CN104176837B - Scale inhibitors - Google Patents
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- CN104176837B CN104176837B CN201410454862.1A CN201410454862A CN104176837B CN 104176837 B CN104176837 B CN 104176837B CN 201410454862 A CN201410454862 A CN 201410454862A CN 104176837 B CN104176837 B CN 104176837B
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Abstract
The present invention relates to a kind of anticorrosion-antiscaling effect Scale inhibitors that is better, the effectively industrial high mineral ion content waste water of process.Comprise component A and the B component of mixing mutually, component A is hydrolytic polymaleic anhydride (HPMA), B component is by methylene-succinic acid (IA), the multipolymer of 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) three kinds of monomer synthesize, in above-mentioned copolymer molecule formula, x, y, z represents methylene-succinic acid (IA) respectively, the mole number of 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP), and x:y:z=(50.3-70.6): (11-16): (33-41), component A and B component are (4-6) in the ratio of mass fraction: 1.
Description
Technical field
The present invention relates to a kind of Scale inhibitors, particularly relate to the Scale inhibitors of the high mineral ion content waste water of a kind of industry.
Background technology
In the waste water of the trade effluent especially heavy metal processing industry such as mine, containing a large amount of mineral substance dissolved; For calcium ion, in concentrated, the mineral lime-ash of recirculated cooling water, the mode such as continuous dissolving of calcium, makes the calcium ion Ca in water
2+concentration constantly raises, and pH value constantly rises, sometimes even more than 11, OH
-increase make in water HCO
3-to CO3
2-transform, Ca
2+with CO3
2-generate CaCO3 crystal, be deposited on pipeline, the pump housing and pool wall, form hard fouling.Except calcium ion, common also have the metal ion such as magnesium ion, iron ion, and the heavy metal ion such as barium ion.
But existing Scale inhibitors, usually under different pH conditions, be difficult to maintain more consistent scale inhibition efficiency, such as hydrolytic polymaleic anhydride (HPMA) is conventional Scale inhibitors monomer, chemical stability and thermostability high, decomposition temperature is more than 330 DEG C, under high temperature (≤350 DEG C) and higher pH (8.3), there is good scale inhibition effect, the scale inhibition time can reach 100 hours, when pH value is at 6-9, HPMA has good scale inhibition efficiency, and scale inhibition performance can reach more than 90%; But when pH value is greater than 9, its scale inhibition efficiency obviously declines, when pH value 10, its scale inhibition performance only about 50%.
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 Scale inhibitors that is better, the effectively industrial high mineral ion content waste water of process.
The invention provides a kind of Scale inhibitors, comprise component A and the B component of mixing mutually, component A is hydrolytic polymaleic anhydride (HPMA), and its molecular formula is
B component is that the molecular formula of described multipolymer is by the multipolymer of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) three kinds of monomer synthesize
In above-mentioned copolymer molecule formula, x, y, z represents the mole number of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) respectively, and x:y:z=(50.3-70.6): (11-16): (33-41);
Described component A and B component are (4-6) in 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-propane 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-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) in described B component: (13-14): (38-40).
Further, described component A and B component in the ratio of mass fraction for 5:1.
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: under the condition of nitrogen protection and Keep agitation, drips initiator solution and AMPS/AMPP mixed solution respectively, carries out copolymerization reaction; Temperature of reaction controls at 80 ± 1 DEG C, and time for adding controls at 1h, after initiator solution and AMPS/AMPP mixed solution dropwise, continues insulation reaction 2-4h, stops heating, and after stirring, cooling, discharging obtains B component solution.
3) component solution A preparation: take maleic anhydride as raw material, toluene is solvent, under the initiation of benzoyl peroxide, polymerization obtains component solution A;
4) Scale inhibitors aqueous solution preparation: component solution A and B component solution are mixed and stirred, the sodium hydroxide solution being then 10% with mass percent adjusts pH to 7, can obtain the Scale inhibitors aqueous solution.
Concrete, above-mentioned steps 1) and step 2) carry out in the four-hole boiling flask that electric mixing device, reflux condensing tube, dropping funnel and thermometer are housed.
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 following outstanding advantage: 1) design and the polymer antisludging agent prepared contains a large amount of carboxyl, thus have critical effect and lattice distortion ability concurrently, scale prevention ability is strong; In polymkeric substance, hydroxy-acid group is too much, can react generate gel, the sulfonic group in 2-acrylamide-2-methyl propane sulfonic (AMPS) with the high volence metal ion in water, can effectively prevent gel from producing and discrete particles thing, stable metal ion; 2) HPMA is with the organic phosphonate compound in 1 ~ 15ppm and B component, has the effect that good suppression incrustation scale generated and peeled off old dirt; 3) copolymer antisludging agent of the present invention can reach 98% to the scale inhibition performance of calcium carbonate scale, can reach 97.4% to the scale inhibition performance of barium sulfate scale, and scale-inhibiting properties is given prominence to; 4) product of the present invention has suitability widely, and corrosion mitigating effect better, effectively processes 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, be described in detail as follows below with preferred embodiment of the present invention.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment one
The invention provides a kind of Scale inhibitors, comprise component A and the B component of mixing mutually, component A is hydrolytic polymaleic anhydride (HPMA), and its molecular formula is
B component is that the molecular formula of described multipolymer is by the multipolymer of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) three kinds of monomer synthesize
In above-mentioned copolymer molecule formula, x, y, z represents the mole number of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) respectively, and x:y:z=(50.3-70.6): (11-16): (33-41); Component A and B component are (4-6) in the ratio of mass fraction: 1.
The ratio of the mole number of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) in B component, 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, thus by the ratio of its mole number of adjustment, 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), and concrete test-results sees the following form:
Table 1 monomer ratio is on the impact of B component performance of antisludging agent
Note: calcium carbonate, calcium phosphate consumption are respectively 12,18mg/L.
Experimental result shows, IA content increases, and resistance CaCO3 ability slightly increases, but its resistance Ca3 (PO4) 2 ability declines on the contrary; Increase AMPS content, its resistance CaCO3 dirt and the dirty ability of Ca3 (PO4) 2 are just in time contrary with increase IA; Increase IA and AMPS content, its resistance CaCO3 dirt and the dirty ability of Ca3 (PO4) 2 rise all to some extent, and this shows that carboxylic IA mainly hinders CaCO3 dirt, and useful to resistance Ca3 (PO4) 2 dirt containing the AMPS of sulfonic acid group simultaneously.If but IA or AMPS too high levels, have a significant impact its percent polymerization, from the actual dosage of minimizing, three's proportioning can only keep within the specific limits.
In order to verify impact on the scale inhibition performance of Scale inhibitors after component A and B component mixing further, do further checking with the ratio x:y:z=60:13.5:39 of IA, AMPS, AMPP mole number in B component, concrete test-results sees the following form:
Table 2 component A, B component proportioning are on the impact of performance of antisludging agent
Note: calcium carbonate, calcium phosphate consumption are respectively 12,18mg/L.
According to upper table, after being mixed with B component by component A, can significantly improve the scale inhibition performance of Scale inhibitors, meanwhile, when in the ratio of mass fraction for 5:1, scale inhibition performance is optimum.
Embodiment two
Component A, B component are used alone, 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 inhibitors of table 3 is scale inhibition performance contrast under high alkali environment
Note: basicity calculates with HCO3-concentration (mg/L), various Scale inhibitors uses equal in quality.
According to upper table, component A and B component used in combination when, even if basicity is higher in sewage, still can obtain good scale inhibition performance.Experiment proves, Scale inhibitors of the present invention, goes for the sewage disposal of pH9-11.5.
Embodiment three
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: under the condition of nitrogen protection and Keep agitation, drips initiator solution and AMPS/AMPP mixed solution respectively, carries out copolymerization reaction; Temperature of reaction controls at 80 ± 1 DEG C, and time for adding controls at 1h, after initiator solution and AMPS/AMPP mixed solution dropwise, continues insulation reaction 2-4h, stops heating, and after stirring, cooling, discharging obtains B component solution.
3) component solution A preparation: take maleic anhydride as raw material, toluene is solvent, under the initiation of benzoyl peroxide, polymerization obtains component solution A;
4) Scale inhibitors aqueous solution preparation: component solution A and B component solution are mixed and stirred, the sodium hydroxide solution being then 10% with mass percent adjusts pH to 7, can obtain the Scale inhibitors aqueous solution.
Above-mentioned steps 1) and step 2) carry out in the four-hole boiling flask that electric mixing device, reflux condensing tube, dropping funnel and thermometer are housed, the initiator adopted 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; under the prerequisite not departing from 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: the component A and the B component that comprise mixing mutually, component A is hydrolytic polymaleic anhydride (HPMA), and its molecular formula is
B component is that the molecular formula of described multipolymer is by the multipolymer of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) three kinds of monomer synthesize
In above-mentioned copolymer molecule formula, x, y, z represents the mole number of methylene-succinic acid (IA), 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) respectively, and x:y:z=(50.3-70.6): (11-16): (33-41);
Described component A and B component are (4-6) in 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 (IA), 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) in described B component: (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 (IA), 2-acrylamide-2-methyl-propane sulfonic acid (AMPS) and 2-acrylamide-2-methyl-propyl phosphonic acids (AMPP) in described B component: (13-14): (38-40).
4. Scale inhibitors according to claim 1, is characterized in that: described component A and B component in the ratio of mass fraction for 5:1.
5. a preparation method for the Scale inhibitors according to any one of Claims 1-4, 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: under the condition of nitrogen protection and Keep agitation, drips initiator solution and AMPS/AMPP mixed solution respectively, carries out copolymerization reaction; Temperature of reaction controls at 80 ± 1 DEG C, and time for adding controls at 1h, after initiator solution and AMPS/AMPP mixed solution dropwise, continues insulation reaction 2-4h, stops heating, and after stirring, cooling, discharging obtains B component solution;
3) component solution A preparation: take maleic anhydride as raw material, toluene is solvent, under the initiation of benzoyl peroxide, polymerization obtains component solution A;
4) Scale inhibitors aqueous solution preparation: component solution A and B component solution are mixed and stirred, the sodium hydroxide solution being then 10% with mass percent adjusts pH to 7, can obtain the Scale inhibitors aqueous solution.
6. Scale inhibitors preparation method according to claim 5, is characterized in that: above-mentioned steps 1) and step 2) carry out in the four-hole boiling flask that electric mixing device, reflux condensing tube, dropping funnel and thermometer are housed.
7. Scale inhibitors preparation method according to claim 5, is characterized in that: described initiator is ammonium persulphate or superoxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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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| 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 |
| 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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