CN115873580A - High-temperature-resistant slow-release foam scrubbing agent and preparation method and application thereof - Google Patents
High-temperature-resistant slow-release foam scrubbing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN115873580A CN115873580A CN202111149638.8A CN202111149638A CN115873580A CN 115873580 A CN115873580 A CN 115873580A CN 202111149638 A CN202111149638 A CN 202111149638A CN 115873580 A CN115873580 A CN 115873580A
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- Prior art keywords
- temperature
- slow
- agent
- release
- reaction
- Prior art date
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- 239000006260 foam Substances 0.000 title claims abstract description 95
- 238000005201 scrubbing Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000004088 foaming agent Substances 0.000 claims abstract description 42
- 239000007787 solid Substances 0.000 claims abstract description 42
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 39
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 24
- 239000000945 filler Substances 0.000 claims abstract description 23
- -1 hydrogen ions Chemical group 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 9
- 125000005156 substituted alkylene group Chemical group 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- 150000001768 cations Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 238000007599 discharging Methods 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 41
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 31
- 238000013268 sustained release Methods 0.000 claims description 31
- 239000012730 sustained-release form Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 235000002639 sodium chloride Nutrition 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 108090000790 Enzymes Proteins 0.000 claims description 9
- 102000004190 Enzymes Human genes 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
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- 238000001179 sorption measurement Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 4
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- 239000011248 coating agent Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
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- 108090000604 Hydrolases Proteins 0.000 claims description 2
- 102000004157 Hydrolases Human genes 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- GOMCKELMLXHYHH-UHFFFAOYSA-L dipotassium;phthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC=C1C([O-])=O GOMCKELMLXHYHH-UHFFFAOYSA-L 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
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- 150000005309 metal halides Chemical class 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
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- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
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- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
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- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000002702 enteric coating Substances 0.000 description 1
- 238000009505 enteric coating Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- JXBPSENIJJPTCI-UHFFFAOYSA-N ethyl cyanate Chemical compound CCOC#N JXBPSENIJJPTCI-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229940045845 sodium myristate Drugs 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 1
- 239000008259 solid foam Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention discloses a high-temperature-resistant slow-release foam scrubbing agent and a preparation method and application thereof, wherein the foam scrubbing agent comprises a slow-release material, a foaming agent, a solid filler and an adhesive; the foaming agent is selected from at least one of the following formulas (I):
R 2 、R 3 each independently from hydrogen, C 1 ～C 10 Or a hydrocarbon radical of C 1 ～C 10 Substituted hydrocarbyl groups of (a); m is selected from hydrogen ions, cations or cationic groups, the repeating M being the same or different; j =1, j' =1 or 0; r 1 Is N (H) J R 4 OR-OR 5 (O) J ‑，J+j’＝1，R 4 Is selected from C 1 ～C 40 Alkylene or C 1 ～C 40 Substituted alkylene of (A), R 5 Is selected from C 1 ～C 40 Alkylene of (C) 1 ～C 40 Substituted alkylene of (2), R 7 C 6 H 4 Or R 7 C 10 H 6 ，R 7 Is C 1 ～C 30 Alkylene or C 1 ～C 30 Substituted alkylene groups of (2). May be used in, but is not limited to, formations having temperatures between 90 and 200 c.
Description
Technical Field
The invention belongs to the field of foam scrubbing agents, and particularly relates to a high-temperature-resistant slow-release foam scrubbing agent as well as a preparation method and application thereof.
Background
The foam drainage gas production has the advantages of simple equipment, convenient construction, low cost, wide applicable well depth range, no influence on the normal production of gas wells and the like. Foam drainage is to inject foam drainage agent into a well through an oil pipe or an oil casing annular space, and foam with certain stability is generated under the stirring of airflow. The liquid phase slipped and deposited in the pipe is changed into foam, the relative density of fluid at the lower part in the pipe is changed, and the continuously produced gas phase displacement foam flows out of the shaft, so that the accumulated liquid in the shaft is discharged, and the purposes of water drainage and gas production are achieved.
The slow release technology is applied in the fields of agriculture, medicines, oilfield chemicals and the like. The slow release technology is applied to the corrosion inhibitor in the oil field on site, such as a slow release type solid corrosion and scale inhibitor applied to the Dongxin oil field, and then is expanded to other directions in the oil field, such as well drilling and cementing cement slurry and the like. The application of the foam discharging agent is very little, for example, a study on a slow release type foaming agent is carried out in patent 201910207263.2, a surfactant foaming agent is mixed with 5-20% of enteric coating, the action time is up to 120 hours (5 days), but the use temperature of the technology is lower than 90 ℃, and the defects of short storage period of less than 3 months, inconsistent batch quality and the like of animal materials exist.
The results show that the insufficient high-temperature resistance of the existing slow-release material and the foam scrubbing agent is a main factor for restricting the development of the foam drainage technology of the high-temperature ultra-deep gas well aiming at the high-temperature gas well above 90 ℃.
Disclosure of Invention
The invention aims to solve the technical problem that the existing foam discharging agent cannot effectively and continuously carry liquid due to high dissolution speed in the high-temperature acidic environment of an ultra-deep gas well, and provides a high-temperature-resistant slow-release foam discharging agent, a preparation method and application thereof.
One of the purposes of the invention is to provide a high-temperature resistant slow-release foam scrubbing agent, which comprises a slow-release material, a foaming agent, a solid filler and an adhesive; wherein the foaming agent is selected from at least one surfactant shown in a formula (I):
in the formula (I), R 2 、R 3 Each independently from hydrogen, C 1 ～C 10 Or a hydrocarbon radical of C 1 ～C 10 Substituted hydrocarbyl groups of (a); m is selected from hydrogen ions, cations or cationic groups, the repeating M are the same or different and two M are not H at the same time; j =1,j' =1 or 0; r is 1 Is N (H) J R 4 OR-OR 5 (O) J -，J+j’＝1，R 4 Is selected from C 1 ～C 40 Alkylene or C of 1 ～C 40 Substituted alkylene of (A), R 5 Is selected from C 1 ～C 40 Alkylene group of (C) 1 ～C 40 Substituted alkylene of (2), R 7 C 6 H 4 Or R 7 C 10 H 6 ，R 7 Is C 1 ～C 30 Alkylene or C of 1 ～C 30 Substituted alkylene groups of (1).
Wherein, C 6 H 4 Is phenylene, C 10 H 6 Is naphthylene. The cation is preferably a metal ion and the cationic group is preferably an ammonium group or a substituted amino group.
In this application, R 1 The amide group is not contained (the amide group is only used at 90 ℃ or below), and the amide group can be used at high temperature.
In a preferred embodiment, in formula (I), R 2 、R 3 Each independently from hydrogen, C 1 ～C 5 Or a hydrocarbon radical of C 1 ～C 5 Substituted hydrocarbyl groups of (a); m is selected from hydrogen ion, cation or cationA subgroup in which the repeating M are the same or different and two M are not H at the same time; j =1, j' =1 or 0; r is 1 Is N (H) J R 4 OR-OR 5 (O) J -，J+j’＝1，R 4 Is C 2 ～C 32 Alkylene or C of 2 ～C 32 Substituted alkylene of (A), R 5 Is R 7 C 6 H 4 Or R 7 C 10 H 6 ，R 7 Is C 1 ～C 24 Alkylene or C of 1 ～C 24 Substituted alkylene groups of (2).
In a further preferred embodiment, in formula (I), R 2 、R 3 Each independently from hydrogen, C 1 ～C 2 Or a hydrocarbon radical of C 1 ～C 2 Substituted hydrocarbyl groups of (a); m is selected from hydrogen, sodium ion, potassium ion, ammonium ion, repeated M is same or different, and two M are not hydrogen at the same time; j =1, j' =1 or 0; r is 1 Is N (H) J R 4 OR-OR 5 (O) J -，J+j’＝1，R 4 Is C 12 ～C 28 Alkylene or C of 12 ～C 28 Substituted hydrocarbylene groups of (a); r is 5 Is R 7 C 6 H 4 、R 7 C 10 H 6 ，R 7 Is C 4 ～C 18 Alkylene or substituted alkylene of (a).
Among them, the inventors found through a lot of experiments that when R is 1 Is N (H) J R 4 The effect (such as high bubble, 5min bubble and liquid carrying rate) is better than that when R is used 1 Is N (H) J R 4 time-OR 5 (O) J -。
In a preferred embodiment, the foaming agent is a combination of a surfactant represented by formula (I) with j ' =0 and a surfactant represented by formula (I) with j ' =1, preferably, wherein the molar ratio of the surfactant represented by formula (I) with j ' =1 in the foaming agent is 10 to 95mol%, preferably 20 to 90mol%.
For example, the molar ratio of the surfactant represented by formula (I) in which j' =1 in the blowing agent is 10mol%, 20mol%, 30mol%, 40mol%, 50mol%, 60mol%, 70mol%, 80mol%, 90mol%, or 95mol%.
In the present invention, the blowing agent optionally further contains (H) j’ R 1 H, wherein R 1 、R 4 、R 5 Have the same definition as formula (I). Preferably, (H) j’ R 1 The molar ratio of H in the blowing agent is 0 to 20mol%, preferably 0 to 15mol%.
For example, (H) j’ R 1 The molar ratio of H in the blowing agent is 0mol%, 5mol%, 10mol%, 15mol% or 20mol%.
In a preferred embodiment, the solid filler is at least one selected from the group consisting of carboxylate, carbonate, bicarbonate, sulfate, bisulfate, phosphate, borate, metal halide, urea, thiourea, and biuret.
In a further preferred embodiment, the solid filler is selected from at least one of sodium carbonate, sodium bicarbonate, sodium borate, sodium chloride, sodium acetate, tartaric acid, sodium tartrate, citric acid, sodium citrate, potassium phthalate, urea, biuret.
In a preferred embodiment, the binder is selected from at least one of dextrin, epoxy resin, polyacrylamide, starch, cellulose, polyethylene glycol.
In a further preferred embodiment, the binder is selected from at least one of polyacrylamide, starch, polyethylene glycol.
In a preferred embodiment, the slow release material is at least one of polyester, polyamide, polyurethane that slowly degrades, hydrolyzes or dissolves under formation conditions.
In the prior art, PVA and enteric acrylic resin are slow release materials, but the PVA and the enteric acrylic resin are copolymerization products generated on carbon-carbon chains, and although hydrolysis and degradation can occur to a certain degree under the influence of pH and temperature, the temperature resistance of the PVA and the enteric acrylic resin is poor, the PVA and the enteric acrylic resin can only achieve a slow release effect at 90 ℃ or even lower temperature, and effective slow release cannot be achieved under the environment of a high-temperature gas well of an ultra-deep well.
In a preferred embodiment, the polyester is formed by polycondensation of polybasic acid and polyhydric alcohol, and has a structural general formula shown in a formula (II);
in the formula (II), R 8 And R 9 Each independently selected from C 2 ～C 30 Alkylene group of (C) 2 ～C 30 Substituted alkylene of (A), C 6 ～C 40 Arylene group of (A) or (C) 6 ～C 40 Copolymerization of one or more than two of the substituted arylene groups; n =1 to 500.
For example, n =1, 5, 10, 30, 50, 70, 90, 100, 150, 200, 250, 300, 350, 400, 450, or 500.
In a further preferred embodiment, the polyester is selected from at least one or more than two copolymerization systems or modification systems of polyethylene terephthalate, polybutylene terephthalate, polyethylene adipate, polybutylene adipate, polyethylene terephthalate, polybutylene terephthalate, and a condensation polymer of poly (diphenyl terephthalate).
In a further preferred embodiment, the polyester is selected from at least one copolymerized or modified system of two or more of polyethylene adipate, polybutylene adipate, polyethylene terephthalate, polybutylene terephthalate polycondensates.
In a preferred embodiment, the polyamide is a polymer containing recurring amide groups- (CONH) -in the main molecular chain, having the general structural formula of formula (III):
in the formula (III), R 10 And R 11 Each independently selected from C 2 ～C 30 Alkylene group of (C) 2 ～C 30 Substituted alkylene of (A), C 6 ～C 40 Arylene group of (A) or (C) 6 ～C 40 Copolymerization of one or more than two kinds of substituted arylene groups; p and q are each independently 1 to 500.
For example, p, q are each independently =1, 5, 10, 30, 50, 70, 90, 100, 150, 200, 250, 300, 350, 400, 450, or 500.
In a further preferred embodiment, the polyamide is selected from at least one or more copolymerization or modification systems of polyamide 6, polyamide 11, polyamide 66, polyamide 1010.
The slow release material is a slow release material with excellent high temperature resistance, has a stable structure before entering the well bottom due to higher glass transition temperature, contains functional groups responding to water in a molecular structure, and gradually breaks off chemical bonds under the environment of a high-temperature acid gas well of an ultra-deep well, so that the effective components of the foam discharging agent are slowly released, and the aim of continuously carrying liquid is fulfilled.
In a preferred embodiment, the weight ratio of the slow-release material, the foaming agent, the solid filler and the adhesive is 1: (0.5-50): (1-50): (0.01-1.0).
In a further preferred embodiment, the weight ratio of the slow-release material, the foaming agent, the solid filler and the binder is 1: (1-15): (2-25): (0.02-0.5).
For example, the weight ratio of the slow-release material to the foaming agent is 1; the weight ratio of the slow-release material to the solid filler is 1; the weight ratio of the slow-release material to the adhesive is 1.
The foaming agent, the slow release material, the solid filler and the adhesive which are key effective components of the foam scrubbing agent have good compatibility to form a slow release solid composition.
The high-temperature resistant slow-release foam scrubbing agent comprises the following components:
firstly, a carboxylate foaming agent containing stable chemical bonds is adopted, the thermal decomposition temperature is 200 ℃ or above, the carboxylate foaming agent is not hydrolyzed or hydrolyzed in a trace amount in an acidic aqueous solution, and the carboxylate foaming agent has good temperature resistance; in addition, the molecular structure of the foaming agent contains heteroatoms responding to pH, protonation reaction can be carried out under an acidic condition to form a quaternary ammonium ion head group, the water solubility of the foaming agent is increased, and the aim of further stabilizing foam is fulfilled by improving the separation pressure between foam liquid membranes, so that the foaming agent is more suitable for the drainage and gas production process of acid gas wells.
Secondly, a high-temperature degradation or high-temperature dissolution type slow release material is adopted, a molecular chain contains ester groups and/or amide groups which respond to temperature and acid, the melting, dissolution and degradation speeds of the slow release material are intelligently regulated and controlled by utilizing the temperature field change from the well mouth to the well bottom, the dissolution speed of the foam scrubbing agent after meeting water is reduced, the effective action time of the foam scrubbing agent is prolonged, and the purpose of reducing the foam scrubbing operation times of opening a well containing acidic gas is achieved.
The second purpose of the invention is to provide a preparation method of the high-temperature resistant sustained-release foam scrubbing agent, which is preferably used for preparing the high-temperature resistant sustained-release foam scrubbing agent of the first purpose of the invention, and comprises the following steps: and mixing the foaming agent, the slow-release material, the solid filler and the adhesive according to the weight ratio to obtain the high-temperature-resistant slow-release foam scrubbing agent.
In a preferred embodiment, the foaming agent, the slow release material, the solid filler and the adhesive are mixed by high-temperature melting, cementing, coating or adsorption impregnation, and preferably by cementing, coating or adsorption impregnation.
In a further preferred embodiment:
the cementitious bond proceeds as follows: mixing the foaming agent and the sustained-release material according to the weight ratio, transferring the mixture into a mold filled with solid filler and adhesive, and performing compression molding to prepare the high-temperature-resistant sustained-release foam scrubbing agent;
or the like, or a combination thereof,
the coating was carried out as follows: mixing the foaming agent, the solid filler and the adhesive according to the weight ratio, pouring the mixture into a mold for compression molding to obtain a foam discharging agent molded body, spraying the slow release material on the surface of the foam discharging agent molded body, and cooling, airing or drying to obtain the high-temperature-resistant slow release foam discharging agent;
preferably, the slow release material for spraying is in a molten state or a solution state.
Or the like, or, alternatively,
the adsorption impregnation is carried out as follows: adding the foaming agent into a solution containing a slow-release material according to the weight ratio, soaking, removing the solvent, mixing with the solid filler and the adhesive, and putting into a mold for compression molding to obtain the high-temperature-resistant slow-release foam scrubbing agent;
preferably, the concentration of the solution containing the sustained-release material is 5 to 60wt% (based on the weight of the sustained-release material).
In a preferred embodiment, the blowing agent is prepared as follows:
(1) Using NCCR 2 ＝CHR 3 And (H) j’ R 1 H, reacting to obtain a cyano intermediate;
wherein R is 1 、R 2 、R 3 Having the same definition as formula (I), i.e., (H) j’ R 1 H is R 4 NH 2 、HOR 5 H or HOR 5 OH(H) j’ R 1 H，R 4 、R 5 Has the same definition as formula (I), x =1 or 0; .
(2) In the presence of a catalyst, the cyano intermediate is reacted in a solution of water and/or alcohol, and then optionally adding a base into the system to continue the reaction to obtain the foaming agent.
Wherein the cyano intermediate has a structural general formula of [ NCCH (R) 2 )CH(R 3 )] j R 1 [CH(R 3 )CH(R 2 )CN] j’ Wherein R is 2 、R 3 、R 1 J, j' have the same definitions as formula (I).
In a preferred embodiment, in step (1), R 2 、R 3 Each independently from hydrogen, C 1 ～C 10 Or C is a hydrocarbon group 1 ～C 10 Substituted hydrocarbyl groups of (a); j' =1 or 0, R 1 Is N (H) J R 4 OR-OR 5 (O) J -，J+j’＝1，R 4 Is selected from C 1 ～C 40 Alkylene or C 1 ～C 40 Substituted alkylene of (A), R 5 Is selected from C 1 ～C 40 Alkylene of (C) 1 ～C 40 Substituted alkylene of (2), R 7 C 6 H 4 Or R 7 C 10 H 6 ，R 7 Is C 1 ～C 30 Alkylene or C 1 ～C 30 Substituted alkylene groups of (1).
In a further preferred embodiment, in step (1), R 2 、R 3 Each independently from hydrogen, C 1 ～C 5 Or C is a hydrocarbon group 1 ～C 5 Substituted hydrocarbyl groups of (a); j' =1 or 0, R 1 Is N (H) J R 4 OR-OR 5 (O) J -，J+j’＝1，R 4 Is C 2 ～C 32 Alkylene or C 2 ～C 32 Substituted alkylene of (2), R 5 Is R 7 C 6 H 4 Or R 7 C 10 H 6 ，R 7 Is C 1 ～C 24 Alkylene or C 1 ～C 24 Substituted alkylene groups of (1).
In a further preferred embodiment, in step (1), R 2 、R 3 Each independently from hydrogen, C 1 ～C 2 Or C is a hydrocarbon group 1 ～C 2 Substituted hydrocarbyl groups of (a); j' =1 or 0, R 1 Is N (H) J R 4 OR-OR 5 (O) J -，J+j’＝1，R 4 Is C 12 ～C 28 Alkylene or C 12 ～C 28 Substituted hydrocarbylene groups of (a); r is 5 Is R 7 C 6 H 4 、R 7 C 10 H 6 ，R 7 Is C 4 ～C 18 Alkylene or substituted alkylene of (a).
In a preferred embodiment, in step (1), NCCR 2 ＝CHR 3 And (H) j’ R 1 The molar ratio of H is (1-15): 1, preferably (1-10): 1.
In a further preferred embodiment, in step (1), NCCR 2 ＝CHR 3 And (H) j’ R 1 The molar ratio of H is (1-2): 1, preferably (1-1.5): 1, and the final product is mainly monocarboxylic acid groups; or, NCCR 2 ＝CHR 3 And (H) j’ R 1 The molar ratio of H is (2-15): 1 and no 2, preferably (2-8): 1, and the final product obtained is a monocarboxylic acid based dicarboxyl combination.
In a preferred embodiment, in step (1), the temperature of the reaction is 20 to 300 ℃; and/or the reaction time is 2-15 h.
For example, in step (1), the temperature of the reaction is 20 ℃, 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃; and/or the reaction time is 2h, 5h, 8h, 10h, 12h or 15h.
In a further preferred embodiment, when NCCR 2 ＝CHR 3 And (H) j’ R 1 When the molar ratio of H is (1-2) to 1 (preferably (1-1.5) to 1), the reaction temperature is 20-300 ℃, and a monocyano intermediate is obtained; and/or, when NCCR 2 ＝CHR 3 And (H) j’ R 1 When the molar ratio of H is (2-15): 1 and 2 is not contained (1) [ preferably (2-8): 1 ], the reaction temperature is 20-300 ℃ to obtain a mixture of a monocyano intermediate and a dicyano intermediate or a dicyano intermediate.
In the present invention, incompletely reacted (H) may be present in the blowing agent j’ R 1 H. Unreacted raw material amine in the cyanation reaction can also undergo an ionization reaction, so that the effective concentration of the foam discharging agent is increased, and the improvement of the foam performance is facilitated.
In a preferred embodiment, in step (1), the NCCR is used 2 ＝CHR 3 Drop adding (H) j’ R 1 And (H) in the reaction kettle.
In a further preferred embodiment, the dropwise addition is carried out at 20 to 40 ℃ and the reaction after completion of the dropwise addition is carried out at 50 to 300 ℃.
For example, the dropwise addition is carried out at 20 ℃,30 ℃ or 40 ℃, and the reaction after the completion of the dropwise addition is carried out at 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃.
In a further preferred embodiment, when NCCR is used 2 ＝CHR 3 And (H) j’ R 1 When the molar ratio of H is (1-2): 1 [ preferably (1-1.5): 1 ], the dropwise addition is carried out at 20-40 ℃, and the reaction after the dropwise addition is carried out at 50-120 ℃ (preferably 2-15H, for example, 5-10H) to obtain a monocyanointermediate; and/or, when NCCR 2 ＝CHR 3 And (H) j’ R 1 When the molar ratio of H is (2 to 15): 1 and 2 is not contained (1) [ (preferably (2 to 8): 1) ], the dropwise addition is carried out at 20 to 40 ℃, the reaction after the completion of the dropwise addition is carried out at 50 to 120 ℃ (preferably 2 to 10 hours, for example, 3 to 8 hours), and the reaction is continued at 130 to 300 ℃ (preferably 1 to 5 hours, for example, 2 to 4 hours) to obtain a mixture of a monocyano intermediate and a dicyano intermediate or a dicyano intermediate.
Wherein, the generation of the dinitrile product is carried out step by step, the mononitrile is generated firstly, the continuous reaction of the mononitrile needs to overcome the steric hindrance, and higher energy is needed, so the reaction temperature must be further increased.
In a preferred embodiment, in step (1), after the completion of the reaction, a reduced pressure treatment is carried out to remove unreacted raw materials, particularly unreacted NCCR 2 ＝CHR 3 。
In a preferred embodiment, in step (2), the catalyst is at least one selected from the group consisting of an acid, a base, and a biological enzyme.
In a further preferred embodiment, the acid is selected from at least one of hydrochloric acid, sulfuric acid, phosphoric acid; and/or the alkali is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; and/or, the biological enzyme is selected from at least one of cyano hydrolase (Nitrilase), cyano Hydratase (NitrilHydratase) and Amidase (Amidase).
In a further preferred embodiment, the molar ratio of the catalyst to the cyano intermediate is (0.01-5): 1, preferably (0.1-3): 1, wherein the molar amount of the cyano intermediate is the molar amount of cyano groups therein.
For example, the molar ratio of the catalyst to the cyano intermediate is 0.01.
In a preferred embodiment, in step (2), the alcohol is at least one selected from methanol, ethanol, propanol, isopropanol, and ethylene glycol.
In a further preferred embodiment, in step (2), when the reaction is carried out in a solution of water and alcohol, the volume ratio of water to alcohol is 7.
Among them, the hydrolysis reaction is preferably carried out in the step (2).
In a preferred embodiment, in step (2), the temperature of the reaction is 20 to 150 ℃; and/or the reaction time is 5-50 h.
In a further preferred embodiment, in step (2), when the catalyst is selected from the group consisting of a base and/or an acid, the reaction is carried out at 40 to 150 ℃, preferably at reflux temperature; when the catalyst is selected from biological enzymes, the reaction is carried out at 20-40 ℃.
In a preferred embodiment, in step (2), when the catalyst is selected from bases, no further base is added to the system; when the catalyst is selected from acid, adding alkali into the system to continue the reaction; when the catalyst is selected from the group consisting of biological enzymes, the reaction is carried out using a buffer solution containing the biological enzymes, for example, the buffer solution is selected from the group consisting of potassium dihydrogen phosphate/sodium hydroxide buffer, potassium dihydrogen phosphate/dipotassium hydrogen phosphate buffer, disodium hydrogen phosphate/citric acid.
In a preferred embodiment, in step (2), the solvent is removed after the reaction is completed, preferably by distillation or distillation under reduced pressure.
In the invention, the high-temperature resistant slow-release foam scrubbing agent is one or a mixture of more than two of a sphere, a rod and a square.
The third purpose of the invention is to provide the application of the high-temperature-resistant slow-release foam discharging agent for the first purpose of the invention or the high-temperature-resistant slow-release foam discharging agent obtained by the preparation method for the second purpose of the invention in liquid drainage and gas production.
The fourth purpose of the invention is to provide a liquid drainage and gas production method, which comprises the following steps:
(1) Soaking the foam water discharging agent of the first purpose of the invention or the high-temperature resistant slow-release foam water discharging agent obtained by the preparation method of the second purpose of the invention into (certain pH value) stratum simulation brine or actual stratum;
(2) And heating (when stratum simulation brine is adopted) or under the action of the temperature of the stratum, slowly dissolving and releasing the high-temperature-resistant slow-release foam discharging agent, and then fully contacting with gas to form foam fluid, and carrying out water in the foam discharging agent solution.
In a preferred embodiment, the gas is at least one of air, nitrogen, methane or natural gas, with or without H 2 S and/or CO 2 An acid gas.
In a preferred embodiment, the gas production method is applicable to a stratum which is a high-temperature acid gas-containing gas reservoir, the temperature of the stratum is 90-200 ℃, the total mineralization degree of stratum saline water is 1000-200000 mg/L, and acid gas H 2 S and/or CO 2 The content of (A) is 0 to 30% (for example, 0 is not contained).
The method for liquid drainage and gas production can also comprise methods such as gas lift, mechanical pumping and the like commonly used in the field.
In the present invention, the content or concentration of the foam discharging agent refers to the content or concentration of the blowing agent represented by the molecular formula (I) in the above technical scheme.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) The liquid drainage gas production method can be used for but not limited to the stratum temperature of 90-200 ℃, the total salinity of stratum salt water of 1000-200000 mg/L and H 2 S and CO 2 A high-temperature gas reservoir containing 0 to 30% (for example, 0 is not contained).
(2) According to the mass percentage, 0.1wt% of foaming agent is used in 0-200,000mg/L salinity saline, the foaming height reaches 167mm before and after high-temperature aging, and the liquid carrying rate reaches 92.1%; the high-temperature resistant slow-release foam water draining agent with the dosage of 0.1wt% is added into mineralized saline with the salinity of 0-200,000mg/L, the foaming height reaches 168mm before and after high-temperature aging, the liquid carrying rate reaches 92.3%, and the high-temperature resistant slow-release foam water draining agent has excellent foaming and liquid carrying performances in an acid environment and achieves better technical effects.
Drawings
FIG. 1 is a schematic view showing a flow of measuring the amount of liquid carried by a foam drainage agent. Wherein, 1 is a constant temperature water bath, 2 is a measuring cup, 3 is circulating water, 4 is a foam collector, 5 is a foaming pipe, 6 is a test solution, 7 is a rotameter, and 8 is a gas cylinder.
FIG. 2 shows the composition of the product in the synthesis of 2a, as measured by HPLC, and the content is normalized by area. Wherein, 1 is octadecyl amine sodium propionate, the content is 98.9 percent; 2 is N-cyanoethyl octadecyl amine with the content of 1.1 percent; 3 is the solvent peak, not integrated.
FIG. 3 shows the composition of the product of the 2b synthesis by HPLC, the content being determined by area normalization. Wherein, 1 is octadecyl amine potassium dipropionate with the content of 59.6 percent; 2 is octadecyl amine potassium propionate content of 41.8%,3 is N, N-dicyanoethyl octadecyl amine, 4 is content of 0.9%, N-cyanoethyl octadecyl amine, content of 0.4%;5 is the solvent peak, not integrated.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be noted that the various features described in the following detailed description may be combined in any suitable manner without contradiction. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art. Nitrilase (nitrilase 1 antibody) was purchased from Shanghai Brasenia schreberi Biotech limited.
The invention adopts a high-temperature aging method to measure the slow release performance of the slow release material, and the specific evaluation method comprises the following steps: the slow release material is immersed in the water solution of a pressure vessel, the pH value is adjusted, and the temperature is raised and the slow release material is aged for a certain time. And cooling, releasing pressure, opening the pressure container, observing the appearance of the slow-release material, judging whether the material is changed and damaged according to the standard of whether the material is agglomerated or not, whether the material can be torn or not and whether the solution is precipitated or not, and deducing the hydrothermal stability of the slow-release material according to the damage time.
The invention adopts the measurement of foaming, foam stabilizing and liquid carrying performances of the foam drainage agent to evaluate the foam drainage performance, and evaluates the high temperature resistance of the foam drainage agent by comparing the foaming, foam stabilizing and liquid carrying performances before and after high-temperature aging, wherein the specific evaluation method comprises the following steps:
(1) Foam row performance
The initial foaming height of the foam drainage agent and the foaming height after a certain period of time were measured by a Roche foam tester (ROSS-Miles method) to evaluate the foaming ability and foam stabilizing ability. Continuously introducing gas with a certain flow rate into the foam water discharging agent solution or the mixed solution of the foam water discharging agent solution and the oil to form foam, measuring the amount of liquid (water, oil and water) carried out by the foam after a certain time, calculating the liquid carrying rate, and evaluating the liquid carrying capacity of the foam water discharging agent solution.
(2) High temperature resistance
And (3) after the foam drainage agent solution is aged at high temperature by adopting a pressure-resistant and acid-resistant aging device, measuring the foam drainage performance and the high-temperature resistance again.
The method for measuring the release rate adopted by the invention comprises the following steps:
(3) Static release rate
Taking a small block of solid sustained-release foam discharging agent with a regular shape, drying in a vacuum oven, measuring the size of the solid sustained-release foam discharging agent, calculating the surface area s of the solid sustained-release foam discharging agent, and accurately weighing the mass m 0 And putting into a container with a sealing cover. Heating the stratum simulated salt water to the required temperature, pouring the stratum simulated salt water into a container containing the solid slow-release foam discharging agent, after a certain time t (ensuring that the solid slow-release foam discharging agent is not completely dissolved), carrying out suction filtration, drying the solid foam discharging agent residues in vacuum, and weighing the mass m 1 The static sustained-release rate θ is calculated according to the following formula (1) 1 。
θ 1 ＝(m 1 -m 0 )/(s×t)
Formula (1)
Wherein, theta 1 : the slow release rate of the solid slow release foam discharging agent is g.cm -2 .d -1 ；m 0 : mass g before dissolution of the solid sustained-release foam discharging agent; m is 1 : the residual mass, g, of the dissolved solid sustained-release foam discharging agent; s: surface area, cm, of solid slow-release foam-discharging agent 2 (ii) a Dissolution time, d.
(4) Dynamic release rate
The difference from the method (3) is that stirring is started during dissolution to simulate the flow of water in a gas well, the control speed is about 1m/s, and the dynamic slow-release speed theta is calculated according to the following formula (2) during slow-release speed measurement 2 。
θ 2 ＝(m 1 -m 0 )/(s×t)
Formula (2)
Wherein, theta 2 : the slow release rate of the solid slow release foam discharging agent is g.cm -2 .d -1 ；m 0 : mass g before dissolution of the solid sustained-release foam discharging agent; m is a unit of 1 : the residual mass, g, of the dissolved solid sustained-release foam discharging agent; s: surface area, cm, of solid slow-release foam-discharging agent 2 (ii) a Dissolution time, d.
[ example 1 ] preparation of blowing agent
(1) Cyanidation to prepare cyano intermediate [ NCCH (R) 2 )CH(R 3 )] j R 1 [CH(R 3 )CH(R 2 )CN] j’ Wherein R is 2 、R 3 、R 1 J, j' have the same definitions as in formula (I).
Synthesis of 1 a: 269.0 g (1.0 mol) of octadecylamine is added into a reaction kettle equipped with a mechanical stirrer, a thermometer and a dropping funnel, 63.6 g (1.2 mol) of acrylonitrile (with a polymerization inhibitor) is slowly dropped into the reaction kettle while stirring, the dropping temperature is controlled to be about 30 ℃, the dropping is finished, the temperature is raised to 80 ℃ for reaction for 7 hours, the unreacted acrylonitrile is removed by reduced pressure evaporation to obtain a cyano compound 1a, the content of the N-cyanoethyl octadecylamine in the product is 95.2 percent and the content of the octadecylamine is 4.8 percent as measured by High Performance Liquid Chromatography (HPLC), and the content adopts an area normalization method, and the result is shown in Table 1.
(2) Preparation of surfactants of formula (I) by hydrolysis
Synthesis of 2 a: adding 44.1 g (1.1 mol) of sodium hydroxide solid and 200 g of ethanol/water solution (ethanol water volume ratio is 1) into a reaction kettle, stirring to dissolve, adding 322.4 g (1.0 mol, M = 322) of 1a, heating to reflux reaction for about 12 hours, taking a small sample, distilling to remove ethanol, acidifying to pH = 2-3 to obtain a carboxylic acid compound, and controlling the reaction progress by infrared spectroscopy, namely at 2230cm -1 The reaction was stopped by the substantial disappearance of the cyano peak on the left and right. After ethanol is distilled off from the rest samples, water is added to adjust the content to be about 35.0%, the pH = 12-13, and the content of the octadecyl amine sodium propionate in the product is 98.9% and the content of the N-cyanoethyl octadecyl amine is 1 by High Performance Liquid Chromatography (HPLC).1% by area normalization, the results are shown in Table 2.
[ example 2 ] preparation of blowing agent
(1) Cyanidation to prepare cyano intermediate [ NCCH (R) 2 )CH(R 3 )] j R 1 [CH(R 3 )CH(R 2 )CN] j’ Wherein R is 2 、R 3 、R 1 J, j' have the same definitions as formula (I).
Synthesis of 1 b: 269.0 g (1.0 mol) of octadecylamine is added into a reaction kettle equipped with a mechanical stirrer, a thermometer and a dropping funnel, 212.0 g (4 mol) of acrylonitrile (with a polymerization inhibitor) is slowly dropped into the reaction kettle under stirring, the dropping temperature is controlled to be about 30 ℃, the dropping temperature is completely raised to 80 ℃ for reaction for 5 hours, the reaction is continued for 3 hours after the dropping is finished, the excessive acrylonitrile is evaporated under reduced pressure to obtain a cyano compound 1b, the content of N, N-dicyanoethyl octadecylamine in the product is 57.2 percent, the content of N-cyanoethyl octadecylamine is 40.9 percent and the content of octadecylamine is 1.9 percent according to High Performance Liquid Chromatography (HPLC), and the results are shown in Table 1.
(2) Preparation of surfactants of formula (I) by hydrolysis
2b Synthesis: adding 117.6 g (2.1 mol) of potassium hydroxide solid and 500 g of isopropanol/water solution (isopropanol water volume ratio 1) -1 The reaction was stopped by the substantial disappearance of the cyano peak on the left and right. After the isopropanol of the rest samples is distilled off, water is added to adjust the content to be about 35.0%, the pH is = 12-13, the content of octadecyl amine dipropionate potassium in the product is 59.6%, the content of octadecyl amine propionate is 41.8%, the content of N, N-dicyanoethyl octadecyl amine is 0.9%, the content of N-cyanoethyl octadecyl amine is 0.4% by High Performance Liquid Chromatography (HPLC), and the result is shown in table 2 by adopting an area normalization method.
[ example 3 ] preparation of blowing agent
(1) Cyanidation to prepare cyano intermediate [ NCCH (R) 2 )CH(R 3 )] j R 1 [CH(R 3 )CH(R 2 )CN] j’ Wherein R is 2 、R 3 、R 1 J, j' have the same definitions as in formula (I).
Reference to the synthesis of 1a, the difference is: substituting dodecylamine for octadecylamine, the molar ratio of acrylonitrile to dodecylamine was 1, 1c was synthesized, and the reaction conditions and product distribution are shown in table 1.
(2) Preparation of surfactants of formula (I) by hydrolysis
2c Synthesis: referring to the preparation of 2a, 2c was synthesized with the product distribution shown in table 2.
[ example 4 ] preparation of blowing agent
(1) Cyanidation to prepare cyano intermediate [ NCCH (R) 2 )CH(R 3 )] j R 1 [CH(R 3 )CH(R 2 )CN] j’ Wherein R is 2 、R 3 、R 1 J, j' have the same definitions as formula (I).
Reference 1b synthesis method, difference is: substituting dodecylamine for octadecylamine, the molar ratio of acrylonitrile to dodecylamine was 5, 1d was synthesized, and the reaction conditions and product distribution are shown in table 1.
(2) Preparation of surfactants of formula (I) by hydrolysis
2d Synthesis: referring to the preparation of 2b, except that solid potassium hydroxide was replaced with solid sodium hydroxide, 2d was synthesized and the product distribution is shown in table 2.
[ example 5 ] preparation of blowing agent
(1) Cyanidation to prepare cyano intermediate [ NCCH (R) 2 )CH(R 3 )] j R 1 [CH(R 3 )CH(R 2 )CN] j’ Wherein R is 2 、R 3 、R 1 J, j' have the same definitions as in formula (I).
Reference to the synthesis of 1a, the difference is: hexadecylamine is adopted to replace octadecylamine, 2-methyl-2-butenenitrile is adopted to replace acrylonitrile, the molar ratio of the 2-methyl-2-butenenitrile to the hexadecylamine is 1.
(2) Preparation of surfactants of formula (I) by hydrolysis
2e Synthesis: 3000 ml of a buffer solution of dipotassium hydrogenphosphate and potassium dihydrogenphosphate having a pH of 7.5 to 8.0, 0.2 mol/liter of nitrilase 1 antibody and 322.1 g (1.0 mol) of 1e were added to the reaction vessel, and hydrolysis was carried out at 30 ℃ for 10 hours. A small amount of sample is dried in vacuum and then the reaction process is controlled by infrared spectrum, namely 2230cm -1 The reaction was stopped by almost disappearance of the cyano peak on the left and right. The content of the remaining sample was adjusted to about 35.0% by adding water, pH = 12-13, and the product contained sodium hexadecylamine (1, 2-dimethyl) propionate 98.8% and N- (1, 2-dimethyl) cyanoethylhexadecylamine 1.2% by HPLC, the contents being determined by area normalization, the results being shown in table 2.
[ example 6 ] preparation of blowing agent
(1) Cyanidation to prepare cyano intermediate [ NCCH (R) 2 )CH(R 3 )] j R 1 [CH(R 3 )CH(R 2 )CN] j’ Wherein R is 2 、R 3 、R 1 J, j' have the same definitions as formula (I).
Reference to the synthesis of 1a, the difference is: hexadecylamine is adopted to replace octadecyl amine, 2-pentenenitrile is adopted to replace acrylonitrile, the molar ratio of the 2-pentenenitrile to the hexadecylamine is 1.
(2) Preparation of surfactants of formula (I) by hydrolysis
2f Synthesis: referring to the preparation of 2e, 2f was synthesized and the product distribution is shown in table 2.
Preparation of blowing agent [ example 7 ]
(1) Cyanidation to prepare cyano intermediate [ NCCH (R) 2 )CH(R 3 )] j R 1 [CH(R 3 )CH(R 2 )CN] j’ Wherein R is 2 、R 3 、R 1 J, j' have the same definitions as formula (I).
Synthesis of 1 g: 278.4 g (1.0 mol) of 4-dodecyl resorcinol and 140.1 g (2.5 mol) of potassium hydroxide are added into a reaction kettle equipped with a mechanical stirring device, a thermometer and a dropping funnel, 318.1 g (6.0 mol) of acrylonitrile (with a polymerization inhibitor) is slowly dropped into the kettle while stirring, the dropping temperature is controlled to be about 30 ℃, the dropping temperature is completely increased to 80 ℃ for reaction for 5 hours, the temperature is increased to 150 ℃ for continuous reaction for 3 hours, raw materials which are not completely reacted are evaporated under reduced pressure, the mixture of water and dichloromethane is added, hydrochloric acid is used for adjusting the mixture to be neutral, water layers are removed by layers, the upper layer is concentrated to obtain a product, and the content of 4-dodecyl resorcinol dicyanoethyl ether in the product is 90.2 percent, the content of 4-dodecyl resorcinol monocyanoyl ether is 8.3 percent, the content of 4-dodecyl resorcinol is 1.5 percent by adopting an area normalization method according to the High Performance Liquid Chromatography (HPLC), and the result is shown in Table 1.
Among them, 4-dodecylresorcinol used in the preparation of 1g is relatively high in activity, so that dinitrile is mainly used in the product.
(2) Preparation of surfactants of formula (I) by hydrolysis
Synthesis of 2 g: adding 100.1 g (2.5 mol) of sodium hydroxide solid and 400 g of isopropanol/water solution (isopropanol water volume ratio 1) -1 The reaction was stopped by the substantial disappearance of the cyano peak on the left and right. After the remaining sample was distilled off isopropanol, water was added to adjust the content to about 35.0%, pH =12 to 13, and the product was found to have a 3,3' - (4-dodecyl) resorcinoxy-dipropionic acid sodium content of 90.4%, a 3- (4-dodecyl-3-cyanoethyloxy) -propionic acid sodium content of 8.5%, a 4-dodecylresorcinoldigy cyanoethyl ether content of 0.7%, and a 4-dodecylresorcinoldigy monocyanoethyl ether content of 0.4% by HPLC, using area normalization, the results of which are shown in table 2.
[ example 8 ] production of blowing agent
(1) Cyanidation to prepare cyano intermediate [ NCCH (R) 2 )CH(R 3 )] j R 1 [CH(R 3 )CH(R 2 )CN] j’ Wherein R is 2 、R 3 、R 1 J, j' have the same definitions as formula (I).
1h synthesis: 262.4 g (1.0 mol) of 4-dodecylphenol and 67.3 g (1.2 mol) of potassium hydroxide are added into a reaction kettle with a mechanical stirrer, a thermometer and a dropping funnel, 63.6 g (1.2 mol) of acrylonitrile (with a polymerization inhibitor) is slowly dripped into the reaction kettle while stirring, the dripping temperature is controlled to be about 30 ℃, the temperature is completely dripped to 80 ℃ for reaction for 5 hours, the raw materials which are not completely reacted are evaporated under reduced pressure, the mixture of water and dichloromethane is added, hydrochloric acid is used for regulating the mixture to be neutral, water layers are removed by layering, the upper layer is concentrated to obtain a product, the content of 4-dodecylphenol cyanoethyl ether in the product is 97.7 percent and the content of 4-dodecylresorcinol is 2.3 percent by High Performance Liquid Chromatography (HPLC), and the results are shown in table 1.
(2) Preparation of surfactants of formula (I) by hydrolysis
Referring to the synthesis of 2a, synthesis gave 2h with product distribution as shown in table 2.
[ example 9 ] preparation of blowing agent
(1) Cyanidation to prepare cyano intermediate [ NCCH (R) 2 )CH(R 3 )] j R 1 [CH(R 3 )CH(R 2 )CN] j’ Wherein R is 2 、R 3 、R 1 J, j' have the same definitions as formula (I).
Synthesis of 1 i: 186.3 g (1.0 mol) of lauryl alcohol and 67.3 g (1.2 mol) of potassium hydroxide are added into a reaction kettle provided with a mechanical stirrer, a thermometer and a dropping funnel, 63.6 g (1.2 mol) of acrylonitrile (with a polymerization inhibitor) is slowly dropped into the kettle while stirring, the dropping temperature is controlled to be about 30 ℃, the dropping temperature is completely increased to 80 ℃ for reaction for 5 hours, raw materials which are not completely reacted are evaporated under reduced pressure, the mixture of water and dichloromethane is added, hydrochloric acid is used for adjusting the mixture to be neutral, water layers are removed by layering, the upper layer is concentrated to obtain a product, the content of lauryl cyanoethyl ether in the product is 95.9 percent and the content of lauryl alcohol is 4.1 percent through High Performance Liquid Chromatography (HPLC), and the results are shown in table 1.
(2) Preparation of surfactants of formula (I) by hydrolysis
Referring to the synthesis of 2a, 2i was synthesized with product distribution as shown in table 2.
[ COMPARATIVE EXAMPLE 1 ] foaming agent
Preparation of a blowing agent having the same main chain length as 2c, but containing no N atoms: mixing sodium myristate and sodium palmitate according to a molar ratio of 1.
TABLE 1
TABLE 2
In Table 2, the molar contents of the monocarboxylate, the biscarboxylate and the cyano intermediate are based on 100mol% of the cyano intermediate obtained in step (1).
[ example 10 ] foaming agent foaming and liquid carrying Properties test
(1) The blowing agents 2a to 2i synthesized in example 1 and the blowing agents D01 synthesized in comparative example 1 were dissolved in deionized water and simulated saline, respectively, to prepare 0.1wt% blowing agent solutions, which were charged into a Roche foam machine, and the initial bubble heights and the post-5 minute foaming heights of the blowing agents 2a to 2i and D01 were measured by the ROSS-Miles method, and the results are shown in Table 3.
(2) 4000mL/min of nitrogen was continuously introduced into the aqueous solutions of the foaming agents 2a to 2i and D01, the amount of water carried out by the foam in 15 minutes was measured, and the liquid carrying rate was calculated, and the results are shown in Table 3. The liquid carrying amount measuring apparatus used is shown in FIG. 1.
(3) The experiment is carried out by adopting a pressure-resistant and acid-resistant aging device, after aging is carried out for 24 hours at 180 ℃, the properties of initial bubble height, foaming height after 5 minutes, liquid carrying rate after 15 minutes and the like are measured again, and the results are shown in table 3.
(4) The pH of the 0.1wt% blowing agent solution was adjusted to 3 with hydrochloric acid to simulate an acid gas environment, and performance tests were conducted as in (1), (2) and (3), and the results are shown in Table 4.
As can be seen by comparing the results of tables 3 and 4, the foaming agent exhibited more excellent foaming properties under strongly acidic conditions than under alkaline conditions. The foaming agent contains nitrogen atoms corresponding to acid, so that unreacted raw material amine in the cyanation reaction can also undergo an ionization reaction, the effective concentration of the foam discharging agent is increased, and the improvement of the foaming performance is facilitated.
TABLE 3
TABLE 4
[ example 11 ] hydrothermal stability test of sustained Release Material
(1) Adding deionized water, 0.2mol/L acetic acid or 0.2mol/L sodium carbonate solution into a pressure container to adjust the pH of the system, weighing the required amount of sodium chloride until the TDS of the water is =10000mg/L, immersing the slow-release material, and heating to 90-150 ℃ for aging for a certain time. And (3) cooling, releasing pressure, opening the pressure container, observing the appearance of the sustained-release material, judging whether the material is changed or damaged according to the standards of whether the material is agglomerated or not, whether the material can be torn or not and whether the solution is precipitated or not, and recording the unchanged time and the damaged time of the sustained-release materials SR01, SR02, SR03, SR04 and the polyacrylic resin, wherein the results are shown in Table 5. Wherein SR01 is formed by copolymerizing terephthalic acid, succinic acid and butanediol according to a molar ratio of 1.5.
TABLE 5
(2) Immersing the slow-release material in a pressure container filled with simulated saline water, and introducing 2MPa H 2 S，1.5MPa CO 2 By N 2 Supplementing pressure to 16MPa, heating to 100-150 ℃, aging for a certain time, cooling and decompressing, opening a pressure container, observing the appearance of the slow-release material, wherein the simulated water TDS =10000mg/L, and the result is shown in Table 6.
TABLE 6
[ example 12 ] preparation of sustained Release dose
A cementing and bonding method: 120 g of each of the foaming agents 2a to 2i prepared in example 1 and D01 synthesized in comparative example 1 and controlled-release materials SR01 to SR04 were mixed uniformly, and then solid fillers and binders were added and further mixed uniformly, and the mixture was put into a mold and press-molded, as shown in Table 7.
Coating method: 120 g of each of the foaming agents 2a to 2i prepared in example 1 are added with solid fillers and adhesives according to a certain mass ratio, evenly mixed on a kneading machine, poured into a grinding tool and pressed and molded. The sustained-release materials SR 01-SR 04 are dissolved in a solvent to prepare a solution with the mass concentration of 10-50% or melt, and the sustained-release foam discharging agent is obtained after the sustained-release material solution is rapidly and uniformly sprayed, dried and molded, and is shown in Table 7.
An adsorption impregnation method: 120 g of each of the foaming agents 2a to 2i prepared in example 1 was added to a solution of a sustained-release material having a mass concentration of 5 to 50% and immersed for a certain period of time, and then the solvent was rapidly removed, and the mixture was uniformly mixed with a solid filler and a binder in a certain mass ratio and then placed in a mold to be press-molded, as shown in Table 7.
TABLE 7
[ example 5 ] Slow Release Performance test of Slow Release foam
The static release rate and the dynamic release rate of the sustained-release material were measured with reference to the aforementioned methods for measuring the static release rate and the dynamic release rate, and the results are shown in Table 8. Wherein, the TDS =100000mg/L of simulated saline, and the pH value is adjusted by saline.
TABLE 8
In table 8, θ 1 represents a static sustained release rate, and θ 2 represents a dynamic sustained release rate. Generally, the larger θ 1 and θ 2, the better the sustained release effect.
[ example 6 ] foaming and liquid carrying Properties of sustained Release foam
The foaming and liquid carrying properties of the sustained release foam formulation prepared in example 4 were measured in the same manner as in example 2, and the results are shown in Table 9. As can be seen by comparing the results in tables 3 and 9, the foaming agent performance is substantially unchanged or slightly improved after the slow release material is added, which shows that the slow release material, the solid filler and the adhesive adopted by the invention have little influence on the foaming, foaming and liquid carrying performances of the foaming agent.
TABLE 9
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (15)
1. A high temperature resistant slow release foam scrubbing agent comprises a slow release material, a foaming agent, a solid filler and an adhesive; wherein the foaming agent is selected from at least one of the surfactants shown in the formula (I):
in the formula (I), R 2 、R 3 Each independently from hydrogen, C 1 ～C 10 Or C is a hydrocarbon group 1 ～C 10 Substituted hydrocarbyl groups of (a); m is selected from hydrogen ions, cations or cationic groups, the repeating M are the same or different and two M are not H at the same time; j =1,j' =1 or 0; r 1 Is N (H) J R 4 OR-OR 5 (O) J -，J+j’＝1，R 4 Is selected from C 1 ～C 40 Alkylene or C of 1 ～C 40 Substituted alkylene of (2), R 5 Is selected from C 1 ～C 40 Alkylene of (C) 1 ～C 40 Substituted alkylene of (2), R 7 C 6 H 4 Or R 7 C 10 H 6 ，R 7 Is C 1 ～C 30 Alkylene or C 1 ～C 30 Substituted alkylene groups of (1).
2. The high temperature resistant sustained release foam-elimination formulation according to claim 1, wherein in formula (I), R is 2 、R 3 Each independently from hydrogen, C 1 ～C 5 Or C is a hydrocarbon group 1 ～C 5 Substituted hydrocarbyl groups of (a); m is selected from hydrogen ions, cations or cationic groups, the repeating M are the same or different and two M are not H at the same time; j =1,j' =1 or 0; r 1 Is N (H) J R 4 OR-OR 5 (O) J -，J+j’＝1，R 4 Is C 2 ～C 32 Alkylene or C 2 ～C 32 Substituted alkylene of (2), R 5 Is R 7 C 6 H 4 Or R 7 C 10 H 6 ，R 7 Is C 1 ～C 24 Alkylene or C 1 ～C 24 Substituted alkylene groups of (2).
3. The high-temperature-resistant slow-release foam discharging agent as claimed in claim 1, wherein the solid filler is at least one selected from carboxylate, carbonate, bicarbonate, sulfate, bisulfate, phosphate, borate, metal halide, urea, thiourea and biuret; preferably, the solid filler is selected from at least one of sodium carbonate, sodium bicarbonate, sodium borate, sodium chloride, sodium acetate, tartaric acid, sodium tartrate, citric acid, sodium citrate, potassium phthalate, urea, biuret.
4. The high-temperature-resistant slow-release foam discharging agent as claimed in claim 1, wherein the binder is at least one selected from dextrin, epoxy resin, polyacrylamide, starch, cellulose and polyethylene glycol; preferably, the binder is selected from at least one of polyacrylamide, starch, polyethylene glycol.
5. The high-temperature-resistant slow-release foam discharging agent as claimed in claim 1, wherein the slow-release material is at least one of polyester, polyamide and polyurethane which slowly degrades, hydrolyzes or dissolves under formation conditions.
6. The high-temperature-resistant slow-release foam-exhausting agent according to any one of claims 1 to 5, wherein the weight ratio of the slow-release material, the foaming agent, the solid filler and the adhesive is 1: (0.5 to 50): (1-50): (0.01 to 1.0), preferably 1: (1-15): (2-25): (0.02-0.5).
7. A method for preparing a high temperature resistant sustained release foam discharging agent, preferably for preparing the high temperature resistant sustained release foam discharging agent of one of claims 1 to 6, the method comprising: and mixing the foaming agent, the slow-release material, the solid filler and the adhesive according to the weight ratio to obtain the high-temperature-resistant slow-release foam scrubbing agent.
8. The method of claim 7, wherein the foaming agent is prepared by:
(1) Using NCCR 2 ＝CHR 3 And (H) j’ R 1 H, reacting to obtain a cyano intermediate;
wherein R is 1 、R 2 、R 3 Has the same definition as formula (I), i.e., (H) j’ R 1 H is R 4 NH 2 、HOR 5 H or HOR 5 OH(H) j’ R 1 H，R 4 、R 5 Has the same definition as formula (I), x =1 or 0;
(2) In the presence of a catalyst, the cyano intermediate is reacted in a solution of water and/or alcohol, and then optionally adding a base into the system to continue the reaction to obtain the foaming agent.
9. The method according to claim 8, wherein in the step (1), NCCR is used 2 ＝CHR 3 And (H) j’ R 1 The molar ratio of H is (1-15): 1, preferably (1-10): 1.
10. The method of claim 9,
in the step (1), the reaction temperature is 20-300 ℃; and/or the reaction time is 2-15 h; and/or the presence of a gas in the atmosphere,
in step (1), NCC is addedR 2 ＝CHR 3 Drop adding (H) j’ R 1 H, performing heat treatment; preferably, the dropwise addition is carried out at 20-40 ℃, and the reaction after the dropwise addition is carried out at 50-300 ℃;
in the step (1), after the completion of the reaction, a pressure-reducing treatment is performed.
11. The method according to claim 8, wherein in the step (2), the catalyst is at least one selected from the group consisting of an acid, a base, and a biological enzyme;
preferably, the acid is selected from at least one of hydrochloric acid, sulfuric acid, phosphoric acid; and/or the alkali is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; and/or, the biological enzyme is selected from at least one of cyano hydrolase, cyano hydratase and amidase;
more preferably, the molar ratio of the catalyst to the cyano intermediate is (0.01-5): 1, preferably (0.1-3): 1, wherein the molar amount of the cyano intermediate is the molar amount of cyano groups therein.
12. The method according to claim 8,
in the step (2), the alcohol is selected from at least one of methanol, ethanol, propanol, isopropanol and ethylene glycol; preferably, when the reaction is carried out in a solution of water and alcohol, the volume ratio of water to alcohol is 7; and/or the presence of a gas in the gas,
in the step (2), the reaction temperature is 20-150 ℃; and/or the reaction time is 5-50 h; and/or the presence of a gas in the gas,
in the step (2), when the catalyst is selected from alkali, no alkali is added into the system; when the catalyst is selected from acid, adding alkali into the system to continue the reaction; when the catalyst is selected from biological enzyme, a buffer solution containing the biological enzyme is adopted for reaction; and/or the presence of a gas in the gas,
in step (2), the solvent is removed after the reaction is completed.
13. The method according to any one of claims 7 to 12, wherein the foaming agent, the slow-release material, the solid filler and the adhesive are mixed by means of high-temperature melting, cementing, coating or adsorption impregnation.
14. Use of the high-temperature resistant slow-release foam discharging agent in any one of claims 1 to 6 or the high-temperature resistant slow-release foam discharging agent in any one of claims 7 to 13 in liquid drainage and gas production.
15. A method of draining liquid and producing gas, comprising:
(1) Immersing the high-temperature-resistant slow-release foam-exhaust agent as defined in one of claims 1 to 6 or the high-temperature-resistant slow-release foam-exhaust agent as defined in one of claims 7 to 13 in a simulated saline water of a stratum or an actual stratum;
(2) Heating or slowly dissolving and releasing the high-temperature-resistant slow-release foam discharging agent under the action of the formation temperature, and then fully contacting with gas to form foam fluid, and carrying out water in the foam discharging agent solution;
preferably, the gas is at least one of air, nitrogen, methane or natural gas, with or without H 2 S and/or CO 2 An acid gas.
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| CN202111149638.8A CN115873580B (en) | 2021-09-29 | High-temperature-resistant slow-release foam discharging agent and preparation method and application thereof |
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