CN105669899A - Novel non-phosphorus quadripolymer scale inhibitor and preparation method thereof - Google Patents
Novel non-phosphorus quadripolymer scale inhibitor and preparation method thereof Download PDFInfo
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- CN105669899A CN105669899A CN201610035987.XA CN201610035987A CN105669899A CN 105669899 A CN105669899 A CN 105669899A CN 201610035987 A CN201610035987 A CN 201610035987A CN 105669899 A CN105669899 A CN 105669899A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
Abstract
The invention discloses a novel non-phosphorus quadripolymer scale inhibitor and a preparation method thereof.The novel non-phosphorus quadripolymer scale inhibitor is characterized by being formed by polymerization of four monomers including itaconic acid, methyl acrylate, acrylamide and 2-acrylamido-2-methylpropane sulfonic acid in an aqueous solution according to a mole ratio of 1:(0.4-0.6):(0.3-0.7):(0.1-0.4), wherein ammonium persulfate serves as an initiator.The prepared scale inhibitor is excellent in inhibition of calcium carbonate scale and calcium phosphate scale and has excellent iron oxide dispersing performance and non-phosphorus high-temperature-resistant performances.The novel non-phosphorus quadripolymer scale inhibitor can be widely applied to the field of industrial water treatment and is low in consumption, a manufacturing process is simple and free of pollution, and high economic benefits and environmental benefits are achieved.
Description
Technical field
This invention relates to a kind of novel non-phosphate quadripolymer Scale inhibitors and its preparation method, and this Scale inhibitors is mainly used in the process of industrial circulating cooling water, is a kind of green scale inhibitor without phosphorus, efficient.
Background technology
Since reform and opening-up, along with the continuous rising with total output value per capita that increases sharply of China's size of population, the supply and demand problem of water resources is constantly intensified. Wherein, first process water faces challenges, and most industry department of China adopts recirculating cooling water system always. But in recirculating cooling water system, owing to recirculated water is by continuous heating and cooling so that in water system, concentration of metal ions increases, and then reach hypersaturated state, or because raised temperature, some metallic salts form precipitation, it is deposited in pipeline, thus forms incrustation scale. Incrustation scale not only can increase the resistance to flow of water, slows down velocity of flow, increases the working cost of recycle pump, but also can affect the heat exchange efficiency of interchanger. Dirt is present in pipeline for a long time, pipeline can be caused underdeposit corrosion, and then more serious accident occurs, and hinders the normal operation of enterprise. Therefore, the treatment process seeking incrustation scale receives the attention of investigator. What wherein obtain most widespread use is exactly polymer antisludging agent.
The utilization ratio improving industrial circulating water is served very crucial effect by the development of Scale inhibitors. From 60 years 20th century, Scale inhibitors starts to be developed, and the dirt dispersion agent used at that time is sodium lignosulfonate etc. mainly, and they have certain scale effect, can partly solve incrustation scale deposition and zinc salt stable problem, but can not meet far away and produce the requirement to scale-inhibiting properties. Progressively develop polymer antisludging agent, it may also be useful to the widest is the polymer antisludging agent containing phosphorus for this reason. Such as Chinese patent, to disclose application number be CN00113316 " a kind of co-polymer of sulfonate containing phosphorus and its production and use ", application number be CN95111773 " a kind of terpolymer water antisludging agent containing phosphorus ", application number is the preparation method that CN03122759 contains ether phosphonic acids sulfonic acid multiple copolymer and multifunctional water treating agent ". But phosphorus can cause body eutrophication, welding, the eighties in 20th century, Scale inhibitors also developed to nontoxic without phosphorus environmentally friendly Scale inhibitors along with environment is to the enhancing of the restriction of discharge of industrial wastes and people's environmental consciousness.Start to study and more mainly contain poly aspartic acid, poly-epoxy succinic acid, such as Chinese patent, to disclose application number be CN02111415 " polyasparagic acid as environment protecting scale inhibitor preparation method ", application number is CN00310101837: " a kind of containing poly-epoxy succinic acid corrosion-mitigation scale-inhibition treatment process ". But its cost is all too high, it is little that enterprise applies. At present not only cost is low for the polycarboxylate Scale inhibitors of research, and can not cause the pollution of phosphorus, also there is good scale-inhibiting properties thus by enterprise's widespread use. Polycarboxylic acid scale inhibitor is a kind of polymkeric substance containing multiple functional groups such as carboxyl, fat base, sulfonic group, amide group. The present invention is after the research and development situation of the domestic and international polycarboxylic acid scale inhibitor of investigation, and continuous summing up experience, have developed a kind of water-soluble novel non-phosphate tetrapolymer Scale inhibitors.
Summary of the invention
The object of the invention is a kind of Phosphateless environmentally friendly, and to calcium carbonate scale, dirty novel quadripolymer Scale inhibitors and its preparation method all with excellent scale-inhibiting properties of calcium phosphate scale.
The object of the present invention can be reached by following measure:
A kind of novel non-phosphate quadripolymer Scale inhibitors, it is characterised in that, described novel non-phosphate polymer antisludging agent is the oligopolymer become by the method copolymerization of radical polymerization in aqueous by A, B, C, D tetra-kinds of monomers, wherein:
A: methylene-succinic acid
B: methyl acrylate
C: acrylamide
D:2-acrylamido-2-methyl propane sulfonic acid
The mol ratio of A, B, C, D tetra-kinds of monomers is A:B:C:D=1:(0.4-0.6): (0.3-0.7): (0.1-0.4)
Above-mentioned novel non-phosphate quadripolymer Scale inhibitors preparation method, step is:
(1) in mass, the acrylamide of 2-6g is made into, with appropriate deionized water dissolving, the aqueous solution that mass percent is 10-20%, mixes with the methyl acrylate of 3mL-6mL, called after solution a; By ammonium persulphate 2g-5g, it is made into the aqueous solution called after solution b of mass percent 10-15% with appropriate deionized water dissolving.
(2) by the 2-acrylamido-2-methyl propane sulfonic acid of the acrylamide of the methylene-succinic acid of 9g, 2-6g, 3-8g with appropriate deionized water dissolving, it is made into the aqueous solution that mass percent is 30-50%, join in four mouthfuls of flasks, it is warming up to 45-75 DEG C, under agitation add Virahol, then solution a and solution b puts into dropping funnel respectively add at the uniform velocity to drip (drip and add the time as 30-45min), after dropwising, it is warming up to 75-95 DEG C. It is incubated 1-6 hour, regulates pH to 7-8 with the sodium hydroxide solution of 30% after cooling, obtain novel non-phosphate quadripolymer Scale inhibitors.
The preparation method of the novel non-phosphate tetrapolymer Scale inhibitors according to right 4, it is characterised in that polymerization temperature is 75-95 DEG C.
The invention has the beneficial effects as follows:
Research shows, the scale inhibition effect that the multiple functional group in polymkeric substance can play. Wherein electronegative after carboxylic acid functional hydrolysis, there is powerful absorption property, the scale-inhibiting properties of calcium carbonate scale is played main effect, and sulfonate functional groups extremely soluble in water in, its acidity is higher than the acidity of carboxylic acid functional, so it is lower to the absorption property of crystal, thus cause sulfonate functional groups to CaCO3Scale inhibition effect do not have carboxyl functional group excellent. But sulfonic acid functional group has good temperature resistance, saline-alkaline tolerance, it is applicable in the water system of high salinity, and Fe can be improved2O3Dispersing property. Ester group, amide group also have absorption property, are adsorbed on the surface of inorganic salt crystallite, it is also possible to play the growth hindering crystallite, destroy the effect of microcrystalline internal structure.
The present invention's polymerization single polymerization monomer methylene-succinic acid used is a kind of unsaturated di-carboxylic acid, utilizes amylo process to produce more, and technique is simple, becomes to produce that cost is lower than similar Chemicals and nontoxic easy degraded. Not only containing amide group but also the sulfonic acid group containing strongly hydrophilic in the molecule of 2-acrylamido-2-methyl propane sulfonic acid, amide group is possible to prevent copolymer gel polymerization, and electric density powerful in sulfonic acid group can make monomer have good adsorptivity and complexing, sulfonic acid group also can strengthen the rigidity of polymer molecular chain simultaneously, it is to increase the thermostability of polymkeric substance. Thus this novel non-phosphate copolymer antisludging agent there is good resistance calcium carbonate scale, calcium phosphate after and the ability of dispersing iron oxide, possess thermostability height, without phosphorus feature simultaneously.
This Macroscopic single crystal technique is simple, and production cost is low, can be used as the process of industrial circulating cooling water, is a kind of green scale inhibitor efficiently.
Embodiment
Embodiment 1
The acrylamide of 2.7g is dissolved in 30ml water, wiring solution-forming a after mixing with the methyl acrylate of 2.5ml; Ammonium persulphate 2.0g is dissolved in 20ml water wiring solution-forming b.
By the methylene-succinic acid of 6g, 2-acrylamido-2-the methyl propane sulfonic acid of 5.1g is dissolved in 120ml water then to join thermometer is housed, in four mouthfuls of flasks of prolong and constant voltage titration funnel, raised temperature to 50 DEG C also stirs, add a certain amount of Virahol (5%wt), then by constant pressure funnel at the uniform velocity volumetric soiutions a and solution b wherein, drip that to add the time be 30min, dropwise rear raised temperature to 85 DEG C, logical nitrogen isothermal reaction 3 hours, cooling, sodium hydroxide solution with 30% regulates pH to 7-8, remember light yellow transparent liquid, it is novel non-phosphate quadripolymer Scale inhibitors.
Embodiment 2
The acrylamide of 1.8g is dissolved in 20ml water, wiring solution-forming a after mixing with the methyl acrylate of 2.5ml; Ammonium persulphate 1.5g is dissolved in 20ml water wiring solution-forming b.
By the methylene-succinic acid of 8.2g, 2-acrylamido-2-the methyl propane sulfonic acid of 2.6g is dissolved in 100ml water then to join thermometer is housed, in four mouthfuls of flasks of prolong and constant voltage titration funnel, raised temperature to 60 DEG C also stirs, add a certain amount of Virahol (5%wt), then by constant pressure funnel at the uniform velocity volumetric soiutions a and solution b wherein, drip that to add the time be 40min, dropwise rear raised temperature to 75 DEG C, logical nitrogen isothermal reaction 3.5 hours, cooling, sodium hydroxide solution with 30% regulates pH to 7-8, remember light yellow transparent liquid, it is novel non-phosphate quadripolymer Scale inhibitors.
Embodiment 3
The acrylamide of 0.8g is dissolved in 10ml water, wiring solution-forming a after mixing with the methyl acrylate of 2.5ml; Ammonium persulphate 1.5g is dissolved in 20ml water wiring solution-forming b.
By the methylene-succinic acid of 9.8g, 2-acrylamido-2-the methyl propane sulfonic acid of 2.6g is dissolved in 130ml water then to join thermometer is housed, in four mouthfuls of flasks of prolong and constant voltage titration funnel, raised temperature to 60 DEG C also stirs, add a certain amount of Virahol (5%wt), then by constant pressure funnel at the uniform velocity volumetric soiutions a and solution b wherein, drip that to add the time be 40min, dropwise rear raised temperature to 70 DEG C, logical nitrogen isothermal reaction 4 hours, cooling, sodium hydroxide solution with 30% regulates pH to 7-8, remember light yellow transparent liquid, it is novel non-phosphate quadripolymer Scale inhibitors.
Embodiment 4
The acrylamide of 2.7g is dissolved in 30ml water, wiring solution-forming a after mixing with the methyl acrylate of 2.5ml;Ammonium persulphate 3.0g is dissolved in 20ml water wiring solution-forming b.
By the methylene-succinic acid of 11g, 2-acrylamido-2-the methyl propane sulfonic acid of 7.8g is dissolved in 200ml water then to join thermometer is housed, in four mouthfuls of flasks of prolong and constant voltage titration funnel, raised temperature to 50 DEG C also stirs, add a certain amount of Virahol (5%wt), then by constant pressure funnel at the uniform velocity volumetric soiutions a and solution b wherein, drip that to add the time be 1h, dropwise rear raised temperature to 85 DEG C, logical nitrogen isothermal reaction 4 hours, cooling, sodium hydroxide solution with 30% regulates pH to 7-8, remember light yellow transparent liquid, it is novel non-phosphate quadripolymer Scale inhibitors.
Embodiment 5
The acrylamide of 1.8g is dissolved in 20ml water, wiring solution-forming a after mixing with the methyl acrylate of 2.5ml; Ammonium persulphate 3.5g is dissolved in 30ml water wiring solution-forming b.
By the methylene-succinic acid of 9.8g, 2-acrylamido-2-the methyl propane sulfonic acid of 7.8g is dissolved in 180ml water then to join thermometer is housed, in four mouthfuls of flasks of prolong and constant voltage titration funnel, raised temperature to 40 DEG C also stirs, add a certain amount of Virahol (5%wt), then by constant pressure funnel at the uniform velocity volumetric soiutions a and solution b wherein, drip that to add the time be 1h, dropwise rear raised temperature to 90 DEG C, logical nitrogen isothermal reaction 4.5 hours, cooling, sodium hydroxide solution with 30% regulates pH to 7-8, remember light yellow transparent liquid, it is novel non-phosphate quadripolymer Scale inhibitors.
Embodiment 6
In embodiment, the measuring method of calcium carbonate scale inhibition performance, calcium phosphate scale inhibition performance and point Indian red ability as follows described in:
To the mensuration of calcium carbonate scale inhibition performance, calcium phosphate scale inhibition performance
The static-state scale inhibition performance test methods of calcium carbonate, calcium phosphate measures according to GB/T16632-2008 and GB/T22626-2008, and the experiment condition of the resistance dirt of calcium carbonate is: Ca2+、HCO3-Concentration be 250mg/L, pH=7-9, temperature is 80 DEG C, and the time is 10h; The resistance dirt experiment condition of calcium phosphate is: Ca2+Concentration is 250mg/L, PO4 3-Concentration be 5mg/L, temperature is 80 DEG C, and the time is 10h, and scale-inhibiting properties is as shown in table 1.
The mensuration of ferric oxide dispersing property
Use FeSO4·7H2O and CaCl2Obtain solution makes wherein Ca2+Concentration is 160mg/L, Fe2+Concentration is 10mg/L, adjusts its pH to be 9 by boric acid solution, then adds a certain amount of polymer antisludging agent, magnetic agitation 15min, leaves standstill, 50 DEG C of constant temperature 5h, and cooling, measures its transmittance T% with spectrophotometer in 420nm.
The measurement result of the calcium carbonate scale inhibition performance of table 1 embodiment, calcium phosphate scale inhibition performance and point Indian red ability
Calcium carbonate is had good scale inhibition effect by the novel non-phosphate quadripolymer Scale inhibitors that this invention selects monomer itaconic acid, methyl acrylate, acrylamide, 2-acrylamido-2-methyl propane sulfonic acid to aggregate into as can be seen from Table 1 when the amount of adding is 30mg/L, scale inhibition performance is more than 98%, calcium phosphate scale is also had good scale-inhibiting properties simultaneously, also there is very strong ferric oxide dispersive ability.
Claims (5)
1. a novel non-phosphate quadripolymer Scale inhibitors, it is characterised in that, described novel non-phosphate quadripolymer Scale inhibitors is the oligopolymer become by Raolical polymerizable copolymerization in aqueous by A, B, C, D tetra-kinds of monomers, wherein:
A: methylene-succinic acid
B: methyl acrylate
C: acrylamide
D:2-acrylamido-2-methyl propane sulfonic acid
The mol ratio of A, B, C, D tetra-kinds of monomers is A:B:C:D=1:(0.4-0.6): (0.3-0.7): (0.1-0.4).
2. require described novel non-phosphate quadripolymer Scale inhibitors according to right 1, it is characterised in that copolymerization of carboxyl, ester group, amide group, these four kinds of officials of sulfonic group being reunited, thus possess efficient scale-inhibiting properties.
3. require described novel quadripolymer Scale inhibitors according to right 1, it is characterised in that, the initiator adopted during four kinds of monomer generation Raolical polymerizables is water-soluble ammonium persulphate.
4. requiring described novel non-phosphate quadripolymer Scale inhibitors preparation method according to right 1, step is:
(1) in mass, the acrylamide of 2-6g is made into, with appropriate deionized water dissolving, the aqueous solution that mass percent is 10-20%, mixes with the methyl acrylate of 3mL-6mL, called after solution a; By ammonium persulphate 2g-5g, it is made into the aqueous solution called after solution b of mass percent 10-15% with appropriate deionized water dissolving.
(2) by the methylene-succinic acid of 7-9g, 2-acrylamido-2-the methyl propane sulfonic acid of 3-8g is with appropriate deionized water dissolving, it is made into the aqueous solution that mass percent is 30-50%, join in four mouthfuls of flasks, it is warming up to 45-75 DEG C, under agitation add Virahol, then solution a and solution b is put into respectively dropping funnel and adds at the uniform velocity to drip (drip and add the time as 30-45min), after dropwising, be warming up to 75-95 DEG C. It is incubated 1-6 hour, regulates pH to 7-8 with the sodium hydroxide solution of 30% after cooling, obtain novel non-phosphate quadripolymer Scale inhibitors.
5. the preparation method of novel non-phosphate quadripolymer Scale inhibitors according to right 4, it is characterised in that polymerization temperature is 75-95 DEG C.
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| CN106084127A (en) * | 2016-08-08 | 2016-11-09 | 安徽炎胜新材料科技有限公司 | A kind of preparation method softening the quadripolymer removed for hard scale |
| CN109133389A (en) * | 2018-10-12 | 2019-01-04 | 山东理工大学 | Non-phosphorus composite scale inhibitor |
| CN113979551A (en) * | 2021-11-22 | 2022-01-28 | 重庆科技学院 | Low-phosphorus multipolymer scale inhibitor, synthesis method, detection method and application |
| CN115196760A (en) * | 2022-06-28 | 2022-10-18 | 中国海洋大学 | High-temperature-resistant scale inhibitor and preparation method and application thereof |
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