CN106608949A - Clay stabilizer and preparation method thereof - Google Patents
Clay stabilizer and preparation method thereof Download PDFInfo
- Publication number
- CN106608949A CN106608949A CN201510700012.XA CN201510700012A CN106608949A CN 106608949 A CN106608949 A CN 106608949A CN 201510700012 A CN201510700012 A CN 201510700012A CN 106608949 A CN106608949 A CN 106608949A
- Authority
- CN
- China
- Prior art keywords
- clay stabilizer
- preparation
- clay
- initiator
- stabilizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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 invention relates to a clay stabilizer and a preparation method thereof. Epichlorohydrin, dimethylamine, allyltrimethylammonium chloride and gamma-(methacryloyloxy)propyltrimethoxysilane undergo a reaction under action of an initiator and a hydrolysis inhibitor for hydrolysis inhibition to produce the clay stabilizer. The clay stabilizer is injected into a stratum and then undergoes a hydrolysis reaction to produce a silicon hydroxyl group for a condensation reaction with stratum clay so that clay hydration expansion and dispersion transfer are controlled, anti-swelling effects are good and molecular weight is low. The clay stabilizer is suitable for a 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 flooding and prevents swollen field.
Background technology
Contain a certain amount of clay mineral in stratum, mainly have kaolinite, montmorillonite, illite and chlorite etc., in oilfield development process（Water filling, acidifying, pressure break）Will expand when these clays run into secondary water or water-based material, disperse, migrating, blocking hole throat, causing in-place permeability to reduce, for hypotonic rate oil reservoir destroys even more serious.In order to mitigate to reservoir damage, clay stabilizer is commonly incorporated in oil field to improve hydration swelling, the dispersion migration of clay.
Can be divided into according to the different clay stabilizers of chemical constitution：Inorganic salts, inorganic many nuclear polymer classes, organic polymer species.
Inorganic salts clay stabilizer has cheap, and short-term preventive effect of expansion is good；Have the disadvantage that multipoint adsorption can not be formed, timeliness is short.
Inorganic many nuclear polymer classes 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 for the high sandstone formation of carbonate content.
Organic polymer species are the most commonly used class clay stabilizers of research.At present, this kind of clay stabilizer using most for organic cation type polymer.This kind of clay stabilizer again based on polyquarternium-type, such as：PDDA, poly- trimethylallylammonium chloride, PAMC etc..Such clay stabilizer has the advantages that heatproof, acidproof, effect duration are long.The organic clay stabilizerses majority for using at present is straight chain type, and easy centering low permeability formation hole throat results in blockage when molecular weight is big, and molecular weight hour preventive effect of expansion is poor, and effect duration is short.
Although existing clay stabilizer has to a certain extent the ability of certain clay stabilization, long-lasting and in middle LOW PERMEABILITY RESERVOIR use Shortcomings.
The content of the invention
Present invention aims to the deficiencies in the prior art, there is provided a kind of clay stabilizer and its preparation technology.
What the purpose of the present invention was achieved through the following technical solutions：
A kind of structural formula of clay stabilizer of the present invention is as follows：
In formula, x, y, z are the integer more than 0；Molecular weight is 4000-12000.
A kind of preparation method of clay stabilizer, it is characterized in that by epoxychloropropane, dimethylamine, pi-allyl trimethyl ammonium chloride, γ-（Methacryloxypropyl）Propyl trimethoxy silicane is obtained by the initiation reaction of initiator, and adds hydrolysis inhibitor during the course of the reaction.
The preparation method of described a kind of clay stabilizer, it is characterised in that with monomer total amount as 1, the mass percent of each monomer is：Epoxychloropropane 60～70%；Dimethylamine 21～38%, pi-allyl trimethyl ammonium chloride 4～8%, γ-（Methacryloxypropyl）Propyl trimethoxy silicane 2～6%, is finally made into the aqueous solution that monomer gross mass percentage concentration is 30%～55%.
A kind of preparation method of described clay stabilizer, it is characterised in that：Initiator is water miscible azo-initiator, hydrogen peroxide, ammonium persulfate-sodium bisulfite redox system or potassium peroxydisulfate-sodium sulfite redox system, and initiator addition is the 0.1～3.0% of monomer gross mass.
The preparation method of described a kind of clay stabilizer, it is characterised in that initiator is ammonium persulfate-sodium bisulfite redox system, sodium sulfite is 1 with Ammonium persulfate. mol ratio:1.0～1.3.
The preparation method of described a kind of clay stabilizer, it is characterised in that sodium sulfite is 1 with Ammonium persulfate. mol ratio:1.2.
A kind of preparation method of described clay stabilizer, it is characterised in that：Hydrolysis inhibitor used is butyl, and addition is 0. 1～the 3.0% of monomer gross mass.
The silicone hydroxyl that Jing is hydrolyzed to form behind the clay stabilizer injection stratum that the present invention is provided can occur condensation reaction with stratum clay, and the hydration swelling for controlling clay is good with dispersion migration, preventive effect of expansion, and molecular weight is low, it is adaptable to low permeability reservoir.
Specific embodiment
In order to be better understood from the present invention, the content of invention is further elucidated with reference to embodiment, but present disclosure is not limited only to the following examples.
Embodiment 1
Add 60.0g epoxychloropropane, temperature of reactor to control at 20 DEG C in reactor, add dimethylamine agueous solution and 4.0g pi-allyl trimethyl ammonium chlorides that 52.5g mass fractions are 40%, 6.0g γ-（Methacryloxypropyl）Propyl trimethoxy silicane, 1.0g butyl, 59.5g water, it is passed through in reactor after nitrogen 30min and adds the sodium sulfite of 0.55g, 1.35g Ammonium persulfate .s are added after 3min, 2～8h is reacted in the case where temperature is for 40 DEG C, reaction is finished and obtains a kind of clay stabilizer, the molecular weight of the clay stabilizer is 5000.
Embodiment 2
Add 65.0g epoxychloropropane, temperature of reactor to control at 20 DEG C in reactor, add dimethylamine agueous solution and 6.0g pi-allyl trimethyl ammonium chlorides that 60.0g mass fractions are 40%, 2.0g γ-（Methacryloxypropyl）Propyl trimethoxy silicane, 1.2g butyl, 206.5g water, it is passed through in reactor after nitrogen 30min and adds the sodium sulfite of 0.55g, 1.35g Ammonium persulfate .s are added after 3min, 2～8h is reacted in the case where temperature is for 40 DEG C, reaction is finished and obtains a kind of clay stabilizer, the molecular weight of the clay stabilizer is 8000.
Embodiment 3
Add 70.0g epoxychloropropane, temperature of reactor to control at 20 DEG C in reactor, add dimethylamine agueous solution and 4.0g pi-allyl trimethyl ammonium chlorides that 95.0g mass fractions are 40%, 2.0g γ-（Methacryloxypropyl）Propyl trimethoxy silicane, 1.2g butyl, 57.0g water, it is passed through in reactor after nitrogen 30min and adds the sodium sulfite of 0.99g, 2.43g Ammonium persulfate .s are added after 3min, 2～8h is reacted in the case where temperature is for 40 DEG C, reaction is finished and obtains a kind of clay stabilizer, the molecular weight of the clay stabilizer is 12000.
Embodiment 4
Add 60.0g epoxychloropropane, temperature of reactor to control at 20 DEG C in reactor, add dimethylamine agueous solution and 8.0g pi-allyl trimethyl ammonium chlorides that 95.0g mass fractions are 40%, 4.0g γ-（Methacryloxypropyl）Propyl trimethoxy silicane, 1.2g butyl, 218.0g water, it is passed through in reactor after nitrogen 30min and adds the sodium sulfite of 0.99g, 2.43g Ammonium persulfate .s are added after 3min, 2～8h is reacted in the case where temperature is for 40 DEG C, reaction is finished and obtains a kind of clay stabilizer, the molecular weight of the clay stabilizer is 6000.
Embodiment 5
0.5g clay stabilizer samples are weighed, 100g is added water to, it is 0.5% clay stabilization agent solution to be made into concentration, according to China National Petroleum industry standard《Water filling clay stabilizer method of evaluating performance SY/T1994 (2002)》, the preventive effect of expansion of the sample under room temperature and Jing after 200 DEG C of heat rolling 24h is tested, test result is shown in Table 1.
The anti-swollen result of the clay stabilizer of table 1
。
Embodiment 6
0.5g clay stabilizer samples are weighed, 100g is added water to, it is 0.5% clay stabilization agent solution to be made into concentration, according to company standard《Q/SH 0053-2010 clay stabilizer technical requirements》Carry out water-fastness rate performance test to sample at room temperature, test result is shown in Table 2.
The above results show that clay stabilizer prepared by the present invention has good heatproof, the ability of water-fastness and good suppression clay swell.
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 more than 0；Molecular weight is 4000-12000.
2. a kind of preparation method of clay stabilizer, it is characterized in that by epoxychloropropane, dimethylamine, pi-allyl trimethyl ammonium chloride, γ-（Methacryloxypropyl）Propyl trimethoxy silicane is obtained by the initiation reaction of initiator, and adds hydrolysis inhibitor during the course of the reaction.
3. the preparation method of clay stabilizer as claimed in claim 2, it is characterised in that with monomer total amount as 1, the mass percent of each monomer is：Epoxychloropropane 60～70%；Dimethylamine 21～38%, pi-allyl trimethyl ammonium chloride 4～8%, γ-（Methacryloxypropyl）Propyl trimethoxy silicane 2～6%, is finally 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 miscible azo-initiator, hydrogen peroxide, ammonium persulfate-sodium bisulfite redox system or potassium peroxydisulfate-sodium sulfite redox system, and initiator addition 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-sodium bisulfite redox system, sodium sulfite is 1 with Ammonium persulfate. mol ratio:1.0～1.3.
6. the preparation method of clay stabilizer as claimed in claim 5, it is characterised in that sodium sulfite is 1 with Ammonium persulfate. mol ratio:1.2.
7. the preparation method of clay stabilizer as claimed in claim 2, it is characterised in that：Hydrolysis inhibitor used is butyl, and addition is the 0.1～3.0% of monomer gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510700012.XA CN106608949B (en) | 2015-10-26 | 2015-10-26 | A kind of clay stabilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510700012.XA CN106608949B (en) | 2015-10-26 | 2015-10-26 | A kind of clay stabilizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106608949A true CN106608949A (en) | 2017-05-03 |
| CN106608949B CN106608949B (en) | 2019-02-22 |
Family
ID=58613244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510700012.XA Active CN106608949B (en) | 2015-10-26 | 2015-10-26 | A kind of clay stabilizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106608949B (en) |
Cited By (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 | Salt-tolerant clay stabilizer for preparing fracturing fluid from oilfield effluent and preparation method thereof |
| CN109054798A (en) * | 2018-07-13 | 2018-12-21 | 中国石油大学(华东) | A kind of preparation method of oil field high temperature clay stabilizer |
| CN114426618A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Polymer type high-temperature-resistant anti-swelling and anti-shrinking agent and preparation method and application thereof |
| CN114478275A (en) * | 2020-10-27 | 2022-05-13 | 中石化南京化工研究院有限公司 | High-temperature-resistant clay stabilizer and preparation method thereof |
| CN114989799A (en) * | 2022-07-18 | 2022-09-02 | 华巍博大(北京)科技有限公司 | Oligomeric cationic type shrinkage-swelling agent composition, oligomeric cationic type shrinkage-swelling agent, and preparation method and application thereof |
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 |
-
2015
- 2015-10-26 CN CN201510700012.XA patent/CN106608949B/en active Active
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 |
Cited By (9)
| 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 | Salt-tolerant clay stabilizer for preparing fracturing fluid from oilfield effluent and preparation method thereof |
| CN109054798A (en) * | 2018-07-13 | 2018-12-21 | 中国石油大学(华东) | A kind of preparation method of oil field high temperature clay stabilizer |
| 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 |
| CN114426618A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Polymer type high-temperature-resistant anti-swelling and anti-shrinking agent and preparation method and application thereof |
| 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 |
| CN114478275A (en) * | 2020-10-27 | 2022-05-13 | 中石化南京化工研究院有限公司 | High-temperature-resistant clay stabilizer and preparation method 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 |
| CN114989799A (en) * | 2022-07-18 | 2022-09-02 | 华巍博大(北京)科技有限公司 | Oligomeric cationic type shrinkage-swelling agent composition, oligomeric cationic type shrinkage-swelling agent, and preparation method and application 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106608949B (en) | 2019-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104418984B (en) | High-temperature resistant clay stabilizer and preparation method thereof | |
| CN106608949A (en) | Clay stabilizer and preparation method thereof | |
| CN106883357B (en) | A kind of pre-crosslinked gel delays swollen microballoon profile control agent and its preparation method and application | |
| CN104449631B (en) | Strong gas wettability nano silicon Xie Shui locks the method for agent, its preparation method and rock surface wettability reversal | |
| CN106479465B (en) | Profile control water shutoff agent and preparation method and application thereof | |
| CN103074050B (en) | A kind of high shale content sandstone reservoir scale protective type many hydrogen retarded acid | |
| CN106188403B (en) | A kind of anti-CO of high temperature and high salt oil deposit2Has channeling blocking agent and preparation method thereof | |
| CN104098738B (en) | A kind of low-molecular-weight clay stabilizer preparation method | |
| CN104449599A (en) | Anti-swelling agent for clay | |
| CN109868126B (en) | Water plugging agent and preparation method and application thereof | |
| CN105754579A (en) | Clay anti-swelling and swelling shrinkage agent and preparation method thereof | |
| CN105505341A (en) | Clay anti-swelling agent | |
| CN110358510B (en) | Strong-sensitive anti-swelling inhibitor for continental facies shale and preparation method thereof | |
| CN108690599B (en) | Erosion acidizing fluid for clay minerals and preparation method thereof | |
| CN103773328A (en) | Clay anti-swelling stabilizer as well as preparation method and application thereof | |
| CN107573918B (en) | Oil reservoir deep full-liquid-phase gas flow diverter and preparation method thereof | |
| CN104140801B (en) | A kind of alumina gel profile control agent and preparation method thereof | |
| CN106987240B (en) | Anti-swelling clay stabilizer for water injection of low-permeability oil reservoir and preparation method thereof | |
| CN109294540B (en) | High-salinity-resistant profile control agent for deep oil reservoir and preparation method thereof | |
| Heidari et al. | Determination of swelling behavior and mechanical and thermal resistance of acrylamide–acrylic acid copolymers under high pressures and temperatures | |
| CN113136185A (en) | Organic water plugging gel for low-temperature hypersalinity oil reservoir | |
| CN108048057B (en) | Profile control agent and profile control method | |
| CN107619660B (en) | Gelled acid thickener and preparation method thereof | |
| CN113088265B (en) | High-temperature-resistant efficient clay stabilizer | |
| CN103641798B (en) | A kind of preparation method of cross-linking agent and crosslinking controllable high-temperature-resgelant gelant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
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. |