CN102415387B - 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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- CN102415387B CN102415387B CN 201110287135 CN201110287135A CN102415387B CN 102415387 B CN102415387 B CN 102415387B CN 201110287135 CN201110287135 CN 201110287135 CN 201110287135 A CN201110287135 A CN 201110287135A CN 102415387 B CN102415387 B CN 102415387B
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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 fordevelopment of the bactericide for the oilfield reinjection water.
Description
Technical field
The present invention relates to the application of a kind of surface-active ion liquid fungicide in the oilfield injection water sterilization.
Background technology
Surface-active ion liquid is a class 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, biological chemistry and petrochemical complex.Also few to the research of surface-active ion liquid in recent years.But, theoretically, can design synthetic kinds of surface active ion liquid by the combination that changes different anionic/cationic.Preparation and the performance of research surface-active ion liquid, new variety, enlarged surface promoting agent Application Areas 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, oil field flood pattern mainly carries out in confined conditions, organic content is very high in the water filling, for various bacteriums provide good living environment, wherein sulphate reducing bacteria (SRB), saprophytic microorganism (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 resources with to the pay attention to day by day of microorganism problem in the waterflood system, development of new, efficient disposing polluted water in oil will become very important task with sterilant.
In people today responsive day by day to this problem of environmental protection, require sterilant that environment is produced few influence of trying one's best, the one, reduce the usage quantity of sterilant, thereby alleviate the burden of environmental purification; Another is after the mission of sterilant is finished, and is broken down into some littler parts, assists the processing of sewage.The surface-active ion liquid that the present invention synthesizes has the characteristic of ionic liquid on the one hand, and nontoxic pollution-free is called as green solvent, has surfactivity simultaneously, reduces surface tension of liquid, and glutinous mud is had the strong effect of peeling off; Contain nitrogen heterocyclic on the other hand and have biodegradability, have allyl group or propenyl 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 sterilant.Therefore, development of new high effective surface active ionic liquid sterilant has very important meaning.
Summary of the invention
The technical problem to be solved in the present invention is to provide the application method of a kind of 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 with dimethyl sulfoxide (DMSO), place ultrasound reactor, 20-25 ℃ ultrasonic, be cooled to 0 ℃ and add the 1-bromoalkane, be warming up to 20-25 ℃ then, ultrasonic reaction, reaction finishes, in reaction, add distilled water, with with the chloroform extraction of distilled water same amount, use the distilled water wash chloroform layer again 4 times, the anhydrous MgSO of chloroform layer
4Drying, suction filtration is removed siccative, and chloroform is removed in underpressure 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 normal hexane mixed solvent after reaction is finished, residual ethyl acetate and normal hexane are removed in underpressure 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 having very high surfactivity, also has stronger bactericidal properties and resistance, for the exploitation of novel germicide has increased new applicable material.That the ultrasonic wave synthetic technology that adopts among the preparation method of the present invention has is simple to operate, mild condition, product yield height, and the advantage that speed of response is fast has reduced the process time significantly, has improved production efficiency.
Embodiment
The preparation of example 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, temperature of reaction is in 20-25 ℃ the ultrasound reactor; ultrasonic 1～2h; be cooled to 0 ℃, slowly splashing into the imidazoles mol ratio with constant pressure funnel respectively under this temperature is bromoalkane (1-n-butyl bromide, the bromo pentane silane of 1:1.5; bromohexane); be warming up to 20～25 ℃ then, ultrasonic reaction 3～4h is after reaction finishes; in reaction, add the distilled water of 20～30mL; with the chloroform extraction of 20～30mL, use again the distilled water wash chloroform layer (4 * 20～30mL), the anhydrous MgSO of chloroform layer
4Dry 8-10h, suction filtration is removed siccative, and chloroform is removed in the filtrate decompression distillation, obtains yellow oily liquids N-alkyl imidazole.
The preparation of example 2 N-butyl-3-octyl group (decyl, dodecyl, tetradecyl) imidazoles surface-active ion liquid
In having the 100mL there-necked flask of drying installation; add N-butyl imidazole and bromooctane (bromodecane, bromododecane, bromotetradecane) respectively; the two mol ratio is 1:1～2; nitrogen protection, beginning ultrasound reactor (ultrasonic 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.(4 * 15～25mL), steaming obtains yellow thick N-butyl-3-octyl group (decyl, dodecyl, tetradecyl) imidazoles surface-active ion liquid except residual mixed solvent to use ethyl acetate and the washing of normal hexane mixed solvent after reaction is finished.
N-butyl-3-octyl group imidazoles surface-active ion product liquid warp
1H-NMR (400MH
Z, CDCl
3,
δ/ ppm relative to TMS) checking is 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) checking is 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) checking is 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-tetradecyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3,
δ/ ppm relative to TMS) checking is 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 example 3 N-amyl group-3-octyl group (decyl, dodecyl, tetradecyl) imidazoles surface-active ion liquid
In having the 100mL there-necked flask of drying installation; add N-amyl group imidazoles and bromooctane (bromodecane, bromododecane, bromotetradecane) respectively; the two mol ratio is 1:1～2; nitrogen protection begins ultrasonic (ultrasonic 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.(4 * 15～25mL), steaming obtains yellow thick N-amyl group-3-octyl group (decyl, dodecyl, tetradecyl) imidazoles surface-active ion liquid except residual mixed solvent to use ethyl acetate and the washing of normal hexane mixed solvent after reaction is finished.
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) checking is 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) checking is 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) checking is 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-tetradecyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3,
δ/ ppm relative to TMS) checking is 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 example 4 N-hexyl-3-octyl group (decyl, dodecyl, tetradecyl) imidazoles surface-active ion liquid
In having the 100mL there-necked flask of drying installation; add N-hexyl imidazoles and bromooctane (bromodecane, bromododecane, bromotetradecane) respectively; the two mol ratio is 1:1～2; nitrogen protection begins ultrasonic (ultrasonic 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.(4 * 15～25mL), residual mixed solvent is removed in underpressure distillation, obtains yellow thick N-hexyl-3-octyl group (decyl, dodecyl, tetradecyl) imidazoles surface-active ion liquid to use ethyl acetate and the washing of normal hexane mixed solvent after reaction is finished.
N-hexyl-3-octyl group imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3,
δ/ ppm relative to TMS) checking is 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) checking is 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) checking is 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-tetradecyl imidazoles surface-active ion product liquid warp
1H-NMR (400 MH
Z, CDCl
3,
δ/ ppm relative to TMS) checking is 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 measurement of surface tension method of embodiment 5 surface-active ion liquid
Preparing volumetric molar concentration respectively with redistilled water is 10
– 1～10
– 5The aqueous solution of the surface-active ion liquid of mol/L, under 25 ℃ of conditions, the surface tension of testing each target product with the full-automatic surface tension instrument of JK 99C type, make surface-active ion liquid aqueous solution surface tension with concentration curve, obtain micelle-forming concentration value (cmc) and the surface tension under micelle-forming concentration (
γ 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.Micelle-forming concentration as N-amyl group-3-dodecyl imidazoles surface-active ion liquid is 0.38 mmol/L, surface tension 33.68 mN/m under micelle-forming concentration.
The application of embodiment 6 in the oilfield injection water sterilization
1. experimental bacteria: saprophytic microorganism, sulphate reducing bacteria, iron bacteria.
2. water sample: select Daqing oil field re-injection water for use.
3. sterilant: synthetic above-mentioned various surface-active ion liquid.
4. concentration of sterilant: 15,30,45,60mg/L.
5. culture medium preparation:
1) saprophytic microorganism culture medium preparation: get extractum carnis 3.0g, peptone 5.0g, sodium-chlor 5.0g puts into beaker with mentioned reagent, add 1000mL distilled water, it is 7.4～7.6 that the dissolving back transfers to the pH value with 10% sodium hydroxide, prepared culture medium is sub-packed in the test tube every pipe 5mL, tampon beyond the Great Wall, wrap with kraft paper, carry out moist heat sterilization, stand-by.
2) sulphate reducing bacteria culture medium preparation: get dipotassium hydrogen phosphate 0.5g, ammonium chloride 1.0g, sal epsom 2.0g, sodium sulfate 0.5g, calcium chloride 0.1g, yeast extract paste 1.0g, Sodium.alpha.-hydroxypropionate 4mL, mentioned reagent is put into beaker, add 1000mL distilled water, it is 7.4～7.6 that the dissolving back transfers to the pH value with 10% sodium hydroxide, pour in the triangular flask, tampon is wrapped with kraft paper beyond the Great Wall, carry out moist heat sterilization, stand-by.
3) iron bacteria culture medium preparation: sal epsom 0.5g, ammonium phosphate 0.5g, potassium primary phosphate 0.5g, calcium chloride 0.5g, SODIUMNITRATE 0.5g, ferric ammonium citrate 10.0g, mentioned reagent is put into beaker, add 1000mL distilled water, it is 6.6～6.8 that the dissolving back transfers to the pH value with 10% sodium hydroxide, prepared culture medium is sub-packed in the test tube, every pipe 5mL, tampon is wrapped with kraft paper beyond the Great Wall, carry out moist heat sterilization, stand-by.
6. sterilization: it is good with paper bag to test required syringe, narrow-mouthed bottle, test tube, transfer pipet, tweezers, test bottle, the good experimental article of useful paper bag and the substratum for preparing put into Autoclave, moist heat sterilization (121
oC, 2 h), standby.The intact experimental article of moist heat sterilization and test used article, the sterilant for preparing all is placed in the super clean bench sterilization 30 min under ultraviolet 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 germ-killing efficiency
At first adopt the quantity of sulphate reducing bacteria in the former water of former water bacteria assay, iron bacteria, thiobacterium, carry out bactericidal assay then.The method of counting of bacterium is counted according to the synopsis that SY/T0532-93 " oilfield injection water bacteria analyzing method-disappearance dilution method " provides.
Analyze sulphate reducing bacteria, saprophytic microorganism 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 germ-killing efficiency data of three kinds of bacteriums being carried out bactericidal assay are as shown in table 2:
The germ-killing efficiency of the different sterilant of table 2
The result shows: the surface-active ion liquid that is synthesized has bacteriostatic action to sulphate reducing bacteria, saprophytic microorganism and the iron bacteria in the Daqing oil field re-injection water, and along with the increase of concentration, fungistatic effect strengthens.
Claims (1)
1. the surface-active ion liquid fungicide application method in the oilfield injection water sterilization, it is characterized in that: employed sterilant has following structure in this method:
N is 4,5,6 in the formula; M is 8,10,12,14;
This sterilant makes by two-step reaction, at first prepare the N-alkyl imidazole, then in the there-necked flask of drying installation is housed, after adding N-alkyl imidazole and long-chain halogenated alkane, at frequency 40 kHz, ultrasonic 25 ~ 35min under the power 100 w conditions stops intermittently ultrasonic reaction of 5 ~ 10min, make water temperature remain on 60～70 ℃, reaction 5～6h; Wash three times with ethyl acetate and normal hexane after reaction is finished, residual ethyl acetate and normal hexane are removed in underpressure distillation, obtain yellow thick imidazoles surface-active ion liquid.
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| CN116283951A (en) * | 2023-03-22 | 2023-06-23 | 广东工业大学 | Quinazoline heterocyclic derivative and preparation method and application thereof |
| CN116751574A (en) * | 2023-06-16 | 2023-09-15 | 中海油田服务股份有限公司 | Ionic liquid-surfactant oil displacement system and preparation method and application thereof |
Citations (2)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5479278A (en) * | 1977-12-05 | 1979-06-25 | Nippon Soda Co Ltd | Imidazolium halide |
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| 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 |
| 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 |
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