CN106631897A - Amidino surfactant with CO2 and N2 switches and preparation method thereof - Google Patents

Amidino surfactant with CO2 and N2 switches and preparation method thereof Download PDF

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Publication number
CN106631897A
CN106631897A CN201611179105.3A CN201611179105A CN106631897A CN 106631897 A CN106631897 A CN 106631897A CN 201611179105 A CN201611179105 A CN 201611179105A CN 106631897 A CN106631897 A CN 106631897A
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China
Prior art keywords
surfactant
switches
preparation
amidino groups
amidino
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CN201611179105.3A
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Chinese (zh)
Inventor
苏俊霖
董汶鑫
邓明毅
周素林
刘路漫
卢俊锋
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Southwest Petroleum University
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Southwest Petroleum University
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Priority to CN201611179105.3A priority Critical patent/CN106631897A/en
Publication of CN106631897A publication Critical patent/CN106631897A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
    • 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
    • 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
    • C09K8/38—Gaseous or foamed well-drilling compositions

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses an amidino surfactant with CO2 and N2 switches and a preparation method thereof, wherein the amidino surfactant with the CO2 and N2 switches is hexadecyl dimethyl acetamidine. The preparation method comprises the following steps of taking and adding 0.01mol of hexadecylamine into a three-mouth flask with an agitator, a reflux condenser and a thermometer, and heating and agitating the hexadecylamine; adding 12mL of dried chloroform into the flask, dropwise adding 0.03mol of already dried dimethyl acetamide into the flask, making an obtained first mixture react for 15 hours, and setting a temperature to be 65 DEG C; dropwise adding phosphorus trichloride into the flask, keeping an obtained second mixture weakly acidic, stopping dropwise adding the phosphorus trichloride, then refluxing and making the second mixture react for 13 hours, and terminating the reaction; carrying out reduced pressure distillation to remove a solvent, recrystallizing an obtained third mixture by using absolute ethyl alcohol, thermally filtering an obtained fourth mixture, and then carrying out rotary evaporation to obtain a light-yellow solid, that is, a product. The selected amidino surfactant with the CO2 and N2 switches is used as a foaming agent for foam drilling fluid; the foaming and the defoaming can be artificially controlled by utilizing the CO2 and N2 switches; the CO2 and N2 switches can be recycled; moreover, CO2 and N2 are green and environment-friendly switches.

Description

A kind of amidino groups CO2And N2Switch surfactant and preparation method thereof
Technical field
The invention belongs to drilling liquid technology field, more particularly to a kind of amidino groups CO2And N2Switch surfactant and its preparation Method.
Background technology
Aerated fluid drilling fluid has become at present a kind of main flow drilling fluid of under balance pressure drilling application, is provided simultaneously with low close The three big advantages such as degree, good foam performance and high circulation.However, because strata condition is complicated, scene carries to spumescence drilling fluid Higher requirement is gone out, such as：Quick foaming, froth breaking, good large rock-carrying ability and the characteristic such as little to formation damage.Quickly bubbling is In order to reduce the density of drilling fluid, accelerate drilling speed；Meanwhile, possessing good antifoam performance again, such oil pump could be past again Pit shaft injects pressure, produces new bubble；In order to the landwaste in shaft bottom is carried out, not so it is that requirement possesses good large rock-carrying ability Bit freezing, drilling well can be caused to carry out；Surfactant Chemistry toxicity is high, although using effect good, environment can be produced Harm, and reservoir is damaged, on the one hand infringement reservoir is because that some surfactants can block hole, reduces reservoir infiltration Property, on the other hand it is because that surfactant can change reservoir wettability drop low oil flow permeability.But usual foam fluid can not Meet these requirements simultaneously.
In sum, usual foam fluid presence foaming, foam time are long, and large rock-carrying ability is poor, to reservoir and environmental hazard Big defect.
The content of the invention
It is an object of the invention to provide a kind of amidino groups CO2And N2Switch surfactant and preparation method thereof, it is intended to solve The presence foaming of usual foam fluid, foam time are long, and large rock-carrying ability is poor, the problem big to reservoir and environmental hazard.
The present invention is achieved in that a kind of amidino groups CO2And N2Switch surfactant, the amidino groups CO2And N2Switch list Face activating agent be hexadecyldimethyl benzyl ammonium ethanamidine, structural formula：
Another object of the present invention is to provide a kind of amidino groups CO2And N2The preparation method of switch surfactant, institute State amidino groups CO2And N2The preparation method of switch surfactant is comprised the following steps：
Step one, takes 0.01mol cetylamines and adds in the there-necked flask with stirring, reflux condensation mode and thermometer, starts Heating and stirring；The chloroform for adding 12mL dried, after backflow starts, at a temperature of maintaining the reflux for after stirring a period of time, starts The DMA that 0.03mol has been dried is added dropwise, is reacted 15 hours, temperature is set in 65 DEG C；
Step 2, is added dropwise phosphorus trichloride, the pH value of real-time testing system so that system maintains faintly acid, stops being added dropwise, Again back flow reaction 13 hours, terminate reaction；
Step 3, vacuum distillation removes solvent, is recrystallized with absolute ethyl alcohol, light yellow solid is rotated to obtain after heat filtering, i.e., For product.
Further, the amidino groups CO2And N2The reaction mechanism of preparation method of switch surfactant is：
Another object of the present invention is to provide one kind by the amidino groups CO2And N2Drilling well prepared by switch surfactant Liquid.
The amidino groups CO that the present invention is provided2And N2Switch surfactant and preparation method thereof, the amidino groups CO of selection2And N2Open Surfactant is closed as foam drilling fluid foaming agent, foaming froth breaking can utilize CO2And N2Switch manual control.By injection CO2Gas makes hexadecyldimethyl benzyl ammonium ethanamidine be converted into hexadecyldimethyl benzyl ammonium ethanamidine bicarbonate, however, etradecyldimethylamine Base ethanamidine bicarbonate is a kind of good foaming agent of frothing capacity, then forms foam drilling fluid, and its schematic diagram is as follows； Afterwards, by injecting N2Drive away CO2Realize that reversible reaction eliminates bubble, and can recycle (by re-injecting CO2Again can be again Secondary generation hexadecyldimethyl benzyl ammonium ethanamidine bicarbonate, produces bubble), and CO2And N2It is a kind of environmental type switch.With with Past foam drilling fluid is compared, and the novel foam drilling fluid foaming speed of the present invention can be with manual control foaming and froth breaking, foaming Fast with antifoaming speed, recycling property is strong.
Description of the drawings
Fig. 1 is amidino groups CO provided in an embodiment of the present invention2And N2The preparation method flow chart of switch surfactant.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that specific embodiment described herein is not used to only to explain the present invention Limit the present invention.
Amidino groups CO provided in an embodiment of the present invention2And N2Switch surfactant is hexadecyldimethyl benzyl ammonium ethanamidine.Structure Formula：
As shown in figure 1, amidino groups CO provided in an embodiment of the present invention2And N2Switch surfactant preparation method include with Lower step：
S101：Take 0.01mol cetylamines to add in the there-necked flask with stirring, reflux condensation mode and thermometer, start to add Heat and stirring；The chloroform for adding 12mL dried, after backflow starts, at a temperature of maintaining the reflux for after stirring a period of time, starts drop Plus the DMA that 0.03mol has been dried, to react 12 hours, temperature is set in 65 DEG C；
S102：It is slowly added dropwise phosphorus trichloride, the pH value of real-time testing system so that system maintains faintly acid, stops drop Plus, then back flow reaction 13 hours, terminate reaction；
S103：Vacuum distillation removes solvent, is recrystallized with absolute ethyl alcohol, light yellow solid is rotated to obtain after heat filtering, as Product.
The application principle of the present invention is further described with reference to specific embodiment.
1 amidino groups CO2And N2Switch surfactant
Amidino groups CO2And N2Switch surfactant is a kind of foam drilling fluid foaming agent and defoamer, and it foams and froth breaking Characteristic passes through manual control CO2And N2Switch is changed, and can be recycled, and CO2And N2It is that a kind of environmental type is opened Close.The present invention has synthesized hexadecyldimethyl benzyl ammonium ethanamidine, a kind of novel amidino CO2And N2Switch surfactant.
The composition principle of 2 hexadecyldimethyl benzyl ammonium ethanamidines
The present invention combines evaporation and forms carbon-to-nitrogen double bon using carbonyl amine.Reaction mechanism is broadly divided into 2 steps：1. nucleophilic adds Into being 2. dehydrated.Synthetic route is：Cetylamine and dimethyl acetamide (below step 3 is the concrete steps of the synthesis) are raw material, Small molecule (H is sloughed Jing after nucleophilic addition2O) it is obtained.Reaction mechanism is：
3rd, the synthesis of hexadecyldimethyl benzyl ammonium ethanamidine
(1) 0.01mol cetylamines are taken to add in the there-necked flask with stirring, reflux condensation mode and thermometer, is begun to warm up And stirring.The chloroform for adding 12mL dried, after backflow starts, at a temperature of maintaining the reflux for after stirring a period of time, starts to be added dropwise The DMA that 0.03mol has been dried, reacts 15 hours, and temperature is set in 65 DEG C.
(2) phosphorus trichloride is slowly added dropwise, the pH value of real-time testing system (notes：PH value should not be tested after being just added dropwise, etc. Treat 10min) so that system maintains faintly acid, stop being added dropwise, then back flow reaction 13 hours, terminate reaction.
(3) vacuum distillation removes solvent, is recrystallized with absolute ethyl alcohol, and light yellow solid is rotated to obtain after heat filtering, as produces Thing.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.

Claims (4)

1. a kind of amidino groups CO2And N2Switch surfactant, it is characterised in that the amidino groups CO2And N2Switching surfactant is Hexadecyldimethyl benzyl ammonium ethanamidine；Structural formula：
2. a kind of amidino groups CO as claimed in claim 12And N2The preparation method of switch surfactant, it is characterised in that the amidine Base CO2And N2The preparation method of switch surfactant is comprised the following steps：
Step one, takes 0.01mol cetylamines and adds in the there-necked flask with stirring, reflux condensation mode and thermometer, begins to warm up And stirring；The chloroform for adding 12mL dried, after backflow starts, at a temperature of maintaining the reflux for after stirring a period of time, starts to be added dropwise The dimethyl acetamide that 0.03mol has been dried, reacts 15 hours, and temperature is set in 65 DEG C；
Step 2, is added dropwise phosphorus trichloride, the pH value of real-time testing system so that system maintains faintly acid, stops being added dropwise, then returns Stream reaction 13 hours, terminates reaction；
Step 3, vacuum distillation removes solvent, is recrystallized with absolute ethyl alcohol, and light yellow solid is rotated to obtain after heat filtering, as produces Thing.
3. the as claimed in claim 2 amidino groups CO2And N2The preparation method of switch surfactant, it is characterised in that described Amidino groups CO2And N2The reaction mechanism of preparation method of switch surfactant is：
4. one kind is by amidino groups CO described in claim 12And N2Drilling fluid prepared by switch surfactant.
CN201611179105.3A 2016-12-19 2016-12-19 Amidino surfactant with CO2 and N2 switches and preparation method thereof Pending CN106631897A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107470341A (en) * 2017-07-26 2017-12-15 昆明理工大学 A kind of restorative procedure of heavy-metal contaminated soil
CN109954449A (en) * 2017-12-26 2019-07-02 南京理工大学 Double tail amidino groups surfactants and preparation method thereof
CN112228018A (en) * 2019-07-15 2021-01-15 中国石油化工股份有限公司 CO with amidino compounds2Oil displacement method
CN114456792A (en) * 2022-01-25 2022-05-10 中国石油大学(华东) Response type particle-reinforced foam system for oil and gas development, preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007056859A1 (en) * 2005-11-15 2007-05-24 Queen's University At Kingston Reversibly switchable surfactants and methods of use thereof
CN102443448A (en) * 2010-10-11 2012-05-09 中国石油化工股份有限公司 Diesel composition and method for increasing oxidation stability of biodiesel
CN102690213A (en) * 2011-03-23 2012-09-26 中国石油天然气集团公司 Synthetic method of N'-long-chain alkyl-N,N-dimethyl amidine
CN103242812A (en) * 2013-05-20 2013-08-14 西南石油大学 Switchable foaming solution for foam drilling and well cleanup on oil and gas field

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007056859A1 (en) * 2005-11-15 2007-05-24 Queen's University At Kingston Reversibly switchable surfactants and methods of use thereof
CN102443448A (en) * 2010-10-11 2012-05-09 中国石油化工股份有限公司 Diesel composition and method for increasing oxidation stability of biodiesel
CN102690213A (en) * 2011-03-23 2012-09-26 中国石油天然气集团公司 Synthetic method of N'-long-chain alkyl-N,N-dimethyl amidine
CN103242812A (en) * 2013-05-20 2013-08-14 西南石油大学 Switchable foaming solution for foam drilling and well cleanup on oil and gas field

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107470341A (en) * 2017-07-26 2017-12-15 昆明理工大学 A kind of restorative procedure of heavy-metal contaminated soil
CN109954449A (en) * 2017-12-26 2019-07-02 南京理工大学 Double tail amidino groups surfactants and preparation method thereof
CN112228018A (en) * 2019-07-15 2021-01-15 中国石油化工股份有限公司 CO with amidino compounds2Oil displacement method
CN114456792A (en) * 2022-01-25 2022-05-10 中国石油大学(华东) Response type particle-reinforced foam system for oil and gas development, preparation method and application thereof

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Application publication date: 20170510