CN103571452B - One is applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitors and Synthesis and applications thereof - Google Patents
One is applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitors and Synthesis and applications thereof Download PDFInfo
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- CN103571452B CN103571452B CN201210262141.1A CN201210262141A CN103571452B CN 103571452 B CN103571452 B CN 103571452B CN 201210262141 A CN201210262141 A CN 201210262141A CN 103571452 B CN103571452 B CN 103571452B
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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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- 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
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
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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
- C09K8/725—Compositions containing polymers
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
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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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Abstract
The present invention relates to one and be applicable to 140 DEG C ~ 160 DEG C of high-temperature acidification corrosion inhibitors and preparation method thereof, it is by A, B two components are formed, component A is by polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt, methylpentynol, oxalic dialdehyde, dimethyl formamide, Natvosol, polyoxyethylene nonylphenol ether E-20 and methyl alcohol are made, B component is by antimonypotassium tartrate, bismuth oxide, vitamins C and 1+1 hydrochloric acid are made, during use, order is by B component, component A adds in acidizing fluid, this acidification corrosion inhibitor is applied to 140 DEG C ~ 160 DEG C deep-wells, 15% ~ 28% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment, zero pour is low, good dispersity in acidizing fluid, there is the corrosion inhibition of extremely excellent high temperature resistant concentrated hydrochloric acid and mud acid corrosion, acidification corrosion inhibitor corrosion inhibition rate >=99%, erosion rate is lower than industry first grade standard.
Description
Technical field
The present invention relates to one and be applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitors and Synthesis and applications thereof.
Background technology
Along with deepening continuously of oil-field development, the well-digging of new input development block increases, and in oil mining process, usually needs to improve recovery ratio by acidifying.The injection of acid causes the corrosion of oil pipe and down-hole hardware, causes very large financial loss.Therefore in oil well acidation, especially high temperature deep well and ultra deep well carry out in the deep-well acidifying of concentrated hydrochloric acid large acid amount, and important task solves the corrosion prevention problem of high temperature acidified liquid to oil pipe and down-hole hardware.In recent years, acidifying is progressively to high temperature deep well development, and in acidizing fluid, high temperature destroys serious to the inhibiter in acidizing fluid, and corrosion mitigating effect is extremely acute to decline, and original inhibiter can not meet high temperature acidified demand.At high temperature there is the shortcomings such as easy coking, layering, dissolution dispersity be stable not in current domestic conventional high temperature resistance acidification corrosion inhibitor, had not both protected oil pipe and down-hole hardware, and can cause again the injury on stratum.
Summary of the invention
The object of the invention is: provide one to be applicable to 140 DEG C ~ 160 DEG C deep-wells, 15% ~ 28% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment, acidification corrosion inhibitor corrosion inhibition rate >=99%, erosion rate is lower than industry first grade standard, good dispersity in hydrochloric acid, mud acid and ethanolic soln, there is better surfactivity, coking is few, and the one that zero pour is low is applicable to 140 DEG C ~ 160 DEG C of high-temperature acidification corrosion inhibitors and preparation method thereof.
The technical solution used in the present invention is:
One, a kind of raw material and formula being applicable to 140 DEG C ~ 160 DEG C of high-temperature acidification corrosion inhibitors:
Raw material comprises:
1, polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt (industrial goods)
Huang Hongzhou edits Chinese tensio-active agent overview one book, Chemical Industry Press the 61st page.
Purposes: new oil gas field acidification corrosion inhibitor component.
Factory: chemical industry system of Xi'an shiyou University.
2, methylpentynol (industrial goods)
What shining outstanding person of Wang Zhonghua etc. writes oil field chemical application manual one book, Sinopec press the 222nd page.
Purposes: acidification corrosion inhibitor component.
3, oxalic dialdehyde (industrial goods)
What shining outstanding person of Wang Zhonghua etc. writes oil field chemical application manual one book, Sinopec press the 222nd page.
Purposes: acidification corrosion inhibitor component.
Factory: chemical plant, Gai County, Liaoning Province.
4, dimethyl formamide (industrial goods) No. CAS: 68-12-2
Purposes: acidification corrosion inhibitor component, aprotonic solvent.
5, Natvosol (industrial goods)
Huang Hongzhou edits Chinese tensio-active agent overview one book, Chemical Industry Press the 434th page.
Another name: HEC
Character: there is the performances such as thickening, suspension, emulsification, dispersion, be usually used in dispersion agent, thickening material etc.
Production unit: jiangsu wuxi Chemical Group company
6, polyoxyethylene nonylphenol ether E-20(industrial goods)
Huang Hongzhou edits Chinese tensio-active agent overview one book, Chemical Industry Press the 340th page.
Another name: octyl phenol polyoxyethylene (20) ether
Purposes: nonionogenic tenside, as high temperature emulsifying agent, stablizer, high density ionogen wetting agent etc.
Production unit: Xingtai area auxiliary reagent factory
7, methyl alcohol (industrial goods) No. CAS: 67-56-1
Purposes: acidification corrosion inhibitor solvent.
8, antimonypotassium tartrate (industrial goods) No. CAS: 28300-74-5
9, bismuth oxide (industrial goods) No. CAS: 1304-76-3
10, vitamins C (industrial goods) No. CAS: 50-81-7
11, hydrochloric acid (industrial goods) No. CAS: 7647-01-0
One is applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitors, and it is made up of A, B two components, and component A weight percent is:
Polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt: 30 ~ 35%;
Methylpentynol: 0.3 ~ 0.6%;
Oxalic dialdehyde: 0.1 ~ 0.3%;
Dimethyl formamide: 2 ~ 5%;
Natvosol: 0.5 ~ 3%
Polyoxyethylene nonylphenol ether E-20:15 ~ 18%
All the other are methyl alcohol; Each weight percentages of components sum is 100%.
B component weight percent is:
Antimonypotassium tartrate: 15 ~ 20%;
Bismuth oxide: 10 ~ 15%;
Vitamins C: 10 ~ 15%;
All the other are 1+1 hydrochloric acid; Each weight percentages of components sum is 100%.
Composition during use is the A liquid of 1.5 ~ 3 weight parts and the B liquid of 1 weight part.
Two, a kind of preparation method being applicable to 140 DEG C ~ 160 DEG C of high-temperature acidification corrosion inhibitors:
Major equipment:
There is the enamel reaction still of 2000L of stirring, heating, cooling and vacuum system.
Component A production method is:
Methyl alcohol 50% is added enamel reaction still in proportion, slowly be warmed up to 55 ~ 60 DEG C, Natvosol is added under continuous stirring state, be stirred to all Natvosols to dissolve completely, again by polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt, methylpentynol, oxalic dialdehyde, dimethyl formamide, polyoxyethylene nonylphenol ether E-20 adds enamel reaction still in proportion, limit edged stirs, stir 30 minutes, finally add the methyl alcohol of remainder and stir 30 minutes, stop heating, cooling limit, limit is stirred, be cooled to normal temperature, obtain one and be applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitor component A.
B component production method is:
1+1 hydrochloric acid is added enamel reaction still in proportion.Slowly be warmed up to 40 ~ 50 DEG C; Secondly, under continuous stirring state, add antimonypotassium tartrate, bismuth oxide, vitamins C, limit edged stirs; Stir 30 minutes; Stop heating; Cooling limit, limit is stirred, and is cooled to normal temperature, obtains one and be applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitor B component.
A kind of using method being applicable to 140 DEG C ~ 160 DEG C of high-temperature acidification corrosion inhibitors: on dosing scene, operating personnel adds the B component and component A that are applicable to 140 DEG C ~ 160 DEG C of high-temperature acidification corrosion inhibitors in turn, the A liquid of 1.5 ~ 3 weight parts and the B liquid of 1 weight part.The total amount adding acidification corrosion inhibitor is 3% ~ 4% of acid solution weight.
The present invention's beneficial effect compared with prior art
1, of the present inventionly 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitors are applicable to, be applicable to 140 DEG C ~ 160 DEG C deep-wells, 15% ~ 28% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment, acidification corrosion inhibitor corrosion inhibition rate >=99%, erosion rate is lower than industry first grade standard, good dispersity in hydrochloric acid, mud acid and ethanolic soln, have better surfactivity, coking is few, and zero pour is low.
2, production technique is simple, need not specific installation.
Embodiment
Embodiment 1: one is applicable to 140 DEG C of high-temperature acidification corrosion inhibitors, and component A weight percent is:
Polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt: 30%;
Methylpentynol: 0.6%;
Oxalic dialdehyde: 0.1%;
Dimethyl formamide: 2%;
Natvosol: 0.5%;
Polyoxyethylene nonylphenol ether E-20:15%;
Methyl alcohol; 51.8%.
B component weight percent is:
Antimonypotassium tartrate: 15%;
Bismuth oxide: 15%;
Vitamins C: 10%;
1+1 hydrochloric acid: 60%.
Composition during use is the A liquid of 3 weight parts and the B liquid of 1 weight part.
Preparation method is:
The preparation method of component A is:
Methyl alcohol 50% is added enamel reaction still in proportion, slowly be warmed up to 55 ~ 60 DEG C, Natvosol is added under continuous stirring state, be stirred to all Natvosols to dissolve completely, again by polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt, methylpentynol, oxalic dialdehyde, dimethyl formamide, polyoxyethylene nonylphenol ether E-20 adds enamel reaction still in proportion, limit edged stirs, stir 30 minutes, finally add the methyl alcohol of remainder and stir 30 minutes, stop heating, cooling limit, limit is stirred, be cooled to normal temperature, obtain one and be applicable to 140 DEG C of high-temperature acidification corrosion inhibitor component A.
The production method of B component is:
1+1 hydrochloric acid is added enamel reaction still in proportion.Slowly be warmed up to 40 ~ 50 DEG C; Secondly, under continuous stirring state, add antimonypotassium tartrate, bismuth oxide, vitamins C, limit edged stirs; Stir 30 minutes; Stop heating; Cooling limit, limit is stirred, and is cooled to normal temperature, obtains one and be applicable to 140 DEG C of high-temperature acidification corrosion inhibitor B component.
Embodiment 2: one is applicable to 140 DEG C of high-temperature acidification corrosion inhibitors, and component A weight percent is:
Polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt: 31%;
Methylpentynol: 0.5%;
Oxalic dialdehyde: 0.15%;
Dimethyl formamide: 3%;
Natvosol: 1%;
Polyoxyethylene nonylphenol ether E-20:15.5%;
Methyl alcohol; 48.85%.
B component weight percent is:
Antimonypotassium tartrate: 16%;
Bismuth oxide: 14%;
Vitamins C: 11%;
1+1 hydrochloric acid: 59%.
Composition during use is the A liquid of 3 weight parts and the B liquid of 1 weight part.
The preparation method that embodiment 2 one kinds is applicable to 140 DEG C of high-temperature acidification corrosion inhibitors is identical with embodiment 1.
Embodiment 3: one is applicable to 150 DEG C of high-temperature acidification corrosion inhibitors, and component A weight percent is:
Polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt: 33%;
Methylpentynol: 0.4%;
Oxalic dialdehyde: 0.2%;
Dimethyl formamide: 4%;
Natvosol: 1.5%;
Polyoxyethylene nonylphenol ether E-20:16%;
Methyl alcohol; 44.9%.
B component weight percent is:
Antimonypotassium tartrate: 17%;
Bismuth oxide: 13%;
Vitamins C: 13%;
1+1 hydrochloric acid: 57%.
Composition during use is the A liquid of 2.5 weight parts and the B liquid of 1 weight part.
The preparation method that embodiment 3 one kinds is applicable to 150 DEG C of high-temperature acidification corrosion inhibitors is identical with embodiment 1.
Embodiment 4: one is applicable to 160 DEG C of high-temperature acidification corrosion inhibitors, and component A weight percent is:
Polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt: 34%;
Methylpentynol: 0.4%;
Oxalic dialdehyde: 0.25%;
Dimethyl formamide: 5%;
Natvosol: 2%;
Polyoxyethylene nonylphenol ether E-20:17%;
Methyl alcohol; 41.35%.
B component weight percent is:
Antimonypotassium tartrate: 19%;
Bismuth oxide: 11%;
Vitamins C: 14%;
1+1 hydrochloric acid: 56%.
Composition during use is the A liquid of 2 weight parts and the B liquid of 1 weight part.
The preparation method that embodiment 4 one kinds is applicable to 160 DEG C of high-temperature acidification corrosion inhibitors is identical with embodiment 1.
Embodiment 5: one is applicable to 160 DEG C of high-temperature acidification corrosion inhibitors, and component A weight percent is:
Polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt: 35%;
Methylpentynol: 0.3%;
Oxalic dialdehyde: 0.3%;
Dimethyl formamide: 5%;
Natvosol: 3%;
Polyoxyethylene nonylphenol ether E-20:18%;
Methyl alcohol; 38.4%.
B component weight percent is:
Antimonypotassium tartrate: 20%;
Bismuth oxide: 10%;
Vitamins C: 15%;
1+1 hydrochloric acid: 55%.
Composition during use is the A liquid of 1.5 weight parts and the B liquid of 1 weight part.
The preparation method that embodiment 5 one kinds is applicable to 160 DEG C of high-temperature acidification corrosion inhibitors is identical with embodiment 1.
Effect:
That prepares according to above 5 embodiments is applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitor performances and all can reaches table 1 test result.
Table 1 the performance test results
Claims (3)
1. be applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitors, it is characterized in that: it is made up of A, B two components, and component A weight percent is:
Polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt: 30 ~ 35%;
Methylpentynol: 0.3 ~ 0.6%;
Oxalic dialdehyde: 0.1 ~ 0.3%;
Dimethyl formamide: 2 ~ 5%;
Natvosol: 0.5 ~ 3%
Polyoxyethylene nonylphenol ether E-20:15 ~ 18%
All the other are methyl alcohol;
Each weight percentages of components sum is 100%;
B component weight percent is:
Antimonypotassium tartrate: 15 ~ 20%;
Bismuth oxide: 10 ~ 15%;
Vitamins C: 10 ~ 15%;
All the other are 1+1 hydrochloric acid;
Each weight percentages of components sum is 100%;
Composition during use is the A liquid of 1.5 ~ 3 weight parts and the B liquid of 1 weight part.
2. the preparation method being applicable to 140 DEG C ~ 160 DEG C of high-temperature acidification corrosion inhibitors according to claim 1, is characterized in that: component A preparation method is:
First, methyl alcohol 50% is added enamel reaction still in proportion, slowly be warmed up to 55 ~ 60 DEG C, Natvosol is added under continuous stirring state, be stirred to all Natvosols to dissolve completely, again by polycyclic aromatic hydrocarbons chloromethyl compound pyridine quaternary ammonium salt, methylpentynol, oxalic dialdehyde, dimethyl formamide, polyoxyethylene nonylphenol ether E-20 adds enamel reaction still in proportion, limit edged stirs, stir 30 minutes, finally add the methyl alcohol of remainder and stir 30 minutes, stop heating, cooling limit, limit is stirred, be cooled to normal temperature, obtain one and be applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitor component A,
B component preparation method is:
First, 1+1 hydrochloric acid is added enamel reaction still in proportion, be slowly warmed up to 40 ~ 50 DEG C; Secondly, under continuous stirring state, add antimonypotassium tartrate, bismuth oxide, vitamins C, limit edged stirs; Stir 30 minutes; Stop heating; Cooling limit, limit is stirred, and is cooled to normal temperature, obtains one and be applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitor B component.
3. the application being applicable to 140 DEG C ~ 160 DEG C of high-temperature acidification corrosion inhibitors according to claim 1, it is characterized in that: for 140 DEG C ~ 160 DEG C deep-wells, 15% ~ 28% concentrated hydrochloric acid or the job execution of soil acid acidizing well production increment, the total amount adding acidification corrosion inhibitor is 3% ~ 4% of acid solution weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210262141.1A CN103571452B (en) | 2012-07-26 | 2012-07-26 | One is applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitors and Synthesis and applications thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210262141.1A CN103571452B (en) | 2012-07-26 | 2012-07-26 | One is applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitors and Synthesis and applications thereof |
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| CN103571452A CN103571452A (en) | 2014-02-12 |
| CN103571452B true CN103571452B (en) | 2016-02-10 |
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| CN110129022B (en) * | 2019-04-19 | 2021-03-09 | 中国石油天然气股份有限公司 | High-temperature-resistant corrosion inhibitor for online acidification and preparation and use methods thereof |
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| CA2049365A1 (en) * | 1990-08-17 | 1992-02-18 | Gene Mancillas | Acid inhibitor composition for use in well acidizing operations |
| US5441929A (en) * | 1994-06-23 | 1995-08-15 | Halliburton Company | Hydrochloric acid acidizing composition and method |
| CN101892042A (en) * | 2010-06-30 | 2010-11-24 | 中国海洋石油总公司 | High temperature acidizing corrosion inhibitor and preparation method thereof |
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2012
- 2012-07-26 CN CN201210262141.1A patent/CN103571452B/en active Active
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|---|---|---|---|---|
| US5034140A (en) * | 1989-11-27 | 1991-07-23 | Halliburton Company | Well acidizing compositions and method |
| CA2049365A1 (en) * | 1990-08-17 | 1992-02-18 | Gene Mancillas | Acid inhibitor composition for use in well acidizing operations |
| US5441929A (en) * | 1994-06-23 | 1995-08-15 | Halliburton Company | Hydrochloric acid acidizing composition and method |
| CN101892042A (en) * | 2010-06-30 | 2010-11-24 | 中国海洋石油总公司 | High temperature acidizing corrosion inhibitor and preparation method thereof |
| CN102585796A (en) * | 2012-01-13 | 2012-07-18 | 西南石油大学 | Acidizing corrosion inhibitor N-(gamma-methylanthracene) pyridine chloride and preparation method thereof |
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