CN104176837A - Scale inhibitor - Google Patents
Scale inhibitor Download PDFInfo
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- CN104176837A CN104176837A CN201410454862.1A CN201410454862A CN104176837A CN 104176837 A CN104176837 A CN 104176837A CN 201410454862 A CN201410454862 A CN 201410454862A CN 104176837 A CN104176837 A CN 104176837A
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Abstract
The invention relates to a scale inhibitor which has a relatively good corrosion and scale inhibition effect and can effectively treat industrial high-mineral-ion wastewater. The scale inhibitor comprises a component A and a component B which are mixed with each other, wherein the component A is hydrolytic polymaleic anhydride (HPMA); the component B is copolymer synthesized by using itaconic acid (IA), 2-acrylamido-2-methyl propyl sulfonic acid (AMPS) and 2-2-acrylamido-2-methyl propyl phosphonic acid (AMPP); in a molecular formula of the copolymer, x, y and z represent mole numbers of IA, AMPS and AMPP respectively, and the ratio of x to y to z is (50.3-70.6) to (11-16) to (33-41); the mass part ratio of the component A to the component B is (4-6) to 1.
Description
Technical field
The present invention relates to a kind of Scale inhibitors, relate in particular to the Scale inhibitors of the high mineral ion content waste water of a kind of industry.
Background technology
Trade effluent is especially in the waste water of the heavy metal processing industry such as mine, the mineral substance that contains a large amount of dissolvings; Take calcium ion as example, and in concentrated, the mineral lime-ash of recirculated cooling water, the modes such as continuous dissolving of calcium, make the calcium ion Ca in water
2+concentration constantly raises, and pH value constantly rises, and sometimes even surpasses 11, OH
-increase make the HCO in water
3 -to CO
3 2-transform Ca
2+with CO
3 2-generate CaCO
3crystal, is deposited on pipeline, the pump housing and pool wall, forms hard fouling.Except calcium ion, common also have the metal ions such as magnesium ion, iron ion, and the heavy metal ion such as barium ion.
Yet existing Scale inhibitors, conventionally under different pH conditions, be difficult to the scale inhibition efficiency that remains more consistent, for example hydrolytic polymaleic anhydride (HPMA) is conventional Scale inhibitors monomer, and chemical stability and thermostability are high, decomposition temperature is more than 330 ℃, under high temperature (≤350 ℃) and higher pH (8.3), have good scale inhibition effect, the scale inhibition time can reach 100 hours, when pH value is during at 6-9, HPMA has good scale inhibition efficiency, and scale inhibition performance can reach more than 90%; But in pH value, be greater than at 9 o'clock, its scale inhibition efficiency obviously declines, and when pH value 10, its scale inhibition performance is 50% left and right only.
Summary of the invention
For solving the problems of the technologies described above, the object of this invention is to provide a kind of corrosion mitigating effect and better, effectively process the Scale inhibitors of industrial high mineral ion content waste water.
The invention provides a kind of Scale inhibitors, comprise component A and the B component of mutual mixing, component A is hydrolytic polymaleic anhydride (HPMA), and its molecular formula is
B component is by methylene-succinic acid (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and three kinds of synthetic multipolymers of monomer of 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP), the molecule of described multipolymer
Formula is
In above-mentioned copolymer molecule formula, x, y, z represents respectively the mole number of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP), and x:y:z=(50.3-70.6): (11-16): (33-41);
It is (4-6) that described component A and B component be take the ratio of mass fraction: 1.
Further, the ratio x:y:z=(55.7-65.6) of the mole number of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) in described B component: (12-15): (35-40).
Further, the ratio x:y:z=(58.4-62.3) of the mole number of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) in described B component: (13-14): (38-40).
Further, to take the ratio of mass fraction be 5:1 for described component A and B component.
The present invention also provides a kind of Scale inhibitors preparation method, comprises the following steps:
1) methylene-succinic acid aqueous solution preparation: be mixed in proportion methylene-succinic acid, sodium hypophosphite and distilled water;
2) copolyreaction: in nitrogen protection and under the condition that continues to stir, drip respectively initiator solution and AMPS/AMPP mixed solution, carry out copolymerization reaction; Temperature of reaction is controlled at 80 ± 1 ℃, and time for adding is controlled at 1h left and right, after initiator solution and AMPS/AMPP mixed solution dropwise, continues insulation reaction 2-4h, stops heating, and stirring, cooling rear discharging obtain B component solution.
3) component A solution preparation: take maleic anhydride as raw material, toluene is solvent, and polymerization obtains component A solution under the initiation of benzoyl peroxide;
4) Scale inhibitors aqueous solution preparation: component A solution and B component solution are mixed and stirred, and the sodium hydroxide solution that the mass percent of then take is 10% is adjusted pH to 7, can obtain the Scale inhibitors aqueous solution.
Concrete, above-mentioned steps 1) and step 2) in the four-hole boiling flask that electric stirring, reflux condensing tube, dropping funnel and thermometer are housed, carry out.
Concrete, described initiator is ammonium persulphate or superoxide.
By such scheme, copolymer antisludging agent containing sulfonic group, phosphonate group and many carboxyls of the present invention has advantages of following outstanding: 1) design and the polymer antisludging agent prepared contains a large amount of carboxyls, thereby having critical effect and lattice distortion ability concurrently, scale inhibition ability is strong; In polymkeric substance, hydroxy-acid group is too much, can react with the high volence metal ion in water and generate gel, and the sulfonic group in 2-acrylamide-2-methyl propane sulfonic (AMPS), can prevent that gel from producing and discrete particles thing, stable metal ion effectively; 2) HPMA is compound with the organic phosphonate in 1～15ppm and B component, has the effect that good inhibition incrustation scale generates and peels off old dirt; 3) copolymer antisludging agent of the present invention can reach 98% to the scale inhibition performance of calcium carbonate scale, to the scale inhibition performance of barium sulfate scale, can reach 97.4%, and scale-inhibiting properties is outstanding; 4) product of the present invention has suitability widely, and corrosion mitigating effect better, is effectively processed industrial high mineral ion content waste water.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technique means of the present invention, and can be implemented according to the content of specification sheets, below with preferred embodiment of the present invention, is described in detail as follows.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment mono-
The invention provides a kind of Scale inhibitors, comprise component A and the B component of mutual mixing, component A is hydrolytic polymaleic anhydride (HPMA), and its molecular formula is
B component is that the molecular formula of described multipolymer is by methylene-succinic acid (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and three kinds of synthetic multipolymers of monomer of 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP)
In above-mentioned copolymer molecule formula, x, y, z represents respectively the mole number of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP), and x:y:z=(50.3-70.6): (11-16): (33-41); It is (4-6) that component A and B component be take the ratio of mass fraction: 1.
The ratio of the mole number of methylene-succinic acid in B component (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP), ratio and the percent polymerization of carboxylic acid and phosphoric acid in Scale inhibitors will be had influence on, and then have influence on the scale inhibition efficiency of Scale inhibitors, thereby by adjusting the ratio of its mole number, fix other experiment condition, to investigate its impact on copolymer polymerization rate and scale-inhibiting properties, comparatively preferred, x:y:z=(55.7-65.6): (12-15): (35-40); Optimal situation is x:y:z=(58.4-62.3): (13-14): (38-40), concrete test-results sees the following form:
The impact of table 1 monomer ratio on B component performance of antisludging agent
Note: calcium carbonate, calcium phosphate consumption are respectively 12,18mg/L.
Experimental result shows, the increase of IA content, resistance CaCO
3ability slightly increases, but its resistance Ca
3(PO
4)
2ability declines on the contrary; Increase AMPS content, it hinders CaCO
3dirt and Ca
3(PO
4)
2dirt ability is just in time contrary with increase IA; Increase IA and AMPS content, it hinders CaCO simultaneously
3dirt and Ca
3(PO
4)
2dirt ability all rises to some extent, and this shows that carboxylic IA mainly hinders CaCO
3dirt, and the AMPS that contains sulfonic acid group is to resistance Ca
3(PO
4)
2dirt is useful.If but IA or AMPS too high levels have a significant impact its percent polymerization, from reducing actual dosage, three's proportioning can only keep within the specific limits.
For further checking component A and B component mix after impact on the scale inhibition performance of Scale inhibitors, with the ratio x:y:z=60:13.5:39 of IA, AMPS, AMPP mole number in B component, do further checking, concrete test-results sees the following form:
Table 2 component A, the impact of B component proportioning on performance of antisludging agent
Note: calcium carbonate, calcium phosphate consumption are respectively 12,18mg/L.
Known according to upper table, after component A is mixed with B component, can significantly improve the scale inhibition performance of Scale inhibitors, meanwhile, in the situation that the ratio of mass fraction of take is 5:1, scale inhibition performance is optimum.
Embodiment bis-
Component A, B component are used separately, and compare with other typical Scale inhibitors, to identify its scale inhibition performance, wherein, in B component, the ratio of IA, AMPS, AMPP mole number is fixed as x:y:z=60:13.5:39, and the ratio of mixture of component A and B component is fixed as 5:1.Concrete test-results sees the following form:
The various Scale inhibitorss of table 3 are scale inhibition performance contrast under high alkali environment
Note: basicity is calculated with HCO3-concentration (mg/L), various Scale inhibitorss are used equal in quality.
Known according to upper table, component A and B component are mixed in situation about using, even basicity is higher in sewage, still can obtain good scale inhibition performance.Experiment showed, Scale inhibitors of the present invention, go for the sewage disposal of pH9-11.5.
Embodiment tri-
The present invention also provides a kind of Scale inhibitors preparation method, comprises the following steps:
1) methylene-succinic acid (IA) aqueous solution preparation: be mixed in proportion methylene-succinic acid (IA), sodium hypophosphite and distilled water;
2) copolyreaction: in nitrogen protection and under the condition that continues to stir, drip respectively initiator solution and AMPS/AMPP mixed solution, carry out copolymerization reaction; Temperature of reaction is controlled at 80 ± 1 ℃, and time for adding is controlled at 1h left and right, after initiator solution and AMPS/AMPP mixed solution dropwise, continues insulation reaction 2-4h, stops heating, and stirring, cooling rear discharging obtain B component solution.
3) component A solution preparation: take maleic anhydride as raw material, toluene is solvent, and polymerization obtains component A solution under the initiation of benzoyl peroxide;
4) Scale inhibitors aqueous solution preparation: component A solution and B component solution are mixed and stirred, and the sodium hydroxide solution that the mass percent of then take is 10% is adjusted pH to 7, can obtain the Scale inhibitors aqueous solution.
Above-mentioned steps 1) and step 2) in the four-hole boiling flask that electric stirring, reflux condensing tube, dropping funnel and thermometer are housed, carry out, the initiator adopting is ammonium persulphate or superoxide.
The above is only the preferred embodiment of the present invention; be not limited to the present invention; should be understood that; for those skilled in the art; do not departing under the prerequisite of the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (7)
1. a Scale inhibitors, is characterized in that: comprise component A and the B component of mutual mixing, component A is hydrolytic polymaleic anhydride (HPMA), and its molecular formula is
B component is that the molecular formula of described multipolymer is by methylene-succinic acid (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and three kinds of synthetic multipolymers of monomer of 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP)
In above-mentioned copolymer molecule formula, x, y, z represents respectively the mole number of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP), and x:y:z=(50.3-70.6): (11-16): (33-41);
It is (4-6) that described component A and B component be take the ratio of mass fraction: 1.
2. Scale inhibitors according to claim 1, is characterized in that: the ratio x:y:z=(55.7-65.6) of the mole number of methylene-succinic acid in described B component (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP): (12-15): (35-40).
3. Scale inhibitors according to claim 2, is characterized in that: the ratio x:y:z=(58.4-62.3) of the mole number of methylene-succinic acid in described B component (IA), 2-acrylamide-2-methyl-propyl sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP): (13-14): (38-40).
4. Scale inhibitors according to claim 1, is characterized in that: it is 5:1 that described component A and B component be take the ratio of mass fraction.
5. according to a preparation method for the Scale inhibitors described in claim 1 to 4 any one, it is characterized in that: comprise the following steps:
1) methylene-succinic acid aqueous solution preparation: be mixed in proportion methylene-succinic acid, sodium hypophosphite and distilled water;
2) copolyreaction: in nitrogen protection and under the condition that continues to stir, drip respectively initiator solution and AMPS/AMPP mixed solution, carry out copolymerization reaction; Temperature of reaction is controlled at 80 ± 1 ℃, and time for adding is controlled at 1h left and right, after initiator solution and AMPS/AMPP mixed solution dropwise, continues insulation reaction 2-4h, stops heating, and stirring, cooling rear discharging obtain B component solution.
3) component A solution preparation: take maleic anhydride as raw material, toluene is solvent, and polymerization obtains component A solution under the initiation of benzoyl peroxide;
4) Scale inhibitors aqueous solution preparation: component A solution and B component solution are mixed and stirred, and the sodium hydroxide solution that the mass percent of then take is 10% is adjusted pH to 7, can obtain the Scale inhibitors aqueous solution.
6. Scale inhibitors preparation method according to claim 1, is characterized in that: above-mentioned steps 1) and step 2) in the four-hole boiling flask that electric stirring, reflux condensing tube, dropping funnel and thermometer are housed, carry out.
7. Scale inhibitors preparation method according to claim 1, is characterized in that: described initiator is ammonium persulphate or superoxide.
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| CN201410454862.1A CN104176837B (en) | 2014-09-09 | 2014-09-09 | Scale inhibitors |
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|---|---|---|---|
| CN201410454862.1A CN104176837B (en) | 2014-09-09 | 2014-09-09 | Scale inhibitors |
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| CN104176837B CN104176837B (en) | 2015-09-16 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669899A (en) * | 2016-01-19 | 2016-06-15 | 辽宁石油化工大学 | Novel non-phosphorus quadripolymer scale inhibitor and preparation method thereof |
| CN107010740A (en) * | 2017-06-12 | 2017-08-04 | 西安工程大学 | A kind of sewage disposal antisludging agent and preparation method thereof |
| CN110563168A (en) * | 2019-09-11 | 2019-12-13 | 宁夏神耀科技有限责任公司 | Scale inhibition and dispersion agent and preparation method thereof |
| CN112794418A (en) * | 2020-12-03 | 2021-05-14 | 嘉兴沃特泰科环保科技股份有限公司 | Feedwater rust-proof RO scale inhibitor and preparation method thereof |
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| CN1313345A (en) * | 2000-03-09 | 2001-09-19 | 湘潭大学 | Sulfonate copolymer containing phosphorus and its preparing process and application |
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| CN102899006A (en) * | 2012-09-20 | 2013-01-30 | 中国石油化工股份有限公司 | Phosphonic acid group-containing polymer drilling fluid viscosity reducer and preparation method thereof |
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| CN103803716A (en) * | 2012-11-09 | 2014-05-21 | 中国石油化工股份有限公司 | Method for recycling reclaimed water in circulating cooling water system |
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Patent Citations (8)
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| US4650591A (en) * | 1985-08-29 | 1987-03-17 | Calgon Corporation | Acrylic acid/2-acrylamido-2-methylpropylsulfonic acid/2-acrylamido-2-methylpropyl phosphonic acid polymers as scale and corrosion inhibitors |
| US4867945A (en) * | 1986-08-04 | 1989-09-19 | Calgon Corporation | Method of inhibiting the corrosion of copper and copper alloys |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669899A (en) * | 2016-01-19 | 2016-06-15 | 辽宁石油化工大学 | Novel non-phosphorus quadripolymer scale inhibitor and preparation method thereof |
| CN107010740A (en) * | 2017-06-12 | 2017-08-04 | 西安工程大学 | A kind of sewage disposal antisludging agent and preparation method thereof |
| CN107010740B (en) * | 2017-06-12 | 2020-08-25 | 西安工程大学 | Scale inhibitor for sewage treatment and preparation method thereof |
| CN110563168A (en) * | 2019-09-11 | 2019-12-13 | 宁夏神耀科技有限责任公司 | Scale inhibition and dispersion agent and preparation method thereof |
| CN112794418A (en) * | 2020-12-03 | 2021-05-14 | 嘉兴沃特泰科环保科技股份有限公司 | Feedwater rust-proof RO scale inhibitor and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN104176837B (en) | 2015-09-16 |
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