CN116120547A - Clay stabilizer and preparation method thereof - Google Patents
Clay stabilizer and preparation method thereof Download PDFInfo
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- CN116120547A CN116120547A CN202310347973.1A CN202310347973A CN116120547A CN 116120547 A CN116120547 A CN 116120547A CN 202310347973 A CN202310347973 A CN 202310347973A CN 116120547 A CN116120547 A CN 116120547A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
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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
- C09K8/60—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention provides a clay stabilizer and a preparation method thereof, and belongs to the technical field of stabilizers. Wherein n=20-100. The clay stabilizer has good anti-swelling effect and temperature resistance, the main chain of the clay stabilizer contains more quaternary ammonium salt cations, has more positive charges, can be adsorbed with a plurality of clay particles simultaneously to form multi-point adsorption, inhibits hydration expansion of clay, has high activity degree of freedom, has strong control effect on dispersion and migration of clay particles, has strong washing resistance, can form a compact hydration film on the surfaces of the clay particles, can prevent and delay contact of water molecules with the surfaces of the clay, and achieves the purpose of preventing hydration expansion of the clay.
Description
Technical Field
The invention relates to the technical field of stabilizers, in particular to a clay stabilizer and a preparation method thereof.
Background
The stratum contains a certain amount of clay minerals, mainly kaolin, montmorillonite, illite, chlorite and the like, and during the development process (water injection, acidification and fracturing) of the oil field, when the clay encounters external water or water-based substances, the clay swells, disperses, moves and plugs pore roar, so that the permeability of the stratum is reduced, and the damage to the low-permeability oil reservoir is more serious. In order to reduce damage to reservoirs, clay stabilizers are often added to the oil field to improve the hydration swelling, dispersion and migration of the clay.
Early use of KCl, NH 4 The simple inorganic salt such as Cl is used as the clay stabilizer, has the defects of large usage amount, certain influence on the performance of well entering liquid, the problems of temperature resistance, acid resistance and the like exist in the last seventy-six century when aluminum hydroxide or zirconium hydroxide is used as the clay stabilizer, and the organic cationic polymer compound is mainly used as the clay stabilizer in the present year, so that the clay stabilizer has the advantages of small usage amount, good performance and long effective period, but has the problem of poor temperature resistance. As in patent CN102786924a, a clay stabilizer prepared by copolymerizing dimethyldiallylammonium chloride and acrylamide is reported to have a good anti-swelling effect; patent CN103571449A discloses a clay stabilizer prepared by reacting epichlorohydrin with short-chain polyquaternium, and has good anti-swelling effect; patent CN103396782a discloses an acidifying clay anti-swelling agent, which is prepared by copolymerizing organic amine and epichlorohydrin, and has good anti-swelling effect; the clay stabilizers introduced above have good anti-swelling effect, good acid and alkali resistance and longer anti-swelling period, but have the temperature resistance which can not meet the deep use requirements of the current development of oil and gas fields, and the clay stabilizers with the temperature resistance higher than 250 ℃ are required to be developed to meet the production requirements.
Disclosure of Invention
The invention aims to provide a clay stabilizer and a preparation method thereof, which have good anti-swelling effect and temperature resistance, can prevent and delay water molecules from contacting with the surface of clay, and achieve the purpose of preventing hydration and swelling of clay.
The technical scheme of the invention is realized as follows:
the invention provides a clay stabilizer, which has a structure shown in a formula I:
wherein n=20-100.
The invention further provides a preparation method of the clay stabilizer, which comprises the following steps:
s1, reacting 2,2' -oxybis (ethylamine) with 1, 4-dichloro-2, 3-epoxybutane under the action of a catalyst to prepare an intermediate polymer;
s2, heating and ring-opening the intermediate polymer prepared in the step S1 in the presence of alkali to prepare the clay stabilizer.
As a further improvement of the present invention, the catalyst in step S1 is at least one selected from the group consisting of triethylamine, triethylenediamine, diethylamine, 1, 8-diazabicyclo undec-7-ene, diphenylurea, ethylenediamine.
As a further improvement of the invention, the molar ratio of the 2,2' -oxybis (ethylamine), the 1, 4-dichloro-2, 3-epoxybutane and the catalyst in the step S1 is 1:1:0.001-0.01.
As a further improvement of the invention, the temperature of the reaction in step S1 is 70-90 ℃ and the time is 2-4h.
As a further improvement of the invention, the mass ratio of the intermediate polymer to the base in step S2 is 10-12:2-3.
As a further improvement of the present invention, the base in step S2 is at least one selected from the group consisting of triethylamine, diethylamine, ethylenediamine, naOH, KOH, potassium carbonate, sodium carbonate.
As a further improvement of the invention, the temperature of the heating ring-opening in the step S2 is 50-70 ℃ and the time is 0.5-1h.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, dissolving 1 molar equivalent of 2,2' -oxybis (ethylamine) and 1 molar equivalent of 1, 4-dichloro-2, 3-epoxybutane in toluene, adding 0.001-0.01 molar equivalent of catalyst, heating to 70-90 ℃, reacting for 2-4 hours, cooling to room temperature, filtering, washing and drying to obtain an intermediate polymer;
s2, adding 10-12 parts by weight of the intermediate polymer prepared in the step S1 and 2-3 parts by weight of alkali into water, heating to 50-70 ℃, performing ring-opening reaction for 0.5-1h, adding acetone, precipitating, filtering, washing and drying to obtain the clay stabilizer.
The invention has the following beneficial effects: the clay stabilizer has good anti-swelling effect and temperature resistance, the main chain of the clay stabilizer contains more quaternary ammonium salt cations, has more positive charges, can be adsorbed with a plurality of clay particles simultaneously to form multi-point adsorption, inhibits hydration expansion of clay, has high activity degree of freedom, has strong control effect on dispersion and migration of clay particles, has strong washing resistance, can form a compact hydration film on the surfaces of the clay particles, can prevent and delay contact of water molecules with the surfaces of the clay, and achieves the purpose of preventing hydration expansion of the clay.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a synthetic route diagram of the clay stabilizer of the invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The present embodiment provides a clay stabilizer.
As shown in fig. 1, the preparation method specifically comprises the following steps:
s1, 1mol of 2,2' -oxybis (ethylamine) and 1mol of 1, 4-dichloro-2, 3-epoxybutane are dissolved in 100mL of toluene, 0.001mol of triethylene diamine is added, the mixture is heated to 70 ℃ for 2h and reacts for 2h, the temperature is reduced to room temperature, and the intermediate polymer is obtained after filtration, washing and drying;
s2, adding 10g of the intermediate polymer prepared in the step S1 and 2g of ethylenediamine into 100mL of water, heating to 50 ℃, performing ring-opening reaction for 0.5h, adding 100mL of acetone, precipitating for 1h, filtering, washing, and drying to obtain the clay stabilizer.
Example 2
The present embodiment provides a clay stabilizer.
As shown in fig. 1, the preparation method specifically comprises the following steps:
s1, 1mol of 2,2' -oxybis (ethylamine) and 1mol of 1, 4-dichloro-2, 3-epoxybutane are dissolved in 100mL of toluene, 0.01mol of diphenyl urea is added, the mixture is heated to 90 ℃ for 4 hours, cooled to room temperature, filtered, washed and dried, and an intermediate polymer is prepared;
s2, adding 12g of the intermediate polymer prepared in the step S1 and 3g of diethylamine into 100mL of water, heating to 70 ℃, performing ring-opening reaction for 1h, adding 100mL of acetone, precipitating for 1h, filtering, washing and drying to obtain the clay stabilizer.
Example 3
The present embodiment provides a clay stabilizer.
As shown in fig. 1, the preparation method specifically comprises the following steps:
s1, 1mol of 2,2' -oxybis (ethylamine) and 1mol of 1, 4-dichloro-2, 3-epoxybutane are dissolved in 100mL of toluene, 0.005mol of triethylene diamine is added, the mixture is heated to 80 ℃ for 3h, cooled to room temperature, filtered, washed and dried, and an intermediate polymer is prepared;
s2, adding 11g of the intermediate polymer prepared in the step S1 and 2.5g of triethylamine into 100mL of water, heating to 60 ℃, performing ring-opening reaction for 1h, adding 100mL of acetone, precipitating for 1h, filtering, washing and drying to obtain the clay stabilizer.
Test example 1
The clay stabilizer prepared in examples 1-3 was weighed to 0.3g, water was added to 100g to prepare a clay stabilizer solution with a concentration of 0.3%, and the anti-swelling effect of the sample after hot rolling at 250℃for 24 hours at room temperature was tested according to the Chinese oil and gas industry standard "evaluation method SY/T1994 (2002) for clay stabilizer for Water injection", and the test results are shown in Table 1.
TABLE 1
As shown in the table above, the clay stabilizers prepared in examples 1-3 of the present invention have good anti-swelling properties and good high temperature resistance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. The clay stabilizer is characterized by having a structure shown in a formula I:
a formula I;
wherein n=20-100.
2. A method of preparing the clay stabilizer according to claim 1, comprising the steps of:
s1, reacting 2,2' -oxybis (ethylamine) with 1, 4-dichloro-2, 3-epoxybutane under the action of a catalyst to prepare an intermediate polymer;
s2, heating and ring-opening the intermediate polymer prepared in the step S1 in the presence of alkali to prepare the clay stabilizer.
3. The method according to claim 2, wherein the catalyst in step S1 is at least one selected from the group consisting of triethylamine, triethylenediamine, diethylamine, 1, 8-diazabicyclo undec-7-ene, diphenylurea, ethylenediamine.
4. The method according to claim 2, wherein the molar ratio of 2,2' -oxybis (ethylamine), 1, 4-dichloro-2, 3-epoxybutane and catalyst in step S1 is 1:1:0.001-0.01.
5. The method according to claim 2, wherein the reaction in step S1 is carried out at a temperature of 70 to 90 ℃ for a time of 2 to 4 hours.
6. The method according to claim 2, wherein the mass ratio of the intermediate polymer to the base in step S2 is 10-12:2-3.
7. The method according to claim 2, wherein the base in step S2 is at least one selected from the group consisting of triethylamine, diethylamine, ethylenediamine, naOH, KOH, potassium carbonate, and sodium carbonate.
8. The method according to claim 2, wherein the temperature of the heated ring-opening in step S2 is 50-70 ℃ for 0.5-1h.
9. The preparation method according to claim 2, characterized by comprising the following steps:
s1, dissolving 1 molar equivalent of 2,2' -oxybis (ethylamine) and 1 molar equivalent of 1, 4-dichloro-2, 3-epoxybutane in toluene, adding 0.001-0.01 molar equivalent of catalyst, heating to 70-90 ℃, reacting for 2-4 hours, cooling to room temperature, filtering, washing and drying to obtain an intermediate polymer;
s2, adding 10-12 parts by weight of the intermediate polymer prepared in the step S1 and 2-3 parts by weight of alkali into water, heating to 50-70 ℃, performing ring-opening reaction for 0.5-1h, adding acetone, precipitating, filtering, washing and drying to obtain the clay stabilizer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310347973.1A CN116120547B (en) | 2023-04-04 | 2023-04-04 | Clay stabilizer and preparation method thereof |
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| CN202310347973.1A CN116120547B (en) | 2023-04-04 | 2023-04-04 | Clay stabilizer and preparation method thereof |
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| CN116120547B CN116120547B (en) | 2023-06-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483750A (en) * | 2002-09-20 | 2004-03-24 | 凯 党 | Cation polymer and expansion-resisting agent containing same |
| CN103396782A (en) * | 2013-07-12 | 2013-11-20 | 中国石油天然气股份有限公司 | Acidizing anti-swelling agent and preparation method thereof |
| US20150299554A1 (en) * | 2012-11-12 | 2015-10-22 | Huntsman Petrochemical Llc | Alkylated Polyetheramines as Clay Stabilizing Agents |
| CN106279661A (en) * | 2015-05-28 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of Cationic Polymers Containing Quaternary Ammonium Salts |
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- 2023-04-04 CN CN202310347973.1A patent/CN116120547B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483750A (en) * | 2002-09-20 | 2004-03-24 | 凯 党 | Cation polymer and expansion-resisting agent containing same |
| US20150299554A1 (en) * | 2012-11-12 | 2015-10-22 | Huntsman Petrochemical Llc | Alkylated Polyetheramines as Clay Stabilizing Agents |
| CN103396782A (en) * | 2013-07-12 | 2013-11-20 | 中国石油天然气股份有限公司 | Acidizing anti-swelling agent and preparation method thereof |
| CN106279661A (en) * | 2015-05-28 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of Cationic Polymers Containing Quaternary Ammonium Salts |
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| CN116120547B (en) | 2023-06-30 |
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Denomination of invention: A clay stabilizer and its preparation method Effective date of registration: 20230921 Granted publication date: 20230630 Pledgee: China Postal Savings Bank Co.,Ltd. Dongying Kenli District sub branch Pledgor: Shandong Haijia Petrochemical Co.,Ltd. Registration number: Y2023980058051 |
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