CN102415387A - Surface active ionic liquid bactericide and application thereof in sterilization of oilfield injection water - Google Patents
Surface active ionic liquid bactericide and application thereof in sterilization of oilfield injection water Download PDFInfo
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- CN102415387A CN102415387A CN2011102871357A CN201110287135A CN102415387A CN 102415387 A CN102415387 A CN 102415387A CN 2011102871357 A CN2011102871357 A CN 2011102871357A CN 201110287135 A CN201110287135 A CN 201110287135A CN 102415387 A CN102415387 A CN 102415387A
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Abstract
The invention discloses a surface active ionic liquid bactericide and an application thereof in sterilization of oilfield injection water. Surface active ionic liquid is obtained by firstly enabling imidazole to be reacted with bromoalkane to get N-alkyl imidazole, then enabling the N-alkyl imidazole to be reacted with long carbon chain bromoalkane and further getting the surface active ionic liquid under ultrasonic auxiliary conditions. The surface tension of the product is determined, thereby indicating that the series of compounds have higher surface activity. The compound obtained according to the invention can be used as the bactericide for the oilfield reinjection water so as to inhibit sulfate-reducing bacteria, iron bacteria and metatrophic bacteria, and the effective sterilization concentration is 30-60mg/L. The bactericide has the advantages of high efficiency, low toxicity, environmental friendliness and strong drug resistance, and a new applicable substance is provided for development of the bactericide for the oilfield reinjection water.
Description
Technical field
The present invention relates to a kind of surface-active ion liquid fungicide, the invention still further relates to the application of this surface-active ion liquid fungicide in the oilfield injection water sterilization.
Background technology
Surface-active ion liquid is one type of environment-friendly type solvent; Non-volatile with it, to the stability of water and air, to the good solubility of inorganic, organic compound and macromolecular material and be widely used in aspects such as electrochemistry, organic synthesis, chemical separating, material preparation, biochemistry and petrochemical industry.Also few to the research of surface-active ion liquid in recent years.But, theoretically, can design synthetic kinds of surface active ion liquid through the combination that changes different anionic/cationic.The preparation and the performance of research surface-active ion liquid, new varieties, enlarged surface activating agent application that not only can the supplementary table surface-active agent, and enlarge the ionic liquid new approach in application.
Domestic oil field great majority are onshore oil field, and oil field flood pattern mainly carries out in confined conditions, and the content of organic matter is very high in the water filling; For various bacteriums provide good living environment; Wherein sulfate reducing bacteria (SRB), saprophytic bacteria (TGB) and iron bacteria (IB) are the various harmful microorganisms of main body, and they can make the oil field pipe equipment corrosion in growth, metabolism, reproductive process; Cause oil layer blocking, cause serious consequence to production.Along with the growing tension of water resource with to the pay attention to day by day of microorganism problem in the flood pattern, development of new, efficient disposing polluted water in oil will become crucial task with bactericide.
In people today responsive day by day to this problem of environmental protection, require bactericide that environment is produced few influence of trying one's best, the one, reduce the usage amount of bactericide, thereby alleviate the burden of the depollution of environment; Another is after the mission of bactericide is accomplished, and is broken down into some littler parts, assists the processing of sewage.The surface-active ion liquid that the present invention synthesizes has ion liquid characteristic on the one hand, and nontoxic pollution-free is called as green solvent, has surface-active simultaneously, reduces surface tension of liquid, and glutinous mud is had the strong effect of peeling off; Contain azacyclo-on the other hand and have biodegradability, have pi-allyl or acrylic in the structure, the chain alkyl structure has possessed sterilization idiocratic.This compounds yet there are no the report that is applied to the oil field as bactericide.Therefore, development of new high effective surface active ionic liquid bactericide has crucial meaning.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of surface-active ion liquid fungicide, and another one goal of the invention of the present invention also is to provide the application of a kind of this surface-active ion liquid fungicide in the oilfield injection water sterilization.
Surface-active ion liquid fungicide of the present invention has following structure:
N in the formula is 4,5,6; M is 8,10,12,14.
The preparation method of surface-active ion liquid of the present invention may further comprise the steps:
1, the preparation of N-alkyl imidazole
In three-necked bottle, add imidazoles and potassium hydroxide, make solvent, place ultrasound reactor with dimethyl sulfoxide (DMSO); 20-25 ℃ ultrasonic, is cooled to 0 ℃ and adds the 1-bromoalkane, is warming up to 20-25 ℃ then; Ultrasonic reaction, reaction finishes, and in reaction, adds distilled water; Use the chloroform extraction with the distilled water same amount, use the distilled water wash chloroform layer again 4 times, chloroform layer is used anhydrous MgSO
4Drying, suction filtration is removed desiccant, and chloroform is removed in decompression distillation, obtains yellow oily liquids N-alkyl imidazole.
2, the preparation of surface-active ion liquid
Begin ultrasonic (frequency 40 kHz, power 100 w) 25～35min after in the three-necked bottle of condensation reflux unit is housed, adding N-alkyl imidazole and long-chain halogenated alkane, stop intermittently ultrasonic reaction of 5～10min, make water temperature remain on 60-70 ℃.Wash three times with ethyl acetate and n-hexane mixed solvent after reaction is accomplished, residual ethyl acetate and n-hexane are removed in decompression distillation, obtain yellow thick imidazoles surface-active ion liquid.
Imidazoles surface-active ion liquid of the present invention is a kind of Green Product, except that having very high surface-active, also has stronger bactericidal properties and pesticide resistance, for the exploitation of novel germicide has increased new applicable material.That the ultrasonic synthetic technology that is adopted among the preparation method of the present invention has is simple to operate, mild condition, product yield are high, and the advantage that reaction velocity is fast has reduced the process time significantly, has improved production efficiency.
Embodiment
The preparation of instance 1 N-alkyl imidazole
In the there-necked flask of 100mL, add imidazoles and potassium hydroxide, the two mol ratio is 1:1～1.2, (10～20mL) make solvent to dimethyl sulfoxide (DMSO); Place frequency 30kHz, power 100w, under the nitrogen protection, reaction temperature is in 20-25 ℃ the ultrasound reactor; Ultrasonic 1-2h is cooled to 0 ℃, under this temperature, uses constant pressure funnel slowly to splash into and bromoalkane (the 1-NBB of imidazoles mol ratio as 1:1.5 respectively; Bromo pentane silane, bromohexane), be warming up to 20-25 ℃ then; Ultrasonic reaction 3-4h after reaction finishes, adds the distilled water of 20～30mL in reaction; With the chloroform extraction of 20～30mL, (4 * 20～30mL), chloroform layer is used anhydrous MgSO to use the distilled water wash chloroform layer again
4Dry 8-10h, suction filtration is removed desiccant, and chloroform is removed in the filtrate decompression distillation, obtains yellow oily liquids N-alkyl imidazole.
The preparation of instance 2 N-butyl-3-octyl group (decyl, dodecyl, myristyl) imidazoles surface-active ion liquid
In having the 100mL there-necked flask of drying installation, add N-butyl imidazole and bromooctane (bromodecane, bromododecane respectively; Bromotetradecane), the two mol ratio is 1:1～2, nitrogen protection; Beginning ultrasound reactor (supersonic frequency 40kHz, power 100w) 25～35min, it is intermittently ultrasonic to stop 5～10min; Make water temperature remain on 60-70 ℃, reaction 5-6h, TLC follows the tracks of reaction.Reaction is accomplished the back and is washed with ethyl acetate and n-hexane mixed solvent that (4 * 15～25mL), steaming obtains yellow thick N-butyl-3-octyl group (decyl, dodecyl, myristyl) imidazoles surface-active ion liquid except that residual mixed solvent.
N-butyl-3-octyl group imidazoles surface-active ion product liquid warp
1H-NMR (400MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.19 (1H, s, imidazole rings), 7.81 (2H, d, imidazole rings), 4.64 (2H, t, N
+CH
2-), 4.03 (2H, q, NCH
2-), 1.68 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.29-1.39 (12H, m, on the imidazole ring side chain-CH
2-), 0.88 (6H, m, 2-CH
3).
N-butyl-3-decyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.20 (1H, s, imidazole rings), 7.79 (2H, d, imidazole rings), 4.66 (2H, t, N
+CH
2-), 4.03 (2H, q, NCH
2-), 1.67 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.30-1.40 (16H, m, on the imidazole ring side chain-CH
2-), 0.89 (6H, m, 2-CH
3).
N-butyl-3-dodecyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.21 (1H, s, imidazole rings), 7.83 (2H, d, imidazole rings), 4.64 (2H, t, N
+CH
2-), 4.05 (2H, q, NCH
2-), 1.69 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.27-1.37 (20H, m, on the imidazole ring side chain-CH
2-), 0.88 (6H, m, 2-CH
3).
N-butyl-3-myristyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.20 (1H, s, imidazole rings), 7.83 (2H, d, imidazole rings), 4.67 (2H, t, N
+CH
2-), 4.04 (2H, q, NCH
2-), 1.67 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.28-1.38 (24H, m, on the imidazole ring side chain-CH
2-), 0.89 (6H, m, 2-CH
3).
The preparation of instance 3 N-amyl group-3-octyl group (decyl, dodecyl, myristyl) imidazoles surface-active ion liquid
In having the 100mL there-necked flask of drying installation, add N-amyl group imidazoles and bromooctane (bromodecane, bromododecane respectively; Bromotetradecane), the two mol ratio is 1:1～2, nitrogen protection; Begin ultrasonic (supersonic frequency 40kHz, power 100w) 25～35min, it is intermittently ultrasonic to stop 5～10min; Make water temperature remain on 60-70 ℃, reaction 5-6h, TLC follows the tracks of.Reaction is accomplished the back and is washed with ethyl acetate and n-hexane mixed solvent that (4 * 15～25mL), steaming obtains yellow thick N-amyl group-3-octyl group (decyl, dodecyl, myristyl) imidazoles surface-active ion liquid except that residual mixed solvent.
N-amyl group-3-octyl group imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.26 (1H, s, imidazole rings), 7.35 (2H, d, imidazole rings), 4.37 (4H, t, NCH
2-, N
+CH
2-), 1.95 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.36-1.41 (14H, m, the last side chain of N-CH
2-), 0.91 (6H, m, 2-CH
3).
N-amyl group-3-decyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.24 (1H, s, imidazole rings), 7.34 (2H, d, imidazole rings), 4.35 (4H, t, NCH
2-, N
+CH
2-), 1.96 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.30-1.40 (18H, m, the last side chain of N-CH
2-), 0.92 (6H, m, 2-CH
3).
N-amyl group-3-dodecyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.23 (1H, s, imidazole rings), 7.33 (2H, d, imidazole rings), 4.36 (4H, t, NCH
2-, N
+CH
2-), 1.93 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.29-1.41 (22H, m, the last side chain of N-CH
2-), 0.89 (6H, m, 2-CH
3).
N-amyl group-3-myristyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.27 (1H, s, imidazole rings), 7.36 (2H, d, imidazole rings), 4.37 (4H, t, NCH
2-, N
+CH
2-), 1.96 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.31-1.41 (26H, m, the last side chain of N-CH
2-), 0.90 (6H, m, 2-CH
3).
The preparation method of instance 4 N-hexyl-3-octyl group (decyl, dodecyl, myristyl) imidazoles surface-active ion liquid
In having the 100mL there-necked flask of drying installation, add N-hexyl imidazoles and bromooctane (bromodecane, bromododecane respectively; Bromotetradecane), the two mol ratio is 1:1～2, nitrogen protection; Begin ultrasonic (supersonic frequency 40kHz, power 100w) 25～25min, it is intermittently ultrasonic to stop 5～10min; Make water temperature remain on 60-70 ℃, reaction 5-6h, TLC follows the tracks of.Reaction is accomplished the back and is washed with ethyl acetate and n-hexane mixed solvent that (4 * 15～25mL), residual mixed solvent is removed in decompression distillation, obtains yellow thick N-hexyl-3-octyl group (decyl, dodecyl, myristyl) imidazoles surface-active ion liquid.
N-hexyl-3-octyl group imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.22 (1H, s, imidazole rings), 7.33 (2H, d, imidazole rings), 4.36 (4H, t, NCH
2-, N
+CH
2-), 1.96 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.28-1.37 (16H, m, on the last side chain of N-CH
2-), 0.89 (6H, m, 2-CH
3).
N-hexyl-3-decyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.26 (1H, s, imidazole rings), 7.38 (2H, d, imidazole rings), 4.39 (4H, t, NCH
2-, N
+CH
2-), 1.98 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.31-1.41 (20H, m, the last side chain of N-CH
2-), 0.91 (6H, m, 2-CH
3).
N-hexyl-3-dodecyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.25 (1H, s, imidazole rings), 7.34 (2H, d, imidazole rings), 4.36 (4H, t, NCH
2-, N
+CH
2-), 1.94 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.29-1.41 (24H, m, the last side chain of N-CH
2-), 0.90 (6H, m, 2-CH
3).
N-hexyl-3-myristyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3, δ/ppm relative to TMS) verify as follows: 10.24 (1H, s, imidazole rings), 7.36 (2H, d, imidazole rings), 4.38 (4H, t, NCH
2-, N
+CH
2-), 1.92 (4H, m, NCH
2-CH
2-, N
+CH
2-CH
2-), 1.28-1.40 (28H, m, the last side chain of N-CH
2-), 0.90 (6H, m, 2-CH
3).
The surface tension test method of embodiment 5 surface-active ion liquid
Using redistilled water to prepare molar concentration respectively is 10
– 1～10
– 5The aqueous solution of the surface-active ion liquid of mol/L; Under 25 ℃ of conditions; Surface tension with each target product of the full-automatic surface tension instrument test of JK 99C type; Make surface-active ion liquid aqueous solution surface tension with concentration curve, obtain critical micelle concentration value (cmc) and the surface tension (γ under critical micelle concentration
Cmc).The result shows that along with the increase of concentration, the surface tension of each surface-active ion liquid aqueous solution all reduces rapidly.Critical micelle concentration like N-amyl group-3-dodecyl imidazoles surface-active ion liquid is 0.38 mmol/L, surface tension 33.68 mN/m under critical micelle concentration.
The application of embodiment 6 in the oilfield injection water sterilization
1. experimental bacteria: saprophytic bacteria, sulfate reducing bacteria, iron bacteria.
2. water sample: select Daqing oil field re-injection water for use.
3. bactericide: synthetic above-mentioned various surface-active ion liquid.
4. concentration of sterilant: 15,30,45,60mg/L.
5. culture medium preparation:
1) saprophytic bacteria culture medium preparation: get beef extract 3.0g, peptone 5.0g, sodium chloride 5.0g; Mentioned reagent is put into beaker, add 1000mL distilled water, use 10% sodium hydroxide to transfer to the pH value after the dissolving and be 7.4-7.6; Prepared culture medium is sub-packed in the test tube every pipe 5mL, tampon beyond the Great Wall; Wrap with brown paper, carry out moist heat sterilization, for use.
2) sulfate reducing bacteria culture medium preparation: get dipotassium hydrogen phosphate 0.5g, ammonium chloride 1.0g, magnesium sulfate 2.0g, sodium sulphate 0.5g, calcium chloride 0.1g, yeast extract 1.0g, sodium lactate 4mL, mentioned reagent is put into beaker, add 1000mL distilled water; Use 10% sodium hydroxide to transfer to the pH value after the dissolving and be 7.4-7.6; Pour in the triangular flask, tampon is wrapped with brown paper beyond the Great Wall; Carry out moist heat sterilization, for use.
3) iron bacteria culture medium preparation: magnesium sulfate 0.5g, ammonium phosphate 0.5g, potassium dihydrogen phosphate 0.5g, calcium chloride 0.5g, sodium nitrate 0.5g, ferric citrate 10.0g puts into beaker with mentioned reagent; Add 1000mL distilled water, use 10% sodium hydroxide to transfer to the pH value after the dissolving and be 6.6-6.8, prepared culture medium is sub-packed in the test tube; Every pipe 5mL, tampon is wrapped with brown paper beyond the Great Wall; Carry out moist heat sterilization, for use.
6. sterilization: it is good with paper bag to test required syringe, narrow-mouthed bottle, test tube, pipette, tweezers, test bottle, the good experimental article of useful paper bag and the medium for preparing put into autoclave, moist heat sterilization (121
oC, 2 h), subsequent use.The intact experimental article of moist heat sterilization and test used article, the bactericide for preparing all is placed in the super-clean bench, 30 min sterilize under uviol lamp.
7. operating process: the step that provides according to SY/T0532-93 " oilfield injection water bacteria analyzing method-disappearance dilution method ".
8. detect the method-test bottle disappearance dilution method of germicidal efficiency
At first adopt the quantity of sulfate reducing bacteria in the former water of former water bacteria assay, iron bacteria, sulphur bacteria, carry out BA then.The method of counting of bacterium is counted according to the table of comparisons that SY/T0532-93 " oilfield injection water bacteria analyzing method-disappearance dilution method " provides.
Analyze sulfate reducing bacteria, saprophytic bacteria and iron bacteria content in the former water water sample of Daqing oil field re-injection water with 5 pipe methods, as shown in table 1:
The former water water determination of table 1 Daqing oil field re-injection water result
9. experimental result: the germicidal efficiency data of three kinds of bacteriums being carried out BA are as shown in table 2:
The germicidal efficiency of the different bactericide of table 2
Claims (3)
1. surface-active ion liquid fungicide, it is characterized in that: this bactericide has following structure:
N is 4,5,6 in the formula; M is 8,10,12,14.
2. according to the preparation method of the said surface-active ion liquid fungicide of claim 1, it is characterized in that: this bactericide makes through two-step reaction, at first prepares the N-alkyl imidazole; Then in the there-necked flask of drying installation is housed, behind adding N-alkyl imidazole and the long-chain halogenated alkane, at frequency 40 kHz; Ultrasonic 25～35min under the power 100 w conditions; Stop intermittently ultrasonic reaction of 5～10min, make water temperature remain on 60-70 ℃, reaction 5-6h; Wash three times with ethyl acetate and n-hexane after reaction is accomplished, residual ethyl acetate and n-hexane are removed in decompression distillation, obtain yellow thick imidazoles surface-active ion liquid.
3. according to of the application of the said surface-active ion liquid fungicide of claim 1 as oilfield reinjection water sterilizing agent.
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|---|---|---|---|
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| CN102415387B CN102415387B (en) | 2013-09-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887873A (en) * | 2012-09-12 | 2013-01-23 | 常州大学 | Ionic liquids with surface active function and preparation method for ionic liquids |
| CN116283951A (en) * | 2023-03-22 | 2023-06-23 | 广东工业大学 | Quinazoline heterocyclic derivative and preparation method and application thereof |
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| DE2519169A1 (en) * | 1975-04-30 | 1976-11-11 | Basf Ag | Naphthoylene benzimidazolium salts - useful as dyes for anionically modified fibres esp. of acrylonitrile polymers |
| JPS5479278A (en) * | 1977-12-05 | 1979-06-25 | Nippon Soda Co Ltd | Imidazolium halide |
| CN102101842A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院兰州化学物理研究所 | Naphthyl-functionalized ionic liquid having abrasion resistance and preparation method thereof |
-
2011
- 2011-09-26 CN CN 201110287135 patent/CN102415387B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2519169A1 (en) * | 1975-04-30 | 1976-11-11 | Basf Ag | Naphthoylene benzimidazolium salts - useful as dyes for anionically modified fibres esp. of acrylonitrile polymers |
| JPS5479278A (en) * | 1977-12-05 | 1979-06-25 | Nippon Soda Co Ltd | Imidazolium halide |
| CN102101842A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院兰州化学物理研究所 | Naphthyl-functionalized ionic liquid having abrasion resistance and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887873A (en) * | 2012-09-12 | 2013-01-23 | 常州大学 | Ionic liquids with surface active function and preparation method for ionic liquids |
| CN116283951A (en) * | 2023-03-22 | 2023-06-23 | 广东工业大学 | Quinazoline heterocyclic derivative and preparation method and application thereof |
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|---|---|
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