CN114773212B - Single-chain dihydroxyl CO 2 Responsive surfactant and use thereof in cleaning fracturing fluid - Google Patents
Single-chain dihydroxyl CO 2 Responsive surfactant and use thereof in cleaning fracturing fluid Download PDFInfo
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- 239000012530 fluid Substances 0.000 title claims abstract description 64
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 55
- 238000004140 cleaning Methods 0.000 title description 6
- 230000004044 response Effects 0.000 claims abstract description 15
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims description 3
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 3
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims 1
- 239000002562 thickening agent Substances 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000693 micelle Substances 0.000 description 8
- 229940043237 diethanolamine Drugs 0.000 description 6
- 150000001412 amines Chemical group 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/14—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- 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
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
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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
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/665—Compositions based on water or polar solvents containing inorganic compounds
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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
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- Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a single-chain dihydroxy CO 2 The responsive surfactant can be used as a thickening agent for preparing recyclable clean fracturing fluid. Dibromoalkane and oleylamine are used as raw materials to obtain an intermediate MB; the intermediate MB reacts with hydrophilic group diethanolamine to prepare single-chain dihydroxyl CO 2 Responsive surfactant with good CO 2 Stimulus response capability, adding the thickener into water to prepare CO 2 The stimulus response clean fracturing fluid has quick response, and the air is introduced to quickly break gel, and CO is introduced to the broken gel again 2 Can be recycled for at least 4 times, and the best product with rheological temperature resistance is at 80 ℃ for 170s ‑1 The shear viscosity is not less than 25 mPa.s, meets the field construction requirement of clean fracturing fluid, and has good application prospect in oilfield fracturing fluid and enhanced recovery ratio.
Description
Technical Field
The invention relates to the technical field of clean fracturing fluid, in particular to a single-chain dihydroxy CO 2 The responsive surfactant is used for cleaning fracturing fluid.
Background
In recent years, stimulus response behavior has become a research hotspot in various discipline fields, which has greatly inspired research into environmental stimulus response type worm-like micelle systems. The functional group with environmental stimulus response is introduced into the molecular structure of the surfactant forming the worm-like micelle, or the component capable of participating in the assembly of the worm-like micelle and having environmental stimulus response is introduced into the system, so that the intelligent worm-like micelle system stimulus response giant micelle system which responds to external environmental stimulus can be formed. As an important component of intelligent colloid material and soft matter, the intelligent worm-like micelle system is used in medicine controlled release, biological tissue engineering, cosmetics and paintingThe fields of materials and the like show great application potential, and thus, the materials and the like are widely concerned. CO 2 The emissions of (2) are increasing year by year, and the greenhouse effect on the environment is also increasingly significant in affecting human survival and development. How to collect, store and utilize CO 2 Creating a sustainable social environment has become a consensus among scientists in all countries. Based on CO in supercritical or pressurized state 2 The development and utilization of (C) have been studied intensively, but are based on CO at normal temperature and pressure 2 Intelligent switch research of absorption and release on certain performances of the system has not attracted attention until recently, such as CO 2 Switch type ionic liquid, solvent, emulsifier and CO 2 Absorbing captured polymers, and the like.
The clean fracturing fluid is the most widely used fracturing fluid in the prior fracturing technology, and the main agent of the clean fracturing fluid is usually quaternary ammonium salt surfactant. The clean fracturing fluid has the advantages of few residues, low damage to the bottom layer and the like, and has good application prospect in the fracturing fluid. With CO 2 The application of the responsive surfactant molecules in clean fracturing fluid systems has great application prospect. Because of CO 2 The responsive surfactant molecules are used as the fracturing fluid thickener, and the fracturing fluid can be recycled by regulating and controlling the gel formation and breaking of the responsive surfactant molecules, so that the responsive surfactant molecules have important research value and practical value for economically and efficiently developing unconventional oil and gas reservoirs and saving energy and reducing emission.
Disclosure of Invention
The invention aims to provide a single-chain dihydroxyCO used for cleaning fracturing fluid 2 A responsive surfactant.
The invention provides single-chain dihydroxyCO 2 A responsive surfactant having the molecular structural formula:
wherein R is an unsaturated hydrocarbon chain with 17 carbon atoms, and n is 2-5.
The above single-chain dihydroxyl CO 2 Preparation method of responsive surfactantThe method comprises the following specific steps:
step (1): dissolving bromoalkane in a mixed solvent of acetonitrile and ethyl acetate, and dropwise adding R-NH 2 Reacting for 8-14h at 45-60 ℃; after the reaction is finished, performing suction filtration to obtain white powder, washing with a NaOH solution with the mass fraction of 30%, extracting and separating liquid with dichloromethane, and performing rotary evaporation to obtain an intermediate MB; wherein R-NH 2 The molar ratio of bromoalkane is 1.0 (1.0-1.1).
Step (2): the intermediate MB, K prepared in step (1) is reacted with 2 CO 3 And diethanolamine in the molar ratio of 1 to 1 (1-1.2), mixing homogeneously in a reaction container, and reflux reaction at 65-85 deg.c for 12-24 hr in sealed condition to obtain single chain dihydroxyCO 2 A responsive surfactant.
Preferably, in step (1), R-NH 2 Is oleylamine, the reaction temperature is 45 ℃, and the reaction time is 8 hours.
Preferably, in the step (1), the molar ratio of acetonitrile to ethyl acetate of the mixed solvent is 1.0 (1.0-1.5).
Preferably, in step (1), the bromoalkane is 1, 2-dibromoethane or 1, 3-dibromopropane or 1, 4-dibromobutane or 1, 5-dibromopentane.
Preferably, in the step (2), the molar ratio of methanol and acetonitrile in the reaction solvent is 1.0 (1.0-1.5); the reaction temperature was 70℃and the reaction time was 18 hours.
Single chain dihydroxy CO 2 The synthetic route of the surfactant is as follows:
the invention also provides a method for preparing the single-chain dihydroxy CO 2 Recyclable clean fracturing fluid with response type surfactant as thickener, wherein the fracturing fluid is prepared from single-chain dihydroxyCO 2 A responsive surfactant and water, wherein the single-chain dihydroxy CO 2 The mass percentage concentration of the responsive surfactant is 2.3-3.5% and the balance of water.
The preparation method of the recyclable clean fracturing fluid comprises the following steps: CO at room temperature 2 Introducing single-chain dihydroxyCO at a speed of 0.3L/min 2 In an aqueous solution prepared from the responsive surfactant and water, the clean fracturing fluid can be obtained by responsive thickening within 3-5 min. When the gel is required to be broken, the gel can be broken by only introducing air for 5-10min, and CO is repeatedly introduced into the gel breaking solution 2 But also can obtain clean fracturing fluid.
The single-chain dihydroxyl CO of the invention 2 Mechanism of action of responsive surfactants in clean fracturing fluids:
the single-chain dihydroxyl CO 2 The responsive surfactant is connected with two hydroxyl groups in tertiary amine groups, so that the surfactant can be uniformly dispersed in aqueous solution and is connected with CO 2 The reaction is protonated, the neutral group is changed into a quaternary amine hydrophilic cationic head group with stronger polarity, and the surface active agent mixed micelle which is protonated and unprotonated in the surface active agent changes the aggregation behavior of substances in the solution, so that the viscosity of the system is increased, and the clean fracturing fluid is obtained; when cleaning dissolved CO in fracturing fluid 2 After being displaced by air introduced into the system, the protonation is reversely carried out, the quaternized surfactant is changed into a tertiary amine long chain again, the mixed micelle disappears, the viscosity of the system is reduced due to aggregation and separation, and the gel breaking of the fracturing fluid is realized; CO is introduced into the gel breaking solution again 2 But also can obtain clean fracturing fluid, repeat the phenomenon, thereby realizing recycling and effectively solving the problem of treatment of flowback fluid.
Compared with the prior art, the invention has the following advantages:
(1) The invention provides single-chain dihydroxyCO 2 The responsive surfactant has good CO 2 The stimulation response capability can be used as a thickening agent to prepare a recyclable clean fracturing fluid, the dosage of the surfactant in the clean fracturing fluid is only 2.3-3.5%, and the clean fracturing fluid can be prepared by CO 2 The gel forming and breaking of the fracturing fluid are intelligently regulated and controlled to realize the recycling of the fracturing fluid, so that the cost of cleaning the fracturing fluid is greatly reduced; clean fracturing fluid is simple to prepare and CO 2 The response to the stimulus is rapid and,air is introduced to break the gel rapidly, and CO is blown into the broken gel again 2 Can be recycled for at least 4 times, and has rheological temperature resistance of 80deg.C and 170s -1 The shearing viscosity is not less than 25 mPa.s, and the field construction requirement of the clean fracturing fluid is met.
(2) The clean fracturing fluid has excellent salt tolerance, can meet the field requirement below 80 ℃, can be used for the fracturing fluid yield increase transformation of medium-low permeability reservoirs, and has good application prospects in oilfield fracturing fluids and recovery ratio improvement.
(3) The invention provides single-chain dihydroxyCO 2 The preparation method of the responsive surfactant takes cheap and easily available oleylamine and bromoalkane as raw materials to obtain an intermediate MB; the intermediate MB and the diethanol amine are further subjected to substitution reaction to prepare the target product, the whole reaction process is simple to operate, the reaction condition is mild, the cost is low, the reaction yield is high, and noble metal is not used as a catalyst.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 shows the single-chain dihydroxyCO obtained in example 1 2 Nuclear magnetic hydrogen spectrum of the responsive surfactant.
Fig. 2 is a graph of the repeated response of the clean fracturing fluid prepared in example 2.
Fig. 3 is a rheological profile of the clean fracturing fluid prepared in example 3.
Fig. 4 is a rheological profile of the clean fracturing fluid prepared in example 4.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
Example 1
Single-chain dihydroxyl CO 2 The preparation method of the responsive surfactant specifically comprises the following steps:
step (1): 1, 2-dibromoethane (37.52 g,200 mmol) was dissolved in 100ml of acetonitrile and ethyl acetate in a molar ratio of 1:1, dropwise adding oil amine (53.4816 g,200 mmol) into the mixed solvent, and reacting at 45 ℃ for 8h; after the reaction is finished, white powder is obtained through suction filtration, naOH solution with the mass fraction of 30% is used for washing, dichloromethane is used for extraction and liquid separation, and lower liquid is subjected to rotary evaporation to obtain an intermediate MB.
Step (2): intermediate MB (37.9 g100 mml), K 2 CO 3 (13.8 g of 100 mml) and diethanolamine (10.5 g of 100 mml) were added to a reaction vessel and mixed uniformly, and a molar ratio of methanol to acetonitrile of 100ml was 1:1, and carrying out reflux reaction for 14 hours at 75 ℃ under the airtight condition to obtain single-chain dihydroxyCO 2 The responsive surfactant was a white paste (yield 84.5%). FIG. 1 shows the single-chain dihydroxyCO obtained in example 1 2 Nuclear magnetic hydrogen spectrum of the responsive surfactant.
Example 2
Single-chain dihydroxyl CO 2 The preparation method of the responsive surfactant comprises the following specific steps:
step (1): 1, 3-dibromopropane (39.3 g,200 mmol) was dissolved in 100ml of acetonitrile and ethyl acetate in a molar ratio of 1:1, dropwise adding oil amine (53.4816 g,200 mmol) into the mixed solvent, and reacting at 45 ℃ for 8h; after the reaction is finished, white powder is obtained through suction filtration, naOH solution with the mass fraction of 30% is used for washing, dichloromethane is used for extraction and liquid separation, and lower liquid is subjected to rotary evaporation to obtain an intermediate MB.
Step (2): intermediate MB (49.9 g100 mml), K 2 CO 3 (13.8 g of 100 mml), and diethanolamine (10.5 g of 100 mml) were added to the reaction vessel and mixed uniformly with 100ml of methanol and acetonitrile in a molar ratio of 1:1, and carrying out reflux reaction for 14 hours at 75 ℃ under the airtight condition to obtain single-chain dihydroxyCO 2 The responsive surfactant was a white paste (yield: 87.6%).
Preparation of clean fracturing fluid: CO was added at a rate of 0.3L/min at room temperature 2 Introducing 3.5% of single-chain dihydroxyCO 2 In the aqueous solution of the responsive surfactant, the solution is clear and transparent and is stickyAnd (5) flicking the fluid to obtain the clean fracturing fluid. Repeatedly introducing air at room temperature for gel breaking and CO 2 The repeated response curves of the clean fracturing fluid prepared by tackifying and testing the viscosity change are shown in figure 2.
Example 3
Single-chain dihydroxyl CO 2 The preparation method of the responsive surfactant comprises the following specific steps:
step (1): 1, 4-dibromobutane (43.18 g,200 mmol) was dissolved in 100ml of acetonitrile and ethyl acetate in a molar ratio of 1:1, dropwise adding oil amine (53.4816 g,200 mmol) into the mixed solvent, and reacting at 45 ℃ for 8h; after the reaction is finished, performing suction filtration to obtain white powder, washing with a NaOH solution with the mass fraction of 30%, extracting and separating the solution with dichloromethane, and performing rotary evaporation on the lower solution to obtain an intermediate MB;
step (2): intermediate MB (40.7 g100 mml), K 2 CO 3 (13.8 g of 100 mml), and diethanolamine (10.5 g of 100 mml) were added to the reaction vessel and mixed uniformly with 100ml of methanol and acetonitrile in a molar ratio of 1:1, and carrying out reflux reaction for 14 hours at 75 ℃ under the airtight condition to obtain single-chain dihydroxyCO 2 The responsive surfactant was a white paste (yield: 81.9%).
Preparation of clean fracturing fluid: CO was added at a rate of 0.3L/min at room temperature 2 Introducing the prepared single-chain dihydroxyCO 2 In the aqueous solution of the surfactant, the mass fraction of the surfactant is 3.5 percent, and the clean fracturing fluid can be prepared after the solution is clear and transparent. The rheology of the resulting clean fracturing fluid was tested at 80 ℃ and the results are shown in figure 3. As can be seen, the rheological temperature resistance is 80℃for 170s -1 The shearing viscosity is not less than 25 mPa.s, and the field construction requirement of the clean fracturing fluid is met.
Example 4
Single-chain dihydroxyl CO 2 The preparation method of the responsive surfactant comprises the following specific steps:
step (1): 1, 5-dibromopentane (45.98 g,200 mmol) was dissolved in 100ml of acetonitrile and ethyl acetate in a molar ratio of 1:1, dropwise adding oil amine (53.4816 g,200 mmol) into the mixed solvent, and reacting at 45 ℃ for 8h; after the reaction is finished, white powder is obtained through suction filtration, naOH solution with the mass fraction of 30% is used for washing, dichloromethane is used for extraction and liquid separation, and lower liquid is subjected to rotary evaporation to obtain an intermediate MB.
Step (2): intermediate MB (42.1 g100 mml), K 2 CO 3 (13.8 g of 100 mml) and diethanolamine (10.5 g of 100 mml) were added to a reaction vessel and mixed uniformly, and a molar ratio of methanol to acetonitrile of 100ml was 1:1, and carrying out reflux reaction for 14 hours at 75 ℃ under the airtight condition to obtain single-chain dihydroxyCO 2 The responsive surfactant was a white paste (yield: 81.9%).
Preparation of clean fracturing fluid: CO was added at a rate of 0.3L/min at room temperature 2 Introducing the prepared single-chain dihydroxyCO 2 In the aqueous solution of the responsive surfactant, the mass fraction of the surfactant is 3.5 percent, and the clean fracturing fluid can be prepared after the solution is clear and transparent. The resulting clean fracturing fluid was tested for viscoelasticity at 80 c and the results are shown in figure 4. As can be seen, the rheological temperature resistance is 80℃for 170s -1 The shearing viscosity is not less than 25 mPa.s, and the field construction requirement of the clean fracturing fluid is met.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalents and modifications can be made to the above-mentioned embodiments without departing from the scope of the invention.
Claims (6)
1. Single-chain dihydroxyl CO 2 The application of the responsive surfactant in preparing the recyclable clean fracturing fluid is characterized in that the fracturing fluid is prepared from single-chain dihydroxyCO 2 A responsive surfactant and water; single chain dihydroxyBased on CO 2 The mass percentage of the responsive surfactant is 2.3-3.5%; single chain dihydroxy CO 2 A responsive surfactant having the molecular structural formula:
wherein R is CH 3 -(CH 2 ) 7 -CH＝CH-(CH 2 ) 8 -n has a value of 2-5;
the preparation method of the fracturing fluid comprises the following steps:
CO at room temperature 2 Introducing single-chain dihydroxyCO at a rate of 0.2L/min 2 In the aqueous solution of the response type surfactant, response thickening is realized, and clean fracturing fluid is obtained; the gel breaking can be realized by introducing air, and CO is repeatedly introduced into the gel breaking solution 2 But also can obtain clean fracturing fluid.
2. The single-chain dihydroxyco of claim 1 2 The application of the responsive surfactant in preparing the recyclable clean fracturing fluid is characterized in that the single-chain dihydroxy CO 2 The preparation method of the responsive surfactant comprises the following steps:
step (1): dissolving bromoalkane in a mixed solvent of acetonitrile and ethyl acetate, dripping oleamide, and reacting for 8-14h at 45-60 ℃; after the reaction is finished, performing suction filtration to obtain white powder, washing with a NaOH solution with the mass fraction of 30%, extracting and separating liquid with dichloromethane, and performing rotary evaporation to obtain an intermediate MB; the bromoalkane is one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane and 1, 5-dibromopentane;
step (2): intermediate MB, K 2 CO 3 And diethanolamine in the molar ratio of 1 to 1 (1-1.2), mixing homogeneously in a reaction container, and reflux reaction at 65-85 deg.c for 12-24 hr in sealed condition to obtain single chain dihydroxyCO 2 A responsive surfactant.
3. The single-chain dihydroxyco of claim 2 2 The application of the responsive surfactant in preparing the recyclable clean fracturing fluid is characterized in that the molar usage ratio of oleylamine to bromoalkane in the step (1) is 1.0 (1.0-1.1).
4. The single-chain dihydroxyco of claim 2 2 The application of the responsive surfactant in preparing the recyclable clean fracturing fluid is characterized in that the molar use ratio of acetonitrile to ethyl acetate in the mixed solvent in the step (1) is 1.0 (1.0-1.5).
5. The single-chain dihydroxyco of claim 2 2 The application of the responsive surfactant in preparing the recyclable clean fracturing fluid is characterized in that the molar use ratio of methanol to acetonitrile in the reaction solvent in the step (2) is 1.0 (1.0-1.5).
6. The single-chain dihydroxyco of claim 2 2 The use of a responsive surfactant for preparing a recyclable clean fracturing fluid, characterized in that in step (2), the reaction temperature is 70 ℃ and the reaction time is 18 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4258061A (en) * | 1970-08-07 | 1981-03-24 | Pfizer Inc. | Interferon induction in animals by amines |
| CN107142099A (en) * | 2017-05-19 | 2017-09-08 | 中国石油大学(华东) | A kind of CO of reusable edible2Response type clean fracturing fluid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258061A (en) * | 1970-08-07 | 1981-03-24 | Pfizer Inc. | Interferon induction in animals by amines |
| CN107142099A (en) * | 2017-05-19 | 2017-09-08 | 中国石油大学(华东) | A kind of CO of reusable edible2Response type clean fracturing fluid |
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