CN112174343A - Green environment-friendly non-phosphorus scale and corrosion inhibitor and preparation method thereof - Google Patents
Green environment-friendly non-phosphorus scale and corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN112174343A CN112174343A CN202011209598.7A CN202011209598A CN112174343A CN 112174343 A CN112174343 A CN 112174343A CN 202011209598 A CN202011209598 A CN 202011209598A CN 112174343 A CN112174343 A CN 112174343A
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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
- C02F5/14—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 phosphorus
- C02F5/145—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 phosphorus combined with inorganic substances
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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
- C02F5/125—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 combined with inorganic substances
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The green environment-friendly non-phosphorus scale and corrosion inhibitor comprises the following components in percentage by mass: 2.5-5.0% of amine dendritic high polymer; 2.0-5.0% of graphene dispersion liquid; 15.0-35.0% of a multipolymer; 5.0-10.0% of maleic acid-acrylic acid copolymer; 3.0-6.0% of 2-phosphate-1, 2, 4-tricarboxylic acid butane; the balance of deionized water; the proportion of each component is 100 percent; the invention mainly solves the problems of low prior art and low scale inhibition performance of the phosphorus-free scale and corrosion inhibitor, is green and environment-friendly, can effectively prevent carbonate scale, sulfate scale and silicate scale from occurring in the system, and simultaneously has better corrosion inhibition effect to ensure the normal operation of the system and the safe production.
Description
Technical Field
The invention belongs to the technical field of water treatment, and relates to a green environment-friendly non-phosphorus scale and corrosion inhibitor and a preparation method thereof.
Background
At present, scale inhibitors in circulating water systems, particularly in open circulating water systems, are serious in scale formation, and mainly comprise polyacrylic acid, organic phosphate and other compounds at home and abroad. The phosphorus-containing formula is easy to generate phosphate scale in a circulating water system, is easy to cause secondary pollution to water, does not meet the requirement of environmental protection, and has the advantages of uneven product performance, low scale and corrosion inhibition performance and single function. Therefore, make internal disorder or usurp developed an environment-friendly non-phosphorus scale and corrosion inhibitor with strong practicability has wide application value.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide the green environment-friendly phosphorus-free scale and corrosion inhibitor and the preparation method thereof, the solubility of scale forming compounds can be effectively improved by the synergistic effect of various functional groups contained in each component, the scale and corrosion inhibition performance of the scale forming compounds is greatly improved after compounding, the physical adsorption and the chemical adsorption of the scale forming compounds are innovatively realized, and the scale and corrosion inhibitor can be used in a wider pH range and temperature suitable for circulating water.
In order to achieve the purpose, the invention adopts the technical scheme that:
a green environment-friendly non-phosphorus scale and corrosion inhibitor comprises the following components in percentage by weight: 2.5-5.0% of amine dendritic high polymer; 2.0-5.0% of graphene aqueous dispersion; 10.0-35.0% of multipolymer; 5.0-10.0% of maleic acid-acrylic acid copolymer; 5.0-10.0% of 2-phosphate-1, 2, 4-tricarboxylic acid butane; the balance of deionized water; the total proportion of all the components is 100 percent.
The amine dendritic high polymer is polyamide-amine dendritic polymer.
The concentration of the graphene aqueous dispersion is 1.5-2.0 mg/ml, graphene oxide in the graphene aqueous dispersion is modified graphene with hydroxyl, carboxyl or carbonyl functional groups on the surface of a carbon layer, and the number of layers is 15-20; the particle size is 5-10 nm.
The multipolymer is obtained by copolymerizing an unsaturated organic monomer containing carboxyl, an unsaturated organic monomer containing ester group and an unsaturated organic monomer containing sulfonic group, and the limiting viscosity number of the multipolymer is 0.035-0.055 dL/g.
The maleic acid-acrylic acid copolymer comprises 45-55% by mass of solid and 9.0% by mass of free monomer (calculated by maleic acid).
The 2-phosphate-1, 2, 4-tricarboxylic acid butane contains active components with the mass percentage of more than or equal to 50%.
The preparation method of the green environment-friendly non-phosphorus scale and corrosion inhibitor comprises the following steps: mixing the multipolymer, the maleic acid-acrylic acid copolymer and the graphene water dispersion according to a proportion, heating to 65-95 ℃, carrying out ultrasonic treatment for 15-20 min, then heating to 105 ℃, adding 2-phosphate-1, 2, 4-tricarboxylic acid butane according to a proportion, carrying out ultrasonic treatment for 15-20 min, adding the amine dendritic high polymer according to a proportion, refluxing for 0.5-l.0 h, adding deionized water according to a proportion, and cooling the materials to obtain the environment-friendly phosphorus-free scale and corrosion inhibitor.
In the green environment-friendly non-phosphorus scale and corrosion inhibitor, the graphene aqueous dispersion is a non-traditional soft material, is prepared from a graphene oxide film, does not precipitate, and has the characteristics of a polymer, a colloid, a film and an amphoteric molecule. The graphene has a high specific surface area and rich functional groups on the surface, the specific surface area can reach 2600 square meters per gram, a large number of active groups on the surface such as carboxyl, carbonyl, hydroxyl, epoxy and the like provide sufficient active sites for the adsorption of pollutants, particularly heavy metals, the trace elimination of the pollutants can be realized, and meanwhile, the compound solubility can be effectively improved through the synergistic effect of various functional groups, so that the scale inhibition performance of the compound is greatly improved.
In the green environment-friendly non-phosphorus scale and corrosion inhibitor, the multipolymer has the performances of scale inhibition, dispersion, corrosion inhibition, temperature resistance and the like, and can be used as a scale inhibition and dispersion agent; in particular to the application of the phosphorus-free environment-friendly corrosion and scale inhibitor in the fields of circulating cooling water systems, oilfield water injection systems, seawater desalination and the like.
In the green environment-friendly phosphorus-free scale and corrosion inhibitor, the maleic acid-acrylic acid copolymer has strong dispersion effect on carbonate and the like, has high thermal stability, can be used under severe conditions such as high temperature of 300 ℃, and has good compatibility and synergistic effect with other water treatment agents. Has good inhibiting effect on the generation of water scales including silicate and phosphate, and has excellent scale inhibition performance and high temperature resistance.
In the green environment-friendly non-phosphorus scale and corrosion inhibitor, the 2-phosphate-1, 2, 4-butane tricarboxylate is a leading scale and corrosion inhibitor at present, has good calcium carbonate and calcium phosphate scale resistance, high temperature resistance, oxidation resistance, chlorine stability resistance, good dispersion performance on high-turbidity and high-iron circulating water, and good compounding synergy.
In the phosphorus-free scale and corrosion inhibitor, the multipolymer and 2-phosphate-1, 2, 4-butane tricarboxylate are used as main components of the scale and corrosion inhibitor, the maleic acid-acrylic acid copolymer is used as an auxiliary corrosion and scale inhibitor, and the graphene aqueous dispersion is added at the same time, so that the green and environment-friendly phosphorus-free corrosion and scale inhibitor is prepared. Wherein the multipolymer, the 2-phosphate-1, 2, 4-tricarboxylic acid butane and the maleic acid-acrylic acid multipolymer have excellent scale and corrosion inhibition effects, and after the three are compounded, the synergistic effect is obvious, and the multipolymer has good degradability and no pollution to the environment. The multipolymer has obvious slow release effect on metals such as carbon steel and the like. The graphene aqueous dispersion has good compatibility with a multipolymer, 2-phosphate-1, 2, 4-tricarboxylic acid butane and a maleic acid-acrylic acid copolymer, and has good adsorption performance. After the components are compounded, the corrosion and scale inhibitor has strong water solubility and stability, can realize long-time storage, has obvious capacity increasing effect on pollutants, particularly heavy metals, and particularly has obvious scale inhibiting effect on calcium, carbonate, sulfate and other ions.
Compared with the prior art, the invention has the following beneficial effects:
1. the synergistic effect of various functional groups contained in each component can effectively improve the solubility of the scale forming compound, the scale and corrosion inhibition performance of the scale forming compound is greatly improved after compounding, the physical adsorption and the chemical adsorption of the scale forming compound are innovatively realized, and the scale forming compound can be used in a wider pH range and temperature suitable for circulating water.
2. The preparation method has the advantages of simple production process, no discharge of three wastes, good medicament stability and water solubility, biodegradable main components, no toxicity, no pollution, no corrosion, environmental protection and environmental friendliness.
Detailed Description
The following examples will help illustrate the invention without limiting its scope.
Example 1:
3.0 percent of amine dendritic high polymer, 4.5 percent of graphene water dispersion, 35.0 percent of multipolymer, 7.5 percent of maleic acid-acrylic acid copolymer and 6.0 percent of 2-phosphate-1, 2, 4-butane tricarboxylate by mass percentage; 44.0% deionized water.
The preparation method of the phosphorus-free scale and corrosion inhibitor comprises the following steps: mixing the multipolymer, the maleic acid-acrylic acid copolymer and the graphene water dispersion according to a proportion, heating to 65-95 ℃, carrying out ultrasonic treatment for 15-20 min, then heating to 105 ℃, adding 2-phosphate-1, 2, 4-tricarboxylic acid butane according to a proportion, carrying out ultrasonic treatment for 15-20 min, adding the amine dendritic high polymer according to a proportion, refluxing for 0.5-l.0 h, adding deionized water according to a proportion, and cooling the materials to obtain the environment-friendly phosphorus-free scale and corrosion inhibitor.
A certain amount of the deep well water (full alkalinity of 5.5mmol/L and total hardness of 7.4mmol/L) along the yellow river bank is taken, 6mg/L of the stock solution of the phosphorus-free scale and corrosion inhibitor is added, the temperature is raised to 45 ℃, the circulating water flow rate is set to be 1000L/h, and a dynamic simulation test of the circulating water is carried out under the open cycle test condition. After the limit concentration ratio of the circulating water in the test is 2.5 times and the concentration ratio is maintained to be about 2.3 times and the continuous operation is carried out for 500 hours, the corrosion rate of the carbon steel is 0.021mm/a, and the scale inhibition rate is 97.5 percent.
Example 2:
2.5 percent of amine dendritic high polymer, 2.5 percent of graphene water dispersion, 20.0 percent of multi-component copolymer, 6.0 percent of maleic acid-acrylic acid copolymer and 4.0 percent of 2-phosphate-1, 2, 4-butane tricarboxylate by mass percentage; 65.0% deionized water.
The preparation method of the phosphorus-free scale and corrosion inhibitor comprises the following steps: mixing the multipolymer, the maleic acid-acrylic acid copolymer and the graphene water dispersion according to a proportion, heating to 65-95 ℃, carrying out ultrasonic treatment for 15-20 min, then heating to 105 ℃, adding 2-phosphate-1, 2, 4-tricarboxylic acid butane according to a proportion, carrying out ultrasonic treatment for 15-20 min, adding the amine dendritic high polymer according to a proportion, refluxing for 0.5-l.0 h, adding deionized water according to a proportion, and cooling the materials to obtain the environment-friendly phosphorus-free scale and corrosion inhibitor.
A certain amount of lake water (full alkalinity of 2.3mmol/L and total hardness of 3.3mmol/L) is taken, 6mg/L of the stock solution of the phosphorus-free scale and corrosion inhibitor is added, the temperature is raised to 45 ℃, the flow rate of circulating water is set to be 1000L/h, and a dynamic simulation test of the circulating water is carried out under the open cycle test condition. After the circulating water in the test is continuously operated for 500 hours at the limit concentration ratio of 4.5 times and the concentration ratio is maintained to be about 4.3 times, the corrosion rate of the carbon steel is 0.035mm/a, and the scale inhibition rate is 98.3%.
Example 3:
4.5 percent of amine dendritic high polymer, 3.5 percent of graphene water dispersion, 25.0 percent of multi-component copolymer, 10.0 percent of maleic acid-acrylic acid copolymer and 3.5 percent of 2-phosphate-1, 2, 4-butane tricarboxylate by mass percentage; 53.5% deionized water.
The preparation method of the phosphorus-free scale and corrosion inhibitor comprises the following steps: mixing the multipolymer, the maleic acid-acrylic acid copolymer and the graphene water dispersion according to a proportion, heating to 65-95 ℃, carrying out ultrasonic treatment for 15-20 min, then heating to 105 ℃, adding 2-phosphate-1, 2, 4-tricarboxylic acid butane according to a proportion, carrying out ultrasonic treatment for 15-20 min, adding the amine dendritic high polymer according to a proportion, refluxing for 0.5-l.0 h, adding deionized water according to a proportion, and cooling the materials to obtain the environment-friendly phosphorus-free scale and corrosion inhibitor.
Taking a certain amount of reservoir water (full alkalinity of 3.2mmol/L and total hardness of 3.5mmol/L), adding sulfuric acid to adjust the full alkalinity of the make-up water to 1.48mmol/L, adding 8mg/L of the stock solution of the phosphorus-free scale and corrosion inhibitor of the embodiment, heating to 45 ℃, setting the flow rate of circulating water to be 1000L/h, and carrying out a dynamic simulation test of the circulating water under the open cycle test condition. After the circulating water in the test is continuously operated for 500 hours at the limit concentration ratio of 7.5 times and the concentration ratio is maintained to be about 7.3 times, the corrosion rate of the carbon steel is 0.041mm/a, and the scale inhibition rate is 98.6 percent.
Claims (7)
1. A green environment-friendly non-phosphorus scale and corrosion inhibitor is characterized in that: the phosphorus-free scale inhibitor comprises the following components in percentage by weight: 2.5-5% of amine dendritic high polymer; 2.0-5.0% of graphene aqueous dispersion; 10-35% of a multipolymer; 5-10% of maleic acid-acrylic acid copolymer; 5-10% of 2-phosphate-1, 2, 4-tricarboxylic acid butane; the balance of deionized water; the total proportion of all the components is 100 percent.
2. The green environment-friendly non-phosphorus scale and corrosion inhibitor according to claim 1, characterized in that: the amine dendritic high polymer is polyamide-amine dendritic polymer.
3. The green environment-friendly non-phosphorus scale and corrosion inhibitor according to claim 1, characterized in that: the concentration of the graphene aqueous dispersion is 1.5-2.0 mg/ml, graphene oxide in the graphene aqueous dispersion is modified graphene with hydroxyl, carboxyl or carbonyl functional groups on the surface of a carbon layer, and the number of layers is 15-20; the particle size is 5-10 nm.
4. The green environment-friendly non-phosphorus scale and corrosion inhibitor according to claim 1, characterized in that: the multipolymer is obtained by copolymerizing an unsaturated organic monomer containing carboxyl, an unsaturated organic monomer containing ester group and an unsaturated organic monomer containing sulfonic group, and the limiting viscosity number of the multipolymer is 0.035-0.055 dL/g.
5. The green environment-friendly phosphorus-free scale and corrosion inhibitor of claim 1, wherein the maleic acid-acrylic acid copolymer comprises 45-55% by mass of solids, and 9.0% by mass of free monomers in terms of maleic acid.
6. The green environment-friendly non-phosphorus scale and corrosion inhibitor according to claim 1, characterized in that: the 2-phosphate-1, 2, 4-tricarboxylic acid butane contains active components with the mass percentage of more than or equal to 50%.
7. The preparation method of the green environment-friendly non-phosphorus scale and corrosion inhibitor of any one of claims 1 to 6, characterized in that: mixing the multipolymer, the maleic acid-acrylic acid copolymer and the graphene water dispersion according to a proportion, heating to 65-95 ℃, carrying out ultrasonic treatment for 15-20 min, then heating to 105 ℃, adding 2-phosphate-1, 2, 4-tricarboxylic acid butane according to a proportion, carrying out ultrasonic treatment for 15-20 min, adding the amine dendritic high polymer according to a proportion, refluxing for 0.5-l.0 h, adding deionized water according to a proportion, and cooling the materials to obtain the environment-friendly phosphorus-free scale and corrosion inhibitor.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011209598.7A CN112174343A (en) | 2020-11-03 | 2020-11-03 | Green environment-friendly non-phosphorus scale and corrosion inhibitor and preparation method thereof |
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| CN202011209598.7A CN112174343A (en) | 2020-11-03 | 2020-11-03 | Green environment-friendly non-phosphorus scale and corrosion inhibitor and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114082305A (en) * | 2021-11-11 | 2022-02-25 | 西安热工研究院有限公司 | Reverse osmosis cleaning agent for microorganism and organic matter pollution and preparation method thereof |
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2020
- 2020-11-03 CN CN202011209598.7A patent/CN112174343A/en active Pending
Patent Citations (6)
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| US6447717B1 (en) * | 1999-06-04 | 2002-09-10 | Donlar Corporation | Composition and method for inhibition of metal corrosion |
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Application publication date: 20210105 |