CN111849453A - Polychlorinated ketol self-acid generator and use method thereof - Google Patents
Polychlorinated ketol self-acid generator and use method thereof Download PDFInfo
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- CN111849453A CN111849453A CN201910359803.9A CN201910359803A CN111849453A CN 111849453 A CN111849453 A CN 111849453A CN 201910359803 A CN201910359803 A CN 201910359803A CN 111849453 A CN111849453 A CN 111849453A
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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
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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
Abstract
The invention relates to a polychlorinated ketone alcohol self-acid generator and a using method thereof, the polychlorinated ketone alcohol self-acid generator comprises polychlorinated ketone alcohol, a low-temperature inhibitor and a medium-temperature catalyst and/or a high-temperature speed accelerator, wherein the polychlorinated ketone alcohol is CnClm (OH) x, n is 2-10, m is not less than n and not more than 2n, x is 2-5, the medium-temperature catalyst is an alkali compound, the low-temperature inhibitor is a hydrocarbon compound, and the high-temperature speed accelerator is an organic compound. According to the polychlorinated ketone alcohol self-acid generator, the low-temperature inhibitor, the medium-temperature catalyst and/or the high-temperature accelerator are/is added into polychlorinated ketone alcohol, so that the self-acid generation rate of the polychlorinated ketone alcohol at different temperatures can be adjusted, and the deep penetration acid fracturing effect on a high-temperature stratum is achieved.
Description
Technical Field
The invention relates to the technical field of petroleum, in particular to a polychlorinated ketone alcohol self-acid generator and a using method thereof.
Background
At present, the autogenous acid at home and abroad has high acid rock reaction speed in high-temperature strata, short acidification radius and small acid liquor penetration distance, and can not achieve deep penetration acid fracturing effect on the high-temperature strata in the process of petroleum exploitation.
Disclosure of Invention
The invention aims to provide a polychlorinated ketone alcohol self-acid generator and a using method thereof, and solves the problems of high reaction speed of self-acid-generating high-temperature formation acid rock, short acidification radius and small acid liquid penetration distance in the prior art.
The technical scheme adopted by the invention for solving the technical problem is as follows: a polychlorinated ketone alcohol self-acid generator comprises a polychlorinated ketone alcohol, a low-temperature inhibitor and a moderate-temperature catalyst and/or a high-temperature speed increasing agent, wherein the polychlorinated ketone alcohol is CnClm (OH) x, n is 2-10, m is not more than n and not more than 2n, and x is 2-5, the moderate-temperature catalyst is a basic compound, the low-temperature inhibitor is a hydrocarbon compound, and the high-temperature speed increasing agent is an organic compound.
In the polychloroketol autoacid of the present invention, the low-temperature inhibitor comprises at least one of an alkane, a halogenated alkane, and an aromatic hydrocarbon which are insoluble in water and have a carbon number of more than 10.
In the polychlorinated ketol self-acid generator of the present invention, the mass of the low-temperature inhibitor is 3 to 15% of the mass of the polychlorinated ketol.
In the polychlorinated ketone alcohol self-acid generator of the present invention, the polychlorinated ketone alcohol self-acid generator comprises a moderate-temperature catalyst, and the moderate-temperature catalyst comprises at least one of organic amine, organic amide and inorganic weak base.
In the polychlorinated ketol self-acid generator of the present invention, the mass of the mesophilic catalyst is 0.01 to 1.5% of the mass of the polychlorinated ketol.
In the polychlorinated ketone alcohol self-acid generator of the present invention, the polychlorinated ketone alcohol self-acid generator includes a high temperature accelerator including at least one of an organic nitrile, an organic oxime, an organic hydroxylamine, and pyridine.
In the polychlorinated ketone alcohol photoacid generator of the present invention, the mass of the high-temperature accelerator is 0.05 to 5% of the mass of the polychlorinated ketone alcohol.
The invention also provides a use method of the polychlorinated ketol self-acid generator, which comprises the following steps: the polychloro-ketone alcohol is mixed with water and then squeezed into the fractures of the high temperature stratum with the fracturing fluid or separately.
In the use method of the invention, the mass ratio of water to polychloroketol is between 1: 1-1: between 0.5.
The implementation of the polychlorinated ketone alcohol self-acid generator and the using method thereof has the following beneficial effects: according to the polychlorinated ketone alcohol self-acid generator, the low-temperature inhibitor, the medium-temperature catalyst and/or the high-temperature accelerator are/is added into polychlorinated ketone alcohol, so that the self-acid generation rate of the polychlorinated ketone alcohol at different temperatures can be adjusted, and the deep penetration acid fracturing effect on a high-temperature stratum is achieved.
Detailed Description
The polychloroketol photoacid generators of the present invention and methods of use are further illustrated by the following examples:
polychloroketol, also known as polychlorosugar, abbreviated as MCS, hardly hydrolyzes at temperatures below 50 ℃ after encountering water, starts to hydrolyze in a moist atmosphere at 90 ℃ and largely hydrolyzes at 130 ℃, see the following reaction formula:
the polychlorinated ketone alcohol self-acid generator is formed by adding a low-temperature inhibitor and a medium-temperature catalyst and/or a high-temperature accelerator into polychlorinated ketone alcohol, namely the polychlorinated ketone alcohol self-acid generator comprises polychlorinated ketone alcohol, the low-temperature inhibitor and the medium-temperature catalyst and/or the high-temperature accelerator, wherein the polychlorinated ketone alcohol is CnClm (OH) x, n is 2-10, m is not less than n and not more than 2n, x is 2-5, the medium-temperature catalyst is an alkaline compound, the low-temperature inhibitor is a hydrocarbon compound, and the high-temperature accelerator is an organic compound.
Wherein the low temperature inhibitor comprises at least one of water-insoluble alkane with carbon number greater than 10, halogenated alkane, and aromatic hydrocarbon, such as white wax oil. The mass of the low temperature inhibitor is 3% to 15% of the mass of the polychloroketol, preferably the mass of the low temperature inhibitor is 7% to 12% of the mass of the polychloroketol, more preferably the mass of the low temperature inhibitor is 10% of the mass of the polychloroketol.
Wherein the medium-temperature catalyst comprises at least one of organic amine, organic amide and inorganic weak base, such as urea. The mass of the medium-temperature catalyst is 0.01 to 1.5% of the mass of the polychloro-ketol, preferably the mass of the medium-temperature catalyst is 0.5 to 1% of the mass of the polychloro-ketol.
Wherein the polychlorinated ketol acid generator comprises high temperature accelerator, which comprises at least one of organic nitrile, organic oxime, organic hydroxylamine, and pyridine, such as DMF (N, N-dimethylformamide). The mass of the high-temperature speed increasing agent is 0.05-5% of that of the polychloro-ketone alcohol, preferably, the mass of the high-temperature speed increasing agent is 0.5-2.5% of that of the polychloro-ketone alcohol.
When the polychlorinated ketol self-acid generator is used, a small amount of MCS and water or xanthan gum solution can be directly mixed to prepare viscous fluid which is extruded into high-temperature stratum fractures needing acid fracturing along with fracturing fluid or independently. Or when in use, a large amount of solid MCS powder with the granularity of more than 800 meshes is directly mixed into the viscous xanthan gum solution to prepare suspension which is extruded into a high-temperature stratum fracture needing acidizing acid fracturing along with the fracturing fluid or independently. After the ground temperature rises again, hydrolysis, hydrochloric acid generation and acid corrosion cracks occur, and the stratum flow conductivity is enlarged.
Wherein the mass ratio of water to the polychloro-ketol is between 1: 1-1: between 0.5. Or the mass ratio of the xanthan gum solution to the polychloro-ketone alcohol is between 1: 1-1: between 0.5.
The polychlorinated keto-alcohol acid generator can be used for independently generating hydrochloric acid to perform acid generation and acid pressing and acidification on carbonate rock and limestone strata, and can also be matched with other reagents and the like to be used as self-generated soil acid to perform acid generation and acid pressing and acidification on sandstone, igneous rock and the like, such as ammonium fluorohydrogenate and the like. The mass percentage concentration of acid obtained after the polychlorinated ketol MCS with the highest concentration completely reacts with water in the invention is converted into hydrochloric acid aqueous solution, and can reach 54.75%.
The following is a detailed description of specific examples.
Example 1:
the polychlorinated ketol is a polychlorinated ketol MCS mixture (wherein C is C) produced by Xinxiang Hongtong science and technology limited3Cl6O2H225-33.3 percent of C6Cl12O3H6Accounting for 33.4 to 50 percent of the mass ratio,
C9Cl18O3H1225% -33.3% of the mass ratio), and distilled water according to the weight ratio of 1: 1, and performing experiments on the reaction speed of the generated hydrochloric acid at 50 ℃, 90 ℃, 130 ℃ and 170 ℃ respectively, and the results are shown in table 1.
Example 2:
the same polychloro-ketol as in example 1 was used with distilled water in a ratio of 1: 1 mass ratio, and adding white wax oil accounting for 3 percent of the mass of the polychloro-ketone alcohol as a low-temperature inhibitor, and performing experiments on the reaction speed of the generated hydrochloric acid at 50 ℃, 90 ℃, 130 ℃ and 170 ℃ respectively, wherein the results are shown in Table 1.
Example 3:
the same polychloro-ketol as in example 1 was used with distilled water in a ratio of 1: 1 mass ratio, and adding white wax oil accounting for 10% of the mass of the polychloro-ketone alcohol as a low-temperature inhibitor, and performing experiments on the reaction speed of the generated hydrochloric acid at 50 ℃, 90 ℃, 130 ℃ and 170 ℃ respectively, and the results are shown in Table 1.
Example 4:
the same polychloro-ketol as in example 1 was used with distilled water in a ratio of 1: 1 mass ratio, and simultaneously adding white wax oil accounting for 15 percent of the mass of the polychloro-ketone alcohol as a low-temperature inhibitor, and performing experiments on the reaction speed of the generated hydrochloric acid at 50 ℃, 90 ℃, 130 ℃ and 170 ℃ respectively, wherein the results are shown in Table 1.
Example 5:
the same polychloro-ketol as in example 1 was used with distilled water in a ratio of 1: 1 mass ratio, and adding urea of 0.01% of the mass of the polychloro-ketone alcohol as a medium temperature catalyst, and performing the experiment of the reaction speed of the generated hydrochloric acid at 50 ℃, 90 ℃, 130 ℃ and 170 ℃ respectively, the results are shown in table 1.
Example 6:
the same polychloro-ketol as in example 1 was used with distilled water in a ratio of 1: 1 mass ratio of white wax oil 10% of the mass of the polychloro-ketol as the low temperature inhibitor, and urea 1% of the mass of the polychloro-ketol as the medium temperature catalyst were mixed and subjected to the test of the reaction speed of the hydrochloric acid formation at 50 deg.C, 90 deg.C, 130 deg.C and 170 deg.C, respectively, and the results are shown in Table 1.
Example 7:
the same polychloro-ketol as in example 1 was used with distilled water in a ratio of 1: 1 mass ratio of white wax oil 10% of the mass of the polychloro-ketol as the low temperature inhibitor, and urea 1.5% of the mass of the polychloro-ketol as the medium temperature catalyst were mixed and subjected to the experiment of the reaction speed of the hydrochloric acid generation at 50 deg.C, 90 deg.C, 130 deg.C and 170 deg.C, respectively, and the results are shown in Table 1.
Example 8:
the same polychloro-ketol as in example 1 was used with distilled water in a ratio of 1: 1 mass ratio, and DMF 0.05% of the mass of the polychloroketol was added as a high temperature accelerator, and the reaction rate of the generated hydrochloric acid was measured at 50 deg.C, 90 deg.C, 130 deg.C and 170 deg.C, respectively, and the results are shown in Table 1.
Example 9:
the same polychloro-ketol as in example 1 was used with distilled water in a ratio of 1: 1 mass ratio of white wax oil 10% of the mass of the polychloro-ketol as a low temperature inhibitor, and DMF 2.5% of the mass of the polychloro-ketol as a high temperature accelerator were mixed and subjected to experiments of the reaction rate of the generated hydrochloric acid at 50 deg.C, 90 deg.C, 130 deg.C and 170 deg.C, respectively, and the results are shown in Table 1.
Example 10:
the same polychloro-ketol as in example 1 was used with distilled water in a ratio of 1: 1 mass ratio of white wax oil 10% of the mass of the polychloro-ketone alcohol as a low temperature inhibitor, and DMF 5% of the mass of the polychloro-ketone alcohol as a high temperature accelerator were mixed and subjected to experiments of the reaction rate of the generated hydrochloric acid at 50 ℃, 90 ℃, 130 ℃ and 170 ℃ respectively, and the results are shown in Table 1.
Table 1:
from the results of the examples in table 1, it can be seen that, in the case of no additive (example 1), the acid production rate of the polychloroprene alcohol is not high (the PH value is reduced from 7 to 5 within 2 hours) at low temperature (50 ℃) when it is exposed to water, but the acid production rate is low at medium and high temperature (90 ℃ -170 ℃), and the requirements of the on-site acid fracturing construction cannot be met at all.
In the case of only adding urea as the medium-temperature catalyst (example 5), although the acid production rate of the polychloro-ketol is high in the case of meeting water at the medium temperature (90 ℃ -130 ℃) (the hydrochloric acid yield can reach more than 95% within 2 hours), the acid production rate of the polychloro-ketol at the low temperature (50 ℃) (the pH value is reduced from 7 to 1.5 within 2 hours) is also fast, and the requirement of on-site acid fracturing construction cannot be met.
In the case of adding only DMF as the high temperature accelerator (example 8), although the acid production rate of the polychloro-ketol is high (the hydrochloric acid yield can reach more than 95% within 2 hours) at the medium and high temperature (130 ℃ -170 ℃) when meeting water, the acid production rate thereof at the low temperature (50 ℃) is very high (the hydrochloric acid yield can reach 25% within 2 hours), and the requirement of the on-site acid fracturing construction can not be met.
While the acid production rate of polychloro-ketol at low temperature (50 ℃) can be maintained at very low speed (the PH value remains 6.5 within 2 hours) when the white wax oil is singly added as the low temperature inhibitor (example 2-4), the acid production rate at medium and high temperature (90 ℃ -170 ℃) is very low, and the requirement of site acid fracturing construction can not be met at all.
Only when the low-temperature inhibitor (white wax oil) is added, and the medium-temperature catalyst (urea) and/or the high-temperature accelerator (DMF) are respectively added, can the polychloroketol be ensured to be rarely hydrolyzed at low temperature (less than or equal to 70 ℃) when meeting water, and hydrochloric acid can be quickly released at medium temperature (70 ℃ -140 ℃) and high temperature (140 ℃ -210 ℃), so as to achieve the purpose of long-penetration acid fracturing construction of the limestone carbonate rock stratum (examples 6, 7, 9 and 10).
From the above results, it can be seen that: the reaction speed of the polychloroketol generating hydrochloric acid when meeting water has positive correlation with temperature, namely the reaction speed is faster when the temperature is higher, and vice versa; suitable low temperature inhibitors (e.g., large alkanes such as white wax oil, aromatic hydrocarbons, halogenated alkanes) can reduce the reaction rate, especially the reaction rate at low temperature; the reaction speed can be accelerated by a proper medium-temperature catalyst (such as organic amine, organic amide and inorganic weak base like urea), especially the medium-temperature reaction speed; suitable high temperature accelerators (such as organic nitriles like DMF, organic oximes, organic hydroxylamines, pyridines) can accelerate the reaction speed, especially the high temperature reaction speed. The use amounts of the low-temperature inhibitor, the medium-temperature catalyst and the high-temperature accelerator are comprehensively adjusted, so that the deep penetration acid fracturing effect on the middle-high temperature limestone carbonate stratum can be achieved.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings, and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (9)
1. A polychlorinated ketone alcohol self-acid generator is characterized by comprising polychlorinated ketone alcohol, a low-temperature inhibitor and a moderate-temperature catalyst and/or a high-temperature accelerator, wherein the polychlorinated ketone alcohol is CnClm (OH) x, n is 2-10, m is not more than n and not more than 2n, x is 2-5, the moderate-temperature catalyst is a basic compound, the low-temperature inhibitor is a hydrocarbon compound, and the high-temperature accelerator is an organic compound.
2. The polychlorinated ketol antacid agent according to claim 1, wherein the low temperature inhibitor comprises at least one of alkanes, halogenated alkanes, aromatic hydrocarbons that are insoluble in water and have a number of carbon atoms greater than 10.
3. The polychlorinated ketol antacid agent according to claim 2, wherein the mass of the low temperature inhibitor is 3% to 15% of the mass of the polychlorinated ketol.
4. The polychlorinated ketol acid generator according to claim 1, wherein the polychlorinated ketol acid generator comprises a mesophilic catalyst comprising at least one of an organic amine, an organic amide, an inorganic weak base.
5. The polychlorinated ketol antacid agent according to claim 4, wherein the mass of the mesophilic catalyst is 0.01% to 1.5% of the mass of the polychlorinated ketol.
6. The polychlorinated ketol acid generator of claim 1, comprising a high temperature rate accelerator comprising at least one of an organic nitrile, an organic oxime, an organic hydroxylamine, pyridine.
7. The polychlorinated ketol antacid agent according to claim 6, wherein the mass of the high temperature accelerator is 0.05 to 5% of the mass of the polychlorinated ketol.
8. A method of using the polychlorinated ketol antacid agent of any one of claims 1 to 7, comprising: the polychloro-ketone alcohol is mixed with water and then squeezed into the fractures of the high temperature stratum with the fracturing fluid or separately.
9. Use according to claim 8, wherein the mass ratio of water to polychloro-ketol is between 1: 1-1: between 0.5.
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| CN102899012A (en) * | 2012-11-14 | 2013-01-30 | 北京世纪中星能源技术有限公司 | Self-born acid and preparation method and application thereof |
| CN106147743A (en) * | 2015-04-23 | 2016-11-23 | 中国石油天然气股份有限公司 | A kind of petroleum-gas fiedl acid stimulation injection agent and preparation method thereof |
| CN104975840A (en) * | 2015-06-18 | 2015-10-14 | 中国石油化工股份有限公司 | Self-born acid composite acid fracturing process for high-temperature deep well carbonate rock reservoir |
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Application publication date: 20201030 |