CN107043620A - A kind of preparation method of liquid carbon dioxide thickening agent - Google Patents
A kind of preparation method of liquid carbon dioxide thickening agent Download PDFInfo
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Abstract
The present invention relates to the preparation method of the liquid carbon dioxide thickening agent for unconventionaloil pool reservoir exploitation.It can solve the problem of conventional mining type is damaged to oil and gas reservoir, its technical scheme：Toluene and water are first added into bottle, add serinol, di-tert-butyl dicarbonate is added dropwise at 0 DEG C, 25 DEG C react 4 hours, distill to obtain intermediate product (1), after add perfluoro caprylic acid in another bottle, thionyl chloride and N are added at 75 DEG C, N dimethylformamides, react 2 hours, distill to obtain intermediate product (2)；Then intermediate product (1) is added in another bottle, 75 DEG C is warming up to and intermediate product (2) is added dropwise, 12 hours obtained intermediate products (3) are reacted at 75 DEG C；Dichloromethane and trifluoroacetic acid are finally added in bottle, intermediate product (3) is added, reacted 2 hours at 25 DEG C, after extraction vacuum drying, 1,6 di-isocyanates is added and reacts 2 minutes to obtain final product.The thickening agent can increase carbon dioxide viscosity, available for fracturing reform.
Description
Technical field
The present invention relates to it is a kind of for unconventionaloil pool reservoir exploitation without using water anhydrous fracturing fluid technology, more particularly to
The preparation method of liquid carbon dioxide thickening agent containing fluorine element, belongs to oil field chemical field.
Background technology
As economic continues to develop, oil and natural gas is used as a kind of energy reserves, it appears more and more important.In recent years
Come, the yield and import volume of China's oil and natural gas increase year by year, 2014, crude oil in China import volume be 3.1 hundred million tons, relatively on
The same period in year increases by 9.5%, the billion cubic meter of Imported gas 530.Increase by 23.8% compared with same period last year.Conventional petroleum resources is
Growing Demand of Oil ＆ Gas can not be met, therefore, the development and utilization of unconventional petroleum resources is increasingly becoming focus of attention.
The features such as unconventionaloil pool reservoir has poor properties, low porosity and low permeability, generally also shows very strong water sensitivity.Cause
This, fracturing reform is a kind of effective means for developing unconventional petroleum resources.Easily make reservoir shape using conventional mining type
Cheng Shuisuo, the permeability reduction of reservoir, so as to be damaged to reservoir, has influence on the effect of fracturing yield increasing.In order to solve routine
Emphasis has gradually been turned to anhydrous pressure break by the injury that mining type is caused to oil and gas reservoir, people, and anhydrous pressure break is in fracturing process
In do not need water substantially.Therefore, developing has important economy and social effect without using the anhydrous fracturing technique of water.
The content of the invention
The purpose of the present invention is：The situation of injury is easily caused to oil and gas reservoir for conventional mining type, spy provides a kind of
The preparation method of liquid carbon dioxide thickening agent.
The present invention provides a kind of preparation method of liquid carbon dioxide thickening agent, and the preparation method comprises the following steps：
The preparation of (1) 1,3- dihydroxypropane -2- t-butyl carbamates：The mixing of first alcohol and water is added into three-necked bottle
The volume ratio of solution, methanol and water is 3:7,0.02mol serinols are added, after stirring is completely dissolved, 0 DEG C is cooled to ice bath
Afterwards, then to three's mixed solution and dripping 0.021~0.023mol di-tert-butyl dicarbonates, during dropwise addition, temperature is protected
Hold after 0 DEG C, 30 minutes, remove ice bath, 25 DEG C of constant temperature is reacted 4 hours, and vacuum distillation is removed after solvent methanol and water, and vacuum is done
It is dry, intermediate product (1) 1,3- dihydroxypropane -2- t-butyl carbamates, as shown in I formulas is made；
(I) 1,3- dihydroxypropanes -2- t-butyl carbamates
(2) preparation of perfluorooctane chloride：0.02mol perfluoro caprylic acids are added into another three-necked bottle, are warming up to after 75 DEG C, according to
Secondary addition 0.021~0.023mol thionyl chlorides and 0.5mol DMFs, condensing reflux, 75 DEG C of reactions 2 of constant temperature
Hour, then vacuum distillation removes excessive unreacted thionyl chloride, intermediate product (2) perfluorooctane chloride is made, such as II formulas institute
Show；
(II) perfluorooctane chloride
The preparation of the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of (3) 1,3- bis-：1,3- dihydroxy is added into three-necked bottle
Propane -2- t-butyl carbamates, are warming up to 75 DEG C, then be slowly added dropwise perfluorooctane chloride, 1,3- dihydroxypropane -2- ammonia
The mol ratio of base t-butyl formate and perfluorooctane chloride is 1:2.1~2.2, condensing reflux, 75 DEG C of constant temperature reacts 12 hours, is made
Intermediate product (3) 1, the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of 3- bis-, as shown in formula III；
(III) the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of 1,3- bis-
(4) preparation of final product [1,6- bis- (1,3- bis- perfluoro caprylic acid propyl ester -2- urea groups)] hexane：Added to three-necked bottle
The mixed solution of dichloromethane and trifluoroacetic acid, dichloromethane is 2 with trifluoroacetic acid volume ratio:1；By the perfluoro caprylic acids third of 1,3- bis-
Ester -2- t-butyl carbamates are added in above-mentioned mixed solution, and 25 DEG C of constant temperature reacts 2 hours, adds saturated sodium bicarbonate,
And add dichloromethane and extracted, organic layer is obtained, organic layer is dried in vacuo, then 1 is added to dry organic layer,
Hexamethylene-diisocyanate, add 1, and hexamethylene-diisocyanate and the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of 1,3- bis- rub
You are than being 1:2.1~2.2, react 2 minutes, obtain final product-liquid carbon dioxide thickening agent, its structure is as shown in IV formulas.
(IV) [1,6- bis- (1,3- bis- perfluoro caprylic acid propyl ester -2- urea groups)] hexane structural formula
The advantages of the present invention are：Fluorine-containing groupses are introduced into thickening agent, thickening agent can be effectively reduced
Required pressure is dissolved in carbon dioxide, improves dissolving situation of the thickening agent in carbon dioxide.Meanwhile, thickening agent is intermolecular
The hydrogen bond action of presence, and the entanglement effect between strand, can effectively play a part of increasing carbon dioxide viscosity.
The method of testing of thickening agent viscosity：The high temperature that thickening agent first is added into rheometer HAAKE MARS according to dosage is high
The closed system of pressure, installs the corollary apparatus of high temperature high pressure enclosed system, is excluded air in closed system using vavuum pump.
Then, liquid carbon dioxide is imported by the sampling valve of high temperature high pressure enclosed system, meanwhile, internal rotor is rotated in adjustment system,
Thickening agent carbon dioxide is set to be sufficiently mixed uniformly, when carbon dioxide is passed into metering, regulating system pressure, temperature make system
Interior carbon dioxide reaches required state, is uniformly mixed, that is, completes the preparation of mixed system, finally, opens rheometer,
Set after experiment parameter, you can the viscosity of test mixing system.
Embodiment
Illustrate the present invention below by example, but present disclosure is not limited solely to the following examples.
Embodiment 1
The preparation of (1) 1,3- dihydroxypropane -2- t-butyl carbamates
6mL deionized water, 14mL methanol are added into three-necked flask, are uniformly mixed, then take 0.02mol serinols
Add in mixed solution, stirring and dissolving completely, is cooled to after 0 DEG C with ice bath, is then slowly added dropwise into three's mixed solution
0.022mol di-tert-butyl dicarbonates, during dropwise addition, temperature is maintained at after 0 DEG C, 30 minutes, removes ice bath, and constant 25 DEG C anti-
Answer 4 hours, after reaction terminates, after being extracted three times using dichloromethane, vacuum distillation removes solvent methanol and water, in 45 DEG C of conditions
Lower vacuum drying 24h, obtains product 1,3- dihydroxypropane -2- t-butyl carbamates.
(2) preparation of perfluorooctane chloride
Take 0.02mol perfluoro caprylic acids to add in another three-necked flask equipped with condenser pipe, be warming up to 75 DEG C, sequentially add
The DMF catalyst of 0.021mol thionyl chlorides chlorinating agent and 0.5mL, 75 DEG C of reaction 2h of stirring constant temperature, takes molten
The white organic phase of lower floor in liquid, rotary evaporation removes thionyl chloride, obtains perfluorooctane chloride.
The preparation of the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of (3) 1,3- bis-
Add 0.01mol 1 into three-necked flask again, 3- dihydroxypropane -2- t-butyl carbamates, then it is slow dropwise
0.022mol perfluorooctane chlorides are added, heat up 75 DEG C of reaction 12h, sequentially adds absolute ether and 5% NaOH solution, solution point
Layer.Organic phase is obtained by extraction, after repeatedly being washed with deionized water, vacuum distillation removes solvent, obtains the perfluoro caprylic acids third of 1,3- bis-
Ester -2- t-butyl carbamates.
(4) preparation of final product [1,6- bis- (1,3- bis- perfluoro caprylic acid propyl ester -2- urea groups)] hexane
Take 0.022mol 1, the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of 3- bis-, be added to trifluoroacetic acid (50mL) and
In the mixed solution of dichloromethane (100mL), 25 DEG C of constant temperature reacts 2 hours, adds saturated sodium bicarbonate, and add dichloromethane
Alkane is extracted, and obtains organic layer, and organic layer is dried in vacuo, then adds the 1,6- of 0.01mol to dry organic layer
Hexamethylene diisocyanate, reacts 2 minutes.Product is repeatedly washed into crude product with the mixed solvent of ethyl acetate and benzene, filtered, vacuum
Dry, obtain final product-liquid carbon dioxide thickening agent [1,6- bis- (1,3- bis- perfluoro caprylic acid propyl ester -2- urea groups)] hexane.
Above-mentioned 1wt%, 2wt%, 3wt% liquid carbon dioxide thickening agent is taken to be added to the height for installing corollary apparatus respectively
In the high-pressure sealed system of temperature；99wt%, 98wt%, 97wt% liquid titanium dioxide are directed respectively into closed system by sampling valve
Carbon.Rotor is rotated, regulating system pressure and temperature value is sufficiently stirred for being completely dissolved thickening agent, that is, complete matching somebody with somebody for mixed system
System；Rheometer is then turned on, setup pressure value is 10MPa, and temperature is 40 DEG C, and the viscosity number for determining mixed system is respectively
1.07mPas, 1.54mPas and 1.96mPas；Compared with the viscosity for the liquid carbon dioxide not thickened, increase respectively
26.8 times, 38.5 times and 49.0 times.
Embodiment 2
The preparation of (1) 1,3- dihydroxypropane -2- t-butyl carbamates
6mL deionized water, 14mL methanol are added into three-necked flask, stirring and dissolving completely, 0 DEG C is cooled to ice bath
Afterwards, 0.021mol di-tert-butyl dicarbonates are then slowly added dropwise into three's mixed solution, during dropwise addition, temperature is maintained at 0
DEG C, after 30 minutes, ice bath is removed, constant 25 DEG C are reacted 4 hours, after reaction terminates, after being extracted three times using dichloromethane, decompression
Solvent methanol and water is distilled off, 24h is dried in vacuo under the conditions of 45 DEG C, product 1,3- dihydroxypropane -2- amino first is obtained
Tert-butyl acrylate.
(2) preparation of perfluorooctane chloride
Take 0.02mol perfluoro caprylic acids to add in another three-necked flask equipped with condenser pipe, be warming up to 75 DEG C, sequentially add
The DMF catalyst of 0.022mol thionyl chlorides chlorinating agent and 0.5mL, 75 DEG C of reaction 2h of stirring constant temperature, takes molten
The white organic phase of lower floor in liquid, rotary evaporation removes thionyl chloride, obtains perfluorooctane chloride.
The preparation of the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of (3) 1,3- bis-
Add 0.01mol 1 into three-necked flask again, 3- dihydroxypropane -2- t-butyl carbamates, then it is slow dropwise
0.021mol perfluorooctane chlorides are added, heat up 75 DEG C of reaction 12h, sequentially adds absolute ether and 5% NaOH solution, solution point
Layer.Organic phase is obtained by extraction, after repeatedly being washed with deionized water, vacuum distillation removes solvent, obtains the perfluoro caprylic acids third of 1,3- bis-
Ester -2- t-butyl carbamates.
(4) preparation of final product [1,6- bis- (1,3- bis- perfluoro caprylic acid propyl ester -2- urea groups)] hexane
Take 0.022mol 1, the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of 3- bis-, be added to trifluoroacetic acid (50mL) and
In the mixed solution of dichloromethane (100mL), 25 DEG C of constant temperature reacts 2 hours, adds saturated sodium bicarbonate, and add dichloromethane
Alkane is extracted, and obtains organic layer, and organic layer is dried in vacuo, then adds the 1,6- of 0.01mol to dry organic layer
Hexamethylene diisocyanate, reacts 2 minutes.Product is repeatedly washed into crude product with the mixed solvent of ethyl acetate and benzene, filtered, vacuum
Dry, obtain final product-liquid carbon dioxide thickening agent [1,6- bis- (1,3- bis- perfluoro caprylic acid propyl ester -2- urea groups)] hexane.
Above-mentioned 1wt%, 2wt%, 3wt% liquid carbon dioxide thickening agent is taken to be added to the height for installing corollary apparatus respectively
In the high-pressure sealed system of temperature；99wt%, 98wt%, 97wt% liquid titanium dioxide are directed respectively into closed system by sampling valve
Carbon.Rotor is rotated, regulating system pressure and temperature value is sufficiently stirred for being completely dissolved thickening agent, that is, complete matching somebody with somebody for mixed system
System；Rheometer is then turned on, setup pressure value is 10MPa, and temperature is 40 DEG C, and the viscosity number for determining mixed system is respectively
1.12mPas, 1.66mPas and 1.87mPas；Compared with the viscosity for the liquid carbon dioxide not thickened, increase respectively
28.0 times, 41.5 times and 46.8 times.
Embodiment 3
The preparation of (1) 1,3- dihydroxypropane -2- t-butyl carbamates
6mL deionized water, 14mL methanol are added into three-necked flask, is uniformly mixed, takes 0.02mol serinols to add
Enter in mixed solution, stirring and dissolving completely, is cooled to after 0 DEG C with ice bath, is then slowly added dropwise into three's mixed solution
0.023mol di-tert-butyl dicarbonates, during dropwise addition, temperature is maintained at after 0 DEG C, 30 minutes, removes ice bath, and constant 25 DEG C anti-
Answer 4 hours, after reaction terminates, after being extracted three times using dichloromethane, vacuum distillation removes solvent methanol and water, in 45 DEG C of conditions
Lower vacuum drying 24h, obtains intermediate product 1,3- dihydroxypropane -2- t-butyl carbamates.
(2) preparation of perfluorooctane chloride
Take 0.02mol perfluoro caprylic acids to add in another three-necked flask equipped with condenser pipe, be warming up to 75 DEG C, sequentially add
The DMF catalyst of 0.023mol thionyl chlorides chlorinating agent and 0.5mL, 75 DEG C of reaction 2h of stirring constant temperature, takes molten
The white organic phase of lower floor in liquid, rotary evaporation removes thionyl chloride, obtains perfluorooctane chloride.
The preparation of the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of (3) 1,3- bis-
Add 0.01mol 1 into three-necked flask again, 3- dihydroxypropane -2- t-butyl carbamates, then it is slow dropwise
0.022mol perfluorooctane chlorides are added, heat up 75 DEG C of reaction 12h, sequentially adds absolute ether and 5% NaOH solution, solution point
Layer.Organic phase is obtained by extraction, after repeatedly being washed with deionized water, vacuum distillation removes solvent, obtains the perfluoro caprylic acids third of 1,3- bis-
Ester -2- t-butyl carbamates.
(4) preparation of final product [1,6- bis- (1,3- bis- perfluoro caprylic acid propyl ester -2- urea groups)] hexane
Take 0.021mol 1, the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of 3- bis-, be added to trifluoroacetic acid (50mL) and
In the mixed solution of dichloromethane (100mL), 25 DEG C of constant temperature reacts 2 hours, adds saturated sodium bicarbonate, and add dichloromethane
Alkane is extracted, and obtains organic layer, and organic layer is dried in vacuo, then adds the 1,6- of 0.01mol to dry organic layer
Hexamethylene diisocyanate, reacts 2 minutes.Product is repeatedly washed into crude product with the mixed solvent of ethyl acetate and benzene, filtered, vacuum
Dry, obtain final product-liquid carbon dioxide thickening agent [1,6- bis- (1,3- bis- perfluoro caprylic acid propyl ester -2- urea groups)] hexane.
Above-mentioned 1wt%, 2wt%, 3wt% liquid carbon dioxide thickening agent is taken to be added to the height for installing corollary apparatus respectively
In the high-pressure sealed system of temperature；99wt%, 98wt%, 97wt% liquid titanium dioxide are directed respectively into closed system by sampling valve
Carbon.Rotor is rotated, regulating system pressure and temperature value is sufficiently stirred for being completely dissolved thickening agent, that is, complete matching somebody with somebody for mixed system
System；Rheometer is then turned on, setup pressure value is 10MPa, and temperature is 40 DEG C, and the viscosity number for determining mixed system is respectively
1.14mPas, 1.47mPas and 2.11mPas；Compared with the viscosity for the liquid carbon dioxide not thickened, increase respectively
28.5 times, 36.8 times and 52.8 times.
Claims (2)
1. a kind of preparation method of liquid carbon dioxide thickening agent, it is characterised in that the preparation method comprises the following steps：
The preparation of (1) 1,3- dihydroxypropane -2- t-butyl carbamates：The mixing that first alcohol and water is added into three-necked bottle is molten
The volume ratio of liquid, methanol and water is 3:7,0.02mol serinols are added, after stirring is completely dissolved, 0 DEG C is cooled to ice bath
Afterwards, then to three's mixed solution and dripping 0.021~0.023mol di-tert-butyl dicarbonates, during dropwise addition, temperature is protected
Hold after 0 DEG C, 30 minutes, remove ice bath, 25 DEG C of constant temperature is reacted 4 hours, and vacuum distillation is removed after solvent methanol and water, and vacuum is done
It is dry, intermediate product 1,3- dihydroxypropane -2- t-butyl carbamates is made；
(2) preparation of perfluorooctane chloride：0.02mol perfluoro caprylic acids are added into another three-necked bottle, are warming up to after 75 DEG C, are added successively
Enter 0.021~0.023mol thionyl chlorides and 0.5ml DMFs, condensing reflux, 75 DEG C of constant temperature reacts 2 hours,
Then vacuum distillation removes excessive unreacted thionyl chloride, and intermediate product perfluorooctane chloride is made；
The preparation of the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of (3) 1,3- bis-：1,3- dihydroxy third is added into three-necked bottle
Alkane -2- t-butyl carbamates, are warming up to 75 DEG C, then be slowly added dropwise perfluorooctane chloride, above-mentioned 1,3- dihydroxypropanes -2-
The mol ratio of t-butyl carbamate and perfluorooctane chloride is 1:2.1~2.2, condensing reflux, 75 DEG C of constant temperature reacts 12 hours, system
Obtain intermediate product 1, the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of 3- bis-；
(4) preparation of final product [1,6- bis- (1,3- bis- perfluoro caprylic acid propyl ester -2- urea groups)] hexane：Dichloro is added to three-necked bottle
The mixed solution of methane and trifluoroacetic acid, the volume ratio 2 of above-mentioned dichloromethane and trifluoroacetic acid:1；By the perfluoro caprylic acids third of 1,3- bis-
Ester -2- t-butyl carbamates are added in above-mentioned mixed solution, and 25 DEG C of constant temperature reacts 2 hours, adds saturated sodium bicarbonate,
And add dichloromethane and extracted, organic layer is obtained, organic layer is dried in vacuo, then 1 is added to dry organic layer,
Hexamethylene-diisocyanate, add 1, and hexamethylene-diisocyanate and the perfluoro caprylic acid propyl ester -2- t-butyl carbamates of 1,3- bis- rub
You are than being 1:2.1~2.2, react 2 minutes, obtain final product liquid carbon dioxide thickening agent.
2. the preparation method of liquid carbon dioxide thickening agent described in claim 1, it is characterised in that：The preparation method is made most
The application of end-product liquid carbon dioxide thickening agent：Above-mentioned 1wt%, 2wt%, 3wt% liquid carbon dioxide thickening agent is taken respectively
It is added in the high temperature high pressure enclosed system for installing corollary apparatus.It is directed respectively into by sampling valve into closed system
99wt%, 98wt%, 97wt% liquid carbon dioxide.Rotor is rotated, regulating system pressure and temperature value is sufficiently stirred for making thickening
Agent is completely dissolved, that is, completes the preparation of mixed system.Rheometer is opened, setup pressure value is 10MPa, and temperature is 40 DEG C, is determined
The viscosity number of mixed system be respectively 1.07mPas, 1.54mPas and 1.96mPas.With the liquid titanium dioxide not thickened
The viscosity of carbon is compared, and increases by 26.8 times, 38.5 times and 49.0 times respectively；This thickening agent as the vaporized carbon fracturing fluid of liquid two weight
Want part, it is adaptable to unconventionaloil pool reservoir such as page rock gas, special low permeability oil field, Oil in Super-low Permeability oil-gas reservoir, fine and close oil gas
The exploitation of oil gas such as hide, can solve water lock, swelling clay mineral, residue that routine fracturing fluid brings tired to formation contaminant, the row of returning
Difficult the problems such as.
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| CN110357794A (en) * | 2019-08-19 | 2019-10-22 | 西南石油大学 | A kind of spy's hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation preparation method of supercritical carbon dioxide thickening agent |
| CN110386883A (en) * | 2019-08-11 | 2019-10-29 | 西南石油大学 | A kind of densification oil-gas reservoir exploitation preparation method of supercritical carbon dioxide thickening agent |
| CN113773438A (en) * | 2021-11-08 | 2021-12-10 | 德仕能源科技集团股份有限公司 | Carbon dioxide thickener for medium-high permeability oil reservoir and preparation method and technology thereof |
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| CN110386883A (en) * | 2019-08-11 | 2019-10-29 | 西南石油大学 | A kind of densification oil-gas reservoir exploitation preparation method of supercritical carbon dioxide thickening agent |
| CN110386883B (en) * | 2019-08-11 | 2020-05-12 | 西南石油大学 | Preparation method of supercritical carbon dioxide thickening agent for exploitation of compact oil and gas reservoir |
| WO2021027237A1 (en) * | 2019-08-11 | 2021-02-18 | 西南石油大学 | Method for preparing supercritical carbon dioxide thickener for exploitation of tight oil and gas reservoirs |
| US11261373B2 (en) * | 2019-08-11 | 2022-03-01 | Southwest Petroleum University | Preparation method of supercritical carbon dioxide thickener for tight oil and gas reservoir |
| CN110357794A (en) * | 2019-08-19 | 2019-10-22 | 西南石油大学 | A kind of spy's hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation preparation method of supercritical carbon dioxide thickening agent |
| CN110357794B (en) * | 2019-08-19 | 2020-02-28 | 西南石油大学 | Preparation method of supercritical carbon dioxide thickening agent for exploitation of ultra-low permeability and ultra-low permeability oil and gas reservoir |
| CN113773438A (en) * | 2021-11-08 | 2021-12-10 | 德仕能源科技集团股份有限公司 | Carbon dioxide thickener for medium-high permeability oil reservoir and preparation method and technology thereof |
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