CN111363532A - Imidazoline Schiff base type high-temperature acidizing corrosion inhibitor - Google Patents
Imidazoline Schiff base type high-temperature acidizing corrosion inhibitor Download PDFInfo
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- CN111363532A CN111363532A CN202010303067.8A CN202010303067A CN111363532A CN 111363532 A CN111363532 A CN 111363532A CN 202010303067 A CN202010303067 A CN 202010303067A CN 111363532 A CN111363532 A CN 111363532A
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- imidazoline
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses an imidazoline Schiff base type high-temperature acidizing corrosion inhibitor which comprises the following components in percentage by mass: 20-30% of alcohol ether imidazoline Schiff base, 8-15% of s-triazine, 1-5% of N-alkyl pyrrolidone, 0.3-0.8% of nonylphenol polyoxyethylene ether, 0.5-2.5% of borax, 10-20% of methanol and the balance of water. The high-temperature acidification corrosion inhibitor has good dissolution and dispersion in acid liquor and obvious corrosion inhibition effect; not only can be suitable for the plugging removal and acidification production increasing operation of oil and gas wells below 90 ℃, but also can be used for slowing down the high H content2S and CO2The corrosion of the oil well produced water to the oil casing.
Description
Technical Field
The invention belongs to the technical field of chemicals for increasing production of oil and gas wells, and particularly relates to a high-temperature acidizing corrosion inhibitor.
Background
In the process of oil and gas resource development, acid fracturing is a main measure for improving the recovery ratio and realizing the yield increase and stable production of oil and gas wells in most oil and gas fields at home and abroad; however, the high-concentration acid liquor can cause serious corrosion to oil well pipe columns and underground metal equipment, and adding a proper corrosion inhibitor into the acid liquor is a common effective means; with the continuous development of the depth of an oil-gas well, the well temperature is continuously increased, the corrosion of acid liquor to metal is intensified, and higher requirements are provided for the performance of the acidizing corrosion inhibitor.
Imidazoline and Schiff base are common acidizing corrosion inhibitors, and can form firm coordination bonds with various metal ions to be popularized and applied in the field of oil and gas field corrosion prevention. In the examples, patents CN 201510171973.6, CN 201910975640.7, CN201810584971.3 and CN201110455518.0 all determine the corrosion rate of the schiff base acidized corrosion inhibitor on an N80 test piece at 90 ℃ and 15% HCl, and the corrosion inhibition effect is significant; the Lide instrument is obtained through experimental research when CT series acidizing corrosion inhibitors are researched, and some corrosion inhibitors with good effect on 15% HCl simply cannot act in 28% HCl; also, corrosion inhibitors for concentrated acids are not necessarily effective in low concentrations of acid. There are few reports on the application of schiff base corrosion inhibitors in 20% HCl to study the corrosion rate of N80 steel at 90 ℃. Therefore, it is particularly necessary to research and develop the acidification corrosion inhibitor with good applicability according to the characteristics of the acid liquor.
Disclosure of Invention
The invention aims to provide an imidazoline Schiff base type high-temperature acidizing corrosion inhibitor which is environment-friendly, low in toxicity, remarkable in corrosion inhibition effect and good in acid liquor compatibility.
In order to achieve the aim, the imidazoline Schiff base type high-temperature acidizing corrosion inhibitor adopted by the invention comprises the following raw materials in percentage by mass:
the imidazoline Schiff base type high-temperature acidizing corrosion inhibitor preferably comprises the following raw materials in percentage by mass:
the structural formula of the alcohol ether-based imidazoline Schiff base is as follows:
wherein R is a carbon chain number of C8~C22M is more than or equal to 5 and less than or equal to 16; preferably, R is a carbon chain number of C12~C18M is more than or equal to 6 and less than or equal to 12. The preparation method comprises the following steps: stirring alcohol ether carboxylic acid shown as a formula I, diethylenetriamine and aluminum oxide according to the molar ratio of 1: 1.00-1.20: 0.02-0.06 for reaction for 4-6 h at 140-220 ℃, and cooling after complete dehydration to obtain an alcohol ether imidazoline intermediate shown as a formula II; adding an alcohol ether imidazoline intermediate and 4- (4-hydroxyphenyl) cyclohexanone into absolute ethyl alcohol according to a molar ratio of 1: 0.8-1.20, slowly dropwise adding glacial acetic acid under stirring at 30-40 ℃, adjusting the pH value of the system to be 4-6, reacting for 2-4 h at 60-80 ℃, cooling to room temperature, filtering, and recrystallizing to obtain the alcohol ether imidazoline Schiff base, wherein the reaction process is as follows:
the N-alkyl pyrrolidone is one or two of N-propyl pyrrolidone, N-hexyl pyrrolidone, N-octyl pyrrolidone and N-lauryl pyrrolidone.
The preparation method of the imidazoline Schiff base type high-temperature acidizing corrosion inhibitor comprises the following steps: according to the mass percentage, firstly, borax is dissolved in water and methanol, then alcohol ether group imidazoline Schiff base, s-triazine, N-alkyl pyrrolidone and nonylphenol polyoxyethylene ether are sequentially added, and the mixture is stirred to be uniform.
The invention has the following beneficial effects:
1. compared with the traditional imidazoline and Schiff base, the molecular structure of the main agent alcohol ether-based imidazoline Schiff base contains more adsorption groups such as ether bonds, imidazoline rings, carbon-nitrogen double bonds, benzene rings and hydroxyl bonds, so that the adsorption capacity of corrosion inhibitor molecules on the metal surface can be enhanced, and the corrosion inhibition effect is enhanced.
2. The s-triazine in the imidazoline Schiff base type high-temperature acidizing corrosion inhibitor is a slow-release bactericide, has good stability, low toxicity and wide pH value application range, and has good compatibility with anionic and cationic surfactants, nonionic surfactants and other industrial additives.
3. The imidazoline Schiff base type high-temperature acidizing corrosion inhibitor disclosed by the invention has the advantages that the N-alkyl pyrrolidone and the nonylphenol polyoxyethylene ether are compounded for use, the dissolving and dispersing effects are enhanced, and the product stability and the acid liquor solubility can be greatly improved.
4. The components in the imidazoline Schiff base type high-temperature acidizing corrosion inhibitor are environment-friendly and low in toxicity, have a good synergistic effect, are good in dissolving dispersibility in acid liquor, have a remarkable corrosion inhibition effect, and can meet the requirement of the corrosion rate of SY/T5405-2019 standard in the petroleum industry in 20% HCl at 90 ℃.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
Taking 1000g of imidazoline Schiff base type high-temperature acidizing corrosion inhibitor as an example, the imidazoline Schiff base type high-temperature acidizing corrosion inhibitor is prepared from the following raw materials:
the preparation method comprises the following steps: firstly, 18g of borax is dissolved in 487g of water and 110g of methanol, then 260g of alcohol ether imidazoline Schiff base, 100g of s-triazine, 20g N-propyl pyrrolidone and 5g of nonylphenol polyoxyethylene ether are sequentially added, and the mixture is stirred and mixed uniformly.
The structural formula of the alcohol ether imidazoline schiff base in the embodiment is shown as follows:
example 2
Taking 1000g of imidazoline Schiff base type high-temperature acidizing corrosion inhibitor as an example, the imidazoline Schiff base type high-temperature acidizing corrosion inhibitor is prepared from the following raw materials:
the preparation method is the same as that of example 1.
The structural formula of the alcohol ether imidazoline schiff base in the embodiment is shown as follows:
example 3
Taking 1000g of imidazoline Schiff base type high-temperature acidizing corrosion inhibitor as an example, the imidazoline Schiff base type high-temperature acidizing corrosion inhibitor is prepared from the following raw materials:
the preparation method is the same as that of example 1.
The structural formula of the alcohol ether imidazoline schiff base in the embodiment is shown as follows:
example 4
Taking 1000g of imidazoline Schiff base type high-temperature acidizing corrosion inhibitor as an example, the imidazoline Schiff base type high-temperature acidizing corrosion inhibitor is prepared from the following raw materials:
the preparation method is the same as that of example 1.
The structural formula of the alcohol ether imidazoline schiff base in the embodiment is shown as follows:
example 5
Taking 1000g of imidazoline Schiff base type high-temperature acidizing corrosion inhibitor as an example, the imidazoline Schiff base type high-temperature acidizing corrosion inhibitor is prepared from the following raw materials:
the preparation method is the same as that of example 1.
The structural formula of the alcohol ether imidazoline schiff base in the embodiment is shown as follows:
comparative examples 1 to 5
The comparative examples 1 to 5 differ from the examples 1 to 5 only in that the alcohol ether-based imidazoline schiff bases in the examples 1 to 5 were replaced with the same amount of the alcohol ether imidazoline intermediates corresponding to the alcohol ether-based imidazoline schiff bases in the examples 1 to 5, respectively.
In order to prove the beneficial effects of the invention, the inventor refers to a determination method of 5 in the standard of test method and evaluation index for corrosion inhibitor performance for acidification (SY/T5405-2019), and performs a normal pressure static corrosion rate test on the imidazoline Schiff base type high temperature acidification corrosion inhibitor prepared in the embodiments 1-5, the corrosion inhibitor of the comparative examples 1-5 and the novel Schiff base oil well acidification corrosion inhibitor disclosed in the invention patent application with publication number CN102559167A (noted as comparative example 6), wherein the test conditions are as follows: 20% HCl, N80, 90 ℃ for 4 h. The test results are shown in Table 1.
TABLE 1 Corrosion Rate of imidazoline Schiff base type high temperature acidizing corrosion inhibitors
Corrosion inhibitor | Addition/% of corrosion inhibitor | Corrosion rate/g/(m)2·h) |
Example 1 | 1.0 | 3.501 |
Example 2 | 1.0 | 3.045 |
Example 3 | 1.0 | 3.928 |
Example 4 | 1.0 | 3.017 |
Example 5 | 1.0 | 3.022 |
Comparative example 1 | 1.0 | 11.558 |
Comparative example 2 | 1.0 | 8.963 |
Comparative example 3 | 1.0 | 9.271 |
Comparative example 4 | 1.0 | 10.636 |
Comparative example 5 | 1.0 | 12.534 |
Comparative example 6 | 1.0 | 7.789 |
As shown in Table 1, when the amount of the corrosion inhibitor added in the 20% hydrochloric acid medium is 1.0%, the corrosion rates of the imidazoline Schiff base type high-temperature acidification corrosion inhibitors prepared in the embodiments 1-5 of the present invention on the N80 test piece at 90 ℃ are all less than or equal to 6 g/(m) of SY/T5405-2019 under the conditions2H) index requirement, the corrosion rate of the comparative examples 1-6 on the N80 test piece at 90 ℃ cannot reach 6 g/(m) in SY/T5405-2H) index requirements.
The inventor further refers to a determination method of 8 in the standard of 'test method and evaluation index for corrosion inhibitor performance for acidification' (SY/T5405-: 1.2g corrosion inhibitor/100 mL 20% HCl, 90 ℃. The test results are shown in Table 2.
TABLE 2 solubility and dispersibility of imidazoline Schiff base type high-temperature acidizing corrosion inhibitor
Corrosion inhibitor | Observation time/h | Dissolution and dispersion conditions | Reach the index |
Example 1 | 4 | The acid liquor is transparent and clear, has no liquid/liquid phase layering and no liquid/solid phase separation | First stage |
Example 2 | 4 | The acid liquor is transparent and clear, has no liquid/liquid phase layering and no liquid/solid phase separation | First stage |
Example 3 | 4 | The acid liquor is transparent and clear, has no liquid/liquid phase layering and no liquid/solid phase separation | First stage |
Example 4 | 4 | The acid liquor is transparent and clear, has no liquid/liquid phase layering and no liquid/solid phase separation | First stage |
Example 5 | 4 | The acid liquor is transparent and clear, has no liquid/liquid phase layering and no liquid/solid phase separation | First stage |
From the test results in table 2, it can be seen that when 20% of HCl in 100mL and 90 ℃ and the maximum addition amount of the corrosion inhibitor is 1.2g, the imidazoline schiff base type high-temperature acidification corrosion inhibitor prepared in the embodiments 1 to 5 of the present invention has good dissolution and dispersion conditions for 4 hours, and meets the first-level index requirement, which indicates that the imidazoline schiff base type high-temperature acidification corrosion inhibitor prepared in the embodiments 1 to 5 of the present invention has good compatibility with acid liquor.
The experimental results shown in tables 1 and 2 show that the imidazoline Schiff base type high-temperature acidification corrosion inhibitor has good corrosion inhibition performance and acid solution dissolution and dispersion performance.
Claims (4)
1. An imidazoline Schiff base type high-temperature acidizing corrosion inhibitor is characterized by comprising the following raw materials in percentage by mass:
the structural formula of the alcohol ether-based imidazoline Schiff base is as follows:
wherein R is a carbon chain number of C8~C22M is more than or equal to 5 and less than or equal to 16.
3. the imidazoline schiff base type high-temperature acidizing corrosion inhibitor according to the claim 1 or 2, which is characterized in that: in the structural formula of the alcohol ether-based imidazoline Schiff base, R is a carbon chain number C12~C18M is more than or equal to 6 and less than or equal to 12.
4. The imidazoline schiff base type high-temperature acidizing corrosion inhibitor according to the claim 1 or 2, which is characterized in that: the N-alkyl pyrrolidone is one or two of N-propyl pyrrolidone, N-hexyl pyrrolidone, N-octyl pyrrolidone and N-lauryl pyrrolidone.
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US20230052367A1 (en) * | 2021-07-02 | 2023-02-16 | The Boeing Company | Corrosion inhibition compositions and associated methods for inhibiting corrosion on metallic substrates |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102021583A (en) * | 2011-01-07 | 2011-04-20 | 陕西省石油化工研究设计院 | Corrosion inhibitor for oil well and preparation method thereof |
CN104831286A (en) * | 2015-04-13 | 2015-08-12 | 长江大学 | Schiff base type acidification corrosion inhibitor, preparation method and applications thereof |
CN106085399A (en) * | 2016-06-27 | 2016-11-09 | 中国石油集团渤海钻探工程有限公司 | Acidifying compounding Imidazoline corrosion inhibitor and preparation method thereof |
CN110577829A (en) * | 2018-06-08 | 2019-12-17 | 中国石油天然气股份有限公司 | Cinnamaldehyde Schiff base acidizing corrosion inhibitor, preparation and use method |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN102021583A (en) * | 2011-01-07 | 2011-04-20 | 陕西省石油化工研究设计院 | Corrosion inhibitor for oil well and preparation method thereof |
CN104831286A (en) * | 2015-04-13 | 2015-08-12 | 长江大学 | Schiff base type acidification corrosion inhibitor, preparation method and applications thereof |
CN106085399A (en) * | 2016-06-27 | 2016-11-09 | 中国石油集团渤海钻探工程有限公司 | Acidifying compounding Imidazoline corrosion inhibitor and preparation method thereof |
CN110577829A (en) * | 2018-06-08 | 2019-12-17 | 中国石油天然气股份有限公司 | Cinnamaldehyde Schiff base acidizing corrosion inhibitor, preparation and use method |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US20230052367A1 (en) * | 2021-07-02 | 2023-02-16 | The Boeing Company | Corrosion inhibition compositions and associated methods for inhibiting corrosion on metallic substrates |
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Address after: No.61 Xiyan Road, Xi'an City, Shaanxi Province 710054 Patentee after: Shaanxi Chemical Research Institute Co.,Ltd. Address before: No.61 Xiyan Road, Xi'an City, Shaanxi Province 710054 Patentee before: SHAANXI RESEARCH DESIGN INSTITUTE OF PETROLEUM CHEMICAL INDUSTRY |