CN110357794A - A kind of spy's hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation preparation method of supercritical carbon dioxide thickening agent - Google Patents
A kind of spy's hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation preparation method of supercritical carbon dioxide thickening agent Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of the hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation supercritical carbon dioxide thickening agent of spy.It can solve the problem of conventional mining method damages oil and gas reservoir.Its technical solution: bottle is put into ice-water bath, and perfluoro octyl ethanol, toluene sulfochloride and pyridine is added, and is reacted 3 hours at 0-20 DEG C, filter paper is added after reaction, ultrasonic wave disperses 1 hour, then removes filter paper, and dilute hydrochloric acid is added and washs 3-5 times to obtain intermediate product (1)；Then (N- tert-butoxycarbonyl) Pehanorm and intermediate product (1) are added in another bottle, potassium carbonate and N-N- dimethylformamide is added, is warming up to 60 DEG C of reactions 4 hours to obtain intermediate product (2)；It is eventually adding trifluoroacetic acid, methylene chloride and intermediate product (2), 50 DEG C are reacted 2 hours, after extraction vacuum drying, 1,6- di-isocyanate are added at 55 DEG C and reacts 2 hours to obtain final product.The thickening agent can increase carbon dioxide viscosity, can be used for fracturing reform and chemical flooding.
Description
Technical field
It without using the anhydrous fracturing fluid of water and is mentioned the present invention relates to a kind of for special hypotonic Oil in Super-low Permeability oil-gas reservoir reservoir exploitation
High recovery rate technology, the in particular to preparation method of the supercritical carbon dioxide thickening agent containing fluorine element, belong to oilfield chemistry
Product field.
Background technique
The features such as special hypotonic Oil in Super-low Permeability oil-gas reservoir reservoir has physical property poor, low porosity and low permeability, usually also shows very strong water
Quick property.Therefore, fracturing reform and later period improve the effective means that recovery ratio is a kind of special hypotonic Oil in Super-low Permeability oil-gas reservoir resource of exploitation.
It is easy that reservoir is made to form water lock, the permeability reduction of reservoir using conventional mining method, to be damaged to reservoir, influences
To the effect of fracturing yield increasing.In order to solve the injury caused by oil and gas reservoir of conventional mining method, people gradually turn to emphasis
Anhydrous pressure break, anhydrous pressure break do not need water substantially in fracturing process.Therefore, the anhydrous fracturing technique without using water is developed
With important economy and society effect.A kind of patent of invention ZL201710416147.2 (system of liquid carbon dioxide thickening agent
Preparation Method) and ZL201710480823.2 (a kind of preparation method of supercritical carbon dioxide thickening agent) can be in special hypotonic Oil in Super-low Permeability
It is used in oil-gas reservoir as fracturing fluid base fluid and raising recovery ratio chemical oil displacement agent, but prepared carbon dioxide densif.es agent is all deposited
In ester group, can only be used under the conditions of lower temperature and few water.In the active oil-gas reservoir effect of higher temperature and edge-bottom water, two
Kind thickening agent thermal stability is deteriorated, and easily hydrolyzes, and causes thickening capabilities to be gradually reduced and even disappears.Based on this, system of the present invention
For a kind of six chain thickening agents of ether-containing key, supercritical carbon dioxide viscosity can be improved and improve the stability of thickening agent.
Summary of the invention
The purpose of the present invention is: the case where easily causing injury to oil and gas reservoir for conventional mining method provides one kind
The special hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation preparation method of supercritical carbon dioxide thickening agent.
The present invention provides a kind of preparation method of hypotonic Oil in Super-low Permeability oil-gas reservoir supercritical carbon dioxide thickening agent of suitable spy, institute
State preparation method the following steps are included:
(1) perfluoro octyl ethanol and tolysulfonyl the preparation to toluene perfluoro octyl sulfonic acid ester: are added into three-necked bottle
The molar ratio 1:1.1-1.2 of chlorine, perfluoro octyl ethanol and paratoluensulfonyl chloride, is eventually adding pyrido and is sufficiently stirred.Keep temperature
Degree is sufficiently stirred at 0-20 DEG C, reacts 3 hours, and filter paper is added after reaction, and ultrasonic wave disperses 1 hour, removes unreacted
Paratoluensulfonyl chloride, then removes filter paper, then is repeatedly washed with 15% dilute hydrochloric acid and removed pyridine, obtains white solid, finally
It is repeatedly washed with distilled water, 40 DEG C are dried in vacuo 3 hours, and intermediate product (1) is made to toluene perfluoro octyl sulfonic acid ester, such as I formula
It is shown；
(I) toluene perfluoro octyl sulfonic acid ester
(2) preparation of (1,2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane
The preparation of (1,2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane: add into three-necked bottle
Enter (N- tert-butoxycarbonyl) Pehanorm and to toluene perfluoro octyl sulfonic acid ester, (N- tert-butoxycarbonyl) trihydroxy methyl
Methylamine and to the ratio between toluene perfluoro octyl sulfonic acid ester be 3.1-3.2:1, add potassium carbonate and n,N-Dimethylformamide, sufficiently
Stirring, be warming up to 60 DEG C of reaction 4h and repeatedly washed with distilled water after reaction, be dried in vacuo intermediate product (2) i.e. (1,
2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamates) methane, structure is as shown in II formula.
(II) (1,2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane (3) final product [1,
6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } hexane preparation: to three-necked bottle be added methylene chloride and three
The mixed solution of fluoroacetic acid, methylene chloride and trifluoroacetic acid volume ratio are 2:1；By 1,2,3- perfluoro capryl ethoxymeyhylene-
4- t-butyl carbamate) methane is add to the above mixed solution, and 50 DEG C of constant temperature are reacted 2 hours, and dichloromethane is added thereto
Alkane extracts 3 times, obtains organic layer, anhydrous Na2SO4Dry organic layer, is added the different dicyanate of 1-6,1, hexamethylene-diisocyanate with
The molar ratio of (1,2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane is 1:2.05-2.10, at 55 DEG C
Under the conditions of react 2 hours, repeatedly wash crude product with the mixed solvent of ethyl acetate and benzene, filter, vacuum drying, finally obtain
Final product [1,6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } hexane, structure is as shown in formula III.
(III) [1,6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } hexane
The advantages and beneficial effects of the present invention are: introducing fluorine-containing groups into thickening agent, thickening agent can be effectively reduced
Required pressure is dissolved in carbon dioxide, improves dissolution situation of the thickening agent in carbon dioxide.Meanwhile thickening agent is intermolecular
Entanglement effect between existing hydrogen bond action and strand can effectively play the role of increasing carbon dioxide viscosity.
Thickening agent is by ehter bond rather than ester bond connects close carbon dioxide group and hydrogen bond crosslinks associative groups, effectively increases thickening agent
Thermal stability and hydrolytic stability can be applied to the hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation of the active spy of edge-bottom water.
The test method of thickening agent viscosity: the high temperature that thickening agent is first added to 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 vacuum pump.
Then, supercritical carbon dioxide is imported by the sampling valve of high temperature high pressure enclosed system, meanwhile, internal rotor turns in adjustment system
It is dynamic, be sufficiently mixed thickening agent carbon dioxide uniformly, when carbon dioxide is passed into metering, regulating system pressure, temperature, make be
Carbon dioxide in system reaches required state, is uniformly mixed, that is, completes the preparation of mixed system, finally, opening rheology
Instrument can test the viscosity of mixed system after setting experiment parameter.
Specific embodiment
Illustrate the present invention below by example, but the contents of the present invention are not limited solely to the following examples.
Embodiment 1
(1) perfluoro octyl ethanol and tolysulfonyl the preparation to toluene perfluoro octyl sulfonic acid ester: are added into three-necked bottle
The molar ratio 1:1.1 of chlorine, perfluoro octyl ethanol and paratoluensulfonyl chloride, is eventually adding pyrido and is sufficiently stirred.Maintain the temperature at 0
DEG C, it is sufficiently stirred, reacts 3 hours, filter paper is added after reaction, ultrasonic wave disperses 1 hour, removes unreacted to toluene sulphur
Then acyl chlorides removes filter paper, then washs 3 times with 15% dilute hydrochloric acid and remove pyridine, obtain white solid, finally with distillation washing
It washs 5 times, 40 DEG C are dried in vacuo 3 hours, and intermediate product (1) is made to toluene perfluoro octyl sulfonic acid ester.
(2) preparation of (1,2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane: into three-necked bottle
(N- tert-butoxycarbonyl) serinol is added and to toluene perfluoro octyl sulfonic acid ester, (N- tert-butoxycarbonyl) serinol and to first
The ratio between benzene perfluoro octyl sulfonic acid ester is 3.2:1, adds potassium carbonate and N, N- dimethylformamide is sufficiently stirred, is warming up to 60
DEG C reaction 4h be washed with distilled water 5 times after reaction, be dried in vacuo to obtain intermediate product (2)-(1,3- perfluoro octyl ethanol third
Ether -2- t-butyl carbamate) propane.
(3) preparation of final product { [1,6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } hexane: to
The mixed solution of methylene chloride and trifluoroacetic acid is added in three-necked bottle, and methylene chloride and trifluoroacetic acid volume ratio are 2:1；Will (1,2,
3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane is add to the above mixed solution, 50 DEG C of constant temperature reactions
2 hours, methylene chloride is added thereto and extracts 3 times, obtains organic layer, anhydrous Na2SO4Dry organic layer, is added 1,6 different dicyan
Acid esters, 1, hexamethylene-diisocyanate and 1,3- perfluoro octyl ethanol propyl ether -2- t-butyl carbamate) molar ratio of propane is 1:
2.05, it reacts 2 hours under the conditions of 55 DEG C, is washed crude product 4 times with the mixed solvent of ethyl acetate and benzene, filtered, vacuum is dry
It is dry, finally obtain final product { [1,6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } hexane.
It takes above-mentioned 1wt%, 2wt%, 3wt% supercritical carbon dioxide thickening agent to be added to respectively and installs corollary apparatus
In high temperature high pressure enclosed system；99wt%, 98wt%, 97wt% overcritical two is directed respectively into closed system by sampling valve
Carbonoxide.Rotor is rotated, regulating system pressure and temperature value, being sufficiently stirred is completely dissolved thickening agent, i.e. completion mixed system
Preparation；It is then turned on rheometer, setup pressure value 29MPa, temperature is 60 DEG C, and it is 100s that shear rate is kept in experiment-1, survey
The viscosity number for determining mixed system is respectively 5.89mPas, 6.24mPas and 7.89mPas；Be respectively do not thicken it is overcritical
147.3 times, 156.0 times and 197.3 times of carbon dioxide viscosity.
Embodiment 2
(1) perfluoro octyl ethanol and tolysulfonyl the preparation to toluene perfluoro octyl sulfonic acid ester: are added into three-necked bottle
The molar ratio 1:1.2 of chlorine, perfluoro octyl ethanol and paratoluensulfonyl chloride, is eventually adding pyrido and is sufficiently stirred.It maintains the temperature at
It 20 DEG C, is sufficiently stirred, reacts 3 hours, filter paper is added after reaction, ultrasonic wave disperses 1 hour, removes unreacted to toluene
Then sulfonic acid chloride removes filter paper, then washs 4 times with 15% dilute hydrochloric acid and remove pyridine, obtain white solid, finally use distilled water
Washing 4 times, 40 DEG C are dried in vacuo 3 hours, and intermediate product (1) is made to toluene perfluoro octyl sulfonic acid ester.
(2) preparation of (1,2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane: into three-necked bottle
(N- tert-butoxycarbonyl) serinol is added and to toluene perfluoro octyl sulfonic acid ester, (N- tert-butoxycarbonyl) serinol and to first
The ratio between benzene perfluoro octyl sulfonic acid ester is 3.1:1, adds potassium carbonate and N, N- dimethylformamide is sufficiently stirred, is warming up to 60
DEG C reaction 4h be washed with distilled water 4 times after reaction, be dried in vacuo to obtain intermediate product (2) i.e. (1,2,3- perfluoro capryl second
Oxygroup methylene -4- t-butyl carbamate) methane.
(3) preparation of final product { [1,6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } hexane: to
The mixed solution of methylene chloride and trifluoroacetic acid is added in three-necked bottle, and methylene chloride and trifluoroacetic acid volume ratio are 2:1；Will (1,2,
3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane is add to the above mixed solution, 50 DEG C of constant temperature reactions
2 hours, methylene chloride is added thereto and extracts 3 times, obtains organic layer, anhydrous Na2SO4Dry organic layer, is added 1,6 different dicyan
Acid esters, 1, hexamethylene-diisocyanate and 1,3- perfluoro octyl ethanol propyl ether -2- t-butyl carbamate) molar ratio of propane is 1:
2.1, it reacts 2 hours under the conditions of 55 DEG C, is washed crude product 4 times with the mixed solvent of ethyl acetate and benzene, filtered, vacuum is dry
It is dry, finally obtain final product { [1,6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } hexane.
It takes above-mentioned 1wt%, 2wt%, 3wt% supercritical carbon dioxide thickening agent to be added to respectively and installs corollary apparatus
In high temperature high pressure enclosed system；99wt%, 98wt%, 97wt% overcritical two is directed respectively into closed system by sampling valve
Carbonoxide.Rotor is rotated, regulating system pressure and temperature value, being sufficiently stirred is completely dissolved thickening agent, i.e. completion mixed system
Preparation；It is then turned on rheometer, setup pressure value 29MPa, temperature is 60 DEG C, it is 100s that shear rate is kept in experiment-1,
The viscosity number for measuring mixed system is respectively 5.85mPas, 6.76mPas and 7.82mPas；It is not thicken super face respectively
146.3 times, 169.0 times and 195.5 times of boundary's carbon dioxide viscosity.
Embodiment 3
(1) perfluoro octyl ethanol and tolysulfonyl the preparation to toluene perfluoro octyl sulfonic acid ester: are added into three-necked bottle
The molar ratio 1:1.15 of chlorine, perfluoro octyl ethanol and paratoluensulfonyl chloride, is eventually adding pyrido and is sufficiently stirred.It maintains the temperature at
It 10 DEG C, is sufficiently stirred, reacts 3 hours, filter paper is added after reaction, ultrasonic wave disperses 1 hour, removes unreacted to toluene
Then sulfonic acid chloride removes filter paper, then washs 5 times with 15% dilute hydrochloric acid and remove pyridine, obtain white solid, finally use distilled water
Washing 5 times, 40 DEG C are dried in vacuo 3 hours, and intermediate product (1) is made to toluene perfluoro octyl sulfonic acid ester
(2) preparation of (1,2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane: into three-necked bottle
(N- tert-butoxycarbonyl) serinol is added and to toluene perfluoro octyl sulfonic acid ester, (N- tert-butoxycarbonyl) serinol and to first
The ratio between benzene perfluoro octyl sulfonic acid ester is 3.15:1, adds potassium carbonate and N, N- dimethylformamide is sufficiently stirred, is warming up to 60
DEG C reaction 4h be washed with distilled water 4 times after reaction, be dried in vacuo to obtain intermediate product (2) i.e. (1,2,3- perfluoro capryl second
Oxygroup methylene -4- t-butyl carbamate) methane.
(3) preparation of final product { [1,6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } hexane: to
The mixed solution of methylene chloride and trifluoroacetic acid is added in three-necked bottle, and methylene chloride and trifluoroacetic acid volume ratio are 2:1；Will (1,2,
3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane is add to the above mixed solution, 50 DEG C of constant temperature reactions
2 hours, methylene chloride is added thereto and extracts 3 times, obtains organic layer, anhydrous Na2SO4Dry organic layer, is added 1,6 different dicyan
Acid esters, 1, hexamethylene-diisocyanate and 1,3- perfluoro octyl ethanol propyl ether -2- t-butyl carbamate) molar ratio of propane is 1:
2.1, it reacts 2 hours under the conditions of 55 DEG C, is washed crude product 5 times with the mixed solvent of ethyl acetate and benzene, filtered, vacuum is dry
It is dry, finally obtain final product { [1,6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } hexane.
It takes above-mentioned 1wt%, 2wt%, 3wt% supercritical carbon dioxide thickening agent to be added to respectively and installs corollary apparatus
In high temperature high pressure enclosed system；99wt%, 98wt%, 97wt% overcritical two is directed respectively into closed system by sampling valve
Carbonoxide.Rotor is rotated, regulating system pressure and temperature value, being sufficiently stirred is completely dissolved thickening agent, i.e. completion mixed system
Preparation；It is then turned on rheometer, setup pressure value 29MPa, temperature is 60 DEG C, it is 100s that shear rate is kept in experiment-1,
The viscosity number for measuring mixed system is respectively 6.43mPas, 6.97mPas and 7.45mPas；It is not thicken super face respectively
160.8 times, 174.3 times and 186.3 times of boundary's carbon dioxide viscosity.
Claims (2)
1. the preparation method that supercritical carbon dioxide thickening agent is used in a kind of hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation of spy, it is characterised in that should
Preparation method the following steps are included:
(1) preparation to toluene perfluoro octyl sulfonic acid ester: perfluoro octyl ethanol and paratoluensulfonyl chloride are added into three-necked bottle, entirely
The molar ratio 1:1.1-1.2 of fluorine octyl ethyl alcohol and paratoluensulfonyl chloride, is eventually adding pyrido and is sufficiently stirred；Maintain the temperature at 0-
It 20 DEG C, is sufficiently stirred, reacts 3 hours, filter paper is added after reaction, ultrasonic wave disperses 1 hour, removes unreacted to toluene
Sulfonic acid chloride, then removes filter paper, then is repeatedly washed with 15% dilute hydrochloric acid and removed pyridine, white solid is obtained, finally with distillation
Water repeatedly washs, and 40 DEG C are dried in vacuo 3 hours, and intermediate product (1) is made to toluene perfluoro octyl sulfonic acid ester；
(2) it the preparation of (1,2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane: is added into three-necked bottle
(N- tert-butoxycarbonyl) Pehanorm and to toluene perfluoro octyl sulfonic acid ester, (N- tert-butoxycarbonyl) trihydroxy methyl first
Amine and to toluene perfluoro octyl sulfonic acid ester molar ratio be 3.1-3.2:1, add potassium carbonate and n,N-Dimethylformamide, sufficiently
Stirring, be warming up to 60 DEG C of reaction 4h and repeatedly washed with distilled water after reaction, be dried in vacuo intermediate product (2) i.e. (1,
2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamates) methane；
(3) preparation of final product { [1,6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } hexane: to three necks
The mixed solution of methylene chloride and trifluoroacetic acid is added in bottle, and methylene chloride and trifluoroacetic acid volume ratio are 2:1；By (1,2,3- is complete
Fluorine octyl ethoxymeyhylene -4- t-butyl carbamate) methane is add to the above mixed solution, and 50 DEG C of constant temperature reactions 2 are small
When, methylene chloride is added thereto and extracts 3 times, obtains organic layer, uses anhydrous Na2SO4Dry organic layer, is added different two cyanic acid of 1-6
Ester, 1, mole of hexamethylene-diisocyanate and (1,2,3- perfluoro capryl ethoxymeyhylene -4- t-butyl carbamate) methane
Than being reacted 2 hours under the conditions of 55 DEG C, repeatedly washing crude product with the mixed solvent of ethyl acetate and benzene for 1:2.05-2.10,
Filtering, vacuum drying, finally obtain final product { [1,6- bis- [(1,2,3- perfluoro capryl ethoxymeyhylene) methylurea base] } oneself
Alkane.
2. the hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation of spy described in claim 1 application of supercritical carbon dioxide thickener, special
Sign is: taking above-mentioned 1wt%, 2wt%, 3wt% supercritical carbon dioxide thickener to be added to respectively and installs corollary apparatus
In high temperature high pressure enclosed system；99wt%, 98wt%, 97wt% overcritical two is directed respectively into closed system by sampling valve
Carbonoxide；Rotor is rotated, regulating system pressure and temperature value, being sufficiently stirred is completely dissolved thickening agent, i.e. completion mixed system
Preparation；Rheometer, setup pressure value 29MPa are opened, temperature is 60 DEG C, measures the viscosity number of mixed system and does not thicken
The viscosity of supercritical carbon dioxide is compared, and increases by 146~197 times.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN116874789A (en) * | 2023-08-03 | 2023-10-13 | 西南石油大学 | Supercritical carbon dioxide thickener with branched structure and preparation method thereof |
| CN117307120A (en) * | 2023-10-18 | 2023-12-29 | 成都赛璐石油科技有限公司 | Supercritical CO 2 Thickening fracturing-gas flooding-foam profile control and flooding yield increasing method |
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| CN116874789B (en) * | 2023-08-03 | 2023-11-24 | 西南石油大学 | Supercritical carbon dioxide thickener with branched structure and preparation method thereof |
| CN117307120A (en) * | 2023-10-18 | 2023-12-29 | 成都赛璐石油科技有限公司 | Supercritical CO 2 Thickening fracturing-gas flooding-foam profile control and flooding yield increasing method |
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