CN104556428B - A kind of corrosion-mitigation scale-inhibition compositions and application thereof - Google Patents
A kind of corrosion-mitigation scale-inhibition compositions and application thereof Download PDFInfo
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- CN104556428B CN104556428B CN201310479105.5A CN201310479105A CN104556428B CN 104556428 B CN104556428 B CN 104556428B CN 201310479105 A CN201310479105 A CN 201310479105A CN 104556428 B CN104556428 B CN 104556428B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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Abstract
The invention discloses a kind of corrosion-mitigation scale-inhibition compositions and application thereof, this corrosion-mitigation scale-inhibition compositions contain cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, containing sulfonic group copolymer and water-soluble inorganic zinc salt, described cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, weight ratio containing sulfonic group copolymer and water-soluble inorganic zinc salt are (1 20): (1 25): (1 30): 1, it is preferably (2 6): (2 7): (2.5 8): 1, wherein, the weight of described water-soluble inorganic zinc salt is in terms of zinc ion.The corrosion-mitigation scale-inhibition compositions that the present invention provides can not be phosphorous, environmentally friendly, and the recirculating cooling water system of acid adding control ph can be met to inhibition and the requirement of scale inhibition, that is, the corrosion-mitigation scale-inhibition compositions of the present invention can show higher corrosion and scale inhibition performance in the recirculating cooling water system of high rigidity high alkalinity.
Description
Technical field
The present invention relates to a kind of corrosion-mitigation scale-inhibition compositions and application thereof, in particular it relates to a kind of without phosphorus multiple
Close corrosion-mitigation scale-inhibition compositions and the application in processing cycle cooling water thereof.
Background technology
Recirculated cooling water chemical treatment method has the history in more than 40 years so far in China's application, uses at present
Corrosion inhibiting and descaling agent in circulating water cooling treatment is many with phosphorus-containing compound as main component, and after discharge, degraded is released
The Phos released will cause the eutrophication of water proximate, promote that the growth of bacterium algae forms " red tide ",
Huge harm is brought to aquaculture and natural, ecological.Along with Environmental protection and water-saving and emission-reducing
Require improves constantly, and the process of recirculated cooling water must be low to raising system cycles of concentration and medicament
Phosphorus, direction without phosphatization are developed.
In recent years, domestic scholars low-phosphorous at circulating water cooling treatment and without phosphatization in terms of carried out some and ground
Study carefully, and achieve certain achievement.Such as: CN1743281A discloses a kind of with 2-phosphonic acid butane
-1,2,4-tricarboxylic acids (PBTCA) and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA), zinc salt, molybdate
Or tungstates and be the low-phosphorous composite scale-inhibiting corrosion inhibitor of main component containing carboxylic acid-based copolymer.
CN1743282A also discloses that a kind of low-phosphorous composite scale-inhibiting corrosion inhibitor, its be mainly composed of PBTCA and/
Or HPAA, poly-aspartate (PASP) and/or poly-epoxy succinic acid and containing carboxylic acid group polymer.Again
As: CN1338437A discloses a kind of method using non-phosphate inhibitor to carry out processing cycle cooling water, slow
Erosion agent mainly contains by C1-C5The substituted Saldox. of alkyl carboxylic acid, it is also possible to substituted containing acyl group
The substituted butanimide of sodium sarcosinate, alkyl, acrylic copolymer, inorganic zinc salt, molybdate etc..
CN1621362A discloses the non-Phosphorus composite anti incrustation eorrosion snhibiter of a kind of recirculated cooling water, this anti-incrustation corrosion inhibitor
By PASP and polyvinyl alcohol, Oxytarch, polyacrylic acid, acrylic acid/esters copolymer, containing sulphur
The acrylic acid/esters copolymer of acidic group, the sodium salt/potassium salt/ammonium salt of organic acid, sodium borate/potassium/ammonium,
Itrogenous organic substance, soluble molybdenum hydrochlorate, soluble tungstate salt, soluble nitrate, solubility nitrous acid
The Multiple components such as salt, soluble zinc salt combines, and is especially suitable for that high calcium is hard and high-alkali hard circulating cooling
Water processes.But, above-mentioned anti-incrustation corrosion inhibitor is primarily adapted for use in the system that recirculated cooling water pH value is higher.
In order to improve further recirculating cooling water system (especially with high rigidity high alkalinity water be supplement water
Recirculating cooling water system) cycles of concentration, the most domestic have been developed for by acid adding control system pH value
Suppress fouling and add the treatment process of circulating cooling water that efficient scale corrosion inhibitor suppression corrosion combines,
The performance of anti-incrustation corrosion inhibitor is just had higher requirement by this, the most phosphorous the most conventional corrosion inhibiter
(including anti-incrustation corrosion inhibitor mentioned above) is the most all not up to corresponding level, follows high rigidity high alkalinity
The scale inhibitor effect of ring cooling water is poor.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that it is high-alkali that one is particularly well-suited to high rigidity
The without phosphorus compound slow corrosion scale inhibition compositions of the circulating water cooling treatment of degree and application thereof.
To achieve these goals, on the one hand, the invention provides a kind of corrosion-mitigation scale-inhibition compositions, should
Corrosion-mitigation scale-inhibition compositions contain cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, containing sulfonic group copolymer
With water-soluble inorganic zinc salt, described cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, containing sulfonic group copolymerization
The weight ratio of thing and water-soluble inorganic zinc salt is (1-20): (1-25): (1-30): 1, is preferably
(2-6): (2-7): (2.5-8): 1, wherein, the weight of described water-soluble inorganic zinc salt is in terms of zinc ion.
On the other hand, present invention also offers the corrosion-mitigation scale-inhibition compositions of the invention described above in processing cycle
Application in cooling water.
The corrosion-mitigation scale-inhibition compositions that the present invention provides can not be phosphorous, environmentally friendly, and can meet
The recirculating cooling water system of acid adding control ph is to inhibition and the requirement of scale inhibition, i.e. the inhibition of the present invention
Scale inhibition compositions can show higher inhibition in the recirculating cooling water system of high rigidity high alkalinity
Scale-inhibiting properties.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The corrosion-mitigation scale-inhibition compositions that the present invention provides contains cyclodextrin type corrosion inhibiting and descaling agent, hydroxy carboxylic acid
Salt, containing sulfonic group copolymer and water-soluble inorganic zinc salt, described cyclodextrin type corrosion inhibiting and descaling agent, hydroxyl carboxylic
Hydrochlorate, weight ratio containing sulfonic group copolymer and water-soluble inorganic zinc salt are (1-20): (1-25): (1-30): 1,
It is preferably (2-6): (2-7): (2.5-8): 1, wherein, the weight of described water-soluble inorganic zinc salt is in terms of zinc ion.
According to the present invention, described cyclodextrin type corrosion inhibiting and descaling agent refer to beta-schardinger dextrin-as skeleton have slow
The cyclodextrin derivative of erosion scale effect, the preferably substituted beta-schardinger dextrin-of amino carboxylic acid, further preferably
Ground, described cyclodextrin type corrosion inhibiting and descaling agent selected from ethylenediaminetetraacetic acid-beta-schardinger dextrin-, aminotriacetic acid-β-
At least one in cyclodextrin and hexamethylene tetraacetic acid-beta-schardinger dextrin-.
According to the present invention, the kind not particularly requirement to described hydroxycarboxylate, can be this area
Conventional various hydroxycarboxylates, for example, it is possible to selected from gluconate, tartrate, citrate
With at least one in malate.Under preferable case, described hydroxycarboxylate selected from sodium gluconate,
Potassium gluconate, sodium tartrate, Soluble tartar., trisodium citrate, potassium citrate, natrium malicum and
At least one in potassium malate.
According to the present invention, described can be commonly used in the art various containing sulfonic containing sulfonic group copolymer
Copolymer, such as, carbon atom quantity is the copolymer of the olefin sulfonic acid of 3-8.It is total to containing sulfonic group with described
On the basis of the total amount of polymers, described carbon number is the mass percent of the olefin sulfonic acid construction unit of 3-8
Usually 10-40%.The described Limiting Viscosity containing sulfonic group copolymer at 30 DEG C is generally
0.065-0.095dL/g。
Under preferable case, described containing sulfonic group copolymer selected from containing 2 '-acrylamide-2-methyl propane sulfonic
At least one in copolymer, the copolymer containing allyl sulphonic acid and the copolymer containing styrene sulfonic acid.
It is selected from acrylic acid and 2 '-acrylamide-2-methyl-prop sulphur containing sulfonic group copolymer it is highly preferred that described
The copolymer of acid, acrylic acid and acrylate and the copolymer of 2 '-acrylamide-2-methyl propane sulfonic, third
Olefin(e) acid and at least in the copolymer of allyl sulphonic acid and the copolymer of maleic acid and styrene sulfonic acid
Kind.It is further preferred that described acrylate is selected from acrylic acid methyl ester., ethyl acrylate and acrylic acid hydroxyl
At least one in propyl ester.
According to the present invention, described water-soluble inorganic zinc salt can be any water miscible inorganic zinc salt, as long as
Zn can be produced after adding to recirculated cooling water2+?.Under preferable case, described water-soluble inorganic zinc
Salt is Zinc vitriol and/or zinc chloride.
According to the present invention, usually, described corrosion-mitigation scale-inhibition compositions can also contain water.Wherein, water
Being only used as solvent to play a role, the height of its content does not interferes with the inhibition of described corrosion-mitigation scale-inhibition compositions
Scale-inhibiting properties, therefore has no particular limits the content of water, it is contemplated that each composition is the most mixed
Close, and make described corrosion-mitigation scale-inhibition compositions preferably play anticorrosion-antiscaling effect, with described corrosion-mitigation scale-inhibition
On the basis of the total amount of compositions, the content of water is preferably 40-80 weight %.
A preferred embodiment of the invention, described corrosion-mitigation scale-inhibition compositions is delayed by cyclodextrin type
Lose antisludging agent, hydroxycarboxylate, form containing sulfonic group copolymer, water-soluble inorganic zinc salt and water.Pass through
This preferred implementation, the corrosion-mitigation scale-inhibition compositions of the present invention can the most in an environment-friendlymanner manner
Realize the purpose of corrosion-mitigation scale-inhibition.
According to the present invention, described corrosion-mitigation scale-inhibition compositions can be obtained by existing various methods, example
As described in can will be formed, the raw material of corrosion-mitigation scale-inhibition compositions prepares according to aforementioned ratio mix homogeneously,
And the step and condition to described mixing is without particular/special requirement.
Present invention also offers the application in processing cycle cooling water of the above-mentioned corrosion-mitigation scale-inhibition compositions.Its
In, the consumption of described corrosion-mitigation scale-inhibition compositions is preferably 20-60mg/L recirculated cooling water, more preferably
25-40mg/L recirculated cooling water.It should be noted that the consumption of corrosion-mitigation scale-inhibition compositions only relates to herein
And the weight (the most only referring to the weight of effective ingredient) of component than water.
It was found by the inventors of the present invention that the corrosion-mitigation scale-inhibition compositions of the present invention is particularly well-suited to high rigidity height
The process of the recirculated cooling water of basicity, it is preferable that the calcium hardness of described recirculated cooling water is
600-1600mg/L, total alkalinity is 50-300mg/L.Wherein, calcium hardness and total alkalinity can respectively refer to
Standard GB/T6910-2006 and GB/T15451-2006 record.
Corrosion-mitigation scale-inhibition compositions according to the present invention, when actually used, after can mixing each raw material
Add in recirculated cooling water, it is also possible to each raw material is directly added into without blend step recirculated cooling water
In, and can be simultaneously introduced, it is also possible to it is sequentially added into.
Hereinafter will be described the present invention by embodiment.In following example, ethylenediamine tetrem
Acid-beta-schardinger dextrin-with reference to " synthesis of novel beta-cyclodextrin derivative and application ", (be good for, 2008 10 by Shen
Month) chapter 3 4.1.5 joint；The preparation method of hexamethylene tetraacetic acid-beta-schardinger dextrin-and ethylenediaminetetraacetic acid-β-
The preparation method of cyclodextrin is identical, simply " ethylenediaminetetraacetic acid " is replaced with " hexamethylene tetraacetic acid "；
Aminotriacetic acid-beta-schardinger dextrin-reference " synthesis of novel beta-cyclodextrin derivative and application " (Shen is good for, and 2008
October in year) chapter 3 4.1.6 joint；In embodiment, the usage amount of composite drug all includes the amount of water.
" cooling water analysis and the test side write with reference to production department of China Petrochemical Corporation and development division
Method " recirculated cooling water described in (1993, information centre of Anqing general petrochemical works publish) is dynamic
The medicament that following example and comparative example are prepared by experimental analogic method carries out inhibition and appraisal of scale mitigating effect.Its
In, the extent of corrosion of metal in the corrosion rate representation unit time, can be used for characterizing corrosion-mitigation scale-inhibition combination
The corrosion inhibition of thing, corrosion rate is the lowest shows that the corrosion inhibition of medicament is the highest；Adhere to rate representation unit
In time the inorganic salt crust in water, biological clay or other impurity metal surface attachment speed, energy
Enough reflect the scale-inhibiting properties of corrosion-mitigation scale-inhibition compositions, adhere to that speed is the lowest shows the scale-inhibiting properties of medicament more
High.In experiment, test tube material is 20#Carbon steel, appearance chromium plating, a size of；
Heat exchanger tube inlet temperature is 32.0 DEG C, and importing and exporting the temperature difference is 10.0 DEG C；It is 100L that system possesses the water yield,
The circulating cooling water yield is 180L/h.Experiment use pH automatic controlling device to add sulphuric acid in system (dense
Degree is 98 weight %).Experiment is as shown in table 1 with circulating cooling water quality, calcium hardness and total alkalinity all with
CaCO3 counts, and respectively refers to GB/T6910-2006 and GB/T15451-2006 and records, the numerical value of table 1
Range Representation is calcium hardness and the excursion of total alkalinity during dynamic simulation experiment.
Table 1
| Experimental water | Calcium hardness (mg/L) | Total alkalinity (mg/L) |
| 1#Recirculated cooling water | 1400-1600 | 50-120 |
| 2#Recirculated cooling water | 1000-1200 | 100-200 |
| 3#Recirculated cooling water | 800-1000 | 150-220 |
| 4#Recirculated cooling water | 600-800 | 200-300 |
Embodiment 1
Weigh 8.0g ethylenediaminetetraacetic acid-beta-schardinger dextrin-and 10.0g sodium gluconate, add in 47.0g water；
(solids content is 30.5 to the copolymer of addition 26.2g acrylic acid and 2 '-acrylamide-2-methyl propane sulfonic
Weight %, Limiting Viscosity when 30 DEG C is 0.075dL/g, acrylic acid and 2 '-acrylamide-2-methyl-prop sulphur
The weight ratio of acid is 3:1)；Add 8.8g Zinc vitriol, stirring and dissolving, obtain 100g and be combined
Medicament.By the usage amount of 100mg/L recirculated cooling water to 1#Recirculated cooling water adds above-mentioned composite medicine
Agent, is circulated cooling water dynamic simulation experiment, the results are shown in Table 2.
Embodiment 2
Weigh 6.0g ethylenediaminetetraacetic acid-beta-schardinger dextrin-and 8.0g sodium tartrate, add in 52.5g water；
Add 29.3g acrylic acid and Hydroxypropyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic copolymer (Gu
Body burden is 30.7 weight %, and Limiting Viscosity when 30 DEG C is 0.081dL/g, acrylic acid, acrylic acid hydroxyl
The weight ratio of propyl ester and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:1)；Add 4.2g zinc chloride,
Stirring and dissolving, obtains 100g composite drug.By the usage amount of 100mg/L recirculated cooling water to 1#Circulation
Cooling water adds above-mentioned composite drug, is circulated cooling water dynamic simulation experiment, the results are shown in Table 2.
Embodiment 3
Weigh 7.0g aminotriacetic acid-beta-schardinger dextrin-and 8.0g potassium gluconate, add in 52.2g water；
(solids content is 30.5 to the copolymer of addition 26.2g acrylic acid and 2 '-acrylamide-2-methyl propane sulfonic
Weight %, Limiting Viscosity when 30 DEG C is 0.075dL/g, acrylic acid and 2 '-acrylamide-2-methyl-prop sulphur
The weight ratio of acid is 3:1)；Add 6.6g Zinc vitriol, stirring and dissolving, obtain 100g and be combined
Medicament.By the usage amount of 120mg/L recirculated cooling water to 2#Recirculated cooling water adds above-mentioned composite medicine
Agent, is circulated cooling water dynamic simulation experiment, the results are shown in Table 2.
Embodiment 4
Weigh 9.0g aminotriacetic acid-beta-schardinger dextrin-and 12.0g trisodium citrate, add in 41.6g water；
Add 32.2g acrylic acid and ethyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic copolymer (Gu
Body burden is 31.1 weight %, and Limiting Viscosity when 30 DEG C is 0.085dL/g, acrylic acid, acrylic acid second
The weight ratio of ester and 2 '-acrylamide-2-methyl propane sulfonic is 4:1:2)；Add 5.2g seven hydrated sulfuric acid
Zinc, stirring and dissolving, obtain 100g composite drug.By the usage amount of 90mg/L recirculated cooling water to 3#
Recirculated cooling water adds above-mentioned composite drug, is circulated cooling water dynamic simulation experiment, the results are shown in Table
2。
Embodiment 5
Weigh 6.0g ethylenediaminetetraacetic acid-beta-schardinger dextrin-and 6.0g Soluble tartar., add in 38.6g water；
Add 39.0g acrylic acid and acrylic acid methyl ester. and 2 '-acrylamide-2-methyl propane sulfonic copolymer (Gu
Body burden is 30.8 weight %, and Limiting Viscosity when 30 DEG C is 0.069dL/g, acrylic acid, acrylic acid first
The weight ratio of ester and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:2)；Add 10.5g zinc chloride, stir
Mix dissolving, obtain 100g composite drug.By the usage amount of 50mg/L recirculated cooling water to 4#Circulating cooling
Water adds above-mentioned composite drug, is circulated cooling water dynamic simulation experiment, the results are shown in Table 2.
Embodiment 6
Weigh 5.0g hexamethylene tetraacetic acid-beta-schardinger dextrin-and 8.0g natrium malicum, add in 60.3g water；
(solids content is 31.2 weight % to the copolymer of addition 25.6g maleic acid and styrene sulfonic acid, when 30 DEG C
Limiting Viscosity be 0.090dL/g, the weight ratio of maleic acid and styrene sulfonic acid is 2:1)；Add 1.0g
Zinc chloride, stirring and dissolving, obtain 100g composite drug.Usage amount by 150mg/L recirculated cooling water
To 1#Recirculated cooling water adds above-mentioned composite drug, is circulated cooling water dynamic simulation experiment, result
It is shown in Table 2.
Embodiment 7
Weigh 8.0g hexamethylene tetraacetic acid-beta-schardinger dextrin-and 10.0g trisodium citrate, add in 26.9g water；
Add 48.9g acrylic acid and Hydroxypropyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic copolymer (Gu
Body burden is 30.7 weight %, and Limiting Viscosity when 30 DEG C is 0.081dL/g, acrylic acid, acrylic acid hydroxyl
The weight ratio of propyl ester and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:1)；Add 6.3g seven and be hydrated sulfur
Acid zinc, stirring and dissolving, obtain 100g composite drug.By the usage amount of 80mg/L recirculated cooling water to
2#Adding above-mentioned composite drug in recirculated cooling water, be circulated cooling water dynamic simulation experiment, result is shown in
Table 2.
Embodiment 8
Weigh 6.0g aminotriacetic acid-beta-schardinger dextrin-and 10.0g potassium malate, add in 57.9g water；Add
(solids content is 30.5 weights to enter the copolymer of 23.0g acrylic acid and 2 '-acrylamide-2-methyl propane sulfonic
Amount %, Limiting Viscosity when 30 DEG C is 0.075dL/g, acrylic acid and 2 '-acrylamide-2-methyl propane sulfonic
Weight ratio be 3:1)；Add 3.1g zinc chloride, stirring and dissolving, obtain 100g composite drug.Press
The usage amount of 130mg/L recirculated cooling water is to 1#Recirculated cooling water adds above-mentioned composite drug, follows
Ring cooling water dynamic simulation experiment, the results are shown in Table 2.
Embodiment 9
Weigh 8.0g ethylenediaminetetraacetic acid-beta-schardinger dextrin-and 7.0g sodium gluconate, add in 40.0g water；
(solids content is 30.2 weight % to the copolymer of addition 39.7g acrylic acid and allyl sulphonic acid, when 30 DEG C
Limiting Viscosity be 0.077dL/g, the weight ratio of acrylic acid and allyl sulphonic acid is 3:1)；Add 5.2g
Zinc vitriol, stirring and dissolving, obtain 100g composite drug.By making of 90mg/L recirculated cooling water
Consumption is to 4#Recirculated cooling water adds above-mentioned composite drug, is circulated cooling water dynamic simulation experiment,
The results are shown in Table 2.
Embodiment 10
Weigh 7.0g aminotriacetic acid-beta-schardinger dextrin-and 5.0g sodium tartrate, add in 49.2g water；Add
Enter 32.5g acrylic acid and acrylic acid methyl ester. and the copolymer (solid of 2 '-acrylamide-2-methyl propane sulfonic
Content is 30.8 weight %, and Limiting Viscosity when 30 DEG C is 0.069dL/g, acrylic acid, acrylic acid methyl ester.
It is 3:1:2 with the weight ratio of 2 '-acrylamide-2-methyl propane sulfonic)；Add 6.3g zinc chloride, stirring
Dissolve, obtain 100g composite drug.By the usage amount of 100mg/L recirculated cooling water to 3#Circulating cooling
Water adds above-mentioned composite drug, is circulated cooling water dynamic simulation experiment, the results are shown in Table 2.
Embodiment 11
Prepare medicament according to the mode of embodiment 10, except for the difference that, replace ethylenediamine tetraacetic with beta-schardinger dextrin-
Acetic acid-beta-schardinger dextrin-, the results are shown in Table 2.
Comparative example 1
Weigh 12.0g sodium tartrate, add in 40.3g water；Add 14.2g poly-epoxy succinic acid (solid
Content is 35.2 weight %, and the trade mark is NC-312, purchased from Nanjing Na Ke water technology company limited)
With the copolymer of 29.3g acrylic acid and Hydroxypropyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic (Gu
Body burden is 30.7 weight %, and Limiting Viscosity when 30 DEG C is 0.081dL/g, acrylic acid, acrylic acid hydroxyl
The weight ratio of propyl ester and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:1)；Add 4.2g zinc chloride,
Stirring and dissolving, obtains 100g composite drug.By the usage amount of 100mg/L recirculated cooling water to 1#Circulation
Cooling water adds above-mentioned composite drug, is circulated cooling water dynamic simulation experiment, the results are shown in Table 2.
Comparative example 2
Weigh beta-schardinger dextrin-and the 4.0g sodium tartrate of 1.0g, add in 53.4g water；Add 8.5g to gather
(solids content is 35.2 weight % to Epoxysuccinic acid, and the trade mark is NC-312, at the Na Keshui of Nanjing
Reason Technology Co., Ltd.) and the copolymer of 26.5g acrylic acid and allyl sulphonic acid (solids content is 30.2
Weight %, Limiting Viscosity when 30 DEG C is 0.077dL/g, and acrylic acid with the weight ratio of allyl sulphonic acid is
3:1)；Add 6.6g Zinc vitriol, stirring and dissolving, obtain 100g composite drug.By 80mg/L
The usage amount of recirculated cooling water is to 3#Recirculated cooling water adds above-mentioned composite drug, is circulated cooling water
Dynamic simulation experiment, the results are shown in Table 2.
Comparative example 3
Weigh 8.0g sodium molybdate, be dissolved in 50.7g water；The PBTCA(effective content adding 4.0g is
50.5 weight %, the trade mark is XF-210, purchased from Jing Kexia peak, Jiangsu Environmental Protection Technology Co., Ltd) and 26.4g
The copolymer of acrylic acid and acrylic acid methyl ester. and Hydroxypropyl acrylate (solids content is 30.3 weight %,
Limiting Viscosity when 30 DEG C is 0.070dL/g, acrylic acid, acrylic acid methyl ester. and the weight of Hydroxypropyl acrylate
Amount ratio is 3:1:2)；Add 10.9g Zinc vitriol, stirring and dissolving, obtain 100g low-phosphorous compound
Medicament.By the usage amount of 100mg/L recirculated cooling water to 2#Recirculated cooling water adds above-mentioned composite medicine
Agent, is circulated cooling water dynamic simulation experiment, the results are shown in Table 2.
Comparative example 4
The PBTCA(effective content weighing 5.0g is 50.5 weight %, and the trade mark is XF-210, purchased from river
Su Jingkexia peak Environmental Protection Technology Co., Ltd), (solids content is 35.2 weight to 11.4g poly-epoxy succinic acid
%, the trade mark is NC-312, purchased from Nanjing Na Ke water technology company limited), 13.0g polyacrylic acid
(solids content is 30.7%, and Limiting Viscosity when 30 DEG C is 0.075dL/g) and 29.7g acrylic acid and third
(solids content is 30.3 weight % to the copolymer of e pioic acid methyl ester and Hydroxypropyl acrylate, limit when 30 DEG C
Viscosity number is 0.070dL/g, and acrylic acid, acrylic acid methyl ester. are 3:1:2 with the weight ratio of Hydroxypropyl acrylate),
Join in 40.9g water, stir, obtain the low-phosphorous composite drug of 100g.Circulate by 100mg/L
The usage amount of cooling water is to 4#Recirculated cooling water adds above-mentioned composite drug, is circulated cooling hydrodynamic(al) state
Simulation experiment, the results are shown in Table 2.
Comparative example 5
Weigh 15.0g sodium molybdate and 3.0g sodium benzoate, be dissolved in 48.3g water；Add the poly-Radix Asparagi of 9.8g
Propylhomoserin (solids content is 40.8 weight %, purchased from Shandong Taihe Water Treatment Co., Ltd.), 9.9g third
(solids content is 30.3 weight % to the copolymer of olefin(e) acid and acrylic acid methyl ester. and Hydroxypropyl acrylate, 30 DEG C
Time Limiting Viscosity be 0.070dL/g, the weight ratio of acrylic acid, acrylic acid methyl ester. and Hydroxypropyl acrylate
For 3:1:2) and 9.8g acrylic acid and Hydroxypropyl acrylate and the copolymerization of 2 '-acrylamide-2-methyl propane sulfonic
(solids content is 30.7 weight % to thing, and Limiting Viscosity when 30 DEG C is 0.081dL/g, acrylic acid, third
The weight ratio of olefin(e) acid hydroxypropyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:1)；Add 4.2g chlorine
Change zinc, stirring and dissolving, obtain the without phosphorus composite drug of 100g.Use by 100mg/L recirculated cooling water
Amount is to 1#Recirculated cooling water adds above-mentioned composite drug, is circulated cooling water dynamic simulation experiment, knot
Fruit is shown in Table 2.
Comparative example 6
Medicament is prepared according to the mode of embodiment 10, except for the difference that, the use of aminotriacetic acid-beta-schardinger dextrin-
Amount is 4.0g, and the weight of zinc chloride is 12.0g, the results are shown in Table 2.
Comparative example 7
Weigh 1.0g aminotriacetic acid-beta-schardinger dextrin-and 5.0g sodium tartrate, add in 40.5g water；Add
(solids content is 40.8 weight %, processes limited purchased from the calm and peaceful water in Shandong Province to enter 14.7g poly-aspartate
Company) and 32.5g acrylic acid and acrylic acid methyl ester. and the copolymer of 2 '-acrylamide-2-methyl propane sulfonic
(solids content is 30.8 weight %, and Limiting Viscosity when 30 DEG C is 0.069dL/g, acrylic acid, propylene
The weight ratio of acid methyl ester and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:2)；Add 6.3g zinc chloride,
Stirring and dissolving, obtains 100g composite drug.By the usage amount of 100mg/L recirculated cooling water to 3#Circulation
Cooling water adds above-mentioned composite drug, is circulated cooling water dynamic simulation experiment, the results are shown in Table 2.
Table 2
| Embodiment | Corrosion rate (mm/a) | Adhere to speed (mcm) |
| Embodiment 1 | 0.018 | 2.5 |
| Embodiment 2 | 0.015 | 1.8 |
| Embodiment 3 | 0.027 | 2.3 |
| Embodiment 4 | 0.024 | 4.2 |
| Embodiment 5 | 0.017 | 7.8 |
| Embodiment 6 | 0.035 | 5.5 |
| Embodiment 7 | 0.028 | 5.3 |
| Embodiment 8 | 0.025 | 4.8 |
| Embodiment 9 | 0.019 | 6.6 |
| Embodiment 10 | 0.026 | 4.7 |
| Embodiment 11 | 0.063 | 10.5 |
| Comparative example 1 | 0.064 | 8.5 |
| Comparative example 2 | 0.068 | 10.3 |
| Comparative example 3 | 0.035 | 6.5 |
| Comparative example 4 | 0.042 | 10.2 |
| Comparative example 5 | 0.085 | 17.8 |
| Comparative example 6 | 0.087 | 15.3 |
| Comparative example 7 | 0.078 | 11.3 |
Result in table 2 shows, the without phosphorus compound slow corrosion scale inhibition compositions that the present invention provides is the most permissible
Meeting the requirement of acid adding control ph circulating water cooling treatment, dynamic simulation experiment test tube corrosion rate is equal
Less than 0.040mm/a, adhering to speed and be respectively less than 8mcm, scale inhibitor effect ratio uses phosphorous inhibition
The effect of scale inhibition compositions (comparative example 3 and comparative example 4) is more preferable.
Additionally, by embodiment 10, embodiment 11, comparative example 1, comparative example 2, comparative example 6 and contrast
Example 7 compares it can be seen that use the cyclodextrin type corrosion inhibiting and descaling agent of preferred kind of the present invention and consumption can
Obtain the most excellent scale inhibitor effect；Especially, comparative example 7 uses the cyclodextrin of not preferred consumption
Type corrosion inhibiting and descaling agent, although the total amount of the effective ingredient in this comparative example is gone forward side by side with the identical of embodiment 10
One step is supplemented with containing carboxyl homopolymer (poly-epoxy succinic acid), and its corrosion and scale inhibition performance is still below according to this
The medicament of inventive embodiments 10 preparation；Although it addition, the anti-incrustation corrosion inhibitor that comparative example 5 provides is the most phosphorous,
But it is difficult to meet requirement under the conditions of low alkalinity, mainly shows as corrosion rate the most up to standard, and adhere to speed
Higher.Therefore, the without phosphorus compound slow corrosion more existing corrosion-mitigation scale-inhibition of scale inhibition compositions that the present invention provides is used
Compositions tool is had large improvement, and is adapted to improve recirculated cooling water cycles of concentration and reduce the double of phosphorus discharge
Important ask.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a corrosion-mitigation scale-inhibition compositions, it is characterised in that this corrosion-mitigation scale-inhibition compositions contains ring
Dextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, containing sulfonic group copolymer and water-soluble inorganic zinc salt, described
Cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, containing sulfonic group copolymer and the weight of water-soluble inorganic zinc salt
Amount than be 1-20:1-25:1-30:1, wherein, the weight of described water-soluble inorganic zinc salt in terms of zinc ion, institute
State cyclodextrin type corrosion inhibiting and descaling agent selected from ethylenediaminetetraacetic acid-beta-schardinger dextrin-, aminotriacetic acid-beta-schardinger dextrin-
With at least one in hexamethylene tetraacetic acid-beta-schardinger dextrin-.
Corrosion-mitigation scale-inhibition compositions the most according to claim 1, wherein, described cyclodextrin type delays
Erosion antisludging agent, hydroxycarboxylate, weight ratio containing sulfonic group copolymer and water-soluble inorganic zinc salt are
2-6:2-7:2.5-8:1。
Corrosion-mitigation scale-inhibition compositions the most according to claim 1, wherein, described hydroxycarboxylate
Selected from sodium gluconate, potassium gluconate, sodium tartrate, Soluble tartar., trisodium citrate, citric acid
At least one in tripotassium, natrium malicum and potassium malate.
Corrosion-mitigation scale-inhibition compositions the most according to claim 1, wherein, described common containing sulfonic group
Polymers selected from the copolymer containing 2 '-acrylamide-2-methyl propane sulfonic, the copolymer containing allyl sulphonic acid and
At least one in copolymer containing styrene sulfonic acid.
Corrosion-mitigation scale-inhibition compositions the most according to claim 4, wherein, described common containing sulfonic group
Polymers is selected from acrylic acid and the copolymer of 2 '-acrylamide-2-methyl propane sulfonic, acrylic acid and acrylate
With the copolymer of 2 '-acrylamide-2-methyl propane sulfonic, the copolymer of acrylic acid and allyl sulphonic acid, with
And at least one in the copolymer of maleic acid and styrene sulfonic acid, described acrylate is selected from acrylic acid first
At least one in ester, ethyl acrylate and Hydroxypropyl acrylate.
Corrosion-mitigation scale-inhibition compositions the most according to claim 1, wherein, described water-soluble inorganic
Zinc salt is Zinc vitriol and/or zinc chloride.
7. according to the corrosion-mitigation scale-inhibition compositions described in any one in claim 1-6, wherein, institute
State corrosion-mitigation scale-inhibition compositions possibly together with water, on the basis of the total amount of described corrosion-mitigation scale-inhibition compositions, water
Content be 40-80 weight %.
8. in claim 1-7, corrosion-mitigation scale-inhibition compositions described in any one cools down in processing cycle
Application in water.
Application the most according to claim 8, wherein, the consumption of described corrosion-mitigation scale-inhibition compositions
For 20-60mg/L recirculated cooling water.
Application the most according to claim 8, wherein, the use of described corrosion-mitigation scale-inhibition compositions
Amount is 25-40mg/L recirculated cooling water.
Application described in 11. according to Claim 8,9 or 10, wherein, described recirculated cooling water
Calcium hardness is 600-1600mg/L, and total alkalinity is 50-300mg/L.
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| CN107304076B (en) * | 2016-04-20 | 2020-05-12 | 中国石油化工股份有限公司 | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof |
| CN107304081B (en) * | 2016-04-20 | 2020-05-12 | 中国石油化工股份有限公司 | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof |
| CN107304077B (en) * | 2016-04-20 | 2020-05-12 | 中国石油化工股份有限公司 | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof |
| CN107304079B (en) * | 2016-04-20 | 2020-05-12 | 中国石油化工股份有限公司 | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof |
| CN107304080B (en) * | 2016-04-20 | 2020-05-12 | 中国石油化工股份有限公司 | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof |
| CN107304082B (en) * | 2016-04-20 | 2020-05-12 | 中国石油化工股份有限公司 | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof |
| CN106430639B (en) * | 2016-07-13 | 2019-07-23 | 中国神华能源股份有限公司 | A kind of processing method of industrial circulating cooling water |
| CN106430638B (en) * | 2016-07-13 | 2019-07-23 | 中国神华能源股份有限公司 | A kind of malic acid composite slow-corrosion scale resistor composition and malic acid composite slow-corrosion scale resistor and its application |
| CN108147559A (en) * | 2017-12-08 | 2018-06-12 | 西安工程大学 | A kind of terpolymer antisludging agent and preparation method thereof |
| CN108706751A (en) * | 2018-07-18 | 2018-10-26 | 林文标 | A kind of research of non-phosphorus scale inhibitor and preparation method thereof |
| CN110963585B (en) * | 2018-09-28 | 2021-09-21 | 中国石油化工股份有限公司 | Non-phosphorus composite corrosion inhibitor and application thereof in low hard water |
| CN110963587B (en) * | 2018-09-28 | 2021-09-21 | 中国石油化工股份有限公司 | Non-phosphorus composite corrosion inhibitor and application thereof in high hard water |
| CN110963588B (en) * | 2018-09-28 | 2021-09-21 | 中国石油化工股份有限公司 | Non-phosphorus composite corrosion inhibitor and application thereof in medium and hard water |
| CN113800653A (en) * | 2020-06-16 | 2021-12-17 | 中国石油化工集团有限公司 | Geothermal fluid scale inhibitor and preparation method and application thereof |
| CN114426338A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Non-phosphorus scale and corrosion inhibitor and preparation method and application thereof |
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