CN111099752B - Phosphorus-free slow-release scale inhibitor and synthesis method thereof - Google Patents
Phosphorus-free slow-release scale inhibitor and synthesis method thereof Download PDFInfo
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- CN111099752B CN111099752B CN201811249610.XA CN201811249610A CN111099752B CN 111099752 B CN111099752 B CN 111099752B CN 201811249610 A CN201811249610 A CN 201811249610A CN 111099752 B CN111099752 B CN 111099752B
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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
Abstract
The invention provides a phosphorus-free slow-release scale inhibitor and a synthesis method thereof, and relates to the field of water treatment. The phosphorus-free slow-release scale inhibitor comprises an active ingredient, an auxiliary agent and water. The active ingredients comprise polyepoxysuccinic acid, thiourea, polyaspartic acid, acrylic copolymer and inorganic sodium salt, and the auxiliary agent is micromolecular alcohol. The preparation method comprises the steps of sequentially adding water, polyepoxysuccinic acid, inorganic sodium salt and thiourea into a container, stirring for 1-3 hours at 50-90 ℃, sequentially adding polyaspartic acid, acrylic copolymer and auxiliary agent, and stirring for 1-2 hours at room temperature to obtain the product. The phosphorus-free composite slow-release scale inhibitor has an excellent slow-release scale inhibition effect and strong market competitiveness, and can improve the dispersing capacity of small dirt particles and improve the slow-release, antirust and scale inhibition performances by adding thiourea and other active ingredients. The formula does not contain any inorganic phosphorus and organic phosphorus compounds, and the paint has excellent safety and environmental protection performance and wide actual application prospect.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a phosphorus-free slow-release scale inhibitor and a synthesis method thereof.
Background
At present, the most effective method for controlling water quality is to add water treatment agents, the research on the water treatment agents is started from the nineteenth century, various water treatment agents are developed through continuous exploration of people, and the effect is continuously improved. Phosphorus-containing polymers have greatly promoted the development of water treatment technology, and are the most common water treatment products in the market at present, but cause great harm to the environment. On the one hand, it aggravates the shortage of water resources; on the other hand, control of phosphorus-containing polymers is also enhanced worldwide. Therefore, research and development of water treatment agents having multiple functions and environmental protection are also in the trend.
Currently, as the oil field exploitation environment becomes increasingly severe, the high hardness and high alkalinity sewage causes higher requirements on the performance of the scale inhibitor. From the research situation of the scale inhibitor in recent years, the research and development of the scale inhibitor are gradually developing from a single compound technology to a diversified compound technology, namely, on the premise of ensuring the scale inhibition performance, other functions are introduced at the same time, so that a more efficient and multifunctional product is developed. Secondly, the development of a non-phosphorus, non-nitrogen and biodegradable environment-friendly scale inhibitor meeting the requirements of environmental protection also becomes the mainstream direction.
In the future development of the Chinese industry, the sustained-release agent is used as an important antiseptic means and is certainly used in the aspects of industrial safety, material loss reduction and the like. With the increasing awareness of environmental protection and safety, those harmful and toxic corrosion inhibitors are limited and prohibited. Such as chromate, mercury salt and the like, while phosphorus-containing compounds such as polyphosphate, organic phosphate and the like are good corrosion inhibitors, but because the phosphorus-containing compounds are easy to cause eutrophication of water bodies, large-area red tide hazards often occur in coastal areas of China, and the water quality is continuously deteriorated. For the purpose of protecting the environment, the development of an environment-friendly corrosion inhibitor which has no destructive effect on the environment is bound to be the future development direction of the slow-release agent.
Preparation and application of a foreign polyepoxysuccinic acid copolymer.
German patent DE4212755 uses epoxy succinate and CaSO at 40-150 deg.C3Or CaSO3·xH2And after the O reaction is carried out for 8 hours, the solution is precipitated and separated to obtain the sulfonated polyepoxysuccinic acid and the salt thereof, and the product has good scale inhibition performance. The epoxy succinate of Betz Dearborn Inc reacts with substances with alkyl or aryl, and the obtained product has good scale and corrosion inhibition functions (US 5871691); hakuto Co Ltd uses epoxy succinic acid molar ratio (3-30) at 50-150 ℃: 1 and citric acid or tartaric acid containing hydroxyl groups to obtain a polyepoxysuccinic acid polymer which is excellent in preventing the deposition of calcium oxalate in the production of paper (JP,2000117292,2004-4-25).
Preparation and application of domestic polyepoxysuccinic acid polymer
The preparation method comprises hydrolyzing maleic anhydride with sodium hydroxide solution, and hydrolyzing with H2O2After cyclization, the product and sodium p-styrene sulfonate are subjected to polymerization reaction under the action of an ammonium persulfate initiator to further obtain a target product of epoxysuccinic acid-p-styrene sulfonate (ESA-SSS), and evaluation results show that the ESA-SSS has better calcium sulfate scale resistance, calcium phosphate scale resistance, zinc ion stabilization and iron oxide dispersion resistance than PESA, and has concentration advantage, while the calcium carbonate scale resistance is not improved but reduced (Nemond university of Industrial 2009).
Compared with the phosphorus-free slow-release scale inhibitor, the phosphorus-free slow-release scale inhibitor provided by the invention has better CaCO inhibition effect3、CaSO4、BaSO4、SrSO4The scale-waiting performance and the slow-release performance and the good environmental protection performance.
Disclosure of Invention
The invention solves the technical problem of providing a phosphorus-free slow-release scale inhibitor with good CaCO control3、CaSO4、BaSO4、SrSO4Has the performance of equal scale and good slow release effect,and is a green novel phosphorus-free slow-release scale inhibitor and a synthesis method thereof.
The technical scheme of the invention is that the phosphorus-free slow-release scale inhibitor comprises active ingredients, an auxiliary agent and water; the active ingredients of the compound comprise polyepoxysuccinic acid, thiourea, polyaspartic acid, acrylic copolymer and inorganic sodium salt, and the auxiliary agent is micromolecular alcohol;
the phosphorus-free slow-release scale inhibitor comprises the following components in percentage by mass:
the acrylic copolymer is one of acrylic acid-acrylate-sulfonate copolymer, maleic acid-acrylic acid copolymer or acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer.
The inorganic sodium salt is one of sodium chloride, sodium carbonate or sodium molybdate.
The auxiliary agent is one of methanol, ethanol, isopropanol or tert-butanol.
A synthesis method of a phosphorus-free slow-release scale inhibitor comprises the following steps: weighing the raw materials according to the weight percentage of each component, sequentially adding water, polyepoxysuccinic acid, inorganic sodium salt and thiourea into a container, stirring for 1-3 hours at 50-90 ℃, sequentially adding polyaspartic acid, acrylic copolymer and auxiliary agent, and stirring for 1-2 hours at room temperature to obtain the product.
The phosphorus-free composite slow-release scale inhibitor has an excellent slow-release scale inhibition effect and strong market competitiveness, and can improve the dispersing capacity of small dirt particles and improve the slow-release, antirust and scale inhibition performances by adding thiourea and other active ingredients. By adding the micromolecular alcohols, the solubility of active ingredients such as thiourea can be effectively improved, the long-term storage and stability are promoted, the intermolecular synergistic effect is enhanced, and the slow release and scale inhibition performance of the compound is further improved. The formula does not contain any inorganic phosphorus and organic phosphorus compounds, and the paint has excellent safety and environmental protection performance and wide actual application prospect.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
All chemical reagents of the present invention are commercially available.
Example 1
Selecting the following raw materials in percentage by weight:
sequentially adding water, polyepoxysuccinic acid, sodium molybdate and thiourea into a container, stirring for 2 hours at 85 ℃, sequentially adding polyaspartic acid, maleic acid-acrylic acid copolymer and ethanol, and stirring for 1 hour at room temperature to obtain a product, wherein the experimental results of the scale inhibition and slow release performance of the sample on a circulating water system are shown in table 2.
Example 2
Selecting raw materials according to weight percentage
Sequentially adding water, polyepoxysuccinic acid, sodium molybdate and thiourea into a container, stirring for 2 hours at 85 ℃, sequentially adding polyaspartic acid, acrylic acid-acrylate-sulfonate copolymer and ethanol, and stirring for 1 hour at room temperature to obtain the product.
Example 3
Selecting raw materials according to weight percentage
Sequentially adding water, polyepoxysuccinic acid, sodium molybdate and thiourea into a container, stirring for 2 hours at 85 ℃, sequentially adding polyaspartic acid, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer and ethanol, and stirring for 1 hour at room temperature to obtain the product.
Application tests and results
1. Sources of experimental samples: see Table 1
TABLE 1 sources of test samples
| Source of medicament | Name of medicament |
| Inventive product example 1 | HSZGJ 1 |
| Inventive product example 2 | HSZGJ 2 |
| Inventive product example 3 | HSZGJ 3 |
2. Calcium carbonate inhibition experiment
2.1 test Water: water distribution: ca2+400ppm，HCO3 -1220ppm。
2.2 Experimental conditions: water temperature of 80 ℃, time of 10h, medicament dosage: 4 ppm.
2.3 Experimental methods: refer to the standard of GB/T16632-.
2.4 Experimental results: see Table 2
3. Calcium sulfate inhibition experiment
3.1 test Water: water distribution: ca2+400ppm，SO4 2+667ppm。
3.2 Experimental conditions: water temperature of 80 ℃, time of 10h, medicament dosage: 4 ppm.
3.3 Experimental methods: refer to the standard of GB/T16632-.
3.4 Experimental results: see Table 2
4. Sustained Release Performance test
4.1 test Water: water distribution: ca2+400ppm，HCO3 -1220ppm。
4.2 Experimental conditions: water temperature of 40 ℃, time of 72h, medicament dosage: 100 ppm.
4.3 Experimental methods: see GB181752-2000
4.4 results of the experiment: see Table 2
TABLE 2 test results
| Name of medicament | Calcium carbonate Scale inhibition Rate (%) | Calcium sulfate Scale inhibition Rate (%) | Corrosion rate (mm/a) |
| HSZGJ 1 | 98.4 | 99.1 | 0.002 |
| HSZGJ 2 | 97.6 | 99.3 | 0.001 |
| HSZGJ 3 | 95.9 | 98.8 | 0.002 |
As can be seen from the above table, the practical application effect of the products of examples 1, 2 and 3 of the invention completely meets the requirements of the invention on the scale inhibition and release performance of a circulating water system.
Claims (1)
1. A phosphorus-free slow-release scale inhibitor is characterized in that: the phosphorus-free slow-release scale inhibitor comprises an active ingredient, an auxiliary agent and water; the active ingredients of the compound comprise polyepoxysuccinic acid, thiourea, polyaspartic acid, acrylic copolymer and inorganic sodium salt, and the auxiliary agent is micromolecular alcohol; the weight percentages of the components are as follows:
the synthesis method of the phosphorus-free slow-release scale inhibitor comprises the following steps: weighing the raw materials according to the weight percentage of each component, sequentially adding water, polyepoxysuccinic acid, inorganic sodium salt and thiourea into a container, stirring for 1-3 hours at 50-90 ℃, sequentially adding polyaspartic acid, acrylic copolymer and auxiliary agent, and stirring for 1-2 hours at room temperature to obtain a product;
the acrylic copolymer is one of acrylic acid-acrylate-sulfonate copolymer, maleic acid-acrylic acid copolymer or acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer;
the inorganic sodium salt is one of sodium chloride, sodium carbonate or sodium molybdate;
the auxiliary agent is one of methanol, ethanol, isopropanol or tert-butanol.
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| CN113149239A (en) * | 2021-04-06 | 2021-07-23 | 重庆电力高等专科学校 | Preparation of corrosion and scale inhibitor for circulating cooling water |
| CN113292170A (en) * | 2021-06-09 | 2021-08-24 | 西安瑞杰实业股份有限公司 | Anti-hardening agent for blast furnace slag treatment system by bottom filtration method, preparation method and application thereof |
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| CN101948189B (en) * | 2010-09-02 | 2012-05-23 | 蓝星环境工程有限公司 | Non-phosphorus reverse osmosis membrane scale inhibitor and preparation method thereof |
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