CN112176348A - Water-soluble corrosion inhibitor and preparation method thereof - Google Patents
Water-soluble corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN112176348A CN112176348A CN202011032572.XA CN202011032572A CN112176348A CN 112176348 A CN112176348 A CN 112176348A CN 202011032572 A CN202011032572 A CN 202011032572A CN 112176348 A CN112176348 A CN 112176348A
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- corrosion inhibitor
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- soluble corrosion
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
- C23F11/1676—Phosphonic acids
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to a water-soluble corrosion inhibitor and a preparation method thereof. The water-soluble corrosion inhibitor comprises the following raw materials in percentage by weight: 35-55% of organic corrosion inhibitor, 5-15% of neutralizing agent, 5-10% of auxiliary agent and the balance of solvent. The preparation method comprises the steps of heating a solvent to a first set temperature, and then sequentially adding an organic corrosion inhibitor, a neutralizer and an auxiliary agent to obtain a raw material mixture; and heating the raw material mixture to a second set temperature, stirring at the second set temperature, and cooling to room temperature to obtain the water-soluble corrosion inhibitor. The corrosion inhibitor has the advantages of difficult volatilization, good stability, strong applicability, good corrosion inhibition effect, high efficiency, environmental protection and the like, and raw materials are easy to obtain and the application range is wide; the preparation method is simple and easy to control in process and is beneficial to large-scale production.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a water-soluble corrosion inhibitor and a preparation method thereof.
Background
Along with the development and production of crude oil, the quality of the crude oil is poorer and poorer, and the proportion of inferior crude oil is increased gradually, so that the corrosion problem of equipment in the petrochemical industry is serious increasingly. The common corrosion is mainly H2S-HCN-NH3-H2O、H2S-CO2-H2O、H2S-NH3-H2O、HCl-H2S-H2O、CO2-H2S-H2O, etc. At present, the corrosion of equipment at home and abroad is mainly solved by two ways of material upgrading and process corrosion prevention.
Wherein, aiming at solving the corrosion problem of equipment by technical anticorrosion measures, the corrosion inhibitor is the simplest, effective and economical method by adding the corrosion inhibitor. The corrosion inhibitor applied to equipment in the petrochemical industry at present has certain defects: the phenomena of oil emulsification, foaming and the like are easily caused by slightly large consumption of some corrosion inhibitors; the pH of some corrosion inhibitors is narrow in use range, and the protection effect is lost along with the change of the pH quality of a corrosion system; some corrosion inhibitors have poor solubility, good film-forming property and poor water solubility; some corrosion inhibitors have narrow application range and are only suitable for a certain corrosion system.
Therefore, the technical scheme of the invention is provided based on the technical scheme.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a water-soluble corrosion inhibitor and a preparation method thereof. The corrosion inhibitor has the advantages of difficult volatilization, good stability, strong applicability, good corrosion inhibition effect, high efficiency, environmental protection and the like, and raw materials are easy to obtain and the application range is wide; the preparation method is simple and easy to control in process and is beneficial to large-scale production.
The scheme of the invention is to provide a water-soluble corrosion inhibitor, which comprises the following raw materials in percentage by weight: 35-55% of organic corrosion inhibitor, 5-15% of neutralizing agent, 5-10% of auxiliary agent and the balance of solvent.
Preferably, the water-soluble corrosion inhibitor is prepared from the following raw materials in percentage by weight: 45% of organic corrosion inhibitor, 10% of neutralizer, 7.5% of auxiliary agent and the balance of solvent.
Preferably, the organic corrosion inhibitor is one of hydroxy ethylidene diphosphoric acid, water-soluble naphthenic acid imidazoline or benzotriazole, or a combination of more than two of the above.
Preferably, the neutralizing agent is one of sodium hydroxide, sodium bicarbonate or polyethylene polyamine, or a combination of two or more of them.
Preferably, the auxiliary agent is one of methanol, ethanol or propiolic alcohol, or a combination of two or more of the above.
Preferably, the solvent is water.
The invention also provides a preparation method of the water-soluble corrosion inhibitor, which comprises the following steps:
(1) heating the solvent to a first set temperature, and then sequentially adding the organic corrosion inhibitor, the neutralizer and the auxiliary agent to obtain a raw material mixture;
(2) and heating the raw material mixture to a second set temperature, stirring at the second set temperature, and cooling to room temperature to obtain the water-soluble corrosion inhibitor.
Preferably, in the step (1), the first set temperature is 50-60 ℃.
Preferably, in the step (2), the second set temperature is 70-80 ℃.
Preferably, in the step (2), the rotation speed of the stirring is 80-100 r/min, and the stirring time is 1-2 h.
The invention has the beneficial effects that:
1. the corrosion inhibitor is a water-soluble liquid product, has the advantages of difficult volatilization, good stability, strong applicability, good corrosion inhibition effect, high efficiency, environmental protection and the like, and has easily available raw materials and wide application range.
2. The preparation method of the corrosion inhibitor has simple and easily-controlled process and is beneficial to large-scale production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The raw material components and the compounding ratios of examples 1 to 7 are shown in Table 1.
TABLE 1 ingredient and proportion (dosage unit is kg)
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Hydroxy ethylidene diphosphoric acid | 35 | / | / | 15 | / | 10 | 10 |
| Water soluble naphthenic acid imidazoline | / | 55 | / | 30 | 20 | / | 15 |
| Benzotriazole | / | / | 45 | / | 25 | 35 | 20 |
| Sodium hydroxide | 5 | / | / | 5 | / | 4 | 3 |
| Sodium bicarbonate | / | 15 | / | 5 | 2 | / | 3 |
| Polyethylene polyamines | / | / | 10 | / | 8 | 6 | 4 |
| Methanol | 5 | / | / | 2.5 | / | 4 | 2 |
| Ethanol | / | 10 | / | 5 | 3 | / | 2 |
| Propargyl alcohol | / | / | 7.5 | / | 4.5 | 3.5 | 3.5 |
| Water (W) | 55 | 20 | 37.5 | 37.5 | 37.5 | 37.5 | 37.5 |
The preparation method of the embodiment 1-3 comprises the following steps:
(1) heating solvent water of corresponding weight to 50 ℃, and sequentially adding hydroxy ethylidene diphosphoric acid (or water-soluble naphthenic acid imidazoline or benzotriazole), sodium hydroxide (or sodium bicarbonate or polyethylene polyamine), and methanol (or ethanol or propiolic alcohol) of corresponding weight to obtain a raw material mixture;
(2) and (2) heating the raw material mixture obtained in the step (1) to 70 ℃, stirring for 1h at the speed of 80r/min, and cooling to room temperature to obtain the water-soluble corrosion inhibitor.
The preparation method of the embodiment 4-6 comprises the following steps:
(a) heating solvent water with corresponding weight to 60 ℃, and then sequentially adding hydroxy ethylidene diphosphoric acid and water-soluble naphthenic acid imidazoline (or water-soluble naphthenic acid imidazoline and benzotriazole, or hydroxy ethylidene diphosphoric acid and benzotriazole), sodium hydroxide and sodium bicarbonate (or sodium bicarbonate and polyethylene polyamine, or sodium hydroxide and polyethylene polyamine), methanol and ethanol (or ethanol and propiolic alcohol, or methanol and propiolic alcohol) with corresponding weight to obtain a raw material mixture;
(b) heating the raw material mixture obtained in the step (a) to 80 ℃, stirring for 2h under the condition of 100r/min, and cooling to room temperature after the stirring is finished to obtain the water-soluble corrosion inhibitor.
The preparation method of the embodiment 7 comprises the following steps:
(i) heating solvent water with corresponding weight to 55 ℃, and then sequentially adding hydroxy ethylidene diphosphoric acid, water-soluble naphthenic acid imidazoline, benzotriazole, sodium hydroxide, sodium bicarbonate, polyethylene polyamine, methanol, ethanol and propiolic alcohol with corresponding weight to obtain a raw material mixture;
(ii) and (i) heating the raw material mixture obtained in the step (i) to 75 ℃, stirring for 1.5h at the speed of 90r/min, and cooling to room temperature to obtain the water-soluble corrosion inhibitor.
In order to test the performance of the corrosion inhibitor, the similar products (comparative examples) sold in the market are selected for comparison with reference to GB/T35509-2017 application and evaluation of the corrosion inhibitor for oil and gas fields.
The evaluation criteria are shown in table 2.
TABLE 2 physical and chemical performance index of corrosion inhibitors
For ease of understanding, the related item content is further explained.
Pour point: the lowest temperature at which the fluid can flow when cooled under specified conditions.
And (3) corrosion inhibition rate: the percentage of the difference obtained by subtracting the corrosion rate after adding the corrosion inhibitor from the corrosion rate without adding the corrosion inhibitor to the ratio of the corrosion rate without adding the corrosion inhibitor.
When the corrosion inhibitor is sampled, the following rules are followed:
(1) randomly sampling corrosion inhibitor samples to be detected, wherein 2 barrels are taken from less than 10 barrels, 4 barrels are taken from less than 50 barrels, 6 barrels are taken from 50 barrels to 100 barrels, and 8 barrels are taken from more than 100 barrels; mixing the selected samples to make the samples uniform and then dividing the samples into two parts, wherein each part is not less than 500 mL; one part is sent for inspection and the other part is ready for inspection. The retention period was three months.
(2) The samples were packed in clear plastic bottles, sealed, labeled and labeled with relevant information as required.
The results of the measurements are shown in tables 3 and 4.
TABLE 3 test results
TABLE 4 test results
Results and discussion:
as can be seen from tables 3 and 4, the corrosion inhibitors obtained in examples 1 to 7 are obviously higher than the standard and better than the comparative examples in the aspects of pour point, emulsification tendency, compatibility, uniform corrosion inhibition rate (static; dynamic) by soaking, corrosion inhibition rate (static; dynamic) by electrochemical method and the like.
Through detection and theoretical analysis, the corrosion inhibitor has the following advantages:
(1) having resistance to corrosion by high hydrogen sulphideWith respect to H2S-HCN-NH3-H2O、 H2S-CO2-H2O、H2S-NH3-H2O、HCl-H2S-H2O、CO2-H2S-H2Corrosion caused by systems such as O and the like has a good corrosion prevention effect;
(2) the corrosion inhibitor has the obvious advantages of low volatility and good corrosion inhibition effect, can effectively form a firm and stable film on the surface of metal, and has good corrosion inhibition effect, thereby preventing dew point corrosion of equipment and pipelines;
(3) can reduce the corrosion under the deposit, does not contain metals and other substances harmful to downstream products and devices, and does not emulsify oil products;
(4) meanwhile, the corrosion inhibitor can act on different corrosive media, and has no adverse effect on the quality of oil;
(5) the corrosion inhibitor has enough chemical stability and thermal stability in a medium, is not influenced by temperature change, and can form a dynamic adsorption protective film on the surface of metal at a certain scouring flow rate;
(6) the corrosion inhibitor has no adverse effect on subsequent devices, sewage treatment devices and the like;
(7) the corrosion inhibitor has the advantages of high corrosion inhibition rate, quick film formation, firm adsorption and convenient use.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The water-soluble corrosion inhibitor is characterized by comprising the following raw materials in percentage by weight: 35-55% of organic corrosion inhibitor, 5-15% of neutralizing agent, 5-10% of auxiliary agent and the balance of solvent.
2. The water-soluble corrosion inhibitor according to claim 1, which is prepared from the following raw materials in percentage by weight: 45% of organic corrosion inhibitor, 10% of neutralizer, 7.5% of auxiliary agent and the balance of solvent.
3. The water-soluble corrosion inhibitor according to claim 1 or 2, wherein the organic corrosion inhibitor is one of hydroxyethylidene diphosphate, water-soluble naphthenic acid imidazoline or benzotriazole, or a combination of two or more thereof.
4. The water-soluble corrosion inhibitor according to claim 1 or 2, wherein the neutralizing agent is one of sodium hydroxide, sodium bicarbonate or polyethylene polyamine, or a combination of two or more thereof.
5. The water-soluble corrosion inhibitor according to claim 1 or 2, wherein the auxiliary is one of methanol, ethanol or propiolic alcohol, or a combination of two or more thereof.
6. The water-soluble corrosion inhibitor according to claim 1 or 2, wherein said solvent is water.
7. A preparation method of the water-soluble corrosion inhibitor of any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) heating the solvent to a first set temperature, and then sequentially adding the organic corrosion inhibitor, the neutralizer and the auxiliary agent to obtain a raw material mixture;
(2) and heating the raw material mixture to a second set temperature, stirring at the second set temperature, and cooling to room temperature to obtain the water-soluble corrosion inhibitor.
8. The method for preparing the water-soluble corrosion inhibitor according to claim 7, wherein the first set temperature in step (1) is 50-60 ℃.
9. The method for preparing the water-soluble corrosion inhibitor according to claim 7, wherein in the step (2), the second set temperature is 70-80 ℃.
10. The preparation method of the water-soluble corrosion inhibitor according to claim 7, wherein in the step (2), the stirring speed is 80-100 r/min, and the stirring time is 1-2 h.
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| CN202011032572.XA CN112176348A (en) | 2020-09-27 | 2020-09-27 | Water-soluble corrosion inhibitor and preparation method thereof |
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| CN202011032572.XA CN112176348A (en) | 2020-09-27 | 2020-09-27 | Water-soluble corrosion inhibitor and preparation method thereof |
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Citations (7)
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| CN1566402A (en) * | 2003-06-27 | 2005-01-19 | 中国石油天然气股份有限公司 | Water-soluble corrosion inhibition neutralizer and preparation method thereof |
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| CN101280222A (en) * | 2008-06-02 | 2008-10-08 | 中国石油化工集团公司 | Water-soluble corrosion inhibitor, preparation and application thereof |
| CN101613622A (en) * | 2009-07-29 | 2009-12-30 | 中国石油化工集团公司 | A kind of composite inhibiter and its production and use |
| US20100264064A1 (en) * | 2007-09-14 | 2010-10-21 | Dorf Ketal Chemicals (1) Private Limited | novel additive for naphthenic acid corrosion inhibition and method of using the same |
| CN102732894A (en) * | 2011-03-31 | 2012-10-17 | 武汉润尔华科技有限公司 | Low-temperature corrosion inhibitor |
| CN109797003A (en) * | 2019-02-01 | 2019-05-24 | 北京乐文科技发展有限公司 | A kind of oil-soluble inhibitor and preparation method thereof |
-
2020
- 2020-09-27 CN CN202011032572.XA patent/CN112176348A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566402A (en) * | 2003-06-27 | 2005-01-19 | 中国石油天然气股份有限公司 | Water-soluble corrosion inhibition neutralizer and preparation method thereof |
| DE102004049544A1 (en) * | 2004-10-12 | 2006-04-13 | Degussa Ag | Radiation-curable modified, unsaturated, amorphous polyesters |
| US20100264064A1 (en) * | 2007-09-14 | 2010-10-21 | Dorf Ketal Chemicals (1) Private Limited | novel additive for naphthenic acid corrosion inhibition and method of using the same |
| CN101280222A (en) * | 2008-06-02 | 2008-10-08 | 中国石油化工集团公司 | Water-soluble corrosion inhibitor, preparation and application thereof |
| CN101613622A (en) * | 2009-07-29 | 2009-12-30 | 中国石油化工集团公司 | A kind of composite inhibiter and its production and use |
| CN102732894A (en) * | 2011-03-31 | 2012-10-17 | 武汉润尔华科技有限公司 | Low-temperature corrosion inhibitor |
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Application publication date: 20210105 |
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