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, the various type of organophosphonic acides materials being conducive to scale inhibition and inhibition that can use for this area routine, 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 acid, L-glutamic acid two methylenephosphonic acid, thionamic acid two methylenephosphonic acid, at least one in taurine two methylenephosphonic acid and polyether-based polyamino methylene phosphonic acid.
In the present invention, namely described without phosphorus poly carboxylic acid and/or without phosphorus condensing model have-COOH structure maybe can be hydrolyzed the polymkeric substance producing-COOH, can be the without phosphorus poly carboxylic acid for the preparation of corrosion inhibiting and descaling agent of this area routine selection and/or without phosphorus condensing model, 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, can produce Zn as long as be added into after in recirculated water
2+.Under preferable case, described zinc salt is zinc sulfate and/or zinc chloride.
Present invention also offers the application of above-mentioned composite slow-corrosion scale resistor in circulating water cooling treatment.
Conventional method can be adopted to prepare composite slow-corrosion scale resistor of the present invention.And when reality uses, by each component of composite slow-corrosion scale resistor of the present invention according to adding in recirculated cooling water after above-mentioned weight ratio mixing, also can add respectively.Add fashionable respectively, 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 adds in recirculated cooling water.
The working concentration of composite slow-corrosion scale resistor of the present invention when reality uses is preferably 30-80mg/L recirculated cooling water, is more preferably 40-65mg/L recirculated cooling water.
Composite slow-corrosion scale resistor of the present invention is specially adapted in the process of medium hardness that calcium hardness and total alkalinity sum are 100-300mg/L, moderate alkalinity water quality (adopting natural ph technique).Composite slow-corrosion scale resistor of the present invention is also specially adapted in the process of high rigidity that calcium hardness and total alkalinity sum are more than 300mg/L, high alkalinity water quality (adopting acid adding adjust pH technique).
In order to microbial growth in controlled circulation water, method of the present invention can also comprise the step be added into by sterilant in recirculated water, described sterilant can add from said components simultaneously or asynchronously, and the various routines that the kind of the sterilant used and amount can be all those skilled in the art are selected, therefore do not repeat them here.
Composite slow-corrosion scale resistor of the present invention has excellent corrosion inhibition and excellent resistance CaCO
3dirt performance, is applicable to the process of recirculated cooling water.
Below will be described the present invention by embodiment, following examples, only for illustration of the present invention, are not limitation of the present invention.
In following examples, the water quality 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/T6910-2006;
Total alkalinity: reference standard GB/T15451-2006;
Total hardness: reference standard GB/T6909-2008;
Cl
-: reference standard GB/T15453-2008;
SO
4 2-: reference standard GB/T14642-2009;
PH value: reference standard GB/T6920-1986;
Specific conductivity: reference standard GB/T6908-2008;
Total molten solid: reference standard GB/T14415-2007;
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 water after cooling
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, with mm/a(millimeter/year) for unit time, 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 the ability that corrosion inhibiting and descaling agent stablizes zinc salt, and steady zinc rate is higher, and illustrate that the stability of zinc salt in recirculated water is better, the calculation formula of steady 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
Take 18.0g oxalic acid, 6.6g Zinc Sulphate Heptahydrate, 15.0g active matter content be 30 % by weight maleic anhydride and Styrene Sulfonic Acid Copolymer (when 30 DEG C, Limiting Viscosity is weight ratio=70/30 of 0.072dl/g, maleic anhydride and styrene sulfonic acid), 16.0g active matter content be 50 % by weight L-glutamic acid two methylenephosphonic acid be dissolved in 42.7g water and be made into corrosion-mitigation scale-inhibition medicament.
Add in test water 1 with the medicament prepared, make the concentration of corrosion inhibiting and descaling agent be 35mg/L test water.
Embodiment 2
Take 20.0g sodium oxalate, 3.15g Zinc Chloride Anhydrous, 20.0g active matter content be 30 % by weight vinylformic acid and Styrene Sulfonic Acid Copolymer (when 30 DEG C, Limiting Viscosity is 0.072dl/g, weight ratio=70/30 of vinylformic acid and styrene sulfonic acid), 33.3g active matter content be 30 % by weight polyacrylic acid (when 30 DEG C, Limiting Viscosity is 0.072dl/g, and weight-average molecular weight is 3000) be dissolved in 23.55g water and be made into corrosion-mitigation scale-inhibition medicament.
With the medicament prepared to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, make the concentration of corrosion inhibiting and descaling agent be 40mg/L test water.
Embodiment 3
Take 25.0g potassium oxalate, 6.6g Zinc Sulphate Heptahydrate, 23.3g active matter content be 30 % by weight ethyl propenoate and Styrene Sulfonic Acid Copolymer (when 30 DEG C, Limiting Viscosity is weight ratio=70/30 of 0.072dl/g, ethyl propenoate and styrene sulfonic acid), 18.0g active matter content be that 50 % by weight 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid are dissolved in 27.1g water and are made into corrosion-mitigation scale-inhibition medicament.
With the medicament prepared to test water 1 and 2(sulfuric acid adjust pH 7.8-8.2) in add, make the concentration of corrosion inhibiting and descaling agent be 45mg/L test water.
Embodiment 4
Take 30.0g sodium bioxalate, 4.2g Zinc Chloride Anhydrous, 26.7g active matter content be 30 % by weight maleic anhydride and allyl sulphonic acid multipolymer (when 30 DEG C, Limiting Viscosity is weight ratio=70/30 of 0.072dl/g, maleic anhydride and allyl sulphonic acid), 12.0g active matter content be that 50 % by weight Amino Trimethylene Phosphonic Acid are dissolved in 27.1g water and are made into corrosion-mitigation scale-inhibition medicament.
With the medicament prepared to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, make the concentration of corrosion inhibiting and descaling agent be 45mg/L test water.
Embodiment 5
Take 35.0g potassium binoxalate, 4.2g Zinc Chloride Anhydrous, 30.0g active matter content be 30 % by weight vinylformic acid and allyl sulphonic acid multipolymer (when 30 DEG C, Limiting Viscosity is weight ratio=70/30 of 0.072dl/g, vinylformic acid and allyl sulphonic acid), 10.0g active matter content be 50 % by weight thionamic acid two methylenephosphonic acid be dissolved in 20.8g water and be made into corrosion-mitigation scale-inhibition medicament.
Add in test water 1 with the medicament prepared, make the concentration of corrosion inhibiting and descaling agent be 50mg/L test water.
Embodiment 6
Take 40.0g oxalic acid, 8.8g Zinc Sulphate Heptahydrate, 26.7g active matter content be 30 % by weight vinylformic acid and vinyl sulfonic acid (when 30 DEG C, Limiting Viscosity is weight ratio=70/30 of 0.072dl/g, vinylformic acid and vinyl sulfonic acid) multipolymer, 24.0g active matter content be 50 % by weight hydrolytic polymaleic anhydride (weight-average molecular weight is 1000) be dissolved in 100.5g water and be made into corrosion-mitigation scale-inhibition medicament.
With the medicament prepared to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, make the concentration of corrosion inhibiting and descaling agent be 65mg/L test water.
Embodiment 7
Take 33.6g sodium oxalate, 2.5g Zinc Chloride Anhydrous, 20.0g active matter content be 30 % by weight vinylformic acid and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer (AA/AMPS, when 30 DEG C, Limiting Viscosity is weight ratio=70/30 of 0.072dl/g, AA and AMPS), 35.0g active matter content be 40 % by weight poly aspartic acid (weight-average molecular weight is 3000) be dissolved in 108.9g water and be made into corrosion-mitigation scale-inhibition medicament.
Add in test water 1 with the medicament prepared, make the concentration of corrosion inhibiting and descaling agent be 50mg/L test water.
Embodiment 8
Take 30.0g oxalic acid, 10.1g Zinc Sulphate Heptahydrate, 26.7g active matter content be 30 % by weight vinylformic acid and acrylamide and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer (AA/AM/AMPS, when 30 DEG C, Limiting Viscosity is weight ratio=70/15/15 of 0.072dl/g, AA, AM and AMPS), 20.0g active matter content be 40 % by weight poly-epoxy succinic acid (weight-average molecular weight is 1000) be dissolved in 113.2g water and be made into corrosion-mitigation scale-inhibition medicament.
With the medicament prepared respectively to test water 1 and 2(sulfuric acid adjust pH 7.8-8.2) in add, make the concentration of corrosion inhibiting and descaling agent be 50mg/L test water.
Embodiment 9
Take 45.0g potassium oxalate, 6.6g Zinc Sulphate Heptahydrate, 20.0g active matter content be 30 % by weight vinylformic acid and methyl acrylate and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer (when 30 DEG C Limiting Viscosity be 0.072dl/g, AA, weight ratio=70/15/15 of methyl acrylate and AMPS), 8.0g active matter content be 50 % by weight glycine two methylenephosphonic acid be dissolved in 20.4g water and be made into corrosion-mitigation scale-inhibition medicament.
Add in test water 1 with the medicament prepared, make the concentration of corrosion inhibiting and descaling agent be 55mg/L test water.
Embodiment 10
Take 25.0g sodium bioxalate, 8.8g Zinc Sulphate Heptahydrate, 23.3g active matter content be 30 % by weight vinylformic acid and vinyl sulfonic acid multipolymer (when 30 DEG C, Limiting Viscosity is weight ratio=70/30 of 0.072dl/g, vinylformic acid and vinyl sulfonic acid), 16.0g active matter content be 50 % by weight two phosphono and sulfonics are dissolved in 26.9g water are made into corrosion-mitigation scale-inhibition medicament.
With the medicament prepared to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, make the concentration of corrosion inhibiting and descaling agent be 55mg/L test water.
Embodiment 11
Take 35.0g oxalic acid, 3.15g Zinc Chloride Anhydrous, 16.7g active matter content be 30 % by weight vinylformic acid and toxilic acid and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer (when 30 DEG C Limiting Viscosity be 0.072dl/g, AA, weight ratio=70/15/15 of toxilic acid and AMPS), 12.0g active matter content be 50 % by weight ethylene diamine tetra methylene phosphonic acid be dissolved in 33.15g water and be made into corrosion-mitigation scale-inhibition medicament.
Add in test water 1 with the medicament prepared, make the concentration of corrosion inhibiting and descaling agent be 50mg/L test water.
Embodiment 12
Take 30.0g oxalic acid, 5.3g Zinc Sulphate Heptahydrate, 20.0g active matter content be 30 % by weight vinylformic acid and Styrene Sulfonic Acid Copolymer (when 30 DEG C, Limiting Viscosity is weight ratio=70/30 of 0.072dl/g, vinylformic acid and styrene sulfonic acid), 12.0g active matter content be 50 % by weight taurine two methylenephosphonic acid be dissolved in 32.7g water and be made into corrosion-mitigation scale-inhibition medicament.
Add in test water 1 with the medicament prepared, make the concentration of corrosion inhibiting and descaling agent be 45mg/L test water.
Embodiment 13
Take 35.0g sodium oxalate, 4.8g Zinc Sulphate Heptahydrate, 26.7g active matter content be 30 % by weight toxilic acid and Styrene Sulfonic Acid Copolymer (when 30 DEG C, Limiting Viscosity is weight ratio=70/30 of 0.072dl/g, toxilic acid and styrene sulfonic acid), 14.0g active matter content be 50 % by weight hydroxyethylidene diphosphonic acid guanidine-acetic acid be dissolved in 19.5g water and be made into corrosion-mitigation scale-inhibition medicament.
With the medicament prepared to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, make the concentration of corrosion inhibiting and descaling agent be 60mg/L test water.
Embodiment 14
Take 30.0g sodium oxalate, 6.6g Zinc Sulphate Heptahydrate, 23.3g active matter content be 30 % by weight toxilic acid and Styrene Sulfonic Acid Copolymer (when 30 DEG C, Limiting Viscosity is 0.072dl/g, weight ratio=70/30 of toxilic acid and styrene sulfonic acid), 12.0g active matter content be 50 % by weight diethylene triamine pentamethylene phosphonic, 20.0g active matter content be 30 % by weight polyacrylic acid (when 30 DEG C, Limiting Viscosity is 0.072dl/g, and weight-average molecular weight is 3000) be dissolved in 108.1g water and be made into corrosion-mitigation scale-inhibition medicament.
With the medicament prepared to test water 2(sulfuric acid adjust pH 7.8-8.2) in add, make the concentration of corrosion inhibiting and descaling agent be 50mg/L test water.
Embodiment 15
Take 20.0g sodium oxalate, 6.6g Zinc Sulphate Heptahydrate, 20.0g active matter content be 30 % by weight methyl acrylate and Styrene Sulfonic Acid Copolymer (when 30 DEG C, Limiting Viscosity is weight ratio=70/30 of 0.072dl/g, methyl acrylate and styrene sulfonic acid), 13.0g active matter content be 50 % by weight polyether-based polyamino methylene phosphonic acid, 17.5g active matter content be 40 % by weight poly-epoxy succinic acid (weight-average molecular weight is 1000) be dissolved in 22.9g water and be made into corrosion-mitigation scale-inhibition medicament.
Add in test water 1 with the medicament prepared, make the concentration of corrosion inhibiting and descaling agent be 75mg/L test water.
Embodiment 16
Take 30.0g oxalic acid, 8.8g Zinc Sulphate Heptahydrate, 26.7g active matter content be 30 % by weight vinylformic acid and acrylamide and 2-methyl-2'-acrylamido propane sulfonic acid multipolymer (when 30 DEG C, Limiting Viscosity is 0.072dl/g, weight ratio=70/15/15 of AA/AM/AMPS), 8.0g active matter content be 50 % by weight 2-phosphonate group-1,2,4-butane tricarboxylate, 20.0g poly aspartic acid (weight-average molecular weight is 3000) are dissolved in 106.5g water and are made into corrosion-mitigation scale-inhibition medicament.
With the medicament prepared respectively to test water 1 and 2(sulfuric acid adjust pH 7.8-8.2) in add, make the concentration of corrosion inhibiting and descaling agent be 55mg/L test water.
Comparative example 1
Corrosion-mitigation scale-inhibition medicament is added according to the mode of embodiment 16, unlike, do not add oxalic acid when preparing corrosion-mitigation scale-inhibition medicament.
Comparative example 2
Corrosion-mitigation scale-inhibition medicament is added according to the mode of embodiment 16, unlike, the amount of the oxalic acid taken when preparing corrosion-mitigation scale-inhibition medicament is 18g.
The evaluation of anticorrosion-antiscaling property
The H of the NaOH with 10 % by weight and/or 5% weight
2sO
4the pH value of the test water having added medicament in each embodiment is adjusted to 7.8-8.2, in 80 ± 1 DEG C of waters bath with thermostatic control, then adopts volumetric flask method to leave standstill 10h, remain Ca in sampling analysis water 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 the test water (H of the NaOH with 10 % by weight and/or 5% weight that each embodiment has added medicament
2sO
4adjust ph is 7.8-8.0) in, steady temperature is 45 ± 1 DEG C, and keep rotating speed to be that 75rpm rotates 72h, the weight of test piece before and after record test, calculates average corrosion rate (F).For test water 2, to keep pH value in whole experimentation 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 added by embodiment, in 80 ± 1 DEG C 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 excellent resistance CaCO
3dirt function, also has Zn in satisfactory stability water
2+ability and corrosion inhibition, be applicable to the process of recirculated cooling water.
Especially, the result of embodiment 16 with comparative example 2 is compared and can find out, use the composite slow-corrosion scale resistor of amount in limited range of the present invention of oxalic acid and/or oxalate 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 characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different 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 is by oxalic acid and/or oxalate, form containing 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 condensing model, 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. composite slow-corrosion scale resistor according to claim 3, 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 acid, L-glutamic acid two methylenephosphonic acid, thionamic acid two methylenephosphonic acid, taurine two methylenephosphonic acid 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 condensing model 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 in claim 1-8 described in any one in circulating water cooling treatment.
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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| 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 |
| CN104276678B (en) * | 2014-10-20 | 2016-08-24 | 佛山市南海区巨人化学品制造有限公司 | A kind of corrosion inhibiting and descaling agent for recirculated cooling water |
| 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 |
| CN108002553A (en) * | 2018-01-31 | 2018-05-08 | 山东大学 | A kind of scale inhibitor for circulating cooling water and preparation method and application |
| CN110803780A (en) * | 2018-08-06 | 2020-02-18 | 中国石油化工股份有限公司 | Zinc salt-containing composite corrosion and scale inhibitor, application thereof and method for inhibiting corrosion of circulating cooling water containing sulfur |
| CN109179699B (en) * | 2018-09-19 | 2020-10-09 | 宁夏神耀科技有限责任公司 | Combined scale inhibition and dispersion agent of coal gasification system and application method thereof |
| 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 |
| CN111573859A (en) * | 2020-04-20 | 2020-08-25 | 大唐东北电力试验研究院有限公司 | Composite corrosion and scale inhibitor for power plant circulating cooling water system based on reclaimed water |
| CN112174343A (en) * | 2020-11-03 | 2021-01-05 | 西安热工研究院有限公司 | Green environment-friendly non-phosphorus scale and corrosion inhibitor and preparation method thereof |
| 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 |
| CN113981427A (en) * | 2021-09-29 | 2022-01-28 | 金瓷科技实业发展有限公司 | Phosphorus-free prefilming agent for industrial circulating water system and preparation method and application thereof |
| CN117819741A (en) * | 2023-12-28 | 2024-04-05 | 枣庄职业学院 | Coated corrosion and scale inhibitor based on modified polyaspartic acid and preparation method thereof |
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