CN103265125B - Quaternary non-phosphorus aggregate type corrosion and scale inhibitor PIAAM and preparation method thereof - Google Patents
Quaternary non-phosphorus aggregate type corrosion and scale inhibitor PIAAM and preparation method thereof Download PDFInfo
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- CN103265125B CN103265125B CN201310217347.7A CN201310217347A CN103265125B CN 103265125 B CN103265125 B CN 103265125B CN 201310217347 A CN201310217347 A CN 201310217347A CN 103265125 B CN103265125 B CN 103265125B
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Abstract
The invention discloses a quaternary non-phosphorus aggregate type corrosion and scale inhibitor PIAAM and a preparation method thereof. The corrosion and scale inhibitor PIAAM is composed of itaconic acid, acrylic acid, 2-acrylamide-2-methyl propanesulfonic acid and methyl methacrylate, sodium persulphate, isopropyl alcohol and water. The corrosion and scale inhibitor PIAAM contains no phosphorous element, meets environmental protection requirement, is excellent in scale inhibition performance, has good iron oxide dispersity and also has the characteristics of corrosion inhibition, high temperature resistance, high alkali resistance and stable molecular structure, and discharge of 'waste water, waste gas and waste residue' is not caused in the whole preparation process. The quaternary non-phosphorus aggregate type corrosion and scale inhibitor product PIAAM is simple in process when being used for treating circulating cooling water, dosage is low, cost is low, and effect is good, so that the quaternary non-phosphorus aggregate type corrosion and scale inhibitor PIAAM has better economic benefit and social benefit.
Description
Technical field
The invention belongs to chemical field, relate to specifically without phosphorus polymerization type corrosion inhibition antisludging agent PIAAM of a kind of quaternary for industrial circulating cooling water system and preparation method thereof.
Background technology
Polymkeric substance corrosion inhibiting and descaling agent is the class novel non-pollution Treatment of Industrial Water medicament growing up the eighties in 20th century.In polymkeric substance corrosion inhibiting and descaling agent, carboxyl, phosphono are the active groups of resistance calcium carbonate scale; Carboxyl, polyoxyethylene groups are the active groups of resistance calcium phosphate scale; Ester group, hydroxyl, sulfonic group, amide group are the active groups that prevents that polymer latex is poly-; Phosphono-carboxylic acids and metal ion carry out chelating, and be adsorbed in metallic surface and there is corrosion inhibition, not facile hydrolysis of phosphono-carboxylic acids, and there is scale-inhibiting properties; Sulfonic acid group has efficient inhibition ability to dirt, and metal ion is had to stabilization.Strong acid root is conducive to the dissolving of Scale inhibitors; weak acid root can effectively suppress the growth of fouling crystal; in the time that a kind of Scale inhibitors contains weak acid root and strong acid root simultaneously; to have better scale-inhibiting properties, the multipolymer that therefore contains phosphono, carboxyl, sulfonic group isoreactivity group is the study hotspot of aggretion type dirt dispersion agent in recent years.At present, the patent such as the CN 98113264 of Chinese patent Granted publication " a kind of composite water disposal agent ", CN 03137603 " polynary composite water treatment agent ", CN 88101807 " Mg-Fe compound type waste-water processing agent and production method thereof ", CN 02145917 " a kind of composite scale-inhibiting corrosion inhibitor and be back to the application in recirculated cooling water containing ammonia-nitrogen sewage ", CN 01133709 " composite scale-inhibiting corrosion inhibitor " and CN 01113457 " a kind of composite water disposal agent taking poly aspartic acid as host " all adopts composite preparation technology.Due to the complexity of industrial cooling circulating water water quality and changeable, need to use multiple aggregation technology to be bonded in polymer molecule containing not isoplastic monomer, give water treatment agent new, the performance of excellence.For a long time, the research and development of China aggretion type water conditioner are mainly taking binary or binary polymerization as main, as CN 01123146 " lower molecular weight (methyl) vinylformic acid (salt) based polymer and its production and use " etc., in formula for a product and use properties, go back imperfection, and most of industrial circulating cooling water treatment agent phosphorus element-containing, these phosphorus compounds are along with waste water finally can be disposed to water body, although phosphorus is nontoxic, but as nutrition source, it can make body eutrophication, causes lake water wawter bloom.Thereby many countries have started the discharge of phosphorus restriction, non-phosphate environment-friendly type water treatment agent has become the focus of domestic and international research and development.In Treatment of Industrial Water field, polycarboxylic acid water conditioner is starting material monomer mainly with maleic anhydride, but not readily biodegradable of maleic anhydride, and long-term accumulated can cause environmental pollution.Methylene-succinic acid is nontoxic biological fermented product, there is good negative electricity dispersing property, can effectively stop cohesion and the deposition of dirt, the polymkeric substance readily biodegradable of methylene-succinic acid and other reactive monomers, production technique is simple, with low cost and product performance are good, is the corrosion inhibiting and descaling agent of " green " environmental protection of having a extensive future.The present invention is in the domestic and international aggretion type water conditioner production technology of investigation, on the basis of CN 101289256 B " a kind of four-element polymerization type corrosion inhibition stopping agent and preparation method thereof " patented invention, select respectively containing-COOH ,-OH ,-SO
3h group and-C=C-COOCH
3the starting material monomer of structural unit: methylene-succinic acid, vinylformic acid, 2-acrylamide-2-methyl propane sulfonic and methyl methacrylate, through repeating orthogonal test, adopt aqua-solution method multiple aggregation technology successfully to prepare the without phosphorus polymerization type corrosion inhibition antisludging agent IA/AA/AMPS/MMA(of quaternary a kind of use properties excellence, eco-friendly and be abbreviated as PIAAM).
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of this invention is to provide the without phosphorus polymerization type corrosion inhibition antisludging agent PIAAM of a kind of quaternary, make its contain-COOH ,-SO
3h ,-OH group and-C=C-COOCH
3structural unit, environmental protection, excellent performance, meet complicacy and the polytropy user demand of industrial cooling circulating water water quality.Another object of the present invention is to provide the preparation method of the without phosphorus polymerization type corrosion inhibition antisludging agent PIAAM of a kind of above-mentioned quaternary.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is:
The without phosphorus polymerization type corrosion inhibition antisludging agent PIAAM of a kind of quaternary, is made up of methylene-succinic acid (IA), vinylformic acid (AA), 2-acrylamide-2-methyl propane sulfonic (AMPS) and methyl methacrylate (MMA), Sodium Persulfate, isopropyl alcohol and water.The mass ratio of each component is preferably: methylene-succinic acid 5 ~ 10, vinylformic acid 10 ~ 30,2-acrylamide-2-methyl propane sulfonic 2 ~ 10, methyl methacrylate 2 ~ 10, Sodium Persulfate 2 ~ 6, Virahol 4 ~ 8, water 100 ~ 150; Optimum quality ratio is: methylene-succinic acid 8, vinylformic acid 15 ~ 25,2-acrylamide-2-methyl propane sulfonic 3 ~ 7, methyl methacrylate 2 ~ 6, Sodium Persulfate 2 ~ 4, Virahol 4 ~ 6, water 100 ~ 120.
Above-mentioned chemical is technical pure.
A preparation method of the without phosphorus polymerization type corrosion inhibition antisludging agent PIAAM of quaternary, comprises the following steps successively:
(1), by vinylformic acid and methyl methacrylate mixed dissolution, obtain solution (I);
(2) separately by 2-acrylamide-2-methyl propane sulfonic, Sodium Persulfate and account for total Water 20 ~ 40% water mix, obtain solution (II);
(3), under condition of heating and stirring, to filling in the reactor of residue water, slowly add successively methylene-succinic acid, Virahol, mixed dissolution; Be heated to 75 ~ 85 DEG C, under the condition of continuously stirring, add solution (I) and (II) simultaneously, control feed rate, reinforced complete in 1 hour.75 ~ 85 DEG C of isothermal reactions 2 ~ 6 hours, are cooled to room temperature, obtain light yellow transparent liquid, i.e. product P IAAM of the present invention.
The without phosphorus polymerization type corrosion inhibition antisludging agent PIAAM of quaternary prepared by the present invention, environmental protection, is applicable to the industry circulating cooling water treatments such as chemical industry, electric power, metallurgy and oil field, can suppress the corrosion to hardware of cooling water scaling and water.
Beneficial effect: compared with prior art, the present invention has the following advantages: (1) adopts aqueous solution four-element polymerization technology to prepare product of the present invention, technological innovation; (2) not phosphorus element-containing of product, environmental benefit is good; (3) treatment process is simple, and dosage is few, cost is low, good product quality; (4) scale-inhibiting properties excellence of the present invention, ferric oxide is had to good dispersiveness, also have the feature such as inhibition, high temperature resistant, resistance to high-alkali, Stability Analysis of Structures, whole production process does not have " waste water, waste gas and waste residue " to discharge, belong to process for cleanly preparing, there is good economic benefit and social benefit.
Embodiment
Below in conjunction with illustrating the present invention.
Embodiment 1
By 10kg vinylformic acid and 2kg methyl methacrylate mixed dissolution, obtain solution (I).2kg 2-acrylamide-2-methyl propane sulfonic, 2kg Sodium Persulfate and 30kg water are mixed, obtain solution (II).Under condition of heating and stirring, to filling in the reactor of 70kg water, slowly add successively 8kg methylene-succinic acid, 2kg Virahol, mixed dissolution; Improve temperature of reaction kettle to 75 ~ 85 DEG C, under continuous stirring condition, add solution (I) and (II) simultaneously, control feed rate, reinforced complete in 1h.Isothermal reaction 2 ~ 6h, is cooled to room temperature, obtains light yellow transparent liquid, i.e. product P IAAM of the present invention.
Embodiment 2
30kg vinylformic acid and 10kg methyl methacrylate are uniformly mixed, obtain solution (I); Separately, by 10kg 2-acrylamide-2-methyl propane sulfonic, 6kg Sodium Persulfate and 50kg water mix and blend, obtain solution (II); Under condition of heating and stirring, get 100kg water and be placed in reactor, slowly add successively 8kg methylene-succinic acid, 8kg Virahol, mixed dissolution; Method and step according to above-described embodiment 1 operate.
Embodiment 3
By 20kg vinylformic acid and 4kg methyl methacrylate, be uniformly mixed, obtain solution (I); Separately by 5kg 2-acrylamide-2-methyl propane sulfonic, 3kg Sodium Persulfate and 30kg water mix and blend, obtain solution (II); Under condition of heating and stirring, get 80kg water and be placed in reactor, slowly add successively 8kg methylene-succinic acid, 5kg Virahol, mixed dissolution; Method and step according to above-described embodiment 1 operate.
Concrete way of contrast
Illustrate the synergistic effect between monomer in polymkeric substance of the present invention according to comparative example 1 ~ 3 below.
Comparative example 1
Except not adding vinylformic acid, other operation stepss are with above-described embodiment 1.
Comparative example 2
Except methylate methyl acrylate not, other operation stepss are with above-described embodiment 1.
Comparative example 3
Except not adding 2-acrylamide-2-methyl propane sulfonic, other operation stepss are with above-described embodiment 1.
Specific performance characterizes
Below according to the performance of quality product test, Synergism Testing and field application test embodiments product of the present invention.
Experiment 1: quality product test
The without phosphorus polymerization type corrosion inhibition antisludging agent PIAAM of quaternary prepared by embodiment 3 carries out testing performance index, the results are shown in Table 1.
Table 1 product quality indicator measured data of the present invention
Product of the present invention, due to methylene-succinic acid, vinylformic acid, 2-acrylamide-2-methyl propane sulfonic and methyl methacrylate monomer interpolymerization, has good dissemination and excellent anticorrosion-antiscaling property.
Experiment 2: Synergism Testing
The result of comparative example 1 ~ 3 Synergism Testing proves, in product of the present invention, methylene-succinic acid, vinylformic acid, 2-acrylamide-2-methyl propane sulfonic and methyl methacrylate monomer are given full play to the polymerization synergistic effect of medicament, can effectively suppress fouling and the corrosion of cooling water circulation pipeline.Testing data is listed in table 2.
The Synergism Testing of table 2 methylene-succinic acid, vinylformic acid, 2-acrylamide-2-methyl propane sulfonic and methyl methacrylate monomer
Experiment 3: field application test
In certain Steel Plant's recirculating cooling water system, apply product of the present invention (embodiment 3) since on June 15th, 2012, according to middle trial run measured data, definite mass concentration that adds medicament is 10mg L
-1, by Steel Plant's cooling water system operational condition and the operation of control index.Through on-the-spot operation half a year, recirculated water clarity obviously improves than before processing, and except turbidity rate (NTU) >92%, steel pipe pipeline corrosion rate is reduced to 0.002218 mm a
-1, be 0.3352 mm a and do not use the corrosion rate of the steel pipe pipeline of medicament of the present invention
-1.Experiment showed, that product of the present invention has improved recirculated cooling water operation conditions, heat-exchange equipment operational excellence, has ensured the continuous operation of production equipment.The water-quality guideline of run duration recirculated cooling water is listed in table 3.
Certain Steel Plant's circulating cooling water quality index of table 3
Rig-site utilization proves: not phosphorus element-containing of product of the present invention, environmental protection; Integrate good corrosion-mitigation scale-inhibition and disperse iron ion performance, also thering is the features such as high temperature resistant, high rigidity or high alkalinity simultaneously.Be 10mg L adding pharmacy quality concentration
-1time, product methylene-succinic acid of the present invention, vinylformic acid, 2-acrylamide-2-methyl propane sulfonic and methyl methacrylate quadripolymer can effectively suppress fouling and the corrosion of recirculated cooling water pipeline.
Claims (3)
1. the without phosphorus polymerization type corrosion inhibition antisludging agent PIAAM of quaternary, is characterized in that: be made up of methylene-succinic acid, vinylformic acid, 2-acrylamide-2-methyl propane sulfonic and methyl methacrylate, Sodium Persulfate, isopropyl alcohol and water, the mass ratio of each component is:
2. the without phosphorus polymerization type corrosion inhibition antisludging agent PIAAM of quaternary according to claim 1, is characterized in that: each constituent mass ratio of described four-element polymerization type corrosion inhibition antisludging agent is:
3. a method of preparing the without phosphorus polymerization type corrosion inhibition antisludging agent PIAAM of quaternary described in claim 1 or 2, is characterized in that, comprises the following steps:
(1), by vinylformic acid and methyl methacrylate mixed dissolution, obtain solution (I);
(2) separately by 2-acrylamide-2-methyl propane sulfonic, Sodium Persulfate with account for the water mixed dissolution of total Water 20～40%, obtain solution (II);
(3), under condition of heating and stirring, to filling in the reactor of residue water, slowly add successively methylene-succinic acid, Virahol, mixed dissolution; Be heated to 75～85 DEG C, under the condition of continuously stirring, add solution (I) and (II) simultaneously, control feed rate, reinforced complete in 1h; 75～85 DEG C of isothermal reaction 2～6h, are cooled to room temperature, obtain light yellow transparent liquid, i.e. product P IAAM of the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103554361B (en) * | 2013-10-25 | 2016-03-30 | 中国海洋石油总公司 | A kind of preparation method of high-efficiency calcium phosphate scale inhibitor |
| CN103539269B (en) * | 2013-11-14 | 2014-11-05 | 南京林业大学 | Compound aggregate type corrosion and scale inhibitor and preparation method thereof |
| CN105542055B (en) * | 2015-12-18 | 2018-01-23 | 成都齐达水处理工程股份有限公司 | Multiple copolymer and its production and use |
| 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 |
| CN115448473B (en) * | 2022-08-29 | 2023-06-20 | 常熟金陵海虞热电有限公司 | Scale inhibitor for circulating cooling water of thermal power plant and preparation method thereof |
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| CN101921359A (en) * | 2010-09-29 | 2010-12-22 | 湖南省原子能农业应用研究所 | Polyacrylic acid or copolymer thereof and preparation method of polyacrylate or copolymer salt thereof |
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| CN1511793A (en) * | 2002-12-29 | 2004-07-14 | 淄博矿业集团有限责任公司 | Polynary itaconic acid copolymer as high efficiency anti-sludging agent and preparing method |
| CN101921359A (en) * | 2010-09-29 | 2010-12-22 | 湖南省原子能农业应用研究所 | Polyacrylic acid or copolymer thereof and preparation method of polyacrylate or copolymer salt thereof |
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