CN114990555A - Metal corrosion inhibitor for resisting carbon dioxide corrosion and preparation method and application thereof - Google Patents
Metal corrosion inhibitor for resisting carbon dioxide corrosion and preparation method and application thereof Download PDFInfo
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- CN114990555A CN114990555A CN202210781261.6A CN202210781261A CN114990555A CN 114990555 A CN114990555 A CN 114990555A CN 202210781261 A CN202210781261 A CN 202210781261A CN 114990555 A CN114990555 A CN 114990555A
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention relates to the technical field of metal corrosion inhibition of oil fields, in particular to a metal corrosion inhibitor for resisting carbon dioxide corrosion and a preparation method and application thereof. The invention discloses a metal corrosion inhibitor for resisting carbon dioxide corrosion, which mainly comprises 16-18% of vegetable oleic acid; 10-12% of amines; 6-7% of an intermediate solvent; 17-18% of aldehydes; 5% of nonionic surfactant; 10% of phosphoric acids; the balance being water. The corrosion inhibitor is used for protecting pipelines of oil wells and gas wells containing carbon dioxide in oil fields, ground oil and gas gathering and transportation systems and sewage treatment systems from corrosion. Has the characteristics of small dosage, low corrosion rate, greenness, no toxicity, environmental protection and the like. The product is easy to dissolve in water, can form a compact protective film on the surface of metal, and prevents metal equipment and pipelines from being corroded by carbon dioxide.
Description
Technical Field
The invention relates to the technical field of metal corrosion inhibition of oil fields, in particular to a metal corrosion inhibitor for resisting carbon dioxide corrosion and a preparation method and application thereof.
Background
In the process of oil and gas field exploitation, CO is often accompanied 2 And H 2 Corrosion of S, wherein CO 2 Corrosion is one of the most common forms of corrosion encountered in oil and gas production and can lead to severe localized corrosion, corrosion of downhole strings, equipment, piping, and the like. Pitting and pitting corrosion are CO 2 The most common form of corrosion, mesa pitting, is one of the most severe cases of corrosion, which has a high perforation rate. Seriously affecting the production and causing huge economic loss. Therefore, adding the carbon dioxide corrosion inhibitor is the most direct and effective solution.
The corrosion inhibitor commonly used at present is basically an adsorption type corrosion inhibitor, and the common corrosion inhibitor comprises organic amine and derivatives thereof, imidazoline and salts thereof or imidazoline derivative quaternary ammonium salts, rosin amine derivatives and the like.
The common imidazoline corrosion inhibitor is generally poor in water solubility, is often incompatible with oil-gas field chemical additives such as organic phosphonic acid scale inhibitors and salt inhibitors, and is very easy to generate phenomena such as layered precipitation. The common imidazoline corrosion inhibitor has poor temperature resistance, and when the temperature is higher than 70 ℃, the corrosion inhibition performance is greatly reduced. Therefore, the corrosion inhibitor which has good compatibility, good temperature resistance and better corrosion inhibition performance is developed, and the economic benefit and the social benefit are good.
Disclosure of Invention
In order to solve the problems of poor water solubility, poor compatibility, low temperature resistance and the like of the carbon dioxide corrosion inhibitor in the prior art, the invention develops the corrosion inhibitor which has the advantages of excellent corrosion inhibition performance, good compatibility, good water solubility, temperature resistance and no toxicity.
In order to achieve the purpose, the invention adopts the following technical scheme;
the metal corrosion inhibitor for resisting carbon dioxide corrosion comprises the following raw material components in percentage by weight: 16-18% of vegetable oleic acid, 10-12% of amine, 6-7% of intermediate solvent, 17-18% of aldehyde, 5% of nonionic surfactant, 10% of phosphoric acid compound and the balance of water.
Preferably, the vegetable oil acid is cotton oil acid or soybean oil acid.
Preferably, the amine is diethylenetriamine or cyclohexylamine.
Preferably, the intermediate solvent is toluene or xylene.
Preferably, the aldehyde is formaldehyde or benzaldehyde.
Preferably, the nonionic surfactant is fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether.
Preferably, the phosphoric acid compound is phosphoric acid or hypophosphorous acid.
The preparation method of the metal corrosion inhibitor for resisting carbon dioxide corrosion comprises a reaction kettle used in the preparation process, and the method comprises the following steps
A, preparing a corrosion inhibitor intermediate:
step 1: taking 16-18% of vegetable oil acid in parts by weight; 10-12% of amines; 6% of intermediate solvent, and sequentially adding the components into a reaction kettle;
step 2: and opening a condenser valve to communicate with the outside.
And step 3: starting hot oil heating, gradually raising the temperature to reflux, and keeping the reflux for about 10 hours.
And 4, step 4: heating is started, steam is condensed in a condenser and then flows back to a water separator, the distillation is stopped when the distillation temperature reaches 200 ℃, circulating water in a kettle is started to cool water, and a corrosion inhibitor intermediate is obtained after cooling;
b, preparing a finished corrosion inhibitor:
step 1: checking whether the reaction kettle is clean, closing each valve of the reaction kettle, and adding water by a pump;
step 2: adding the corrosion inhibitor intermediate into a reaction kettle;
and step 3: according to the weight of the corrosion inhibitor intermediate, slowly adding aldehydes into the reaction kettle;
and 4, step 4: slowly dripping phosphoric acid, and controlling the temperature below 50 ℃.
And 5: adding 5% of nonionic surfactant, heating to 80 ℃, and keeping the temperature for 2 hours;
step 6: and (4) detecting the finished product corrosion inhibitor, discharging, labeling and warehousing.
The corrosion inhibitor can be used for protecting the corrosion of oil wells and gas wells containing carbon dioxide in oil fields, ground oil and gas gathering and transportation systems and equipment pipelines of sewage treatment systems.
Has the advantages that: the corrosion inhibitor for resisting carbon dioxide corrosion has the characteristics of small addition amount, high corrosion inhibition rate, environment friendliness, no toxicity, no pollution to the environment and the like, and can be dissolved in water at any ratio. According to the molecular design theory, the corrosion inhibitor molecule contains a plurality of adsorption centers such as nitrogen, oxygen, phosphorus, sulfur and the like, and the plurality of adsorption centers interact with each other, so that the corrosion inhibitor not only has a particularly good inhibition effect on carbon dioxide corrosion, but also has a good inhibition effect on hydrogen sulfide corrosion. Through indoor experiments and oilfield field experiments, when the using concentration of the corrosion inhibitor is 50mg/L, the corrosion inhibition efficiency can reach more than 90-95%. Compared with the prior similar corrosion inhibitor, the corrosion inhibition rate is improved by more than 10-20% under the same concentration.
Detailed Description
Comparative example 1
The metal corrosion inhibitor for resisting carbon dioxide corrosion comprises the following raw material components in percentage by weight: 16% of cotton oil acid, 6% of dimethylbenzene, 17% of benzaldehyde, 5% of fatty alcohol-polyoxyethylene ether, 10% of hypophosphorous acid and the balance of water.
The preparation method of the metal corrosion inhibitor comprises the following steps:
a, preparing a corrosion inhibitor intermediate:
step 1: the preparation method comprises the following steps of (1) taking the cotton oil acid and the dimethylbenzene according to the weight parts, and sequentially adding the components into a reaction kettle;
step 2: and opening a condenser valve to communicate with the outside.
And step 3: starting hot oil heating, gradually raising the temperature to reflux, and keeping the reflux for 9-10 hours.
And 4, step 4: heating is started, steam is condensed in a condenser and then flows back to a water separator, the distillation is stopped when the distillation temperature reaches 200 ℃, circulating water cooling water in a kettle is started, and the temperature is reduced to obtain a corrosion inhibitor intermediate;
b, preparing a finished corrosion inhibitor:
step 1: checking whether the reaction kettle is clean, closing each valve of the reaction kettle, and adding water by a pump;
step 2: adding the corrosion inhibitor intermediate into a reaction kettle;
and step 3: according to the weight of the corrosion inhibitor intermediate, slowly adding benzaldehyde into the reaction kettle;
and 4, step 4: slowly dripping hypophosphorous acid, and controlling the temperature below 50 ℃.
And 5: adding fatty alcohol-polyoxyethylene ether, heating to 80 ℃, and keeping the temperature for 2 hours;
step 6: and (4) detecting the finished product corrosion inhibitor, discharging, labeling and warehousing.
Comparative example 2
The metal corrosion inhibitor for resisting carbon dioxide corrosion comprises the following raw material components in percentage by weight: 12% of diethylenetriamine, 6% of xylene, 5% of fatty alcohol-polyoxyethylene ether, 10% of hypophosphorous acid, 17% of benzaldehyde and the balance of water.
A, preparing a corrosion inhibitor intermediate:
step 1: taking diethylenetriamine and xylene according to parts by weight, and sequentially adding the components into a reaction kettle;
step 2: and opening a condenser valve to communicate with the outside.
And step 3: starting hot oil heating, gradually raising the temperature to reflux, and keeping the reflux for about 10 hours.
And 4, step 4: heating is started, steam is condensed in a condenser and then flows back to a water separator, the distillation is stopped when the distillation temperature reaches 200 ℃, circulating water cooling water in a kettle is started, and the temperature is reduced to obtain a corrosion inhibitor intermediate;
b, preparing a finished corrosion inhibitor:
step 1: checking whether the reaction kettle is clean, closing each valve of the reaction kettle, and adding water by a pump;
step 2: adding the corrosion inhibitor intermediate into a reaction kettle;
and step 3: according to the weight of the corrosion inhibitor intermediate, slowly adding benzaldehyde into the reaction kettle;
and 4, step 4: slowly adding hypophosphorous acid dropwise, and controlling the temperature below 50 ℃.
And 5: adding fatty alcohol-polyoxyethylene ether, heating to 80 ℃, and keeping the temperature for 2 hours;
step 6: and (4) detecting the finished product corrosion inhibitor, discharging, labeling and warehousing.
Example 1
The metal corrosion inhibitor for resisting carbon dioxide corrosion comprises the following raw material components in percentage by weight: 16% of cotton oil acid, 10% of diethylenetriamine, 6% of xylene, 17% of benzaldehyde, 10% of hypophosphorous acid, 5% of fatty alcohol-polyoxyethylene ether and 36% of water.
A, preparing a corrosion inhibitor intermediate:
step 1: taking the oleic acid, the diethylenetriamine and the xylene according to the weight parts, and sequentially adding the components into a reaction kettle;
step 2: and opening a condenser valve to be communicated with the outside.
And step 3: starting hot oil heating, gradually raising the temperature to reflux, and keeping the reflux for about 10 hours.
And 4, step 4: heating is started, steam is condensed in a condenser and then flows back to a water separator, the distillation is stopped when the distillation temperature reaches 200 ℃, circulating water in a kettle is started to cool water, and a corrosion inhibitor intermediate is obtained after cooling;
b, preparing a finished corrosion inhibitor:
step 1: checking whether the reaction kettle is clean, closing each valve of the reaction kettle, and adding water by a pump;
step 2: adding the corrosion inhibitor intermediate into a reaction kettle;
and 3, step 3: according to the weight of the corrosion inhibitor intermediate, slowly adding benzaldehyde into the reaction kettle;
and 4, step 4: slowly adding hypophosphorous acid dropwise, and controlling the temperature below 50 ℃.
And 5: adding fatty alcohol-polyoxyethylene ether, heating to 80 ℃, and keeping the temperature for 2 hours;
step 6: and (4) detecting the finished product corrosion inhibitor, discharging, labeling and warehousing after the detection is qualified.
Example 2
The metal corrosion inhibitor for resisting carbon dioxide corrosion comprises the following raw material components in percentage by weight: 17% of cotton oil acid, 12% of diethylenetriamine, 6% of xylene, 17% of benzaldehyde, 10% of hypophosphorous acid, 5% of fatty alcohol-polyoxyethylene ether and 33% of water.
A, preparing a corrosion inhibitor intermediate:
step 1: the preparation method comprises the following steps of (1) taking the oleic acid, the diethylenetriamine and the xylene according to the weight parts, and sequentially adding the components into a reaction kettle;
step 2: and opening a condenser valve to be communicated with the outside.
And step 3: starting hot oil heating, gradually raising the temperature to reflux, and keeping the reflux for about 10 hours.
And 4, step 4: heating is started, steam is condensed in a condenser and then flows back to a water separator, the distillation is stopped when the distillation temperature reaches 200 ℃, circulating water cooling water in a kettle is started, and the temperature is reduced to obtain a corrosion inhibitor intermediate;
b, preparing a finished corrosion inhibitor:
step 1: checking whether the reaction kettle is clean, closing each valve of the reaction kettle, and adding water by using a pump;
step 2: adding the corrosion inhibitor intermediate into a reaction kettle;
and step 3: according to the weight of the corrosion inhibitor intermediate, slowly adding benzaldehyde into the reaction kettle;
and 4, step 4: slowly dripping hypophosphorous acid, and controlling the temperature below 50 ℃.
And 5: adding fatty alcohol-polyoxyethylene ether, heating to 80 ℃, and keeping the temperature for 2 hours;
step 6: and (4) detecting the finished product corrosion inhibitor, discharging, labeling and warehousing.
Example 3
The metal corrosion inhibitor for resisting carbon dioxide corrosion comprises the following raw material components in percentage by weight: 16% of soya-bean oil acid, 10% of cyclohexylamine, 6% of xylene, 17% of formaldehyde, 10% of hypophosphorous acid, 5% of alkylphenol polyoxyethylene ether and 36% of water.
A, preparing a corrosion inhibitor intermediate:
step 1: taking the soya-bean oil acid according to parts by weight; cyclohexylamine; adding the components into a reaction kettle in sequence;
step 2: and opening a condenser valve to be communicated with the outside.
And step 3: starting hot oil heating, gradually raising the temperature to reflux, and keeping the reflux for about 10 hours.
And 4, step 4: heating is started, steam is condensed in a condenser and then flows back to a water separator, the distillation is stopped when the distillation temperature reaches 200 ℃, circulating water in a kettle is started to cool water, and a corrosion inhibitor intermediate is obtained after cooling;
b, preparing a finished corrosion inhibitor:
step 1: checking whether the reaction kettle is clean, closing each valve of the reaction kettle, and adding water by a pump;
step 2: adding the corrosion inhibitor intermediate into a reaction kettle;
and step 3: according to the weight of the corrosion inhibitor intermediate, slowly adding formaldehyde into the reaction kettle;
and 4, step 4: slowly dripping hypophosphorous acid, and controlling the temperature below 50 ℃.
And 5: adding alkylphenol polyoxyethylene, heating to 80 ℃, and keeping the temperature for 2 hours;
step 6: and (4) detecting the finished product corrosion inhibitor, discharging, labeling and warehousing.
Example 4
The metal corrosion inhibitor for resisting carbon dioxide corrosion comprises the following raw material components in percentage by weight: 16% of soya-bean oil acid, 12% of cyclohexylamine, 6% of xylene, 17% of benzaldehyde, 10% of hypophosphorous acid, 5% of alkylphenol polyoxyethylene and 36% of water.
A, preparing a corrosion inhibitor intermediate:
step 1: taking the soya-bean oil acid according to parts by weight; cyclohexylamine; adding the components into a reaction kettle in sequence;
step 2: and opening a condenser valve to communicate with the outside.
And step 3: starting hot oil heating, gradually raising the temperature to reflux, and keeping the reflux for about 10 hours.
And 4, step 4: heating is started, steam is condensed in a condenser and then flows back to a water separator, the distillation is stopped when the distillation temperature reaches 200 ℃, circulating water cooling water in a kettle is started, and the temperature is reduced to obtain a corrosion inhibitor intermediate;
b, preparing a finished corrosion inhibitor:
step 1: checking whether the reaction kettle is clean, closing each valve of the reaction kettle, and adding water by a pump;
step 2: adding the corrosion inhibitor intermediate into a reaction kettle;
and 3, step 3: according to the weight of the corrosion inhibitor intermediate, slowly adding benzaldehyde into the reaction kettle;
and 4, step 4: slowly dripping 10% hypophosphorous acid, and controlling the temperature below 50 ℃.
And 5: adding 5% of alkylphenol polyoxyethylene, heating to 80 ℃, and keeping the temperature for 2 hours;
step 6: and (4) detecting the finished product corrosion inhibitor, discharging, labeling and warehousing.
Effect test
In order to verify the corrosion inhibition performance of the metal corrosion inhibitor for resisting carbon dioxide corrosion, the corrosion rate of the corrosion inhibitor is evaluated by simulating field corrosion water quality by adopting a weightlessness method indoors according to the petroleum and natural gas industry standard Q/SY 126-. The corrosion medium for the experiment is prepared water, the specific preparation requirements refer to 6.2.9 regulations in Q/SY 126- 2 The corrosion rate of the corrosion inhibitor is measured according to the specification of B.6.4. The experimental material is carbonSteel (type: Q235 size: 50 mm. times.25 mm. times.2.0 mm), comparative examples 1-2, and examples 1-3 the results are shown in the following tables.
The experiment results show that the vegetable oleic acid and the amine play a crucial role in the metal corrosion inhibitor prepared by the invention, are key factors for determining the corrosion inhibition performance of the product, and the product has unqualified corrosion inhibition performance without adding the vegetable oleic acid or the amine. Meanwhile, vegetable oleic acid and amines are added, so that the corrosion rate is qualified and the performance is excellent when different dosing concentrations are added.
The corrosion inhibitor has the characteristics of good compatibility, good water solubility, temperature resistance, no toxicity and the like. The corrosion inhibitor can form a compact protective film on the metal surface, and solves the problem of CO in the exploitation, gathering and transportation processes of oil and gas wells 2 Corrosion to metal pipelines, equipment and the like.
And (3) analyzing an experimental result:
the high-temperature acidification corrosion inhibitor has low dosage and excellent corrosion inhibition performance in hydrochloric acid and earth acid media at the temperature of 90-140 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The metal corrosion inhibitor for resisting carbon dioxide corrosion is characterized by comprising the following raw material components in percentage by weight: 16-18% of vegetable oleic acid, 10-12% of amine, 6-7% of intermediate solvent, 17-18% of aldehyde, 5% of nonionic surfactant, 10% of phosphoric acid compound and the balance of water.
2. The metal corrosion inhibitor of claim 1, wherein the vegetable oil acid is a cotton oil acid or a soya oil acid.
3. The metal corrosion inhibitor according to claim 1, wherein the amine is diethylenetriamine or cyclohexylamine.
4. The metal corrosion inhibitor of claim 1 wherein said intermediate solvent is toluene or xylene.
5. The metal corrosion inhibitor of claim 1, wherein the aldehyde is formaldehyde or benzaldehyde.
6. The metal corrosion inhibitor of claim 1, wherein the nonionic surfactant is fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether.
7. The metal corrosion inhibitor according to claim 1, wherein the phosphoric acid compound is phosphoric acid or hypophosphorous acid.
8. A process for preparing a metal corrosion inhibitor according to any one of claims 1 to 7, characterized in that the following steps are used:
a, preparing a corrosion inhibitor intermediate:
step 1: sequentially weighing vegetable oleic acid, amines and an intermediate solvent, and adding the vegetable oleic acid, the amines and the intermediate solvent into a reaction kettle;
step 2: opening a condenser valve to communicate with the outside;
and step 3: starting hot oil for heating, gradually heating to reflux, and keeping the reflux for 9-11 hours;
and 4, step 4: heating is started, steam is condensed in a condenser and then flows back to a water separator, the distillation is stopped when the distillation temperature reaches 200 ℃, and circulating water cooling water in a kettle is started to obtain a corrosion inhibitor intermediate;
b, preparing a finished corrosion inhibitor:
step 1: closing each valve of the reaction kettle, and adding water;
step 2: adding the corrosion inhibitor intermediate into a reaction kettle;
and step 3: slowly adding aldehydes into the reaction kettle;
and 4, step 4: slowly dripping phosphoric acid compounds, and controlling the temperature below 50 ℃;
and 5: adding a nonionic surfactant, heating to 80 ℃, and preserving the heat for 2 hours to obtain the finished product of the corrosion inhibitor.
9. Use of a metal corrosion inhibitor according to any of claims 1 to 7 for protection against corrosion of carbon dioxide-containing equipment lines.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966774A (en) * | 2006-09-04 | 2007-05-23 | 长庆石油勘探局 | Corrosion inhibitor resistant to H2S and CO2 |
| 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 |
| CN104846379A (en) * | 2015-06-02 | 2015-08-19 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | Preparation method of vegetable oil acid based imidazoline carbon dioxide corrosion inhibitor |
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- 2022-07-05 CN CN202210781261.6A patent/CN114990555A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966774A (en) * | 2006-09-04 | 2007-05-23 | 长庆石油勘探局 | Corrosion inhibitor resistant to H2S and CO2 |
| 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 |
| CN104846379A (en) * | 2015-06-02 | 2015-08-19 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | Preparation method of vegetable oil acid based imidazoline carbon dioxide corrosion inhibitor |
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