CN104556428A - Composition for corrosion inhibition and scale inhibition and application of composition - Google Patents

Composition for corrosion inhibition and scale inhibition and application of composition Download PDF

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Publication number
CN104556428A
CN104556428A CN201310479105.5A CN201310479105A CN104556428A CN 104556428 A CN104556428 A CN 104556428A CN 201310479105 A CN201310479105 A CN 201310479105A CN 104556428 A CN104556428 A CN 104556428A
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corrosion
water
acid
multipolymer
inhibition
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CN201310479105.5A
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Chinese (zh)
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CN104556428B (en
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王岽
吴颖
郦和生
冯婕
魏新
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12Treatment 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/22Eliminating or preventing deposits, scale removal, scale prevention

Abstract

The invention discloses a composition for corrosion inhibition and scale inhibition and application of the composition. The composition for corrosion inhibition and scale inhibition contains a cyclodextrin type corrosion inhibition and scale inhibition agent, a hydroxy carboxylate, a copolymer containing an sulfonic group and a water-soluble inorganic zinc salt, wherein the weight ratio of the cyclodextrin type corrosion inhibition and scale inhibition agent to the hydroxy carboxylate to the copolymer containing the sulfonic group to the water-soluble inorganic zinc salt is (1-20): (1-25): (1-30): 1, preferably (2-6): (2-7): (2.5-8): 1, and the weight of the water-soluble inorganic zinc salt is calculated by zinc ions. The composition for corrosion inhibition and scale inhibition provided by the invention can not contain phosphorus and is environment-friendly; furthermore, the requirements of a circulating cooling water system of which the pH value is controlled through adding acid on corrosion inhibition and scale inhibition are met, namely the composition for corrosion inhibition and scale inhibition disclosed by the invention can represent relatively high corrosion inhibition and scale inhibition performance in the high-hardness and high-alkalinity circulating cooling water system.

Description

A kind of corrosion-mitigation scale-inhibition composition and application thereof
Technical field
The present invention relates to a kind of corrosion-mitigation scale-inhibition composition and application thereof, particularly, relate to a kind of without phosphorus compound slow corrosion scale inhibition composition and the application in cycle for the treatment of water coolant thereof.
Background technology
Recirculated cooling water chemical treatment method has the history in more than 40 years so far in China's application, the current corrosion inhibiting and descaling agent for circulating water cooling treatment is main component mainly with P contained compound, discharge the inorganic phosphorus discharged of degrading afterwards and will cause the eutrophication of water proximate, promote the growth of bacterium algae and form " red tide ", bringing huge harm to aquaculture and natural, ecological.What require along with Environmental protection and water-saving and emission-reducing improves constantly, and the process of recirculated cooling water must to raising system cycles of concentration and medicament be low-phosphorous, without the future development of phosphatization.
In recent years, domestic scholars is low-phosphorous and without having carried out some researchs in phosphatization at circulating water cooling treatment, and achieves certain achievement.Such as: CN1743281A discloses a kind of with 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA), zinc salt, molybdate or tungstate and be the low-phosphorous composite scale-inhibiting corrosion inhibitor of main component containing carboxylic acid-based copolymer.CN1743282A also discloses a kind of low-phosphorous composite scale-inhibiting corrosion inhibitor, and its main component is PBTCA and/or HPAA, poly aspartic acid (PASP) and/or poly-epoxy succinic acid and contains carboxylic acid group polymer.For another example: CN1338437A discloses a kind of method using non-phosphate inhibitor to carry out cycle for the treatment of water coolant, mainly contain by C in inhibiter 1-C 5the salicylaldoxime that alkyl carboxylic acid replaces, can also contain the succinimide, acrylic copolymer, inorganic zinc salt, molybdate etc. of the sodium sarcosinate of acyl substituted, alkyl replacement.CN1621362A discloses a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter of recirculated cooling water, this anti-incrustation corrosion inhibitor by PASP and polyvinyl alcohol, Sumstar 190, polyacrylic acid, acrylic acid/esters multipolymer, combine containing Multiple components such as sulfonic acrylic acid/esters multipolymer, organic acid sodium salt/sylvite/ammonium salt, Sodium Tetraborate/potassium/ammonium, itrogenous organic substance, soluble molybdenum hydrochlorate, soluble tungstate salt, soluble nitrate, solubility nitrite, soluble zinc salts, is especially applicable to the hard and high-alkali hard circulating water cooling treatment of high calcium.But above-mentioned anti-incrustation corrosion inhibitor is mainly applicable to the higher system of recirculated cooling water pH value.
In order to improve the cycles of concentration of recirculating cooling water system (especially with the recirculating cooling water system that high rigidity high alkalinity water is make up water) further, domestic having developed suppresses fouling and adds efficient scale corrosion inhibitor to suppress to corrode the treatment process of circulating cooling water combined by acid adding Controlling System pH value at present, this just has higher requirement to the performance of anti-incrustation corrosion inhibitor, not phosphorous inhibiter (comprising anti-incrustation corrosion inhibitor mentioned above) conventional at present does not also all reach corresponding level, poor to the scale inhibitor effect of high rigidity high alkalinity recirculated cooling water.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of without phosphorus compound slow corrosion scale inhibition composition and the application thereof that are specially adapted to the circulating water cooling treatment of high rigidity high alkalinity are provided.
To achieve these goals, on the one hand, the invention provides a kind of corrosion-mitigation scale-inhibition composition, this corrosion-mitigation scale-inhibition composition contain cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, containing sulfonic group multipolymer and water-soluble inorganic zinc salt, described cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, be (1-20) containing the weight ratio of sulfonic group multipolymer and water-soluble inorganic zinc salt: (1-25): (1-30): 1, be preferably (2-6): (2-7): (2.5-8): 1, wherein, the weight of described water-soluble inorganic zinc salt is in zine ion.
On the other hand, present invention also offers the application of corrosion-mitigation scale-inhibition composition in cycle for the treatment of water coolant of the invention described above.
Corrosion-mitigation scale-inhibition composition provided by the invention can not be phosphorous, environmentally friendly, and the recirculating cooling water system that can meet acid adding control ph is to the requirement of inhibition and scale inhibition, that is, corrosion-mitigation scale-inhibition composition of the present invention can show higher corrosion and scale inhibition performance in the recirculating cooling water system of high rigidity high alkalinity.
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.
Corrosion-mitigation scale-inhibition composition provided by the invention contain cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, containing sulfonic group multipolymer and water-soluble inorganic zinc salt, described cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, be (1-20) containing the weight ratio of sulfonic group multipolymer and water-soluble inorganic zinc salt: (1-25): (1-30): 1, be preferably (2-6): (2-7): (2.5-8): 1, wherein, the weight of described water-soluble inorganic zinc salt is in zine ion.
According to the present invention, described cyclodextrin type corrosion inhibiting and descaling agent refers to beta-cyclodextrin to be the cyclodextrin derivative with corrosion-mitigation scale-inhibition effect of skeleton, be preferably the beta-cyclodextrin that aminocarboxylic acid replaces, further preferably, described cyclodextrin type corrosion inhibiting and descaling agent is selected from least one in ethylenediamine tetraacetic acid (EDTA)-beta-cyclodextrin, nitrilotriacetic acid-beta-cyclodextrin and hexamethylene dinitrilo-tetraacetic acid-beta-cyclodextrin.
According to the present invention, to the special requirement of the kind of described hydroxycarboxylate, the various hydroxycarboxylates that can commonly use for this area, such as, can be selected from least one in gluconate, tartrate, citrate plus malate salt.Under preferable case, described hydroxycarboxylate is selected from least one in Sunmorl N 60S, Potassium Gluconate, sodium tartrate, soluble tartrate, trisodium citrate, citric acid tri potassium, sodium malate and potassium malate.
According to the present invention, describedly can contain sulfonic multipolymer for conventional various in this area containing sulfonic group multipolymer, such as, carbon atom quantity is the multipolymer of the olefin sulfonic acid of 3-8.With the described total amount containing sulfonic group multipolymer for benchmark, described carbonatoms is that the mass percent of the olefin sulfonic acid structural unit of 3-8 is generally 10-40%.The described Limiting Viscosity of sulfonic group multipolymer at 30 DEG C that contain is generally 0.065-0.095dL/g.
Under preferable case, the described at least one being selected from the multipolymer containing 2 '-acrylamide-2-methyl propane sulfonic, the multipolymer containing allyl sulphonic acid containing sulfonic group multipolymer and containing in the multipolymer of styrene sulfonic acid.
More preferably, the described at least one be selected from containing sulfonic group multipolymer in the multipolymer of the multipolymer of vinylformic acid and 2 '-acrylamide-2-methyl propane sulfonic, vinylformic acid and acrylate and 2 '-acrylamide-2-methyl propane sulfonic, vinylformic acid and the multipolymer of allyl sulphonic acid and the multipolymer of toxilic acid and styrene sulfonic acid.Further preferably, described acrylate is selected from least one in methyl acrylate, ethyl propenoate and Propylene glycol monoacrylate.
According to the present invention, described water-soluble inorganic zinc salt can be any water miscible inorganic zinc salt, can produce Zn as long as be added into after in recirculated cooling water 2+.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 composition can also contain water.Wherein, water only plays a role as solvent, the height of its content can not affect the corrosion and scale inhibition performance of described corrosion-mitigation scale-inhibition composition, therefore the content of water is had no particular limits, but consider the abundant mixing of each composition, and make described corrosion-mitigation scale-inhibition composition better play anticorrosion-antiscaling effect, with the total amount of described corrosion-mitigation scale-inhibition composition for benchmark, the content of water is preferably 40-80 % by weight.
A preferred embodiment of the invention, described corrosion-mitigation scale-inhibition composition is by cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, form containing sulfonic group multipolymer, water-soluble inorganic zinc salt and water.By this preferred implementation, corrosion-mitigation scale-inhibition composition of the present invention can realize the object of corrosion-mitigation scale-inhibition better in eco-friendly mode.
According to the present invention, described corrosion-mitigation scale-inhibition composition can be obtained by existing various method, such as can mix being formed the raw material of described corrosion-mitigation scale-inhibition composition according to aforementioned ratio and obtain, and to the step of described mixing and condition without particular requirement.
Present invention also offers the application of above-mentioned corrosion-mitigation scale-inhibition composition in cycle for the treatment of water coolant.Wherein, the consumption of described corrosion-mitigation scale-inhibition composition is preferably 20-60mg/L recirculated cooling water, is more preferably 25-40mg/L recirculated cooling water.It should be noted that, the consumption of corrosion-mitigation scale-inhibition composition only relates to the weight (namely only referring to the weight of effective constituent) of component than water herein.
The present inventor finds, corrosion-mitigation scale-inhibition composition of the present invention is specially adapted to the process of the recirculated cooling water of high rigidity high alkalinity, and preferably, the calcium hardness of described recirculated cooling water is 600-1600mg/L, and total alkalinity is 50-300mg/L.Wherein, calcium hardness and total alkalinity can record by reference standard GB/T6910-2006 and GB/T15451-2006 respectively.
According to corrosion-mitigation scale-inhibition composition of the present invention, when reality uses, can add after each raw material mixing again in recirculated cooling water, also each raw material directly can be added in recirculated cooling water without mixing step, and can add simultaneously, also can add successively.
Below will be described the present invention by embodiment.In following examples, ethylenediamine tetraacetic acid (EDTA)-beta-cyclodextrin saves with reference to " synthesis of novel beta-cyclodextrin derivative and application " (Shen is good for, in October, 2008) chapter 3 4.1.5; The preparation method of hexamethylene dinitrilo-tetraacetic acid-beta-cyclodextrin is identical with the preparation method of ethylenediamine tetraacetic acid (EDTA)-beta-cyclodextrin, just " ethylenediamine tetraacetic acid (EDTA) " is replaced with " hexamethylene dinitrilo-tetraacetic acid "; Nitrilotriacetic acid-beta-cyclodextrin saves with reference to " synthesis of novel beta-cyclodextrin derivative and application " (Shen is good for, in October, 2008) chapter 3 4.1.6; In embodiment, the usage quantity of compound includes the amount of water.
Inhibition and appraisal of scale mitigating effect is carried out with reference to the medicament of circulating cooling water dynamic simulated experiments method to following examples and comparative example preparation recorded in " water coolant analysis and test method " (1993, information center of Anqing general petrochemical works publishes) that production department of China PetroChemical Corporation and development division write.Wherein, corrosion of metal degree in the erosion rate representation unit time, can be used for the corrosion inhibition characterizing corrosion-mitigation scale-inhibition composition, erosion rate is lower shows that the corrosion inhibition of medicament is higher; Adhere to inorganic salt crust, biological clay or other impurity in the rate representation unit time in water metallic surface attachment speed, the scale-inhibiting properties of corrosion-mitigation scale-inhibition composition can be reflected, adhere to that speed is lower shows that the scale-inhibiting properties of medicament is higher.In experiment, test tube material is 20 #carbon steel, appearance chromium plating, is of a size of ; Heat transfer 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, and the circulating cooling water yield is 180L/h.Adopt pH automatic control equipment in system, add sulfuric acid (concentration is 98 % by weight) in experiment.Experiment circulating cooling water quality is as shown in table 1, calcium hardness and total alkalinity are all in CaCO3, record with reference to GB/T6910-2006 and GB/T15451-2006 respectively, the numerical range of table 1 represents the variation range of calcium hardness and total alkalinity in dynamic simulation experiment process.
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
Take 8.0g ethylenediamine tetraacetic acid (EDTA)-beta-cyclodextrin and 10.0g Sunmorl N 60S, add in 47.0g water; Add the multipolymer (solids content is 30.5 % by weight, and Limiting Viscosity when 30 DEG C is 0.075dL/g, and the weight ratio of vinylformic acid and 2 '-acrylamide-2-methyl propane sulfonic is 3:1) of 26.2g vinylformic acid and 2 '-acrylamide-2-methyl propane sulfonic; Add 8.8g Zinc vitriol again, stirring and dissolving, obtain 100g compound.By the usage quantity of 100mg/L recirculated cooling water to 1 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Embodiment 2
Take 6.0g ethylenediamine tetraacetic acid (EDTA)-beta-cyclodextrin and 8.0g sodium tartrate, add in 52.5g water; (solids content is 30.7 % by weight to add the multipolymer of 29.3g vinylformic acid and Propylene glycol monoacrylate and 2 '-acrylamide-2-methyl propane sulfonic, Limiting Viscosity when 30 DEG C is 0.081dL/g, and the weight ratio of vinylformic acid, Propylene glycol monoacrylate and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:1); Add 4.2g zinc chloride again, stirring and dissolving, obtain 100g compound.By the usage quantity of 100mg/L recirculated cooling water to 1 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Embodiment 3
Take 7.0g nitrilotriacetic acid-beta-cyclodextrin and 8.0g Potassium Gluconate, add in 52.2g water; Add the multipolymer (solids content is 30.5 % by weight, and Limiting Viscosity when 30 DEG C is 0.075dL/g, and the weight ratio of vinylformic acid and 2 '-acrylamide-2-methyl propane sulfonic is 3:1) of 26.2g vinylformic acid and 2 '-acrylamide-2-methyl propane sulfonic; Add 6.6g Zinc vitriol again, stirring and dissolving, obtain 100g compound.By the usage quantity of 120mg/L recirculated cooling water to 2 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Embodiment 4
Take 9.0g nitrilotriacetic acid-beta-cyclodextrin and 12.0g trisodium citrate, add in 41.6g water; (solids content is 31.1 % by weight to add the multipolymer of 32.2g vinylformic acid and ethyl propenoate and 2 '-acrylamide-2-methyl propane sulfonic, Limiting Viscosity when 30 DEG C is 0.085dL/g, and the weight ratio of vinylformic acid, ethyl propenoate and 2 '-acrylamide-2-methyl propane sulfonic is 4:1:2); Add 5.2g Zinc vitriol again, stirring and dissolving, obtain 100g compound.By the usage quantity of 90mg/L recirculated cooling water to 3 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Embodiment 5
Take 6.0g ethylenediamine tetraacetic acid (EDTA)-beta-cyclodextrin and 6.0g soluble tartrate, add in 38.6g water; (solids content is 30.8 % by weight to add the multipolymer of 39.0g vinylformic acid and methyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic, Limiting Viscosity when 30 DEG C is 0.069dL/g, and the weight ratio of vinylformic acid, methyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:2); Add 10.5g zinc chloride again, stirring and dissolving, obtain 100g compound.By the usage quantity of 50mg/L recirculated cooling water to 4 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Embodiment 6
Take 5.0g hexamethylene dinitrilo-tetraacetic acid-beta-cyclodextrin and 8.0g sodium malate, add in 60.3g water; Add the multipolymer (solids content is 31.2 % by weight, and Limiting Viscosity when 30 DEG C is 0.090dL/g, and the weight ratio of toxilic acid and styrene sulfonic acid is 2:1) of 25.6g toxilic acid and styrene sulfonic acid; Add 1.0g zinc chloride again, stirring and dissolving, obtain 100g compound.By the usage quantity of 150mg/L recirculated cooling water to 1 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Embodiment 7
Take 8.0g hexamethylene dinitrilo-tetraacetic acid-beta-cyclodextrin and 10.0g trisodium citrate, add in 26.9g water; (solids content is 30.7 % by weight to add the multipolymer of 48.9g vinylformic acid and Propylene glycol monoacrylate and 2 '-acrylamide-2-methyl propane sulfonic, Limiting Viscosity when 30 DEG C is 0.081dL/g, and the weight ratio of vinylformic acid, Propylene glycol monoacrylate and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:1); Add 6.3g Zinc vitriol again, stirring and dissolving, obtain 100g compound.By the usage quantity of 80mg/L recirculated cooling water to 2 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Embodiment 8
Take 6.0g nitrilotriacetic acid-beta-cyclodextrin and 10.0g potassium malate, add in 57.9g water; Add the multipolymer (solids content is 30.5 % by weight, and Limiting Viscosity when 30 DEG C is 0.075dL/g, and the weight ratio of vinylformic acid and 2 '-acrylamide-2-methyl propane sulfonic is 3:1) of 23.0g vinylformic acid and 2 '-acrylamide-2-methyl propane sulfonic; Add 3.1g zinc chloride again, stirring and dissolving, obtain 100g compound.By the usage quantity of 130mg/L recirculated cooling water to 1 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Embodiment 9
Take 8.0g ethylenediamine tetraacetic acid (EDTA)-beta-cyclodextrin and 7.0g Sunmorl N 60S, add in 40.0g water; Add the multipolymer (solids content is 30.2 % by weight, and Limiting Viscosity when 30 DEG C is 0.077dL/g, and the weight ratio of vinylformic acid and allyl sulphonic acid is 3:1) of 39.7g vinylformic acid and allyl sulphonic acid; Add 5.2g Zinc vitriol again, stirring and dissolving, obtain 100g compound.By the usage quantity of 90mg/L recirculated cooling water to 4 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Embodiment 10
Take 7.0g nitrilotriacetic acid-beta-cyclodextrin and 5.0g sodium tartrate, add in 49.2g water; (solids content is 30.8 % by weight to add the multipolymer of 32.5g vinylformic acid and methyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic, Limiting Viscosity when 30 DEG C is 0.069dL/g, and the weight ratio of vinylformic acid, methyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:2); Add 6.3g zinc chloride again, stirring and dissolving, obtain 100g compound.By the usage quantity of 100mg/L recirculated cooling water to 3 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Embodiment 11
Medicament is prepared according to the mode of embodiment 10, unlike, replace ethylenediamine tetraacetic acid (EDTA)-beta-cyclodextrin with beta-cyclodextrin, the results are shown in Table 2.
Comparative example 1
Take 12.0g sodium tartrate, add in 40.3g water; (solids content is 35.2 % by weight to add 14.2g poly-epoxy succinic acid, the trade mark is NC-312, purchased from Nanjing Na Ke water technology company limited) and the multipolymer of 29.3g vinylformic acid and Propylene glycol monoacrylate and 2 '-acrylamide-2-methyl propane sulfonic (solids content is 30.7 % by weight, Limiting Viscosity when 30 DEG C is 0.081dL/g, and the weight ratio of vinylformic acid, Propylene glycol monoacrylate and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:1); Add 4.2g zinc chloride again, stirring and dissolving, obtain 100g compound.By the usage quantity of 100mg/L recirculated cooling water to 1 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Comparative example 2
Take beta-cyclodextrin and the 4.0g sodium tartrate of 1.0g, add in 53.4g water; (solids content is 35.2 % by weight to add 8.5g poly-epoxy succinic acid, the trade mark is NC-312, purchased from Nanjing Na Ke water technology company limited) and the multipolymer of 26.5g vinylformic acid and allyl sulphonic acid (solids content is 30.2 % by weight, Limiting Viscosity when 30 DEG C is 0.077dL/g, and the weight ratio of vinylformic acid and allyl sulphonic acid is 3:1); Add 6.6g Zinc vitriol again, stirring and dissolving, obtain 100g compound.By the usage quantity of 80mg/L recirculated cooling water to 3 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Comparative example 3
Take 8.0g Sodium orthomolybdate, be dissolved in 50.7g water; The PBTCA(effective content adding 4.0g is 50.5 % by weight, the trade mark is XF-210, purchased from Jing Kexia peak, Jiangsu Environmental Protection Technology Co., Ltd) and the multipolymer of 26.4g vinylformic acid and methyl acrylate and Propylene glycol monoacrylate (solids content is 30.3 % by weight, Limiting Viscosity when 30 DEG C is 0.070dL/g, and the weight ratio of vinylformic acid, methyl acrylate and Propylene glycol monoacrylate is 3:1:2); Add 10.9g Zinc vitriol again, stirring and dissolving, obtain the low-phosphorous compound of 100g.By the usage quantity of 100mg/L recirculated cooling water to 2 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Comparative example 4
The PBTCA(effective content taking 5.0g is 50.5 % by weight, the trade mark is XF-210, purchased from Jing Kexia peak, Jiangsu Environmental Protection Technology Co., Ltd), (solids content is 35.2 % by weight to 11.4g poly-epoxy succinic acid, the trade mark is NC-312, purchased from Nanjing Na Ke water technology company limited), (solids content is 30.7% to 13.0g polyacrylic acid, Limiting Viscosity when 30 DEG C is 0.075dL/g) and the multipolymer of 29.7g vinylformic acid and methyl acrylate and Propylene glycol monoacrylate (solids content is 30.3 % by weight, Limiting Viscosity when 30 DEG C is 0.070dL/g, vinylformic acid, the weight ratio of methyl acrylate and Propylene glycol monoacrylate is 3:1:2), join in 40.9g water, stir, obtain the low-phosphorous compound of 100g.By the usage quantity of 100mg/L recirculated cooling water to 4 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Comparative example 5
Take 15.0g Sodium orthomolybdate and 3.0g Sodium Benzoate, be dissolved in 48.3g water, (solids content is 40.8 % by weight to add 9.8g poly aspartic acid, purchased from Shandong Taihe Water Treatment Co., Ltd.), (solids content is 30.3 % by weight to the multipolymer of 9.9g vinylformic acid and methyl acrylate and Propylene glycol monoacrylate, Limiting Viscosity when 30 DEG C is 0.070dL/g, vinylformic acid, the weight ratio of methyl acrylate and Propylene glycol monoacrylate is 3:1:2) and the multipolymer of 9.8g vinylformic acid and Propylene glycol monoacrylate and 2 '-acrylamide-2-methyl propane sulfonic (solids content is 30.7 % by weight, Limiting Viscosity when 30 DEG C is 0.081dL/g, vinylformic acid, the weight ratio of Propylene glycol monoacrylate and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:1), add 4.2g zinc chloride again, stirring and dissolving, obtain the without phosphorus compound of 100g.By the usage quantity of 100mg/L recirculated cooling water to 1 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Comparative example 6
Medicament is prepared according to the mode of embodiment 10, unlike, the consumption of nitrilotriacetic acid-beta-cyclodextrin is 4.0g, and the weight of zinc chloride is 12.0g, the results are shown in Table 2.
Comparative example 7
Take 1.0g nitrilotriacetic acid-beta-cyclodextrin and 5.0g sodium tartrate, add in 40.5g water; (solids content is 40.8 % by weight to add 14.7g poly aspartic acid, purchased from Shandong Taihe Water Treatment Co., Ltd.) and the multipolymer of 32.5g vinylformic acid and methyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic (solids content is 30.8 % by weight, Limiting Viscosity when 30 DEG C is 0.069dL/g, and the weight ratio of vinylformic acid, methyl acrylate and 2 '-acrylamide-2-methyl propane sulfonic is 3:1:2); Add 6.3g zinc chloride again, stirring and dissolving, obtain 100g compound.By the usage quantity of 100mg/L recirculated cooling water to 3 #add above-mentioned compound in recirculated cooling water, carry out circulating cooling water dynamic simulated experiments, the results are shown in Table 2.
Table 2
Embodiment Erosion 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, without phosphorus compound slow corrosion scale inhibition composition provided by the invention can meet the requirement of acid adding control ph circulating water cooling treatment completely, dynamic simulation experiment test tube erosion rate is all less than 0.040mm/a, adhere to speed and be all less than 8mcm, scale inhibitor effect is than the better effects if adopting phosphorous corrosion-mitigation scale-inhibition composition (comparative example 3 and comparative example 4).
In addition, embodiment 10, embodiment 11, comparative example 1, comparative example 2, comparative example 6 and comparative example 7 relatively can be found out, adopt the cyclodextrin type corrosion inhibiting and descaling agent of preferred kind of the present invention and consumption can obtain more excellent scale inhibitor effect; Especially, comparative example 7 adopts the cyclodextrin type corrosion inhibiting and descaling agent of not preferred consumption, although the total amount of the effective constituent in this comparative example is with the identical of embodiment 10 and further supplemented with containing carboxyl homopolymer (poly-epoxy succinic acid), its corrosion and scale inhibition performance is still lower than the medicament prepared according to the embodiment of the present invention 10; In addition, although the anti-incrustation corrosion inhibitor that comparative example 5 provides is not phosphorous, be difficult to meet the demands under low alkalinity condition, main manifestations is that erosion rate is not up to standard, and it is higher to adhere to speed.Therefore, without phosphorus compound slow corrosion scale inhibition composition provided by the invention more existing corrosion-mitigation scale-inhibition composition tool is had large improvement, and is adapted to the double requirements improving recirculated cooling water cycles of concentration and reduce phosphorus discharge.
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 (9)

1. a corrosion-mitigation scale-inhibition composition, it is characterized in that, this corrosion-mitigation scale-inhibition composition contain cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, containing sulfonic group multipolymer and water-soluble inorganic zinc salt, described cyclodextrin type corrosion inhibiting and descaling agent, hydroxycarboxylate, be 1-20:1-25:1-30:1 containing the weight ratio of sulfonic group multipolymer and water-soluble inorganic zinc salt, be preferably 2-6:2-7:2.5-8:1, wherein, the weight of described water-soluble inorganic zinc salt is in zine ion.
2. corrosion-mitigation scale-inhibition composition according to claim 1, wherein, described cyclodextrin type corrosion inhibiting and descaling agent is selected from least one in ethylenediamine tetraacetic acid (EDTA)-beta-cyclodextrin, nitrilotriacetic acid-beta-cyclodextrin and hexamethylene dinitrilo-tetraacetic acid-beta-cyclodextrin.
3. corrosion-mitigation scale-inhibition composition according to claim 1, wherein, described hydroxycarboxylate is selected from least one in Sunmorl N 60S, Potassium Gluconate, sodium tartrate, soluble tartrate, trisodium citrate, citric acid tri potassium, sodium malate and potassium malate.
4. corrosion-mitigation scale-inhibition composition according to claim 1, wherein, describedly be selected from multipolymer containing 2 '-acrylamide-2-methyl propane sulfonic containing sulfonic group multipolymer, containing allyl sulphonic acid multipolymer and containing styrene sulfonic acid multipolymer at least one, be preferably selected from the multipolymer of vinylformic acid and 2 '-acrylamide-2-methyl propane sulfonic, the multipolymer of vinylformic acid and acrylate and 2 '-acrylamide-2-methyl propane sulfonic, the multipolymer of vinylformic acid and allyl sulphonic acid, and at least one in the multipolymer of toxilic acid and styrene sulfonic acid, described acrylate is selected from methyl acrylate, at least one in ethyl propenoate and Propylene glycol monoacrylate.
5. corrosion-mitigation scale-inhibition composition according to claim 1, wherein, described water-soluble inorganic zinc salt is Zinc vitriol and/or zinc chloride.
6. according to the corrosion-mitigation scale-inhibition composition in claim 1-5 described in any one, wherein, described corrosion-mitigation scale-inhibition composition is also containing water, and with the total amount of described corrosion-mitigation scale-inhibition composition for benchmark, the content of water is 40-80 % by weight.
7. the application of corrosion-mitigation scale-inhibition composition in cycle for the treatment of water coolant in claim 1-6 described in any one.
8. application according to claim 7, wherein, the consumption of described corrosion-mitigation scale-inhibition composition is 20-60mg/L recirculated cooling water, is preferably 25-40mg/L recirculated cooling water.
9. the application according to claim 7 or 8, wherein, the calcium hardness of described recirculated cooling water is 600-1600mg/L, and total alkalinity is 50-300mg/L.
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