CN106608949B - A kind of clay stabilizer and preparation method thereof - Google Patents
A kind of clay stabilizer and preparation method thereof Download PDFInfo
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- CN106608949B CN106608949B CN201510700012.XA CN201510700012A CN106608949B CN 106608949 B CN106608949 B CN 106608949B CN 201510700012 A CN201510700012 A CN 201510700012A CN 106608949 B CN106608949 B CN 106608949B
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- clay stabilizer
- clay
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- stabilizer
- ammonium persulfate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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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
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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
- C09K8/84—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
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained 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
- 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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- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention relates to a kind of clay stabilizers and preparation method thereof, the clay stabilizer is by epoxychloropropane, dimethylamine, allyl trimethyl ammonium chloride, γ-(methacryloxypropyl) propyl trimethoxy silicane passes through the initiation reaction of initiator under certain condition, and hydrolysis inhibitor is added during the reaction and inhibits hydrolysis, end of reaction obtains clay stabilizer, with stratum clay condensation reaction can occur for the silicone hydroxyl through hydrolyzing to form after the clay stabilizer injects stratum, the hydration swelling and dispersion for controlling clay are migrated, preventive effect of expansion is good, and molecular weight is low, suitable for low permeability reservoir.
Description
Technical field
The present invention relates to a kind of clay stabilizer and preparation method thereof, clay stabilizer prepared by the present invention is suitable for oil field
Fill the water and prevent swollen field.
Background technique
Contain a certain amount of clay mineral in stratum, mainly has kaolinite, montmorillonite, illite and chlorite etc., in oil
Field development process (water filling, acidification, pressure break) will expand when these clays encounter secondary water or water-based material, disperse,
Migration, blocking hole throat, cause in-place permeability to reduce, and hypotonic rate oil reservoir are destroyed even more serious.In order to mitigate to storage
Layer injures, and is commonly incorporated into clay stabilizer in oil field to improve the hydration swelling of clay, dispersion migration.
It can be divided into according to the different clay stabilizers of chemical structure: inorganic salts, inorganic multicore polymerization species, You Jiju
Close species.
Inorganic salts clay stabilizer have it is cheap, short-term preventive effect of expansion is good；The disadvantage is that multiple spot absorption cannot be formed,
Timeliness is short.
Inorganic multicore polymerization species mainly have hydroxy Al, zirconyl hydroxy, iron carbonyl etc..This kind of clay stabilizer can effectively prevent
Clay swell and migration, but acid resistance is poor, it is impossible to be used in the high sandstone formation of carbonate content.
Organic polymer species are the most commonly used a kind of clay stabilizers of research.Currently, this kind of clay stabilizer is using most
Mostly is organic cation type polymer.This kind of clay stabilizer again based on polyquarternium-type, such as: poly dimethyl allyl
Ammonium chloride, poly- trimethylallylammonium chloride, cationic polyacrylamide etc..Such clay stabilizer have heatproof, it is acidproof, have
The advantages that effect phase is long.Organic clay stabilizers majority used at present is straight chain type, and centering low permeability formation is easy when molecular weight is big
Hole throat results in blockage, and molecular weight hour preventive effect of expansion is poor, and validity period is short.
Although existing clay stabilizer has the ability of certain clay stabilization to a certain extent, in long-term effect
And in middle LOW PERMEABILITY RESERVOIR use aspect Shortcomings.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of clay stabilizer and its preparation process.
What the purpose of the present invention was achieved through the following technical solutions:
A kind of structural formula of clay stabilizer of the invention is as follows:
In formula, x, y, z are the integer greater than 0；Molecular weight is 4000-12000.
A kind of preparation method of clay stabilizer, it is characterized in that by epoxychloropropane, dimethylamine, allyl trimethyl ammonia chloride
Ammonium, γ-(methacryloxypropyl) propyl trimethoxy silicane are made by the initiation reaction of initiator, and added during the reaction
Enter hydrolysis inhibitor.
A kind of preparation method of the clay stabilizer, it is characterised in that with monomer total amount for 1, the quality hundred of each monomer
Divide ratio are as follows: epoxychloropropane 60~70%；Dimethylamine 21~38%, allyl trimethyl ammonium chloride 4~8%, γ-(methacryl
Oxygen) propyl trimethoxy silicane 2~6%, finally it is made into the aqueous solution that monomer gross mass percentage concentration is 30%~55%.
The preparation method of a kind of clay stabilizer, it is characterised in that: initiator is the initiation of water-soluble azo
Agent, hydrogen peroxide, ammonium persulfate-sodium bisulfite redox system or potassium peroxydisulfate-sodium hydrogensulfite redox system, draw
Send out 0.1~3.0% that agent additional amount is monomer gross mass.
The preparation method of a kind of clay stabilizer, it is characterised in that initiator is ammonium persulfate-sodium bisulfite
Redox system, sodium hydrogensulfite and ammonium persulfate molar ratio are 1:1.0~1.3.
The preparation method of a kind of clay stabilizer, it is characterised in that sodium hydrogensulfite is with ammonium persulfate molar ratio
1:1.2。
The preparation method of a kind of clay stabilizer, it is characterised in that: hydrolysis inhibitor used is diethylene glycol
Butyl ether, additional amount are 0. 1~the 3.0% of monomer gross mass.
The silicone hydroxyl through hydrolyzing to form can occur with stratum clay behind clay stabilizer injection provided by the invention stratum
Condensation reaction, hydration swelling and dispersion migration, the preventive effect of expansion for controlling clay are good, and molecular weight is low, is suitable for low permeability reservoir.
Specific embodiment
In order to better understand the present invention, the content of invention is furtherd elucidate below with reference to embodiment, but of the invention interior
Appearance is not limited only to the following examples.
Embodiment 1
60.0g epoxychloropropane is added into reactor, temperature of reactor is controlled at 20 DEG C, and 52.5g mass fraction is added
For 40% dimethylamine agueous solution and 4.0g allyl trimethyl ammonium chloride, 6.0g γ-(methacryloxypropyl) propyl trimethoxy
Base silane, 1.0g butyl, 59.5g water are passed through the bisulfite of addition 0.55g after nitrogen 30min into reactor
1.35g ammonium persulfate is added after 3min for sodium, reacts 2~8h at being 40 DEG C in temperature, end of reaction obtains a kind of clay stabilization
Agent, the molecular weight of the clay stabilizer are 5000.
Embodiment 2
65.0g epoxychloropropane is added into reactor, temperature of reactor is controlled at 20 DEG C, and 60.0g mass fraction is added
For 40% dimethylamine agueous solution and 6.0g allyl trimethyl ammonium chloride, 2.0g γ-(methacryloxypropyl) propyl trimethoxy
Base silane, 1.2g butyl, 206.5g water are passed through the bisulfite of addition 0.55g after nitrogen 30min into reactor
1.35g ammonium persulfate is added after 3min for sodium, reacts 2~8h at being 40 DEG C in temperature, end of reaction obtains a kind of clay stabilization
Agent, the molecular weight of the clay stabilizer are 8000.
Embodiment 3
70.0g epoxychloropropane is added into reactor, temperature of reactor is controlled at 20 DEG C, and 95.0g mass fraction is added
For 40% dimethylamine agueous solution and 4.0g allyl trimethyl ammonium chloride, 2.0g γ-(methacryloxypropyl) propyl trimethoxy
Base silane, 1.2g butyl, 57.0g water are passed through the bisulfite of addition 0.99g after nitrogen 30min into reactor
2.43g ammonium persulfate is added after 3min for sodium, reacts 2~8h at being 40 DEG C in temperature, end of reaction obtains a kind of clay stabilization
Agent, the molecular weight of the clay stabilizer are 12000.
Embodiment 4
60.0g epoxychloropropane is added into reactor, temperature of reactor is controlled at 20 DEG C, and 95.0g mass fraction is added
For 40% dimethylamine agueous solution and 8.0g allyl trimethyl ammonium chloride, 4.0g γ-(methacryloxypropyl) propyl trimethoxy
Base silane, 1.2g butyl, 218.0g water are passed through the bisulfite of addition 0.99g after nitrogen 30min into reactor
2.43g ammonium persulfate is added after 3min for sodium, reacts 2~8h at being 40 DEG C in temperature, end of reaction obtains a kind of clay stabilization
Agent, the molecular weight of the clay stabilizer are 6000.
Embodiment 5
0.5g clay stabilizer sample is weighed, 100g is added water to, being made into concentration is 0.5% clay stabilization agent solution, in
State's oil and gas industry standard " water filling use clay stabilizer method of evaluating performance SY/T1994 (2002) ", test at room temperature with
And the preventive effect of expansion of the sample after 200 DEG C of heat rollings for 24 hours, test result are shown in Table 1.
1 clay stabilizer of table prevents swollen result
。
Embodiment 6
0.5g clay stabilizer sample is weighed, 100g is added water to, being made into concentration is 0.5% clay stabilization agent solution, according to enterprise
Industry standard " Q/SH 0053-2010 clay stabilizer technical requirements " carries out water-fastness rate performance test to sample at room temperature, surveys
Test result is shown in Table 2.
The above results show that clay stabilizer prepared by the present invention has good heatproof, water-fastness and good suppression
The ability of clay swell processed.
Claims (7)
1. a kind of clay stabilizer, it is characterised in that its molecular structural formula is as follows:
In formula, x, y, z are the integer greater than 0；Molecular weight is 4000-12000.
2. the preparation method of clay stabilizer as described in claim 1, it is characterized in that by epoxychloropropane, dimethylamine, allyl
Base trimethyl ammonium chloride, γ-(methacryloxypropyl) propyl trimethoxy silicane are made by the initiation reaction of initiator, and
Hydrolysis inhibitor is added in reaction process.
3. the preparation method of clay stabilizer as claimed in claim 2, it is characterised in that with monomer total amount for 1, each monomer
Mass percent are as follows: epoxychloropropane 60~70%；Dimethylamine 21~38%, allyl trimethyl ammonium chloride 4~8%, γ-(methyl
Acryloyl-oxy) propyl trimethoxy silicane 2~6%, finally it is made into the aqueous solution that monomer gross mass percentage concentration is 30%~55%.
4. the preparation method of clay stabilizer as claimed in claim 2, it is characterised in that: initiator is water-soluble azo
Initiator, ammonium persulfate-sodium bisulfite redox system or potassium peroxydisulfate-sodium hydrogensulfite redox system cause
Agent additional amount is the 0.1~3.0% of monomer gross mass.
5. the preparation method of clay stabilizer as claimed in claim 4, it is characterised in that initiator is ammonium persulfate-sulfurous acid
Hydrogen sodium redox system, sodium hydrogensulfite and ammonium persulfate molar ratio are 1:1.0~1.3.
6. the preparation method of clay stabilizer as claimed in claim 5, it is characterised in that sodium hydrogensulfite rubs with ammonium persulfate
You are than being 1:1.2.
7. the preparation method of clay stabilizer as claimed in claim 2, it is characterised in that: hydrolysis inhibitor used is diethyl
Glycol butyl ether, additional amount are the 0.1~3.0% of monomer gross mass.
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| CN106608949B true CN106608949B (en) | 2019-02-22 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329902A (en) * | 2018-01-23 | 2018-07-27 | 中国石油天然气股份有限公司 | A kind of salt tolerant clay stabilizer and preparation method thereof of oil field water outlet preparing fracturing fluid |
| CN109054798B (en) * | 2018-07-13 | 2020-10-16 | 中国石油大学(华东) | Preparation method of high-temperature clay stabilizer for oil field |
| CN114426618B (en) * | 2020-10-14 | 2024-03-22 | 中国石油化工股份有限公司 | Polymer type high-temperature-resistant anti-swelling and shrinking agent and preparation method and application thereof |
| CN114478275B (en) * | 2020-10-27 | 2024-01-16 | 中石化南京化工研究院有限公司 | High-temperature-resistant clay stabilizer and preparation method thereof |
| CN114989799B (en) * | 2022-07-18 | 2022-10-25 | 华巍博大(北京)科技有限公司 | Oligomeric cationic shrinking and swelling agent composition, oligomeric cationic shrinking and swelling agent, and preparation method and application thereof |
Citations (4)
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|---|---|---|---|---|
| US4580633A (en) * | 1983-12-21 | 1986-04-08 | Union Oil Company Of California | Increasing the flow of fluids through a permeable formation |
| WO2006013596A1 (en) * | 2004-08-06 | 2006-02-09 | Lamberti S.P.A. | Shale inhibitors for the petroleum industry |
| CN1786103A (en) * | 2005-10-18 | 2006-06-14 | 中国石油大学(华东) | Clay anti expansion agent for high temperature acidification |
| CN104418984A (en) * | 2013-09-04 | 2015-03-18 | 中国石油化工股份有限公司 | High-temperature resistant clay stabilizer and preparation method thereof |
-
2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4580633A (en) * | 1983-12-21 | 1986-04-08 | Union Oil Company Of California | Increasing the flow of fluids through a permeable formation |
| WO2006013596A1 (en) * | 2004-08-06 | 2006-02-09 | Lamberti S.P.A. | Shale inhibitors for the petroleum industry |
| CN1786103A (en) * | 2005-10-18 | 2006-06-14 | 中国石油大学(华东) | Clay anti expansion agent for high temperature acidification |
| CN104418984A (en) * | 2013-09-04 | 2015-03-18 | 中国石油化工股份有限公司 | High-temperature resistant clay stabilizer and preparation method thereof |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Co-patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Patentee after: China Petroleum & Chemical Corp. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Co-patentee before: Nanhua Group Research Institute Patentee before: China Petroleum & Chemical Corp. |
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