CN102745824A - Environment-friendly type water-processing corrosion and scale inhibitor and preparation method thereof - Google Patents
Environment-friendly type water-processing corrosion and scale inhibitor and preparation method thereof Download PDFInfo
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- CN102745824A CN102745824A CN2012102392766A CN201210239276A CN102745824A CN 102745824 A CN102745824 A CN 102745824A CN 2012102392766 A CN2012102392766 A CN 2012102392766A CN 201210239276 A CN201210239276 A CN 201210239276A CN 102745824 A CN102745824 A CN 102745824A
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Abstract
The invention discloses an environment-friendly type water-processing corrosion and scale inhibitor and a preparation method thereof. The environment-friendly type water-processing corrosion and scale inhibitor is a sulfonated epoxysuccinic acid/sodium gluconate copolymer, according to the environment-friendly type water-processing corrosion and scale inhibitor which is prepared by the preparation method provided by the invention, the sulfonated epoxysuccinic acid/sodium gluconate copolymer is obtained by polymerizing sulfonated polyepoxysuccinic acid as a host and sodium gluconate after the sodium gluconate is grafted, the copolymer does not contain phosphorus, can be biologically degraded and has good corrosion and scale inhibiting actions, and moreover, because a plurality of polar groups, such as hydroxyl groups, carboxylic groups, and ether groups are introduced into the copolymer, the chelating action of the sulfonated epoxysuccinic acid on metallic ions and the dispersing capability of the sulfonated epoxysuccinic acid for calcium carbonate scale, calcium phosphate scale and zinc scale are enhanced through the introduction of the polar groups, so that the corrosion and scale inhibiting actions of the sulfonated epoxysuccinic acid are enhanced.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of environment-friendly type water treating corrosion and scale inhibitor and preparation method thereof.
Background technology
The recirculated cooling water treatment technology has a very important role, but also affects to environment in the use of the medicament of circulating water treatment simultaneously water saving, problem such as energy-saving and cost-reducing.In cooling water system, water temperature is higher than under the various occasions of envrionment temperature, and the fouling meeting of inorganic salt such as lime carbonate, calcium phosphate brings serious consequence.The effectively protection against corrosion and prevent fouling of scientific utilization water treatment agent, thereby the utilization ratio of raising equipment and water and reach the purpose of practicing thrift the water source and the energy.
In recent years; In water treatment field, using basic, the water technology of not regulating the pH value are growing, wherein add the corrosion-mitigation scale-inhibition medicament; Low-phosphorous, without phosphorus prescription application more and more widely, without phosphorus green water treatment agent has become the hot subject of domestic and international water conditioner research aspect.
U.S. Pat P5062962 and U.S. Pat P5147555 show that poly-epoxy succinic acid has good scale inhibition effect to lime carbonate, calcium sulfate, permanent white; And has a good corrosion inhibition; Because its without phosphorus, no nitrogen, biodegradable belongs to green chemical truly.
Sunmorl N 60S also is a kind of environment-friendly type water treatment agent, is easy to biolysis.
Yet two kinds of materials of poly-epoxy succinic acid and Sunmorl N 60S are during separately as water conditioner, and its actual corrosion-mitigation scale-inhibition effect is not good, the condition of water quality of harshness difficult to deal with.
Summary of the invention
The objective of the invention is to deficiency to above-mentioned prior art; A kind of environment-friendly type water treating corrosion and scale inhibitor is provided; In the multipolymer that forms, introduce the various polarity group; Enhancing reaches the dispersive ability to calcium carbonate scale, calcium phosphate scale and zinc dirt to the sequestering action of metals ion, thereby reaches better inhibition and scale effect.
For achieving the above object, the technical scheme that the present invention takes is: a kind of environment-friendly type water treating corrosion and scale inhibitor is provided, it is characterized in that: this environment-friendly type water treating corrosion and scale inhibitor has following structure:
M is Na in the formula
+, K
+, NH
4 +, H
+, (Ca
2+)
1/2In at least a ion, n representes the polymerization degree, n=1 ~ 50.
The preparation method of said environment-friendly type water treating corrosion and scale inhibitor is characterized in that: may further comprise the steps:
A, dissolving are used deionized water dissolving with raw material maleic anhydride, Sodium Pyrosulfite, Sunmorl N 60S;
B, adjusting pH value, slow adding mass concentration is 30% sodium hydroxide solution under agitation condition, conditioned reaction liquid pH value is 8～9;
C, heating in water bath, heating in water bath to 50～60 ℃, the reaction times is 1～4 hour;
D, epoxidation reaction; Add sodium wolframate as catalyzer, divide 5 batches to add mass concentration 30% ydrogen peroxide 50 then, every batch of ydrogen peroxide 50 joining day is spaced apart 20 minutes; It is 5 ~ 6 that every batch of ydrogen peroxide 50 adds the pH value of using the sodium hydroxide solution of mass concentration 30% to control reaction solution in the back; Control reaction temperature is 60～70 ℃, and after ydrogen peroxide 50 all added, the epoxidation reaction of maleic anhydride was carried out in reaction in 1～3 hour;
E, ring opening copolymer reaction, the solution that steps d is obtained is warming up to 80～100 ℃, adds calcium hydroxide and carries out the ring opening copolymer reaction, and the reaction times is 1～3 hour; After-filtration is accomplished in reaction, underpressure distillation dewaters, and obtains yellow viscous liquid and is sulfonation Epoxysuccinic acid/Sunmorl N 60S multipolymer;
Wherein: the mol ratio of above-mentioned raw materials maleic anhydride, Sodium Pyrosulfite, Sunmorl N 60S is 1:0.5:0.1～1:1:1;
The add-on of above-mentioned sodium wolframate is that the mol ratio of sodium wolframate and maleic anhydride is 0.05:1～0.08:1;
The add-on of above-mentioned ydrogen peroxide 50 is that the mol ratio of ydrogen peroxide 50 and maleic anhydride is 1:1～1:0.5;
The add-on of above-mentioned calcium hydroxide is that the mol ratio of calcium hydroxide and maleic anhydride is 0.005:1～0.2:1.
Synthetic route of the present invention can be described below:
The Sunmorl N 60S that adopts among the present invention can adopt other gluconate to substitute, like Potassium Gluconate, calglucon, glucono-etc.; The sodium hydroxide solution that the present invention adopts also can take other basic soln to substitute, like potassium hydroxide solution, ammoniacal liquor etc.
The purity of maleic anhydride, Sodium Pyrosulfite, Sunmorl N 60S, sodium wolframate and calcium hydroxide that the present invention adopts is analytical pure; Wherein, sodium wolframate is Na
2WO
42H
2O.
Environment-friendly type water treating corrosion and scale inhibitor provided by the invention is sulfonation Epoxysuccinic acid/Sunmorl N 60S multipolymer; The poly-epoxy succinic acid of environment-friendly type water treating corrosion and scale inhibitor through preparation method provided by the invention preparation after with sulfonation is the main body; Grafting Sunmorl N 60S post polymerization obtains sulfonation Epoxysuccinic acid/Sunmorl N 60S multipolymer, and this multipolymer is not only not phosphorous, biodegradable; Has good corrosion-mitigation scale-inhibition effect; And owing to introduce the various polarity group in the polymkeric substance, like hydroxyl, carboxylic acid group, ether etc., the introducing of these polar groups; Strengthen poly-epoxy succinic acid to the sequestering action of metals ion and to the dirty dispersive ability of calcium carbonate scale, calcium phosphate scale and zinc, thereby strengthened the inhibition and the scale effect of poly-epoxy succinic acid.
Embodiment
Below in conjunction with embodiment and experimental example the present invention is carried out detailed description, but they not to starve further restriction to the present invention.
Embodiment 1: in the four-hole boiling flask of being furnished with TM, pH meter, prolong, whisking appliance, tap funnel, add 33.7g maleic anhydride, 57.0g Sodium Pyrosulfite and 8.5g Sunmorl N 60S, mix.Add the 60ml deionized water dissolving; Under agitation slowly adding mass concentration and be 30% sodium hydroxide solution conditioned reaction liquid pH value is 8 ~ 9; The reaction 1 ~ 4 hour that is hydrolyzed of heating in water bath to 50 ~ 60 ℃, maleic anhydride; Add the 8.02g sodium wolframate as catalyzer; Dividing 5 batches of adding total amounts then is mass concentration 30% ydrogen peroxide 50 of 47.0g, and every batch of ydrogen peroxide 50 joining day is spaced apart 20 minutes, and it is 5 ~ 6 that every batch of ydrogen peroxide 50 adds back use mass concentration 30% sodium hydroxide solution control reacting liquid pH value; Control reaction temperature is 60 ~ 70 ℃; After ydrogen peroxide 50 all adds, reacted 1 ~ 3 hour, carry out the epoxidation reaction of maleic anhydride; Again the solution that obtains is warming up to 80 ~ 100 ℃, adds 3.0g calcium hydroxide and carry out the ring opening copolymer reaction, the reaction times is 1 ~ 3 hour; After-filtration is accomplished in reaction, underpressure distillation dewaters, and obtains yellow viscous liquid and is sulfonation Epoxysuccinic acid/Sunmorl N 60S multipolymer.
Embodiment 2～12 reactions step such as embodiment 1, each material consumption is as shown in table 1.
The performance test experiment:
1, the test of the lime carbonate static-state scale inhibition performance of the product that obtains of embodiment 1 ~ 12 is carried out with reference to " State Standard of the People's Republic of China GB/T16632-2008, the mensuration tosca method of water conditioner scale-inhibiting properties ";
2, " the calcium phosphate sedimentation " in the test of the calcium phosphate static-state scale inhibition performance of the product that obtains of embodiment 1 ~ 12 " water coolant analysis and experimental technique " (Sinopec press, 1993) of writing with reference to China PetroChemical Corporation carried out;
3, " the zinc salt sedimentation " in the stability of the zine ion of the product that obtains of embodiment 1 ~ 12 test " water coolant analysis and experimental technique " (Sinopec press, 1993) of writing with reference to China PetroChemical Corporation carried out;
4, the test of the corrosion inhibition of the product that obtains of embodiment 1 ~ 12 is carried out with reference to " State Standard of the People's Republic of China GB/T 18175-2000, the mensuration of water conditioner corrosion inhibition-rotary hanging plate method "; Adopt on the RC-III type rotary hanging plate corrosion tester and carry out the corrosion inhibition experiment, 45 ℃ of temperature, rotating speed 76r/min, not preparatory film lacing film, experimental period 72 hours, the test piece of 20# carbon steel, 50mm * 25mm * 2mm; Corrosion-mitigation scale-inhibition experimental water matter index is as shown in table 2; Concrete anticorrosion-antiscaling effect situation is as shown in table 3.
Table 1: the raw material and the composition of preparation sulfonation Epoxysuccinic acid/Sunmorl N 60S multipolymer:
Table 2: the corrosion-mitigation scale-inhibition experimental water is from water distribution, and its water-quality guideline is as follows:
| Hardness is (with CaCO 3Meter)/mg.L -1 | Basicity is (with CaCO 3Meter)/mg.L -1 |
| 500 | 500 |
Table 3: corrosion and scale inhibition performance test result
Annotate: [a] lime carbonate scale inhibition experimental pharmacy concentration is 15mg/L;
[b] calcium phosphate scale inhibition experimental pharmacy concentration is 25mg/L;
[c] zinc salt scale inhibition experimental pharmacy concentration is 20mg/L;
[d] inhibition experimental pharmacy concentration is 50mg/L.
Claims (2)
1. environment-friendly type water treating corrosion and scale inhibitor, it is characterized in that: this environment-friendly type water treating corrosion and scale inhibitor has following structure:
M is Na in the formula
+, K
+, NH
4 +, H
+, (Ca
2+)
1/2In at least a ion, n representes the polymerization degree, n=1 ~ 50.
2. the preparation method of the described environment-friendly type water treating corrosion and scale inhibitor of claim 1 is characterized in that: may further comprise the steps:
A, dissolving are used deionized water dissolving with raw material maleic anhydride, Sodium Pyrosulfite, Sunmorl N 60S;
B, adjusting pH value, slow adding mass concentration is 30% sodium hydroxide solution under agitation condition, conditioned reaction liquid pH value is 8～9;
C, heating in water bath, heating in water bath to 50～60 ℃, the reaction times is 1～4 hour;
D, epoxidation reaction; Add sodium wolframate as catalyzer, divide 5 batches to add mass concentration 30% ydrogen peroxide 50 then, every batch of ydrogen peroxide 50 joining day is spaced apart 20 minutes; It is 5 ~ 6 that every batch of ydrogen peroxide 50 adds the pH value of using the sodium hydroxide solution of mass concentration 30% to control reaction solution in the back; Control reaction temperature is 60～70 ℃, and after ydrogen peroxide 50 all added, the epoxidation reaction of maleic anhydride was carried out in reaction in 1～3 hour;
E, ring opening copolymer reaction, the solution that steps d is obtained is warming up to 80～100 ℃, adds calcium hydroxide and carries out the ring opening copolymer reaction, and the reaction times is 1～3 hour; After-filtration is accomplished in reaction, underpressure distillation dewaters, and obtains yellow viscous liquid and is sulfonation Epoxysuccinic acid/Sunmorl N 60S multipolymer;
Wherein: the mol ratio of above-mentioned raw materials maleic anhydride, Sodium Pyrosulfite, Sunmorl N 60S is 1:0.5:0.1～1:1:1;
The add-on of above-mentioned sodium wolframate is that the mol ratio of sodium wolframate and maleic anhydride is 0.05:1～0.08:1;
The add-on of above-mentioned ydrogen peroxide 50 is that the mol ratio of ydrogen peroxide 50 and maleic anhydride is 1:1～1:0.5;
The add-on of above-mentioned calcium hydroxide is that the mol ratio of calcium hydroxide and maleic anhydride is 0.005:1～0.2:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730850A (en) * | 2012-07-11 | 2012-10-17 | 成都润兴消毒药业有限公司 | Environment-friendly water treatment corrosion and scale inhibitor and preparation method thereof |
| CN104071905A (en) * | 2014-06-25 | 2014-10-01 | 山东省泰和水处理有限公司 | Production method for epoxy succinic acid copolymer water treatment agent |
| CN105198098A (en) * | 2014-11-06 | 2015-12-30 | 马鞍山市鸿伟环化有限公司 | Preparation method of environment-friendly corrosion and scale inhibitor |
| CN106830377A (en) * | 2017-03-08 | 2017-06-13 | 陕西理工学院 | A kind of preparation method of antisludging agent |
| CN111848946A (en) * | 2020-07-30 | 2020-10-30 | 兰州交通大学 | Glutamine graft modified polyepoxysuccinic acid and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730850A (en) * | 2012-07-11 | 2012-10-17 | 成都润兴消毒药业有限公司 | Environment-friendly water treatment corrosion and scale inhibitor and preparation method thereof |
| CN104071905A (en) * | 2014-06-25 | 2014-10-01 | 山东省泰和水处理有限公司 | Production method for epoxy succinic acid copolymer water treatment agent |
| CN105198098A (en) * | 2014-11-06 | 2015-12-30 | 马鞍山市鸿伟环化有限公司 | Preparation method of environment-friendly corrosion and scale inhibitor |
| CN105198098B (en) * | 2014-11-06 | 2017-09-15 | 马鞍山市鸿伟环化有限公司 | A kind of preparation method of environmental type corrosion inhibiting and descaling agent |
| CN106830377A (en) * | 2017-03-08 | 2017-06-13 | 陕西理工学院 | A kind of preparation method of antisludging agent |
| CN111848946A (en) * | 2020-07-30 | 2020-10-30 | 兰州交通大学 | Glutamine graft modified polyepoxysuccinic acid and preparation method and application thereof |
| CN111848946B (en) * | 2020-07-30 | 2022-12-23 | 兰州交通大学 | Glutamine graft modified polyepoxysuccinic acid and preparation method and application thereof |
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| CN102745824B (en) | 2014-04-23 |
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