CN113174041A - Polyether corrosion inhibitor, preparation method and application thereof - Google Patents
Polyether corrosion inhibitor, preparation method and application thereof Download PDFInfo
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- CN113174041A CN113174041A CN202110460526.8A CN202110460526A CN113174041A CN 113174041 A CN113174041 A CN 113174041A CN 202110460526 A CN202110460526 A CN 202110460526A CN 113174041 A CN113174041 A CN 113174041A
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- polyether
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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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
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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
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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Abstract
The invention provides a polyether corrosion inhibitor, which is polyether amine sodium tetraacetate, wherein the molecular weight of the polyether amine sodium tetraacetate is 900-2500; the invention also provides a preparation method of the corrosion inhibitor, which comprises the steps of feeding, dropwise adding chloroacetic acid and liquid alkali, and carrying out heat preservation reaction. The polyether amine corrosion inhibitor is insoluble in water, has good chelating performance, has a large number of ether bond structures in the structure, can be well cooperated with the corrosion inhibitor, and shows good corrosion inhibition performance; the corrosion inhibitor disclosed by the invention does not contain elements such as sulfur, phosphorus and the like, can replace the traditional organic phosphine corrosion inhibitor in many fields, and is green and environment-friendly.
Description
Technical Field
The invention relates to the technical field of fine chemical synthesis, in particular to a polyether corrosion inhibitor and a preparation method thereof.
Background
In the industrial production and operation process, metal corrosion can occur, which not only damages the color, appearance, mechanical property and the like of the metal, but also directly reduces the quality grade of the product and even leads to the scrapping of the workpiece.
To prevent the metal from being damaged by corrosion, the main protection method at present is to use antirust grease. The principle is that when the anti-rust grease is coated on the surface of metal, the polar part of the oil-soluble corrosion inhibitor molecule in the anti-rust grease forms directional adsorption on the interface of oil and metal, and the nonpolar part forms a layer of hydrophobic protective film on the surface of the metal, so that the movement of related charges or substances participating in corrosion reaction is hindered, and the corrosion rate is slowed down. The antirust performance of the antirust grease mainly depends on the mutual matching and synergistic interaction among the corrosion inhibitors.
Research shows that the corrosion inhibiting effect of the oil soluble corrosion inhibitor is affected by the polar group and nonpolar group structure in the molecule, the type of metal ions, the solubility in oil, the temperature and other factors. The excellent oil-soluble corrosion inhibitor not only has good antirust property, but also has proper low-temperature oil solubility and high-temperature colloid stability. The more carbon atoms in the hydrocarbyl chain in the oil-soluble corrosion inhibitor molecule, the better the rust inhibition of the corrosion inhibitor, but as the hydrocarbyl group grows, the oil solubility decreases, especially the low-temperature solubility decreases, so when preparing a rust preventive oil for use at low temperatures, the combination of the rust inhibition and the low-temperature solubility must be considered. Different corrosion inhibitors have different adsorption force properties and different adsorption firmness degrees, so the desorption temperature is different. Generally, the more polar the corrosion inhibitor molecule, the more strongly adsorbed and the more difficult it is to desorb. At present, oil-soluble corrosion inhibitors are various in variety and have the characteristics, and the finding of the composition which can effectively cooperate and synergize with other corrosion inhibitors can realize high-efficiency corrosion inhibition performance under various high-temperature and low-temperature and strong acid environments is the center of gravity of the current research direction.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a polyether corrosion inhibitor and a preparation method thereof, and the following purposes are realized:
the corrosion inhibitor has corrosion inhibition performance, is used in combination with other corrosion inhibitors, and remarkably improves the corrosion inhibition performance through synergistic effect;
in order to solve the technical problems, the invention adopts the following technical scheme:
the polyether corrosion inhibitor is polyetheramine sodium tetraacetate, and the molecular weight of the polyetheramine sodium tetraacetate is 900-2500.
The following is a further improvement of the above technical solution:
a preparation method of polyether corrosion inhibitor comprises the following steps:
step (1) charging
Adding quantitative polyetheramine and isobutanol into a reaction kettle, adding a small amount of high molecular weight polyetheramine tetraacetic acid sodium product, starting stirring and refluxing,
step (2) dropwise adding chloroacetic acid and liquid alkali
And heating to 85 +/-2 ℃, starting to dropwise add chloroacetic acid aqueous solution and liquid alkali according to a certain flow rate, adjusting the pH value of the reaction system within the range of 9.0-11.0 by controlling the dropwise adding rate of the liquid alkali, and finishing the dropwise adding of chloroacetic acid within 1-2 h.
Step (3) of heat preservation reaction
And heating to 95 +/-5 ℃, carrying out heat preservation reaction for 2-4 h, and continuously adjusting the pH value of the reaction system to be within the range of 9.0-11.0 by controlling the dropping rate of the liquid caustic soda in the heat preservation process.
Step (4) separation
And after the materials are kept warm and are kept stand for layering, separating an organic phase and a water phase, carrying out negative pressure external steaming separation on the organic phase to obtain products of polyetheramine sodium tetraacetate and isobutanol, recycling the isobutanol, and carrying out external steaming drying on the water phase to obtain industrial-grade sodium chloride.
Further, the added polyetheramine sodium tetraacetate in the step (1) is used as a target product and is used as a phase transfer catalyst, and the adding mass of the polyetheramine sodium tetraacetate is 3-5% of the using amount of the polyetheramine.
Further, the molecular weight of the polyetheramine in the step (1) is more than 500, preferably 600-2000; more preferably 600 or 2000;
furthermore, in the step (1), the mass ratio of the polyether amine to the isobutanol is 1: (0.5 to 1).
In the step (2), the mass fraction of the chloroacetic acid aqueous solution is 40-50%, and the mass fraction of the liquid alkali is 45-50%. The molar ratio of the polyether amine to the chloroacetic acid is 1 (3.9-4.2);
the molar ratio of the polyether amine to the total amount of sodium hydroxide is 1: 8.2-8.4.
Further, the dropping speed of the chloroacetic acid aqueous solution in the step (2) is determined by the total amount of the chloroacetic acid aqueous solution and the dropping time, and the dropping speed of the liquid alkali is determined by the acceleration rate of the chloroacetic acid aqueous solution drops and the pH value of the system.
Further, the external evaporation negative pressure in the step (4) is-0.09 MPa to-0.08 MPa.
The invention uses high molecular weight polyether amine and chloroacetic acid as raw materials to synthesize a novel corrosion inhibitor, namely polyether amine sodium tetraacetate, under alkaline condition; isobutanol is the reaction solvent phase.
Compared with the prior art, the invention has the beneficial effects that:
(1) the molecular weight of the polyether amine sodium tetraacetate prepared by the invention is 9000-2500, the content of the effective component is 99.08-99.12wt%, the content of the chloride ion is 0.1-0.13wt%, and the content of the sodium glycolate is 0.22-0.26 wt%.
(2) The polyether amine sodium tetraacetate prepared by the method has good corrosion inhibition performance, and the corrosion inhibition rate is 91.21-92.75 wt%.
(3) The polyether amine sodium tetraacetate can be well cooperated with other corrosion inhibitors to improve corrosion inhibition performance, and is compounded with the oleic acid imidazoline according to the mass ratio of 1:5, so that the corrosion inhibition rate is 96.6-96.86 wt%.
(4) The polyether amine sodium tetraacetate does not contain elements such as sulfur, phosphorus and the like, and is green and environment-friendly.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Part of raw material specifications are as follows:
the polyether amine is polyether amine D600 or polyether amine D2000.
Example 1
Step (1) charging
300g of polyetheramine D600, 150g of isobutanol and 9g of polyetheramine (D600) sodium tetraacetate are added to the reaction vessel, and the stirring and reflux apparatus is switched on.
Step (2) dropwise adding chloroacetic acid and liquid alkali
After the mixture is uniformly mixed, the temperature in the reaction kettle is raised to 85 ℃, 472.5g of chloroacetic acid aqueous solution with the content of 40wt% is dripped according to the flow of 472.5g/h, simultaneously 45wt% of liquid alkali is dripped according to the flow of 310g/h, the pH value of the reaction solution is controlled to be 9.5 by slightly adjusting the dripping speed of the alkali solution, and the dripping time of the chloroacetic acid aqueous solution is 1 hour.
Step (3) of heat preservation reaction
And (3) continuing to heat, starting heat preservation when the temperature in the reaction kettle reaches 94 ℃, continuing to control the pH value of the reaction system to be 9.5 by finely adjusting the dropping rate of the liquid caustic soda, finishing heat preservation after 2 hours, and dropping 364g of the liquid caustic soda.
Step (4) separation
After the materials are kept warm and are kept stand for layering, an organic phase and a water phase are separated, isobutanol is distilled out from the organic phase under the pressure of-0.09 MPa, the isobutanol is recycled, and residues in the kettle are 459g of polyetheramine sodium tetraacetate with the mass fraction of 99.12wt%, which is marked as M1. The aqueous phase was evaporated and dried to give 235g of sodium chloride.
Through detection, the content of chloride ions in the obtained product is 0.13wt%, and the content of sodium glycolate in the obtained product is 0.26 wt%.
Example 2
Step (1) charging
400g of polyetheramine D2000, 400g of isobutanol and 20g of polyetheramine (D2000) sodium tetraacetate are added to the reaction vessel, and the stirring and reflux apparatus is switched on.
Step (2) dropwise adding chloroacetic acid and liquid alkali
After the mixture is uniformly mixed, the temperature in the reaction kettle is raised to 85 ℃, 158.8g of chloroacetic acid aqueous solution with the content of 50wt% is dripped according to the flow of 79.4g/h, 50wt% of liquid alkali is dripped according to the flow of 65g/h, the pH value of the reaction solution is controlled to be 10.5 by fine adjustment of the alkali liquor dripping speed, and the dripping time of the chloroacetic acid aqueous solution is 2 hours.
Step (3) of heat preservation reaction
And continuously heating the temperature in the reaction kettle to 97 ℃, keeping the temperature, continuously controlling the pH value of the reaction system to 10.5 by finely adjusting the dropping rate of the liquid caustic soda in the heat preservation process, finishing the heat preservation after 4 hours, and dropping 168g of the liquid caustic soda.
Step (4) of heat preservation reaction
After the materials are kept warm and are kept stand for layering, an organic phase and a water phase are separated, isobutanol is distilled out from the organic phase under the pressure of-0.08 MPa, the isobutanol is recycled, and 463g of polyetheramine sodium tetraacetate with the mass fraction of 99.08wt% is obtained as M2 in the residue in the kettle. The aqueous phase was evaporated and dried to obtain 120g of sodium chloride.
The detection shows that the content of chloride ions in the obtained product is 0.10 weight percent, and the content of sodium glycolate is 0.22 weight percent.
Example 3 comparison of Performance test
Compounding the M1 and the M2 with oleic acid imidazoline according to the mass ratio of 1:5, and marking as L1 and L2;
dodecenylsuccinic acid and oleic acid imidazoline are compounded according to the mass ratio of 1:5 and are marked as X;
the hexadecyl succinic acid monomethyl ester and the oleic acid imidazoline are compounded according to the mass ratio of 1:5 and are marked as Y.
In the case of the same mass of water treatment agent (on a dry basis), the measurements give the following values:
(the corrosion inhibition rate refers to the determination of the corrosion inhibition performance of the water treatment agent: a rotary hanging sheet method GB/T18175-2014)
As can be seen from the above table, the polyetheramine corrosion inhibitor synthesized by the invention has good corrosion inhibition performance, and can be compounded with water treatment with other functions to effectively improve the overall corrosion inhibition performance through synergistic effect.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A polyether corrosion inhibitor is characterized in that: the corrosion inhibitor is polyetheramine sodium tetraacetate, and the molecular weight of the polyetheramine sodium tetraacetate is 900-2500.
2. A preparation method of polyether corrosion inhibitor is characterized by comprising the following steps: the preparation method comprises the steps of feeding, dropwise adding chloroacetic acid and liquid alkali, and carrying out heat preservation reaction.
3. The preparation method of the polyether corrosion inhibitor as claimed in claim 2, wherein the polyether corrosion inhibitor comprises the following steps: and adding the polyether amine, isobutanol and a small amount of polyether amine sodium tetraacetate product into a reaction kettle.
4. The method for preparing polyether corrosion inhibitor according to claim 3, wherein the method comprises the following steps: the mass of the polyetheramine sodium tetraacetate is 3-5 wt% of the amount of the polyetheramine; the molecular weight of the polyether amine is more than 500; the mass ratio of the polyether amine to the isobutanol is 1: (0.5 to 1).
5. The preparation method of the polyether corrosion inhibitor as claimed in claim 2, wherein the polyether corrosion inhibitor comprises the following steps: and dropwise adding chloroacetic acid and liquid alkali, heating to 85 +/-2 ℃, starting dropwise adding chloroacetic acid aqueous solution and alkali solution according to a certain flow rate, and adjusting the pH value of the reaction system to be within the range of 9.0-11.0.
6. The method for preparing polyether corrosion inhibitor according to claim 5, wherein the method comprises the following steps: the molar ratio of the polyether amine to the chloroacetic acid is 1 (3.9-4.2); the dropping time of the chloroacetic acid is 1-2 h.
7. The method for preparing polyether corrosion inhibitor according to claim 5, wherein the method comprises the following steps:
the mass concentration of the chloroacetic acid aqueous solution is 40-50%, and the mass concentration of the alkali solution is 45-50%.
8. The preparation method of the polyether corrosion inhibitor as claimed in claim 2, wherein the polyether corrosion inhibitor comprises the following steps: and (3) performing heat preservation reaction, heating to 95 +/-5 ℃, performing heat preservation reaction for 2-4 h, and continuously adjusting the pH value of the reaction system to be within the range of 9.0-11.0 by controlling the dropping rate of the alkali solution in the heat preservation process.
9. The method for preparing polyether corrosion inhibitor according to claim 8, wherein the polyether corrosion inhibitor comprises the following steps:
the total molar ratio of the polyether amine to the alkali is 1 (8.2-8.4).
10. The application of the polyether corrosion inhibitor in water treatment is characterized in that: the corrosion inhibitor is polyetheramine sodium tetraacetate, and the molecular weight of the polyetheramine sodium tetraacetate is 900-; the polyether amine sodium tetraacetate is independently applied in water treatment or the polyether amine sodium tetraacetate and the oleic acid imidazoline are compounded according to the mass ratio of 1:5 and then are applied in a combined manner.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007024186A1 (en) * | 2007-01-11 | 2008-07-31 | Afton Chemical Corp. | Methods and compositions for reducing deposits in engines burning ethanol-containing fuels and a corrosion inhibitor |
| CN101654303A (en) * | 2008-08-18 | 2010-02-24 | 天津大港油田科远石油工程有限责任公司 | Corrosion inhibitor suitable for complex wastewater of oilfield and preparation method thereof |
| CN102660744A (en) * | 2012-04-20 | 2012-09-12 | 唐山冀油瑞丰化工有限公司 | Corrosion inhibitor for treating oilfield produced water and preparation method thereof |
| CN102978624A (en) * | 2012-12-06 | 2013-03-20 | 中国石油集团工程设计有限责任公司 | Oil-gas field gas transmission pipeline corrosion inhibitor and preparation method thereof |
| WO2014086026A1 (en) * | 2012-12-06 | 2014-06-12 | 中国石油集团工程设计有限责任公司 | Oil-gas field gas transmission pipeline corrosion inhibitor and preparation method thereof |
| CN108264891A (en) * | 2017-12-29 | 2018-07-10 | 南京华洲新材料有限公司 | A kind of oil-soluble inhibitor and preparation method thereof |
-
2021
- 2021-04-27 CN CN202110460526.8A patent/CN113174041B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007024186A1 (en) * | 2007-01-11 | 2008-07-31 | Afton Chemical Corp. | Methods and compositions for reducing deposits in engines burning ethanol-containing fuels and a corrosion inhibitor |
| CN101654303A (en) * | 2008-08-18 | 2010-02-24 | 天津大港油田科远石油工程有限责任公司 | Corrosion inhibitor suitable for complex wastewater of oilfield and preparation method thereof |
| CN102660744A (en) * | 2012-04-20 | 2012-09-12 | 唐山冀油瑞丰化工有限公司 | Corrosion inhibitor for treating oilfield produced water and preparation method thereof |
| CN102978624A (en) * | 2012-12-06 | 2013-03-20 | 中国石油集团工程设计有限责任公司 | Oil-gas field gas transmission pipeline corrosion inhibitor and preparation method thereof |
| WO2014086026A1 (en) * | 2012-12-06 | 2014-06-12 | 中国石油集团工程设计有限责任公司 | Oil-gas field gas transmission pipeline corrosion inhibitor and preparation method thereof |
| CN108264891A (en) * | 2017-12-29 | 2018-07-10 | 南京华洲新材料有限公司 | A kind of oil-soluble inhibitor and preparation method thereof |
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Address after: 277000 No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province Patentee after: Shandong Taihe Technology Co.,Ltd. Address before: 277000 No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province Patentee before: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. |