CN115537188A - Clay stabilizer composition and application thereof - Google Patents
Clay stabilizer composition and application thereof Download PDFInfo
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- CN115537188A CN115537188A CN202110728941.7A CN202110728941A CN115537188A CN 115537188 A CN115537188 A CN 115537188A CN 202110728941 A CN202110728941 A CN 202110728941A CN 115537188 A CN115537188 A CN 115537188A
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- clay stabilizer
- stabilizer composition
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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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
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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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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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
- C09K8/56—Compositions for consolidating loose sand or the like around wells without excessively decreasing the permeability thereof
- C09K8/57—Compositions based on water or polar solvents
- C09K8/575—Compositions based on water or polar solvents containing organic compounds
- C09K8/5751—Macromolecular compounds
- C09K8/5755—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
- C09K8/608—Polymer compositions
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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
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
Abstract
The invention provides a clay stabilizer composition and application thereof, wherein the clay stabilizer composition comprises the following components in percentage by mass: 2.0-35.0% of amine compound, 5.0-60.0% of nitrogenous salt, 2.0-50.0% of metal salt and water for balancing. The clay stabilizer composition has a certain shrinkage-expansion function while having an anti-expansion function, has a shrinkage-expansion effect on hydrated and expanded clay, reduces the influence of hydration expansion of the clay on formation pores, and has the potential value of recovering the formation pore permeability and reducing the water injection pressure.
Description
Technical Field
The invention relates to the technical field of oil exploitation, in particular to a clay stabilizer composition and application thereof.
Background
With the decrease of easily-exploited oil fields, low-permeability oil fields have gradually become the main battlefield for crude oil exploitation in China. In order to improve the effect of tertiary oil recovery and avoid the influence of water injection or steam on the pores of the bottom layer, the development of clay stabilizers with high inhibition has been receiving more and more attention from the industry. Clay minerals are widely present in oil reservoirs, and 97% of oil reservoirs worldwide contain clay minerals to varying degrees. Due to the high water sensitivity of clay minerals, clay stabilizers are added during the development process to reduce the hydration swelling and migration of clay.
The clay stabilizer provided by the prior art has limited anti-swelling effect, and cannot recover the porosity of hydrated and swollen clay.
Disclosure of Invention
In view of the above, in order to solve the problems in the prior art, the invention provides a clay stabilizer composition and an application thereof, wherein the clay stabilizer composition has a certain shrinkage-expansion function while having an anti-expansion function, has a shrinkage-expansion effect on clay which has been hydrated and expanded, reduces the influence of hydration and expansion of the clay on formation pores, and has a potential value of recovering the formation pore permeability and reducing the water injection pressure.
According to a first aspect of the present invention, there is provided a clay stabilizer composition comprising, in mass fractions: 2.0 to 35.0 percent of amine compound, 5.0 to 60.0 percent of nitrogenous salt, 2.0 to 50.0 percent of metal salt and the balance of water.
According to some embodiments of the invention, the amine compound comprises:
a polyamine; and/or
One or more of ethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine and benzylamine.
Further, the amine compound is a water-soluble amine compound.
According to some embodiments of the invention, the polyamine comprises the following structural formula:
wherein m is an arbitrary number from 0 to 15, preferably from 2 to 8, more preferably from 2 to 3;
n is an arbitrary number from 0 to 15, preferably from 2 to 8, more preferably from 2 to 3, and n is not 0 at the same time;
R 1 、R 2 、R 3 each independently is at least one of a C1-C4 linear chain or a fatty group containing a side chain, preferably a C2-C3 linear chain or a fatty group containing 1 carbon in a side chain, and more preferably a C3 fatty group containing 1 carbon in a side chain;
R 4 、R 5 each independently hydrogen or C1-C6 alkyl, preferably at least one of methyl, ethyl and hydrogen, more preferably at least one of methyl or hydrogen, more preferably hydrogen.
According to some embodiments of the invention, the amine compound has a relative molecular mass of 60 to 2000, preferably 60 to 500, more preferably 100 to 300.
According to some embodiments of the invention, the nitrogen-containing salt comprises one or more of tetramethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, ammonium chloride, and ammonium citrate;
preferably one or more of tetramethylammonium chloride, ammonium chloride and benzyltrimethylammonium chloride;
more preferably benzyltrimethylammonium chloride.
According to some embodiments of the invention, the metal salt comprises:
Al 3+ 、Mg 2+ 、Zr 4+ 、Fe 3+ 、K + at least one of inorganic acid salts of (a); and/or
Al 3+ 、Mg 2+ 、Zr 4+ 、Fe 3+ 、K + At least one of organic acid salts of (a);
according to some embodiments of the invention, the metal salt comprises:
Al 3+ 、Mg 2+ 、Zr 4+ 、Fe 3+ 、K + at least one of hydrochloride, sulfate and nitrate or a hydrolysate thereof; and/or
Al 3+ 、Mg 2+ 、Zr 4+ 、Fe 3+ 、K + At least one of formate, acetate, adipate and citrate of (a) or a hydrolysate thereof;
more preferably Mg 2+ At least one of hydrochloride, sulfate and nitrate.
According to some embodiments of the invention, the method comprises the following steps: 2.0 to 35.0 percent of amine compound, 5.0 to 60.0 percent of nitrogenous salt, 2.0 to 50.0 percent of metal salt and water.
Preferably, the composition comprises 2.5-5% of amine compound, 15-25% of nitrogenous salt, 15-35% of metal salt and water;
more preferably, the amine compound is 3.5-4.5%, the nitrogen-containing salt is 19-24%, the metal salt is 25-30%, and water, wherein the amine comprises the following structural formula:
wherein R is 1 Is CH 2 ；
R 2 ，R 3 Is C 3 H 6 ；
R 4 、R 5 Is H;
m is an arbitrary number from 1 to 4, and n is an arbitrary number from 1 to 4.
According to a third aspect of the present invention there is also provided the use of a clay stabilizer composition as described above in oil recovery technology.
The invention has the beneficial effects that:
on the basis of compounding the amine compound and the small cationic compound, the metal salt is utilized to dissociate positive charge ions in water and adsorb on the surface of the clay, and the surface hydration layer is compressed to play a role in inhibiting hydration and shrinkage and swelling of the clay, so that the clay has a higher anti-swelling effect, and the shrinkage and swelling effect has the effects of flocculating and compressing the inter-lamellar spacing of the clay hydrated.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Along with the promotion of oil field exploitation technique, the clay stabilizer's application is more and more extensive, and the kind is more and more, according to the main three stages of difference of chemical composition and mechanism of action: (1) In the early stage of clay stabilizers with inorganic salts, inorganic salt ions such as K are mainly used + Embedding into clay crystal structure to neutralize electronegativity; (2) In the 70 s, inorganic polynuclear polymer and cationic surfactant are used for stabilizing clay, and hydrophobic layers are formed on the surfaces of clay particles to prevent the clay from being further hydrated; (3) Researches and experiments for stabilizing clay by using cationic organic polymers are mainly carried out after 80 years, and the representative products comprise cationic polyacrylamide, polyamine compounds, hyperbranched molecules and the like with certain molecular weight.
The clay anti-swelling agent in the prior art mainly comprises amine, nitrogen-containing salt, polyalcohol and water. The content of each component is calculated by mass fraction as 3-80% of amine and 3-60% of nitrogenous salt; 2-30% of polyol and the balance of water. The clay anti-swelling agent disclosed by the patent is high in high-temperature anti-swelling rate and suitable for low-permeability reservoirs.
In view of the above background, the following detailed description of the present invention will be provided in conjunction with specific embodiments.
It should be noted that, the reagents used in the embodiments of the present invention, except for the polyamine compound synthesized by itself, are all commercially available conventional products, and all the reagents are analytically pure or chemically pure. The synthesis of polyamine compounds is referred to related documents: research on synthesis process of polyether amine detergent, songlong, qiao.
Example 1
Weighing 0.8g of triethanolamine (analytically pure/chemically pure), 6.4g of tetramethylammonium chloride (analytically pure/chemically pure), and ZrOCl 2 ·8H 2 8.0g of O (analytically pure/chemically pure) and 13.6g of deionized water are fully mixed in a beaker to prepare the clay stabilizer.
Example 2
Weighing 1.0g triethanolamine (same as example 1), 4.8g tetramethylammonium chloride (same as example 1), zrOCl 2 ·8H 2 8.0g of O (same as example 1) and 13.6g of deionized water were thoroughly mixed in a beaker to obtain a clay stabilizer.
Example 3
0.8g of prepared amine (purified to more than 99%), 4.8g of benzyltrimethylammonium chloride (analytically/chemically pure) 2 ·6H 2 4.0g of O (analytically pure/chemically pure) and 13.6g of deionized water are fully mixed in a beaker to prepare the clay stabilizer. Wherein the amine has the chemical structure
Wherein R is 1 Is CH 2 ，R 2 And R 3 Is C 2 H 4 ，R 4 And R 5 Is H, m is 2-3, n is 2-3.
Example 4
0.8g of prepared amine (purified to more than 99%), 4.8g of benzyltrimethylammonium chloride (same as in example 3) 2 ·6H 2 6.0g of O (same as example 3) and 13.6g of deionized water were thoroughly mixed in a beaker to obtain a clay stabilizer. Wherein the amine has the chemical structure
Wherein R is 1 Is CH 2 ，R 2 ，R 3 Is CH (CH) 3 )CH 2 ，R 4 And R 5 Is H, m is 2 to 3, n is 2 to 3.
Example 5
1.2g of prepared amine (purified to more than 99%), 4.8g of benzyltrimethylammonium chloride (same as in example 3/4) 2 ·6H 2 6.0g of O (same as example 3/4) and 13.6g of deionized water were thoroughly mixed in a beaker to obtain a clay stabilizer. Wherein the amine has the chemical structure of
Wherein R is 1 Is CH 2 ，R 2 And R 3 Is C 2 H 4 ，R 4 And R 5 Is H, m is 2 to 3, n is 2 to 3.
Example 6
Weighing 1.2g of prepared amine (purified to more than 99%), 4.8g of tetraethylammonium chloride (analytically pure/chemically pure), 8.0g of HCOOK (product type, manufacturer, parameters, analytically pure/chemically pure) and 13.6g of deionized water, and fully mixing in a beaker to prepare the clay stabilizer. Wherein the amine has the chemical structure of
Wherein R is 1 Is CH 2 ，R 2 ，R 3 Is straight chain C 3 H 6 ，R 4 And R 5 Is H, m is 2-3, n is 2-3.
Example 7
Weighing 1.2g of self-made amine (purified to more than 99%), 4.8g of tetraethylammonium chloride (same as example 6), and AlCl 3 (analytically pure/chemically pure) 8.0g and deionized water 13.6g in a beakerA clay stabilizer. Wherein the amine has the chemical structure of
Wherein R is 1 Is CH 2 ，R 2 ，R 3 Is C 2 H 2 ，R 4 And R 5 Is CH 3 M is 2 to 3, n is 2 to 3.
Example 8
1.2g of benzylamine (analytically pure/chemically pure), 4.8g of tetramethylammonium chloride (same as in example 6/7), 8.0g of KCl (analytically pure/chemically pure) and 13.6g of deionized water were weighed and mixed thoroughly in a beaker to prepare a clay stabilizer.
Example 9
1.2g of prepared amine (purified to more than 99%), 4.8g of benzyltrimethylammonium chloride (same as in example 3/4) 2 ·6H 2 6.0g of O (same as example 3/4) and 13.6g of deionized water were thoroughly mixed in a beaker to obtain a clay stabilizer. Wherein the amine has the chemical structure of
Wherein R is 1 Is CH 2 ，R 2 ，R 3 Is C 3 H 6 (side chain containing 2 carbons), R 4 、R 5 Is H, m is 2-3, n is 2-3.
Example 10
1.2g of prepared amine (purified to more than 99%), 4.8g of benzyltrimethylammonium chloride (same as in example 3/4) 2 ·6H 2 6.0g of O (same as example 3/4) and 13.6g of deionized water were thoroughly mixed in a beaker to obtain a clay stabilizer. Wherein the amine has the chemical structure
Wherein R is 1 Is CH 2 ，R 2 ，R 3 Is C 2 H 4 ，R 4 And R 5 Is H, m is 5 to 8, n is 5 to 8.
Comparative example 1
Taking example 4 as an example, mgCl, a metal salt, was not added 2 ·6H 2 And O, preparing a clay stabilizer for comparison. 0.8g of the same amine as in example 4, 4.8g of benzyltrimethylammonium chloride and 13.6g of deionized water were weighed out and mixed thoroughly in a beaker to obtain a clay stabilizer.
Comparative example 2
Using example 7 as an example, alCl was not added as a metal salt 3 ·6H 2 And O, preparing a clay stabilizer for comparison. 1.2g of the same amine as in example 7, 4.8g of tetraethylammonium chloride and 13.6g of deionized water were weighed out and mixed in a beaker to obtain a clay stabilizer.
The anti-swelling rate is tested according to the performance evaluation method of the clay stabilizer for water injection SY/T5971-2016, and the steps are as follows: weighing 0.5g of sodium bentonite, adding the sodium bentonite into a 10mL centrifuge tube, adding deionized water to 10mL scale, fully shaking, standing for 2h at room temperature, loading into a centrifuge, centrifuging at 1500r/min for 15min, and reading the volume V of the sodium bentonite in water 2 . Adopting the same steps to replace clear water with clay stabilizer aqueous solution with certain concentration, and measuring the volume V of the centrifuged soil 1 . Measuring volume V of soil by using kerosene instead of water 0 。
In the formula: eta-anti-swelling rate,%; v 0 Volume of sodium bentonite in kerosene, mL; v 1 Volume of sodium bentonite in clay stabilizer, mL; v 2 Volume of sodium bentonite in clear water, mL;
the shrinkage-expansion rate is evaluated by a centrifugation method commonly used in the literature, and the steps are as follows:
weighing 0.5g of sodium bentonite, adding into a 10mL centrifuge tube, adding deionized water to 10mL scale, shaking thoroughly, standing at room temperature for 2h, placing into a centrifuge, and centrifuging at 1500r/min for 15min, reading the volume V of the sodium bentonite in the water 1 . Pouring out deionized water, adding a certain amount of swelling agent, shaking thoroughly, standing for 2h, placing into a centrifuge, centrifuging at 1500r/min for 15min, reading out volume V of sodium bentonite in swelling agent solution 2 。
In the formula: s-shrinkage-expansion ratio,%; mL; v 1 Volume of sodium bentonite in clear water, mL; v 2 Volume of sodium bentonite after addition of clay stabilizer, mL;
the swell-proof ratio and the swell-shrinkage ratio of each example of the present invention and the comparative example were measured according to the above-mentioned test methods and are shown in Table 1.
TABLE 1 Clay stabilizer Performance evaluation test
From the above results, it can be seen that the clay stabilizer composition prepared by the present invention has a certain shrinkage-swelling effect while inhibiting hydration-swelling of the clay. In the comparative example, positive charge ions dissociated in water due to the lack of metal salt are adsorbed on the clay surface, so that the clay does not have obvious shrinkage-expansion performance.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.
Claims (9)
1. A clay stabilizer composition, comprising, in mass fraction: 2.0 to 35.0 percent of amine compound, 5.0 to 60.0 percent of nitrogenous salt, 2.0 to 50.0 percent of metal salt and water.
2. The clay stabilizer composition according to claim 1, wherein the amine compound comprises:
a polyamine; and/or
One or more of ethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine and benzylamine.
3. The clay stabilizer composition of claim 2, wherein the polyamine has the following structural formula:
wherein m is an arbitrary number from 0 to 15, preferably from 2 to 8, more preferably from 2 to 3;
n is an arbitrary number from 0 to 15, preferably from 2 to 8, more preferably from 2 to 3, and n is not 0 at the same time;
R 1 、R 2 、R 3 each independently is at least one of a C1-C4 linear chain or a fatty group containing a side chain, preferably a C2-C3 linear chain or a fatty group containing 1 carbon in a side chain, and more preferably a C3 fatty group containing 1 carbon in a side chain;
R 4 、R 5 each independently hydrogen or C1-C6 alkyl, preferably at least one of methyl, ethyl and hydrogen, more preferably at least one of methyl or hydrogen, more preferably hydrogen.
4. A clay stabilizer composition according to any one of claims 1-3, wherein the amine compound has a relative molecular mass of 60-2000, preferably 60-500, more preferably 100-300.
5. The clay stabilizer composition of any one of claims 1-4, wherein the nitrogen-containing salt comprises one or more of tetramethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, ammonium chloride, and ammonium citrate;
preferably one or more of tetramethylammonium chloride, ammonium chloride and benzyltrimethylammonium chloride;
more preferably benzyltrimethylammonium chloride.
6. The clay stabilizer composition according to any one of claims 1-5, wherein the metal salt comprises:
Al 3+ 、Mg 2+ 、Zr 4+ 、Fe 3+ 、K + at least one inorganic acid salt of (a); and/or
Al 3+ 、Mg 2+ 、Zr 4+ 、Fe 3+ 、K + At least one of organic acid salts of (1).
7. The clay stabilizer composition according to claim 6, wherein the metal salt comprises: al (aluminum) 3+ 、Mg 2+ 、Zr 4+ 、Fe 3+ 、K + At least one of hydrochloride, sulfate and nitrate or a hydrolysate thereof; and/or
Al 3+ 、Mg 2+ 、Zr 4+ 、Fe 3+ 、K + At least one of formate, acetate, adipate and citrate of (a) or a hydrolysate thereof;
more preferably Mg 2+ At least one of hydrochloride, sulfate and nitrate.
8. The clay stabilizer composition according to any one of claims 1-7, comprising, in mass fractions: 2.0 to 35.0 percent of amine compound, 5.0 to 60.0 percent of nitrogenous salt, 2.0 to 50.0 percent of metal salt and water;
preferably, the composition comprises 2.5-5% of amine compound, 15-25% of nitrogen-containing salt, 15-35% of metal salt and water;
more preferably, 3.5 to 4.5 percent of amine compound, 19 to 24 percent of nitrogenous salt, 25 to 30 percent of metal salt and water;
wherein the amine compound has the following structural formula:
wherein R is 1 Is CH 2 ；
R 2 ，R 3 Is C 3 H 6 ；
R 4 、R 5 Is H;
m is an arbitrary number from 1 to 4, and n is an arbitrary number from 1 to 4.
9. Use of a clay stabilizer composition as claimed in any one of claims 1 to 8 in oil recovery technology.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060289164A1 (en) * | 2005-06-24 | 2006-12-28 | Innovative Chemical Technologies Canada Ltd. | Clay control additive for wellbore fluids |
| CN104449599A (en) * | 2014-10-30 | 2015-03-25 | 中国石油化工股份有限公司 | Anti-swelling agent for clay |
| CN112457838A (en) * | 2020-11-25 | 2021-03-09 | 陕西科技大学 | Novel acid-resistant and salt-resistant shrinking and swelling agent and preparation method thereof |
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2021
- 2021-06-29 CN CN202110728941.7A patent/CN115537188A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060289164A1 (en) * | 2005-06-24 | 2006-12-28 | Innovative Chemical Technologies Canada Ltd. | Clay control additive for wellbore fluids |
| CN104449599A (en) * | 2014-10-30 | 2015-03-25 | 中国石油化工股份有限公司 | Anti-swelling agent for clay |
| CN112457838A (en) * | 2020-11-25 | 2021-03-09 | 陕西科技大学 | Novel acid-resistant and salt-resistant shrinking and swelling agent and preparation method thereof |
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