CN107099280B - Temperature-resistant diverting agent for acidification operation and preparation method and application thereof - Google Patents
Temperature-resistant diverting agent for acidification operation and preparation method and application thereof Download PDFInfo
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- CN107099280B CN107099280B CN201610097278.4A CN201610097278A CN107099280B CN 107099280 B CN107099280 B CN 107099280B CN 201610097278 A CN201610097278 A CN 201610097278A CN 107099280 B CN107099280 B CN 107099280B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- 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
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- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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Abstract
The invention provides a temperature-resistant steering agent and a preparation method thereof, wherein the steering agent consists of a viscoelastic betaine surfactant and a sulfate and/or sulfonate of alkylphenol polyoxyethylene, and the mass ratio of the surfactant to the sulfate and/or sulfonate is 0.5-2: 1. the invention also provides a diverting acid containing the diverting agent, and the diverting acid can be used for a stratum with the temperature of more than 100 ℃.
Description
Technical Field
The invention relates to a temperature-resistant diverting agent for acidizing an oil reservoir stratum and a preparation method and application thereof.
Background
Satisfactory oil and gas production from low permeability reservoirs is often difficult to obtain from natural energy alone, often requiring acidizing operations on reservoir formations. The acidizing operation is a process of dissolving and eroding the pores and cracks of the stratum by using acid liquor so as to improve the permeability of the stratum. In the acidizing operation, acid liquid preferentially enters a stratum with high permeability, and an interval with low permeability is not treated. In the prior art, the problem is generally solved by adding a diverter to the acid solution. The function of the diverter is achieved by: HCl in acid with CaCO in rock in pores and fractures of formations3Reaction takes place, HCl is continuously consumed, Ca2+Continuously generating; ca when the pH value increases to a certain value (generally about 2)2+Molecules of the diverting agent are mutually connected, the viscosity of the acid liquor is obviously increased, gel is finally formed to block gaps or cracks where the acid liquor is located, and the rest acid liquor is diverted to an area which is not yet acidified, so that the acidified diverting is realized.
The diverting agent may be a viscoelastic surfactant such as betaine surfactant, quaternary ammonium salt surfactant, alkyl amine oxide surfactant, etc. The formation temperature is generally between 60 ℃ and 150 ℃, and the temperature resistance of the diverting agents is not ideal and is not suitable for high-temperature formations with the temperature of more than 100 ℃.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a temperature-resistant diverting agent and a preparation method thereof, wherein the diverting agent can be used for a high-temperature stratum with the temperature of more than 100 ℃; the invention also provides a diverting acid containing the diverting agent and an acidification operation method using the diverting acid.
The present invention is explained in detail below.
The invention provides a temperature-resistant steering agent for acidification operation, which consists of a viscoelastic betaine surfactant and a sulfate and/or sulfonate of alkylphenol polyoxyethylene, wherein the mass ratio of the two is (0.5-2): 1.
according to the invention, the mass ratio of the viscoelastic betaine surfactant to the sulfate and/or sulfonate of alkylphenol ethoxylates is preferably 0.8-1.25: 1.
according to the invention, the viscoelastic betaine surfactant may be selected from one or more of oleamidopropyl betaine, cocamidopropyl betaine and erucamidopropyl betaine.
According to the invention, the number average degree of polymerization of the polyoxyethylene ether is 3-15; the carbon number of the alkyl group is 6-15.
According to the invention, the sulfuric ester salt of alkylphenol polyoxyethylene can be nonylphenol polyoxyethylene ether sulfuric ester salt or octylphenol polyoxyethylene ether sulfuric ester salt; the sulfonate of alkylphenol polyoxyethylene can be nonylphenol polyoxyethylene sulfonate or octylphenol polyoxyethylene sulfonate.
The invention also provides another temperature-resistant steering agent for acidification operation, which consists of 0.5-40 parts by mass of viscoelastic betaine surfactant, 0.5-40 parts by mass of alkylphenol polyoxyethylene sulfate and/or sulfonate, 0.1-10 parts by mass of C1-C5 alcohol and 0.5-40 parts by mass of water; wherein the mass ratio of the viscoelastic betaine surfactant to the sulfuric ester salt and/or sulfonate of alkylphenol polyoxyethylene is (0.5-2): 1.
the viscoelastic betaine surfactant, the sulfuric acid ester salt and/or the sulfonic acid salt of alkylphenol ethoxylates, the mass ratio of the two and the like are the same as those described above, and the details are not repeated herein.
According to the invention, the alcohol of C1-C5 can be one or more selected from ethanol, propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, ethylene glycol, glycerol and pentaerythritol.
The invention provides a preparation method of a second temperature-resistant diverting agent, which comprises the following steps:
(1) adding alcohol of C1-C5 into water;
(2) gradually adding a viscoelastic betaine surfactant into the solution obtained in the step (1) under stirring;
(3) and (3) adding sulfuric ester salt and/or sulfonate of alkylphenol polyoxyethylene into the solution obtained in the step (2).
According to the present invention, there is no particular limitation on the form of stirring, and conventional mechanical stirring, electromagnetic stirring or emulsifying machines may be employed, for example.
According to the present invention, a uniform solution can be conveniently prepared by the aforementioned preparation method. Mixing the components directly does not form a homogeneous solution immediately and the dissolution process may take a long time.
The invention provides a temperature-resistant diverting acid for acidification operation, which contains any one of the diverting agents.
According to the invention, the mass fraction of the viscoelastic betaine surfactant in the diverting acid is 3-20%, preferably 5-12%.
The method for producing the diverting acid of the present invention is not particularly limited as long as the diverting agent described above is dissolved in the acid solution. The present invention preferably uses a second diverting agent to prepare the diverting acid, which is rapidly soluble in the acid solution.
The invention also provides a method for carrying out acidizing operation on the oil reservoir stratum, wherein the used acid is the temperature-resistant diverting acid.
According to the invention, the temperature of the reservoir formation is typically between 60 ℃ and 150 ℃, for example between 60 ℃ and 120 ℃, or between 80 ℃ and 150 ℃.
Detailed Description
All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The numerical points disclosed in the specification include not only the numerical points specifically disclosed but also the endpoints of each numerical range, and any combination of these numerical points should be considered as the range disclosed or described in the present invention, regardless of whether the numerical pairs are disclosed herein.
The invention is further illustrated by the following examples.
In the examples and comparative examples, each of the agents used was a commercially available product.
In the test examples, an HAAKE MARS III rheometer (Thermo Fisher Scientific, USA) was used at 170s-1And (5) after shearing for 60min, measuring the viscosity of the system.
Example 1
1g of n-propanol was added to 39g of deionized water; gradually adding 32g erucamidopropyl betaine (from Shanghai Yincong New Material science and technology Co., Ltd.) under stirring for 30 min; then 28g of sodium nonylphenol polyoxyethylene ether (10) sulfonate (purchased from Nanjing engine chemical research institute and having a number average polymerization degree of 10) is added, and the mixture is continuously stirred for 30min to obtain a uniform solution, wherein the solution is the diverting agent.
And (3) adding hydrochloric acid and water into the diverting agent to ensure that the final mass fraction of the hydrochloric acid is 15 percent and the final mass fraction of the erucamide propyl betaine is 2.67 percent to prepare a uniform solution, wherein the solution is the diverting acid, the viscosity of the solution is 20mPa & s at normal temperature, and the solution is numbered as A-1.
Test example 1
Calcium chloride was added to diverting acid A-1 to make the mass fraction of calcium chloride 3%, the pH of the diverting acid solution was adjusted to 2 with sodium hydroxide, and the viscosity was measured at 100 ℃ and the results are shown in Table 1.
Comparative example 1
A diverter was prepared as in example 1, except that: the diverting agent was only erucamidopropyl betaine and was used in an amount of 60 g.
The diverting acid was prepared as in example 1, except that: the diverter is added in an amount to give a final mass fraction of 5% erucamidopropylbetaine. The diverting acid had a viscosity of 15 mPas at room temperature and was numbered B-1.
Test comparative example 1
Calcium chloride was added to diverting acid B-1 to a calcium chloride concentration of 3%, the pH of the diverting acid solution was adjusted to 2 with sodium hydroxide, and the viscosity was measured at 100 ℃ and the results are shown in Table 1.
Comparative example 2
A diverter was prepared as in example 1, except that: the sodium salt of nonylphenol polyoxyethylene ether (10) sulfonic acid was replaced with sodium dodecylbenzenesulfonate.
The diverting acid having a viscosity of 10 mPas at ordinary temperature and numbered B-2 was prepared in the same manner as in example 1.
Test comparative example 2
Calcium chloride was added to diverting acid B-2 to a calcium chloride concentration of 3%, the pH of the diverting acid solution was adjusted to 2 with sodium hydroxide, and the viscosity was measured at 100 ℃ and the results are shown in Table 1.
Example 2
2g of n-butanol is added to 38g of deionized water; gradually adding 36g of oleamidopropyl betaine (from Shanghai Yincong New Material science and technology Co., Ltd.) under stirring for 20 min; then 24g of nonylphenol polyoxyethylene ether (7) sodium sulfate (purchased from Nanjing engine chemical research institute and having a number average degree of polymerization of 7) is added, and the mixture is continuously stirred for 30min to obtain a uniform solution, wherein the solution is the diverting agent.
And (3) adding hydrochloric acid and water into the diverting agent to ensure that the mass fraction of the hydrochloric acid is 20% and the final mass fraction of the erucamide propyl betaine is 4.2% to prepare a uniform solution, wherein the solution is the diverting acid, the viscosity of the diverting acid is 25mPa & s at normal temperature, and the diverting acid is numbered as A-2.
Test example 2
Calcium chloride was added to diverting acid A-2 to give a calcium chloride concentration of 4%, the pH of the diverting acid solution was adjusted to 2 with sodium hydroxide, and the viscosity was measured at 120 ℃ and the results are shown in Table 1.
Comparative example 3
The diverter was prepared as in example 2, except that: the diverting agent was oleamidopropyl betaine alone, used in an amount of 60 g.
The diverting acid was prepared as in example 2, except that: the diverter was added in an amount to give a final mass fraction of oleic acid amidopropyl betaine of 7%. The diverting acid had a viscosity of 15 mPas at room temperature and was numbered B-3.
Test comparative example 3
Calcium chloride was added to diverting acid B-3 to give a calcium chloride concentration of 4%, the pH of the diverting acid solution was adjusted to 2 with sodium hydroxide, and the viscosity was measured at 120 ℃ and the results are shown in Table 1.
Comparative example 4
The diverter was prepared as in example 2, except that: sodium nonylphenol polyoxyethylene ether (7) sulfate was replaced with sodium lauryl sulfate.
The diverting acid having a viscosity of 15 mPas at ordinary temperature and numbered B-4 was prepared in the same manner as in example 2.
Test comparative example 4
Calcium chloride was added to diverting acid B-4 to give a calcium chloride concentration of 4%, the pH of the diverting acid solution was adjusted to 2 with sodium hydroxide, and the viscosity was measured at 120 ℃ and the results are shown in Table 1.
TABLE 1
| Numbering | viscosity/mPas |
| Test example 1 | 110 |
| Comparative test example 1 | 30 |
| Comparative test example 2 | 18 |
| Test example 2 | 100 |
| Comparative test example 3 | 25 |
| Comparative test example 4 | 17 |
The results in table 1 show that the temperature-resistant diverting agent provided by the invention greatly improves the viscosity of a diverting acid system at high temperature and can adapt to more formation conditions.
Claims (9)
1. A temperature-resistant steering agent for acidification operation comprises, by mass, 0.5-40 parts of a viscoelastic betaine surfactant, 0.5-40 parts of a sulfuric ester salt and/or a sulfonate of alkylphenol polyoxyethylene, 0.1-10 parts of C1-C5 alcohol and 0.5-40 parts of water; wherein the mass ratio of the viscoelastic betaine surfactant to the sulfuric ester salt and/or sulfonate of alkylphenol polyoxyethylene is (0.5-2): 1.
2. the temperature-resistant steering agent according to claim 1, wherein the mass ratio of the viscoelastic betaine surfactant to the sulfate and/or sulfonate of alkylphenol ethoxylates is 0.8-1.25: 1.
3. the temperature-resistant diverter according to claim 1, wherein the viscoelastic betaine surfactant is selected from one or more of oleamidopropyl betaine, cocamidopropyl betaine, and erucamidopropyl betaine.
4. The temperature-resistant steering agent according to claim 1, wherein the number average degree of polymerization of the polyoxyethylene ether is 3 to 15; the carbon number of the alkyl group is 6-15.
5. A method of making the temperature resistant diverting agent of claim 1, comprising:
(1) adding alcohol of C1-C5 into water;
(2) gradually adding a viscoelastic betaine surfactant into the solution obtained in the step (1) under stirring;
(3) and (3) adding sulfuric ester salt and/or sulfonate of alkylphenol polyoxyethylene into the solution obtained in the step (2).
6. A temperature-resistant diverting acid for use in acidizing operations which comprises a diverting agent as claimed in any one of claims 1 to 4.
7. The temperature-resistant diverting acid according to claim 6, wherein the mass fraction of the viscoelastic betaine surfactant in the diverting acid is 3-20%.
8. A method of acidizing an oil reservoir formation wherein the acid used is the temperature resistant diverting acid of claim 6.
9. The acidizing process of claim 8, wherein the reservoir formation is at a temperature of from 60 ℃ to 120 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610097278.4A CN107099280B (en) | 2016-02-23 | 2016-02-23 | Temperature-resistant diverting agent for acidification operation and preparation method and application thereof |
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| CN201610097278.4A CN107099280B (en) | 2016-02-23 | 2016-02-23 | Temperature-resistant diverting agent for acidification operation and preparation method and application thereof |
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| CN107099280B true CN107099280B (en) | 2020-02-28 |
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| CN110358514B (en) * | 2019-07-02 | 2021-11-30 | 中国石油天然气股份有限公司 | Aggregation type water-soluble temporary plugging agent and preparation method thereof |
| CN111574990A (en) * | 2020-05-08 | 2020-08-25 | 中国石油集团渤海钻探工程有限公司 | Sludge dispersants for acidified liquor systems |
| CN111778009A (en) * | 2020-07-10 | 2020-10-16 | 陕西华天能源科技有限公司 | Composite steering micelle acid acidification de-plugging liquid and preparation method thereof |
| CN116120910A (en) * | 2023-02-22 | 2023-05-16 | 西安博宏石油科技有限公司 | Acidizing steering agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020983A (en) * | 2009-09-12 | 2011-04-20 | 中国石油化工股份有限公司 | Viscosity-variable diverting acid for improving stratigraphic acidified section |
| CN102504799A (en) * | 2011-11-29 | 2012-06-20 | 西南石油大学 | Acidification diverter composition |
| CN102858883A (en) * | 2010-02-12 | 2013-01-02 | 罗地亚管理公司 | Rheology Modifier Compositions And Methods Of Use |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020983A (en) * | 2009-09-12 | 2011-04-20 | 中国石油化工股份有限公司 | Viscosity-variable diverting acid for improving stratigraphic acidified section |
| CN102858883A (en) * | 2010-02-12 | 2013-01-02 | 罗地亚管理公司 | Rheology Modifier Compositions And Methods Of Use |
| CN102504799A (en) * | 2011-11-29 | 2012-06-20 | 西南石油大学 | Acidification diverter composition |
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