CN103467301A - Method for preparing small-molecular-weight Gemini cation-type anti-swelling agent for low-permeability reservoir - Google Patents
Method for preparing small-molecular-weight Gemini cation-type anti-swelling agent for low-permeability reservoir Download PDFInfo
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- CN103467301A CN103467301A CN2013104534817A CN201310453481A CN103467301A CN 103467301 A CN103467301 A CN 103467301A CN 2013104534817 A CN2013104534817 A CN 2013104534817A CN 201310453481 A CN201310453481 A CN 201310453481A CN 103467301 A CN103467301 A CN 103467301A
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Abstract
The invention relates to cation-type anti-swelling agents, in particular to a method for preparing a small-molecular-weight Gemini cation-type anti-swelling agent for a low-permeability reservoir. Saturated dihalide and tertiary alkyl are selected, wherein the molar ratio of the saturated dihalide and the tertiary alkyl is 1:2-1:3. Under the reaction pressure of 0-0.30MPa, at the reaction temperature of 90 DEG C-150DEG C and under the condition of phase transfer catalysts, the saturated dihalide and the tertiary alkyl are synthesized to obtain the Gemini cation-type anti-swelling agent with the molecular weight being 200-1000. Compared with the prior art, the small-molecular-weight Gemini cation-type anti-swelling agent for the low-permeability reservoir has the advantages that the molecular weight of the Gemini cation-type anti-swelling agent is small and within the range of 200-1000, and the anti-swelling agent cannot reduce the permeability of the low-permeability reservoir; in addition, due to the fact that the molecular structure of the Gemini cation-type anti-swelling agent is in the shape of Gemini, one molecule contains two cation hydrophilic groups, adsorbing capacity on reservoir clay is strong, the clay is strongly restrained from hydrating and swelling, storage-layer fluid and external liquid cannot flush the Gemini cation-type anti-swelling agent down and bring the Gemini cation-type anti-swelling agent away easily, and the stabilizing effect to the clay is enduring.
Description
Technical field
the present invention relates to cationic expansion-resisting agent, particularly a kind of LOW PERMEABILITY RESERVOIR with the Shuangzi sun of small molecules amount the preparation method from formula type expansion-resisting agent.
Background technology
in recent years, along with progressively going deep into of oil field prospecting, exploitation, LOW PERMEABILITY RESERVOIR becomes important development field.Hypotonic, special LOW PERMEABILITY RESERVOIR has the characteristics such as Reservoir Permeability is low, pore constriction is little, reservoir poor properties, sensitive minerals content is high, susceptibility is strong, and the prevention oil reservoir is one of gordian technique of crude oil production because clay swelling causes zone permeability to reduce.Prevent that the clay swelling in LOW PERMEABILITY RESERVOIR from being to use anti-clayswelling agent with the common method of migration injury rate of permeation.Because low permeability pay pore throat radius, rate of permeation are low, the cationic clay expansion-resisting agent that relative molecular weight is large often seriously reduces the rate of permeation of low-permeability oil deposit, therefore the anti-clayswelling agent of small molecules amount has played and has prevented clay swelling and migration in the development of low-permeability oil reservoir process, keeps the effect of Reservoir Permeability.
just begin one's study and use dissimilar anti-clayswelling agent as far back as the late 1950s people.As important Oilfield Chemicals, the development of anti-clayswelling agent is organic cation till now from initial inorganic salts.Disclosed a kind of clay antiswelling agent for petroleum extraction of PetroChina Company Ltd. and preparation method thereof (CN101921366) is by diallyl ammonium chloride and three synthetic side chain cationic polymers expansion-resisting agents of triallyl ammonium chloride; The disclosed a kind of clay anti expansion agent for high temperature acidification of China Petroleum Univ. (East-China) (CN1786103) is by epoxypropyltrimethylchloride chloride and the synthetic siliceous positively charged ion expansion-resisting agent of gamma-amino propyl triethoxy silicomethane; The disclosed a kind of expansion-resisting agent of Tianjin Coudé scholar development in science and technology company limited and production technique (CN102786924) thereof are by the composite expansion-resisting agent formed of cationic polymers; The patent (US2010210484) of INNOVATIVE CHEMZCAL TECHNOLOGI application is the polyquaternium expansion-resisting agent of different molecular weight.
Summary of the invention
the purpose of this invention is to provide the small molecules amount Shuangzi cationic clay expansion-resisting agent preparation method that a kind of low-permeability oil deposit is used, this expansion-resisting agent is for water filling, pressure break, acidifying and well control fluid, prevent reservoir medium clay soil expansion migration, reduce LOW PERMEABILITY RESERVOIR permeability injury degree.
the present invention adopts following technical scheme:
the preparation method of the small molecules amount Shuangzi cationic clay expansion-resisting agent that a kind of low-permeability oil deposit is used, the mol ratio of saturated dihalide and tertiary alkane is 1:2～3; At reaction pressure 0～0.30MPa, 90 ℃～150 ℃ of temperature of reaction, it is synthetic under the phase-transfer catalyst condition that to obtain molecular weight be the cationic expansion-resisting agent of 200～1000 Shuangzi.
adopt the present invention of technique scheme compared with prior art, advantage is: its molecular weight, in 200～1000 scopes, expansion-resisting agent can not cause the reduction of rate of permeation to LOW PERMEABILITY RESERVOIR.In addition because its molecular structure is double type, contain two cationic hydrophilic groups in a molecule, adsorptive power on the oil reservoir clay is very strong, strongly inhibited hydration and expansion of clay not only, and reservoir fluid and external liquid is difficult to it is rinsed and takes away, to the effect of clay stabilization, be lasting; Expansion-resisting agent of the present invention anti-swollen rate at normal temperatures can reach 90%, to the LOW PERMEABILITY RESERVOIR rate of permeation without injury, high-temperature resistance is strong, under 150 ℃, anti-swollen rate can reach 87.5%, there is good compatibleness with local water, can be used for the aspects such as water filling, pressure break, perforating fluid, acidifying and well control fluid of LOW PERMEABILITY RESERVOIR.
preferred version of the present invention is:
saturated dihalide is 1.2-ethylidene periodide, 1.2-ethylene dibromide, 1.4-dibromobutane or 1.4-dichlorobutane.
tertiary amine is Trimethylamine 99, triethylamine, trolamine or N, N-xylidine.
phase-transfer catalyst is Macrogol 200, poly(oxyethylene glycol) 400, Tetrabutyl amonium bromide, tetrabutylammonium chloride or picoline.
Embodiment
below in conjunction with specific embodiment, the present invention will be further described.
embodiment 1
in the 500ml there-necked flask, add 120ml distilled water, 0.20g Tetrabutyl amonium bromide and 15.0g N, N-xylidine, be warming up to 95 ℃, drips 16.2g1.2-ethylidene periodide.Under atmospheric pressure state, the 102 ℃ of back flow reaction 12h that heat up, regulate pH value 8～9 with 5%NaOH solution (mass ratio), obtain brown liquid, be the cationic expansion-resisting agent of Shuangzi, active principle is N, N '-tetramethyl-phenylbenzene two iodate second two ammoniums, molecular weight is 516.
embodiment 2
in the 500ml there-necked flask, add 150ml distilled water, 1.5g polyoxyethylene glycol and 45.5g trimethylamine aqueous solution (36%), be warming up to 80 ℃, drips 25.0g1.4-dibromobutane, after dropwising.Under atmospheric pressure state, be warming up to 100～105 ℃ of lower back flow reaction 8～9h, regulate material pH value 8～9 with 5% hydrochloric acid soln (mass ratio), then at 100～105 ℃ of lower back flow reaction 4h, obtain the light brown transparent liquid, be the cationic expansion-resisting agent of Shuangzi, active principle is N, N '-hexamethyl bromination fourth two ammoniums, molecular weight is 275.
embodiment 3
in 500ml magnetic agitation pressure reactor, add 120ml distilled water, 0.30g Tetrabutyl amonium bromide and 28.5g trolamine, drip 17.0g1.4-dibromobutane at 80～85 ℃, after dropwising, at 120～125 ℃, pressure is to react 6h under 0.15～0.20MPa, be cooled to 80～90 ℃, unload after normal pressure, regulate material pH value 8～9 with 5%NaOH solution (mass ratio), then be warming up to 120～125 ℃, pressure is 0.15～0.20MPa, lower reaction 4h.Be cooled to 40～50 ℃, regulating the material pH value is 8, obtains light yellow transparent liquid, is the cationic expansion-resisting agent of Shuangzi, and active principle is N, N '-six ethanol based bromination fourth two ammoniums, and molecular weight is 365.
embodiment 4
in 500ml magnetic agitation pressure reactor, add 120ml distilled water, 2.5g poly(oxyethylene glycol) 400 and the 137g trolamine aqueous solution (40% quality is than the aqueous solution), drip 30.0g1.4-dichlorobutane at 85～95 ℃, after dropwising, be warming up to 115～125 ℃, pressure 0.10～0.15MPa, lower reaction, 10h, then be cooled to room temperature, regulating the material pH value with 5% hydrochloric acid soln is 8, obtains light yellow transparent liquid, be the cationic expansion-resisting agent of Shuangzi, active principle is N, N '-Hexaethyl chlorination fourth two ammoniums, and molecular weight is 228.
experiment content:
1. anti-swollen rate experiment
according to PetroChina Company Limited.'s industry standard " SY/T5762-1995 fracture acidizing clay stabilizer method of evaluating performance ", measured the anti-clayswelling rate of four embodiment Shuangzi positively charged ion expansion-resisting agents.
as can be seen from Table 1, the cationic expansion-resisting agent of Shuangzi of the present invention all is greater than 80% in room temperature and 150 ℃ of lower clay swell rates.
table 1 carries out the experiment of anti-clayswelling rate with the cationic expansion-resisting agent of Shuangzi of the present invention
2. antiscour experiment
initially: clay is surveyed expansion height by centrifuging after adding the abundant aquation of expansion-resisting agent, calculates anti-swollen rate.
～5 times: the solution after centrifugal is discarded to supernatant liquor, add after distilled water and again stir, aging, centrifugal, survey anti-swollen rate.
table 2 data can find out, the cationic expansion-resisting agent preventive effect of expansion of Shuangzi of the present invention is good, and after having replaced with clay, abrasion resistance is fine.
table 2 carries out the scour resistance experiment with the cationic expansion-resisting agent of Shuangzi of the present invention
| Wash away number of times | Initially | 1 time | 2 times | 3 times | 4 times | 5 times |
| Anti-swollen rate | 87.5% | 87.5% | 84.7% | 88.5% | 88.5% | 88.5% |
3. core damage experiment
carried out the formation damage experiment with the hypotonic storage in above-mentioned anti-clayswelling agent and Ji Dong oil field fort, south, experimentation is: with find time saturated core invade bubble 24 hours of local water, then survey rock core local water rate of permeation; Then in rock core, inject the injected water 5PV containing this expansion-resisting agent, survey the rate of permeation of rock core.Experimental result is in Table 3, and the injury rate of rock core is lower, and the expansion-resisting agent effect is better.
table 3 carries out the experiment of low permeability formation core damage with small molecules anti-clayswelling agent of the present invention
4. with of the fracturing fluid compatibleness experiment
the compatibleness of this expansion-resisting agent and fracturing fluid system: this expansion-resisting agent is added in the pressure break system after stirring in the RS6000 rotational rheometer of packing into, and to the sample heating, controlling temperature is 120 ± 0.2 ℃/min, controls rotor with shearing rate 170s
-1
rotate, sample is sheared continuously and is degraded under heating condition, and when apparent viscosity is reduced to 50mPas, corresponding shear time is as the constant temperature cutting performance of sample, the conservation rate of viscosity is higher, impact on the pressure break system is less, and expansion-resisting agent of the present invention is on the pressure break system without impact, and compatibleness is good.
above disclosed be only specific embodiments of the invention; although the present invention has disclosed the present invention with preferred embodiment; but the present invention is not limited thereto; any those skilled in the art is not within breaking away from essential scope of the present invention; the present invention is carried out to various changes, all be considered as within protection scope of the present invention.
Claims (4)
1. the preparation method of the cationic expansion-resisting agent of Shuangzi of small molecules amount for a LOW PERMEABILITY RESERVOIR, it is characterized in that: choose saturated dihalide and tertiary alkane, both mol ratios are 1:2～3; At reaction pressure 0～0.30MPa, 90 ℃～150 ℃ of temperature of reaction, it is synthetic under the phase-transfer catalyst condition that to obtain molecular weight be the cationic expansion-resisting agent of 200～1000 Shuangzi.
2. the preparation method of the cationic expansion-resisting agent of Shuangzi of small molecules amount for LOW PERMEABILITY RESERVOIR according to claim 1, it is characterized in that: saturated dihalide is 1.2-ethylidene periodide, 1.2-ethylene dibromide, 1.4-dibromobutane or 1.4-dichlorobutane.
3. the preparation method of the cationic expansion-resisting agent of Shuangzi of small molecules amount for LOW PERMEABILITY RESERVOIR according to claim 1, it is characterized in that: tertiary amine is Trimethylamine 99, triethylamine, trolamine or N, N-xylidine.
4. the preparation method of the cationic expansion-resisting agent of Shuangzi of small molecules amount for LOW PERMEABILITY RESERVOIR according to claim 1, it is characterized in that: phase-transfer catalyst is Macrogol 200, poly(oxyethylene glycol) 400, Tetrabutyl amonium bromide, tetrabutylammonium chloride or picoline.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119854A (en) * | 2014-08-01 | 2014-10-29 | 青岛蓬勃石油技术服务有限公司 | Anti-swelling clay stabilizer and preparation method thereof |
| CN105017032A (en) * | 2015-03-27 | 2015-11-04 | 河南维诺生物科技有限公司 | Organic diammonium compound, as well as synthetic method and use thereof |
| CN105885815A (en) * | 2016-04-20 | 2016-08-24 | 河南省科学院高新技术研究中心 | Method for preparing gemini surfactant by one-pot method |
| JP2018035121A (en) * | 2016-09-02 | 2018-03-08 | 東ソー株式会社 | Cationic gemini type surfactant |
| CN111100290A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Vegetable oil asphalt cation amide resin with double functions of anti-swelling and sand control |
| CN111808598A (en) * | 2020-08-26 | 2020-10-23 | 肯特催化材料股份有限公司 | Clay anti-swelling agent |
| CN112745233A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Small-molecule clay stabilizer suitable for low-permeability oil reservoir and preparation method thereof |
| CN112969771A (en) * | 2018-10-31 | 2021-06-15 | 沙特阿拉伯石油公司 | Additive for oil and gas drilling and production |
| CN115232016A (en) * | 2022-09-23 | 2022-10-25 | 江苏富淼科技股份有限公司 | Clay anti-swelling agent solution and preparation method thereof |
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| CN101279219A (en) * | 2008-01-03 | 2008-10-08 | 天津师范大学 | Bis-quaternary ammonium salt cationic surfactant, preparation and use thereof |
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| CN101279219A (en) * | 2008-01-03 | 2008-10-08 | 天津师范大学 | Bis-quaternary ammonium salt cationic surfactant, preparation and use thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119854A (en) * | 2014-08-01 | 2014-10-29 | 青岛蓬勃石油技术服务有限公司 | Anti-swelling clay stabilizer and preparation method thereof |
| CN105017032A (en) * | 2015-03-27 | 2015-11-04 | 河南维诺生物科技有限公司 | Organic diammonium compound, as well as synthetic method and use thereof |
| CN105885815A (en) * | 2016-04-20 | 2016-08-24 | 河南省科学院高新技术研究中心 | Method for preparing gemini surfactant by one-pot method |
| CN105885815B (en) * | 2016-04-20 | 2018-09-04 | 河南省科学院高新技术研究中心 | A method of preparing Gemini surface active agent |
| JP2018035121A (en) * | 2016-09-02 | 2018-03-08 | 東ソー株式会社 | Cationic gemini type surfactant |
| CN111100290B (en) * | 2018-10-25 | 2022-07-19 | 中国石油化工股份有限公司 | Vegetable oil asphalt cation amide resin with double functions of anti-swelling and sand control |
| CN111100290A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Vegetable oil asphalt cation amide resin with double functions of anti-swelling and sand control |
| CN112969771A (en) * | 2018-10-31 | 2021-06-15 | 沙特阿拉伯石油公司 | Additive for oil and gas drilling and production |
| CN112745233A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Small-molecule clay stabilizer suitable for low-permeability oil reservoir and preparation method thereof |
| CN111808598A (en) * | 2020-08-26 | 2020-10-23 | 肯特催化材料股份有限公司 | Clay anti-swelling agent |
| CN111808598B (en) * | 2020-08-26 | 2022-05-20 | 肯特催化材料股份有限公司 | Clay anti-swelling agent |
| CN115232016A (en) * | 2022-09-23 | 2022-10-25 | 江苏富淼科技股份有限公司 | Clay anti-swelling agent solution and preparation method thereof |
| CN115232016B (en) * | 2022-09-23 | 2022-12-20 | 江苏富淼科技股份有限公司 | Clay anti-swelling agent solution and preparation method thereof |
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Application publication date: 20131225 |