CN102533245B - Mannich base metal iodide corrosion inhibitor and preparation method thereof - Google Patents
Mannich base metal iodide corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN102533245B CN102533245B CN 201110425009 CN201110425009A CN102533245B CN 102533245 B CN102533245 B CN 102533245B CN 201110425009 CN201110425009 CN 201110425009 CN 201110425009 A CN201110425009 A CN 201110425009A CN 102533245 B CN102533245 B CN 102533245B
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- metal iodide
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Abstract
The invention discloses a Mannich base metal iodide corrosion inhibitor and a preparation method thereof. The Mannich base metal iodide corrosion inhibitor comprises components of the following mass percentage: 15 to 30 percent of the metal iodide of a condensate of ketone, aldehyde and amine, and 70 to 85 percent of complex, wherein the complex is made up of following materials with mass percentof: 5 to 15 percent of cetylpyridinium chloride, 5 to 20 percent of emulsifier, and 65 to 80 percent of solvent. The metal iodide of a condensate of ketone, aldehyde and amine can be obtained by reaction of the metal iodide and the condensate of ketone, aldehyde and amine synthesized with 1-naphthy lamine, paraformaldehyde, and ethyl phenyl ketone. The problem that other corrosion inhibitors can be easily decomposed at high temperature can be solved, the inconvenience in production caused by toxic material can be reduced, acidification and corrosion of hydrochloric acid at high temperature can be inhibited, the problem of corrosion by strong acid during the acidification fracturing of petroleum exploitation can be solved, and the goal of protecting oil pipes can be achieved.
Description
Technical field
The invention belongs to the petroleum refining technology field, be specifically related to the inhibiter technology of oil refining process.
Background technology
The high-temperature acidification corrosion inhibitor research of China is started late, until the seventies middle and later periods just progressively carry out, but very fast in research and application facet raising, in the eighties after mid-term, multiple acidification corrosion inhibitor has been produced in successively research and development, has solved the need of production in part oil field.Mannich base is used as acidification corrosion inhibitor has had certain scale, and has obtained good application.Be exactly the Mannich base that generates with aniline, methyl phenyl ketone, urotropine reaction and propiolic alcohol is composite forms such as 7801 type inhibiter of Central China University of Science and Technology development, erosion rate is＜80g/ (m in 150 ℃, 28%HCl solution
2H); Sky, the river 1-2 type inhibiter of Natural Gas in Sichuan Research Institute is the Mannich base that generates with aniline, pimelinketone, formaldehyde reaction and propiolic alcohol is composite forms, and erosion rate is＜80g/ (m in 150 ℃, 28%HCl solution equally
2H).
With the continuous appearance of high temperature deep well, inhibiter is had higher requirement.The shortcomings such as Mannich base at high temperature easily decomposes, compound toxicity is larger have had a strong impact on the performance of inhibiter.Solving on the easy resolution problem of Mannich base high temperature, form the thing that boils together by composite metal-salt abroad, satisfy the needs of high temperature, such as thiocarbamide, formaldehyde, the methyl phenyl ketone reaction of mentioning in the patent (App1.No.66817), composite butter of antimony reaches 0.005lb/ft 300 °F of (approximately 149 ℃) erosion rates again
2(12.21g/ (m
2H)), but butter of antimony corrodibility is very strong, makes troubles for the production of inhibiter.
Summary of the invention
Weak point for above prior art exists the purpose of this invention is to provide a kind of acidification corrosion inhibitor that suppresses the high temp. salt acid corrosion, solves China's strong acid etching problem in oil production acid fracturing process, to reach the purpose to protection of oil pipes.
A kind of Mannich base metal iodide corrosion inhibitor provided by the invention, by percentage to the quality, it consists of: the metal iodide 15～30% of aldehyde ketone amine condenses, compound 70～85%, wherein the compound composition is by percentage to the quality: cetylpyridinium chloride 5～15%, emulsifying agent 5～20%, solvent 65～80%, the metal iodide structural formula of described aldehyde ketone amine condenses is:
M represents metallic copper or potassium.
Further, described emulsifying agent is fat alcohol and ethylene oxide condensate or polyoxyethylene nonylphenol ether.
Further, described solvent is one or both in methyl alcohol, ethanol, the primary isoamyl alcohol.
The preparation method of a kind of Mannich base metal iodide corrosion inhibitor provided by the invention comprises following processing step:
(1) aldehyde ketone amine condenses is synthetic
Naphthalidine, Paraformaldehyde 96, Propiophenone are added in the there-necked flask with 1: 1.5: 1 mol ratio, then adding toluene (wherein the mol ratio of toluene and naphthalidine is 4: 1) mixes, take the hydrochloric acid of mass percent 30% as catalyzer regulator solution pH value between 2～3, be warming up to again 110 ℃ of refluxing toluene temperature, insulation reaction 5 hours, obtain aldehyde ketone amine condenses, its reaction formula is:
(2) metal iodide of aldehyde ketone amine condenses is synthetic
The metal iodide that adds its total mass 25～50% in described aldehyde ketone amine condenses stirs and is warming up to 30～50 ℃, and reaction can obtain the metal iodide of aldehyde ketone amine condenses in 1～2 hour, and its reaction formula is:
M represents metallic copper or potassium;
(3) preparation of Mannich base metal iodide corrosion inhibitor
By percentage to the quality, following raw material is mixed, stirring under normal temperature gets final product:
The metal iodide 15～30% of aldehyde ketone amine condenses, compound 70～85%, wherein the compound composition is cetylpyridinium chloride 5～15% by percentage to the quality, emulsifying agent 5～20%, solvent 65～80%.
Preferably, the metal iodide of the synthetic aldehyde ketone amine condenses described in the processing step (2), its temperature of reaction is 50 ℃, the reaction times is 1 hour.
Further, the raw material naphthalidine described in the processing step (1) also can be the 2-naphthylamines.
Further, described metal iodide is potassiumiodide or cuprous iodide.
The using method of inhibiter of the present invention is: directly add the inhibiter of mass percent 2～3% in the acidizing fluid, stirring gets final product.
After adding inhibiter of the present invention in the acidization, the corrosion speed of N80 oil pipe all meets the requirement of oil and gas industry standard SY/T 5404-1996, and has the following advantages: 1) solved at high temperature labile shortcoming of Mannich base; 2) reduced the inconvenience that the toxic substances such as propiolic alcohol, butter of antimony bring production; 3) satisfied in the present acidizing treatment process protection to the N80 oil pipe.
Embodiment
Embodiment 1
Naphthalidine, Paraformaldehyde 96, Propiophenone are added in the there-necked flask with 1: 1.5: 1 mol ratio, then adding toluene (wherein the mol ratio of toluene and naphthalidine is 4: 1) mixes, take the hydrochloric acid of mass percent 30% as catalyzer regulator solution pH value 2.0, be warming up to again 110 ℃ of refluxing toluene temperature, insulation reaction 5 hours obtains aldehyde ketone amine condenses; The cuprous iodide that adds above-mentioned aldehyde ketone amine condenses gross weight 50% stirs and is warming up to 50 ℃, reacts 2 hours, namely obtains the Mannich base iodide; Respectively that 30% Mannich base iodide, 10% cetylpyridinium chloride, 10% polyoxyethylene nonylphenol ether, 50% methanol mixed stir and get final product again with mass percent.
Embodiment 2
2-naphthylamines, Paraformaldehyde 96, Propiophenone are added in the there-necked flask with 1: 1.5: 1 mol ratio, then adding toluene (wherein the mol ratio of toluene and naphthalidine is 4: 1) mixes, take the hydrochloric acid of mass percent 30% as catalyzer regulator solution pH value 2.0, be warming up to again 110 ℃ of refluxing toluene temperature, insulation reaction 5 hours obtains aldehyde ketone amine condenses; The cuprous iodide that adds above-mentioned aldehyde ketone amine condenses gross weight 50% stirs and is warming up to 50 ℃, reacts 1 hour, namely obtains the Mannich base iodide; Respectively that 20% Mannich base iodide, 11.5% cetylpyridinium chloride, 8.5% polyoxyethylene nonylphenol ether, 20% Virahol, 40% methanol mixed stir and get final product again with mass percent.
Embodiment 3
Naphthalidine, Paraformaldehyde 96, Propiophenone are added in the there-necked flask with 1: 1.5: 1 mol ratio, then adding toluene (wherein the mol ratio of toluene and naphthalidine is 4: 1) mixes, take the hydrochloric acid of mass percent 30% as catalyzer regulator solution pH value 3.0, be warming up to again 110 ℃ of refluxing toluene temperature, insulation reaction 5 hours obtains aldehyde ketone amine condenses; The potassiumiodide that adds above-mentioned aldehyde ketone amine condenses gross weight 30% stirs and is warming up to 50 ℃, reacts 2 hours, namely obtains the Mannich base iodide; Respectively that 15% Mannich base iodide, 10% cetylpyridinium chloride, 5% polyoxyethylene nonylphenol ether, 60% ethanol mixing and stirring get final product again with mass percent.
Embodiment 4
Naphthalidine, Paraformaldehyde 96, Propiophenone are added in the there-necked flask with 1: 1.5: 1 mol ratio, then adding toluene (wherein the mol ratio of toluene and naphthalidine is 4: 1) mixes, take the hydrochloric acid of mass percent 30% as catalyzer regulator solution pH value 2.0, be warming up to again 110 ℃ of refluxing toluene temperature, insulation reaction 5 hours obtains aldehyde ketone amine condenses; The cuprous iodide that adds above-mentioned aldehyde ketone amine condenses gross weight 30% stirs and is warming up to 50 ℃, reacts 1 hour, namely obtains the Mannich base iodide; Respectively that 30% Mannich base iodide, 10% cetylpyridinium chloride, 10% fat alcohol get final product with ethylene oxide condensate, 50% Virahol mixing and stirring again with mass percent.
Embodiment 5
Naphthalidine, Paraformaldehyde 96, Propiophenone are added in the there-necked flask with 1: 1.5: 1 mol ratio, then adding toluene (wherein the mol ratio of toluene and naphthalidine is 4: 1) mixes, take the hydrochloric acid of mass percent 30% as catalyzer regulator solution pH value between 2～3, be warming up to again 110 ℃ of refluxing toluene temperature, insulation reaction 5 hours obtains aldehyde ketone amine condenses; The potassiumiodide that adds above-mentioned aldehyde ketone amine condenses gross weight 25% stirs and is warming up to 50 ℃, reacts 1 hour, namely obtains the Mannich base iodide; Respectively that 30% Mannich base iodide, 8.5% cetylpyridinium chloride, 10% polyoxyethylene nonylphenol ether, 51.5% methanol mixed stir and get final product again with mass percent.
Embodiment 6
2-naphthylamines, Paraformaldehyde 96, Propiophenone are added in the there-necked flask with 1: 1.5: 1 mol ratio, then adding toluene (wherein the mol ratio of toluene and naphthalidine is 4: 1) mixes, take the hydrochloric acid of mass percent 30% as catalyzer regulator solution pH value 2.0, be warming up to again 110 ℃ of refluxing toluene temperature, insulation reaction 5 hours obtains aldehyde ketone amine condenses; The cuprous iodide that adds above-mentioned aldehyde ketone amine condenses gross weight 25% stirs and is warming up to 30 ℃, reacts 2 hours, namely obtains the Mannich base iodide; Respectively that 30% Mannich base iodide, 10% cetylpyridinium chloride, 10% polyoxyethylene nonylphenol ether, 50% methanol mixed stir and get final product again with mass percent.
When using inhibiter of the present invention, can be directly in the acidizing fluid inhibiter of adding mass percent 2～3%, stirring gets final product.
It is corrosion simulated that the inhibiter that makes by above-described embodiment carries out laboratory environment, and in 28% hydrochloric acid soln, 150 ℃ of test temperatures use the N80 steel to carry out the corrosion test evaluation, obtain inhibiter corrosion test evaluation result as shown in table 1 below.
Table 1 inhibiter corrosion test evaluation result
SY/T 5405-96 High Temperature High Pressure Dynamic Corrosion rate determination condition and inhibiter evaluation index that reference table 2 provides, can find out by table 1 and the contrast of table 2, the inhibiter that embodiment makes is significantly in the effect aspect the acid corrosion of inhibition high temp. salt, the corrosion speed of N80 oil pipe is all met the requirement of oil and gas industry standard SY/T 5404-1996.
Table 2SY/T 5405-96 High Temperature High Pressure Dynamic Corrosion rate determination condition and inhibiter evaluation index
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to example the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (7)
1. Mannich base metal iodide corrosion inhibitor, by percentage to the quality, it consists of: the metal iodide 15～30% of aldehyde ketone amine condenses, compound 70～85%, wherein the compound composition is by percentage to the quality: cetylpyridinium chloride 5～15%, emulsifying agent 5～20%, solvent 65～80%, the metal iodide structural formula of described aldehyde ketone amine condenses is:
M represents metallic copper or potassium.
2. Mannich base metal iodide corrosion inhibitor according to claim 1, it is characterized in that: described emulsifying agent is polyoxyethylene nonylphenol ether.
3. Mannich base metal iodide corrosion inhibitor according to claim 1, it is characterized in that: described solvent is one or both in methyl alcohol, ethanol, the primary isoamyl alcohol.
4. the preparation method of Mannich base metal iodide corrosion inhibitor claimed in claim 1 is characterized in that, the method comprises following processing step:
(1) aldehyde ketone amine condenses is synthetic
Naphthalidine, Paraformaldehyde 96, Propiophenone are added in the there-necked flask with the mol ratio of 1:1.5:1, then adding with the naphthalidine mol ratio is that the toluene of 4:1 mixes, regulate gained pH of mixed value take the hydrochloric acid of mass percent 30% as catalyzer between 2～3, be warming up to again 110 ℃ of refluxing toluene temperature, insulation reaction 5 hours obtains aldehyde ketone amine condenses;
(2) metal iodide of aldehyde ketone amine condenses is synthetic
The metal iodide that adds aldehyde ketone amine condenses total mass 25～50% in described aldehyde ketone amine condenses stirs and is warming up to 30～50 ℃, and reaction can obtain the metal iodide of aldehyde ketone amine condenses in 1～2 hour;
(3) preparation of Mannich base metal iodide corrosion inhibitor
By percentage to the quality, following raw material is mixed, stirring under normal temperature gets final product:
The metal iodide 15～30% of aldehyde ketone amine condenses, compound 70～85%, wherein the compound composition is by percentage to the quality: cetylpyridinium chloride 5～15%, emulsifying agent 5～20%, solvent 65～80%.
5. the preparation method of Mannich base metal iodide corrosion inhibitor according to claim 4 is characterized in that: the metal iodide of the synthetic aldehyde ketone amine condenses described in the processing step (2), and its temperature of reaction is 50 ℃, the reaction times is 1 hour.
6. the preparation method of Mannich base metal iodide corrosion inhibitor according to claim 4 is characterized in that: replace the raw material naphthalidine described in the processing step (1) with the 2-naphthylamines.
7. the preparation method of each described Mannich base metal iodide corrosion inhibitor according to claim 4-6, it is characterized in that: described metal iodide is potassiumiodide or cuprous iodide.
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| CN103571448B (en) * | 2012-07-26 | 2016-05-11 | 中国石油天然气集团公司 | One is applicable to 160 DEG C～180 DEG C high-temperature acidification corrosion inhibitors and preparation and application |
| CN103642480B (en) * | 2013-11-27 | 2016-04-27 | 钱程 | A kind of Novel high-temperature resistant acidification corrosion inhibitor |
| CN103881696B (en) * | 2014-03-11 | 2016-09-14 | 山东聚鑫化工有限公司 | Highly-water-soluble, high temperature resistant Mannich base corrosion inhibiter intermediate and preparation method |
| CN106398679A (en) * | 2016-09-05 | 2017-02-15 | 四川省威尔敦化工有限公司 | Acidizing corrosion inhibitor used in self-diverting acid system as well as preparation method and application thereof |
| CN107502333B (en) * | 2017-08-29 | 2019-10-22 | 中国石油集团渤海钻探工程有限公司 | A kind of quinoline and the compound acidification corrosion inhibitor of novel Mannich base |
| CN107987822A (en) * | 2017-12-06 | 2018-05-04 | 唐山市金沙工贸有限公司 | High-temperature acidification corrosion inhibitor and preparation method thereof and application |
| CN108219905A (en) * | 2017-12-30 | 2018-06-29 | 谢新昇 | A kind of preparation method of permanent seal cooling anticorrosive emulsified oil |
| CN109265402B (en) * | 2018-09-21 | 2020-06-09 | 中国石油天然气集团有限公司 | Organic acid system Mannich base acidizing corrosion inhibitor and preparation method thereof |
| CN113136188B (en) * | 2021-03-25 | 2022-08-09 | 四川澳凯化工有限公司 | Mannich base metal complex corrosion inhibitor, preparation method and use method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3422120A (en) * | 1966-05-10 | 1969-01-14 | Upjohn Co | 1,1 - bis(3,4 - methylenedioxyphenyl)-2-methyl-3-(tert-amino)propanols and derivatives thereof |
| CN101379045A (en) * | 2006-01-04 | 2009-03-04 | 科聚亚公司 | Diaromatic amine derivatives as antioxidants |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3422120A (en) * | 1966-05-10 | 1969-01-14 | Upjohn Co | 1,1 - bis(3,4 - methylenedioxyphenyl)-2-methyl-3-(tert-amino)propanols and derivatives thereof |
| CN101379045A (en) * | 2006-01-04 | 2009-03-04 | 科聚亚公司 | Diaromatic amine derivatives as antioxidants |
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