CN101607766A - A kind of preparation that is used for the corrosion inhibiting and descaling agent of high alkaline high chlorine circulating cooling water - Google Patents
A kind of preparation that is used for the corrosion inhibiting and descaling agent of high alkaline high chlorine circulating cooling water Download PDFInfo
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- CN101607766A CN101607766A CNA2009101133334A CN200910113333A CN101607766A CN 101607766 A CN101607766 A CN 101607766A CN A2009101133334 A CNA2009101133334 A CN A2009101133334A CN 200910113333 A CN200910113333 A CN 200910113333A CN 101607766 A CN101607766 A CN 101607766A
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Abstract
The preparation that is used for the corrosion inhibiting and descaling agent of high alkaline high chlorine circulating cooling water provided by the invention, prepare with parts by weight: poly-epoxy succinic acid 23-25 part, 2-phosphonic acids butane-1,2,4-tricarboxylic acid 23-25 part, inhibition synergistic agent 12-15 part, Sunmorl N 60S 10-15 part, alkyl epoxy carboxylate salt 5-8 part, benzotriazole 2-3 part, pure water 10-20 part.Preparation process: get in the 400-420 kilogram industrial phosphoric acid adding reactor and stir, in 30-35 minute, slowly add trolamine 140-160 kilogram, stirred 50～60 minutes, be incubated 40～80 ℃, add the pure water of 385-400 kilogram, stirred 20～30 minutes; Under agitation add 45-55 kilogram zinc oxide, stirred 90～120 minutes, be incubated 40～80 ℃, get the inhibition synergistic agent; Poly-epoxy succinic acid is added 2-phosphonic acids butane-1,2, in the 4-tricarboxylic acid, mix, add alkyl epoxy carboxylate salt, pure water and Sunmorl N 60S successively with the solution of inhibition synergistic agent, stirred 30～40 minutes, be incubated 20～35 ℃, add benzotriazole then, stirred 30～60 minutes, be incubated 20～35 ℃, promptly get composite slow-corrosion scale resistor.
Description
Technical field
The present invention relates to be used for the corrosion inhibiting and descaling agent of recirculating cooling water system, be particularly useful for the preparation of the corrosion inhibiting and descaling agent of high alkaline high chlorine circulating cooling water system.
Background technology
The circulating water treatment agent of adopting all is applied in electricity and leads less than 3000 μ s/cm at present, and methyl orange alkalinity is less than 500mg/L (in lime carbonate), and chloride ion content is less than the scope of 300mg/L; But because western provinces and cities water quality basicity and chloride ion content are higher, cause that methyl orange alkalinity can reach 1000mg/L in the recirculated water, chloride ion content can reach 3000mg/L, and actual motion shows as the deposition of calcium dirt.Cl
-Belong to the severe corrosive ion,, penetrate the pore on passive film surface easily and produce point corrosion because its radius is little; During other fouling, Cl
-Can rely on it to enter under the dirt and Fe than strong penetrating power
2+Reaction generates FeCl
2, FeCl
2Further hydrolysis generates Fe (OH)
2And HCl, cause corrosion region solution to be strongly-acid, corrosion of metal is speeded up, simultaneously Cl
-Still cause copper sheet spot corrosion and stress corrosion cracking.
Handle the method for this class water, the main employing hanged down the cycles of concentration operation or added the sour basicity in the water that reduces, and adds the water stabilizer that contains polyacrylic acid and multipolymer thereof simultaneously.This method is unsatisfactory in actually operating, runs counter to " energy-saving and emission-reduction " when low cycles of concentration moves; If add acid, the technological operation complexity, sour many equipment corrosions quicken, and the few fouling of acid is difficult to control.
It is the patent of 200610024183.6 " a kind of corrosion inhibiting and descaling agents that are applicable to high-chlorine and high-calcium water-quality " that retrieval obtains application number, has disclosed calcium ion safe level in the raising water coolant, impels the calcium dirt to clear up, the formation of control incrustation scale.Though but related corrosion inhibiting and descaling agent has good corrosion and scale inhibition performance under the aqueous condition of the high chlorine of high calcium, use in the water system of high pH value, and scale-inhibiting properties is reduced greatly, zinc salt is separated out with sedimentary form easily simultaneously.
The present invention is intended to overcome the shortcoming of prior art, and a kind of low-phosphorous environmentally friendly corrosion inhibiting and descaling agent that can have good corrosion and scale inhibition performance in high alkaline high chlorine circulating cooling water is provided.
Summary of the invention
The objective of the invention is: a kind of corrosion inhibiting and descaling agent that is used for high alkaline high chlorine circulating cooling water is provided, select synthetic with synergistic agent by preparation, make corrosion inhibiting and descaling agent synergy, produce strong synergy, verify after testing that particularly corrosion and fouling to suppressing circulating water system have special effect, become the product innovation of green chemical industry.
The object of the present invention is achieved like this: a kind of preparation that is used for the corrosion inhibiting and descaling agent of high alkaline high chlorine circulating cooling water, raw material is prepared with parts by weight: by poly-epoxy succinic acid 23-25 part, 2-phosphonic acids butane-1,2,4-tricarboxylic acid 23-25 part, inhibition synergistic agent 12--15 part, Sunmorl N 60S 10-15 part, alkyl epoxy carboxylate salt 5-8 part, benzotriazole 2-3 part, pure water 10-20 part is formed; And obtain through preparation process; Wherein:
The preparation of a, inhibition synergistic agent is got in the 400-420 kilogram industrial phosphoric acid adding reactor and is stirred, and slowly adds trolamine 140-160 kilogram then in 30-35 minute, and evenly stirring 50～60 minutes and keeping temperature is 40～80 ℃; The pure water that adds the 385-400 kilogram then evenly stirred 20～30 minutes; Add 45-55 kilogram zinc oxide under the state that stirs, evenly stirring 90～120 minutes and keeping temperature is 40～80 ℃, until generating the water white transparency body;
B, poly-epoxy succinic acid is added 2-phosphonic acids butane-1,2, in the 4-tricarboxylic acid;
A, the b solution that makes of step is added alkyl epoxy carboxylate salt, pure water and Sunmorl N 60S after mixing successively, evenly stirred 30～40 minutes, keeping temperature is 20～35 ℃, add benzotriazole then, evenly stirring 30～60 minutes and kept temperature is 20～35 ℃, promptly gets composite slow-corrosion scale resistor.
The preparation of described corrosion inhibiting and descaling agent, said preparation is suitable for the open type recirculating cooling water system, and pH value is 8.0～9.5; Chloride ion content is 100mg/L-3000mg/L, basicity in lime carbonate at 300～1000mg/L.
The preparation of described corrosion inhibiting and descaling agent, said preparation are benchmark with the moisturizing, and dosage is 8mg/L-10mg/L.
The preparation of described corrosion inhibiting and descaling agent, the industrial phosphoric acid of selecting for use, trolamine, zinc oxide, 2-phosphonic acids butane-1,2,4-tricarboxylic acid, benzotriazole, Sunmorl N 60S are the commercial industrial product; The poly-epoxy succinic acid solids content is greater than 30%; Alkyl epoxy carboxylate salt solids content is greater than 30%; Pure water is three grades of water; The inhibition synergistic agent solid content of preparation is greater than 40%.
The 2-phosphonic acids butane-1,2 that the present invention selects for use, the 4-tricarboxylic acid, three carboxyls and a phosphonate group are arranged, have the sequestering power stronger, demonstrated stronger inhibition and scale inhibition ability metal ion, acid-and base-resisting and oxygenant effect are arranged, hydrolysis, Heat stability is good o'clock still do not take place in pH＞14; Under, the high-temperature condition hard, high-alkali at height, it is good cathode type inhibiter that scale-inhibiting properties is better than HEDP, ATMP.
The characteristics of the alkyl epoxy carboxylate salt that the present invention selects for use are nontoxic, ability chlorine, heatproof, and good especially lime carbonate scale-inhibiting properties is arranged, and can replace the non-phosphate high-effect Scale inhibitors of organic phosphoric acid.
It is a kind ofly to have without phosphorus non-N structure that this product is selected poly-epoxy succinic acid for use, and biodegradable environmentally friendly water conditioner.Poly-epoxy succinic acid has very strong alkali-resistivity, has the scale inhibitor double effects concurrently, has inserted Sauerstoffatom and make its scale-inhibiting properties be better than organic phospho acid base polymer Scale inhibitors commonly used greatly in polymer molecule.And poly-epoxy succinic acid and 2-phosphonic acids butane-1,2, the 4-tricarboxylic acid has good synergistic function, so both composite uses, and not only scale inhibition effect is good, has also reduced the content of PBTCA phosphorus relatively, thereby has satisfied the environmental requirement of low-phosphorous discharging.
The Sunmorl N 60S that the present invention selects for use is the corrosion inhibiting and descaling agent of multi-hydroxy carboxy acid's type, it in the aqueous solution to Fe
2+, Cu
2+, Ca
2+Plasma has fabulous complex ability, to containing this ionic salt good deactivation is arranged, and cooperates with inhibiter to present synergistic effect.
The present invention does contrast, the performance of testing authentication product and practicality with the corrosion inhibiting and descaling agent and the ethylenediamine tetramethylene sodium phosphate of the adaptation high alkaline high chlorine circulating cooling water of gained.
Form preparation: 35 parts of ethylenediamine tetramethylene sodium phosphates, 2-phosphonic acids butane-1,2,10 parts of 4-tricarboxylic acid, 16 parts of PAPE, 0.4 part of Zinc Sulphate Heptahydrate, surplus is a pure water.
Water quality preparation: Ca
2+2000mg/L, Mg
2+480mg/L, PH=10, Cl
-3000mg/L; Adopt standard GB/T 16632-1996 CaCO3 sedimentation test scale-inhibiting properties, 80 ℃ of experiment water temperatures; Adopt standard GB/T 18175-2000 rotary hanging plate method to carry out the corrosion inhibition test, 80 ℃ of experiment water temperatures, 75 rev/mins of rotating speeds move 72 hours; Experimental result is as follows.
In the table
| Recombiner | Consumption mg/L | Scale inhibition performance % | Erosion rate mm/a | Phenomenon |
| Embodiment 1 | ??10 | ??92.5 | ??0.0263 | Surface-brightening has rainbow film |
| Embodiment 2 | ??10 | ??93.4 | ??0.0226 | Surface-brightening has rainbow film |
| Embodiment 3 | ??10 | ??91.2 | ??0.0297 | Surface-brightening has rainbow film |
| Comparative Examples | ??10 | ??73.4 | ??0.0756 | There is spot corrosion on the surface |
Learnt that by last table the result who adds corrosion inhibiting and descaling agent obviously is better than contrast, mainly is effectively to have controlled high basicity fouling tendency and the point corrosion of steel equipment in the homochlorcyclizine border, control indexes is in the specialized range of GB50050.
The green product innovation of the present invention's design has new approaches in the preparation of selecting materials, demonstrate fully the permanent mechanism of environment protection in preparation, and particularly the synthetic synergistic agent gets both the synergism of composite slow release Scale inhibitors and restraining effect, shows technical progress.
Embodiment
Embodiment 1
Raw material is prepared with parts by weight: by 23 parts of poly-epoxy succinic acids, 2-phosphonic acids butane-1,2, and 25 parts of 4-tricarboxylic acid, 15 parts of inhibition synergistic agent, 12 parts of Sunmorl N 60Ss, 8 parts of alkyl epoxy carboxylate salts, 2 parts of benzotriazoles, 15 parts of compositions of pure water; And through preparation; Wherein:
The preparation of a, inhibition synergistic agent is got in 420 kilograms of industrial phosphoric acids adding reactors and is stirred, and slowly adds 140 kilograms of trolamines then in 30 minutes, and evenly stirring 50 minutes and keeping temperature is 40 ℃; The pure water that adds 390 kilograms then evenly stirred 20 minutes; Add 50 kilograms of zinc oxide under the state that stirs, evenly stirring 90 minutes and keeping temperature is 40 ℃, until generating the water white transparency body;
B, poly-epoxy succinic acid is added 2-phosphonic acids butane-1,2, in the 4-tricarboxylic acid;
A, the b solution that makes of step is added alkyl epoxy carboxylate salt, pure water and Sunmorl N 60S after mixing successively, evenly stirred 30 minutes, keeping temperature is 20 ℃, adds benzotriazole then, evenly stirring 30 minutes and kept temperature is 20 ℃, promptly gets corrosion inhibiting and descaling agent.
Embodiment 2
Raw material is prepared with parts by weight: by 24 parts of poly-epoxy succinic acids, 2-phosphonic acids butane-1,2, and 24 parts of 4-tricarboxylic acid, 12 parts of inhibition synergistic agent, 15 parts of Sunmorl N 60Ss, 5 parts of alkyl epoxy carboxylate salts, 3 parts of benzotriazoles, 17 parts of compositions of pure water; And through preparation; Wherein:
The preparation of a, inhibition synergistic agent is got in 400 kilograms of industrial phosphoric acids adding reactors and is stirred, and slowly adds 160 kilograms of trolamines then in 35 minutes, and evenly stirring 60 minutes and keeping temperature is 80 ℃; The pure water that adds 400 kilograms then evenly stirred 30 minutes; Add 40 kilograms of zinc oxide under the state that stirs, evenly stirring 120 minutes and keeping temperature is 80 ℃, until generating the water white transparency body;
B, poly-epoxy succinic acid is added 2-phosphonic acids butane-1,2, in the 4-tricarboxylic acid;
A, the b solution that makes of step is added alkyl epoxy carboxylate salt, pure water and Sunmorl N 60S after mixing successively, evenly stirred 40 minutes, keeping temperature is 35 ℃, adds benzotriazole then, evenly stirring 60 minutes and kept temperature is 35 ℃, promptly gets corrosion inhibiting and descaling agent.
Embodiment 3
Raw material is prepared with parts by weight: by 25 parts of poly-epoxy succinic acids, 2-phosphonic acids butane-1,2, and 23 parts of 4-tricarboxylic acid, 13 parts of inhibition synergistic agent, 10 parts of Sunmorl N 60Ss, 6 parts of alkyl epoxy carboxylate salts, 3 parts of benzotriazoles, 20 parts of compositions of pure water; And through preparation; Wherein:
The preparation of a, inhibition synergistic agent is got in 410 kilograms of industrial phosphoric acids adding reactors and is stirred, and slowly adds 150 kilograms of trolamines then in 33 minutes, and evenly stirring 55 minutes and keeping temperature is 65 ℃; The pure water that adds 385 kilograms then evenly stirred 22 minutes; Add 55 kilograms of zinc oxide under the state that stirs, evenly stirring 100 minutes and keeping temperature is 65 ℃, until generating the water white transparency body;
B, poly-epoxy succinic acid is added 2-phosphonic acids butane-1,2, in the 4-tricarboxylic acid;
A, the b solution that makes of step is added alkyl epoxy carboxylate salt, pure water and Sunmorl N 60S after mixing successively, evenly stirred 38 minutes, keeping temperature is 30 ℃, adds benzotriazole then, evenly stirring 55 minutes and kept temperature is 28 ℃, promptly gets corrosion inhibiting and descaling agent.
The recirculating cooling water system that embodiment 2 corrosion inhibiting and descaling agents is used for certain power plant for self-supply of sylvite factory.At the scene during 4 times of cycles of concentration, circulating water quality pH value 9.5, chlorion 1429.6mg/L, the moisturizing added amount of chemical is 8mg/L, effectively controlled fouling and corrosion condition, every index all is controlled in the set quota scope of GB50050, and on-the-spot service condition is good.
Claims (4)
1. preparation that is used for the corrosion inhibiting and descaling agent of high alkaline high chlorine circulating cooling water, it is characterized in that: raw material is prepared with parts by weight: by poly-epoxy succinic acid 23-25 part, 2-phosphonic acids butane-1,2,4-tricarboxylic acid 23-25 part, inhibition synergistic agent 12--15 part, Sunmorl N 60S 10-15 part, alkyl epoxy carboxylate salt 5-8 part, benzotriazole 2-3 part, pure water 10-20 part is formed; And obtain through preparation process; Wherein:
The preparation of a, inhibition synergistic agent is got in the 400-420 kilogram industrial phosphoric acid adding reactor and is stirred, and slowly adds trolamine 140-160 kilogram then in 30-35 minute, and evenly stirring 50～60 minutes and keeping temperature is 40～80 ℃; The pure water that adds the 385-400 kilogram then evenly stirred 20～30 minutes; Add 45-55 kilogram zinc oxide under the state that stirs, evenly stirring 90～120 minutes and keeping temperature is 40～80 ℃, until generating the water white transparency body;
B, poly-epoxy succinic acid is added 2-phosphonic acids butane-1,2, in the 4-tricarboxylic acid;
A, the b solution that makes of step is added alkyl epoxy carboxylate salt, pure water and Sunmorl N 60S after mixing successively, evenly stirred 30～40 minutes, keeping temperature is 20～35 ℃, add benzotriazole then, evenly stirring 30～60 minutes and kept temperature is 20～35 ℃, promptly gets composite slow-corrosion scale resistor.
2. the preparation of corrosion inhibiting and descaling agent according to claim 1 is characterized in that: said preparation is suitable for the open type recirculating cooling water system, and pH value is 8.0～9.5; Chloride ion content is 100mg/L-3000mg/L, basicity in lime carbonate at 300～1000mg/L.
3. the preparation of corrosion inhibiting and descaling agent according to claim 1 is characterized in that: said preparation is benchmark with the moisturizing, and dosage is 8mg/L--10mg/L.
4. the preparation of corrosion inhibiting and descaling agent according to claim 1 is characterized in that: the industrial phosphoric acid of selecting for use, trolamine, zinc oxide, 2-phosphonic acids butane-1,2, and 4-tricarboxylic acid, benzotriazole, Sunmorl N 60S are the commercial industrial product; The poly-epoxy succinic acid solids content is greater than 30%; Alkyl epoxy carboxylate salt solids content is greater than 30%; Pure water is three grades of water; The inhibition synergistic agent solid content of preparation is greater than 40%.
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