CN103184042A - Gemini surfactant for tertiary oil recovery and preparation and application thereof - Google Patents
Gemini surfactant for tertiary oil recovery and preparation and application thereof Download PDFInfo
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- CN103184042A CN103184042A CN2011104467620A CN201110446762A CN103184042A CN 103184042 A CN103184042 A CN 103184042A CN 2011104467620 A CN2011104467620 A CN 2011104467620A CN 201110446762 A CN201110446762 A CN 201110446762A CN 103184042 A CN103184042 A CN 103184042A
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- active agent
- oil recovery
- preparation
- surface active
- tertiary oil
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000011084 recovery Methods 0.000 title claims abstract description 23
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 24
- 239000012044 organic layer Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000005917 acylation reaction Methods 0.000 claims abstract description 4
- 230000029936 alkylation Effects 0.000 claims abstract description 4
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 4
- 230000010933 acylation Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000013543 active substance Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- -1 Succinic anhydried Chemical compound 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 7
- 239000010813 municipal solid waste Substances 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- KKHUSADXXDNRPW-UHFFFAOYSA-N malonic anhydride Chemical compound O=C1CC(=O)O1 KKHUSADXXDNRPW-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 238000010792 warming Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- ATWLRNODAYAMQS-UHFFFAOYSA-N 1,1-dibromopropane Chemical compound CCC(Br)Br ATWLRNODAYAMQS-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000402 conductometric titration Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a gemini surfactant for tertiary oil recovery and preparation and application thereof; firstly, adding alkylbenzene and an alkylation catalyst into a reactor 1, and preheating to 20-50 ℃; dropwise adding halogenated alkane into the reactant, heating to 40-80 ℃, and reacting for 2-5 h; adding anhydride and solvent into the reactor 2, adding acylation catalyst, dripping the reaction product after 30min, and reacting at 20-30 ℃ for 0.5-3 h; adding dilute acid solution and crushed ice, slowly pouring the product of step two into a beaker, uniformly mixing, standing and layering; neutralizing the organic layer with alkaline liquor until the pH value is 7-9, and removing the solvent under reduced pressure to obtain the gemini surfactant; with Na2CO3The minimum use concentration can reach 0.002% -0.005%, and the interfacial tension can reach 10% when the concentration of the surfactant is more than 20mg/L-3mN/m。
Description
Technical field
The present invention relates to a kind of used for tertiary oil recovery Gemini surface active agent and preparation and application.
Background technology
Tertiary oil recovery (especially compound petroleum driving and recovering) is the important means that improves oil recovery factor, and that tensio-active agent plays a part in combination flooding is very important, therefore directly influence interfacial tension, oil displacement efficiency and crude oil demulsification etc. between flooding system/crude oil, relevant combination flooding is active research field comparatively with the research of tensio-active agent always.The on-the-spot applied tertiary oil recovery tensio-active agent in oil field is based on sulfonated petro-leum and heavy alkylbenzene sulfonate at present.
It is the method for feedstock production heavy alkylbenzene sulfonate that patent ZL01136653.2, ZL99106077.6, CN1486976A provide respectively with the heavy alkyl benzene, but the heavy alkylbenzene sulfonate of these method preparations is applicable to highly basic NaOH, and working concentration is higher.Patent ZL02140719.3 provides a kind of method of weak base heavy alkylbenzene sulfonate, but this method need be carried out rectifying cutting, complicated process of preparation to heavy alkyl benzene.Patent CN1426833A provides a kind of preparation method who is suitable for the alkyl benzene sulfonate surfactant of weak base, but needs composite 15%～20% Virahol in the prepared heavy alkylbenzene sulfonate of this method.
Patent CN101185866A provides the preparation method of a kind of pair of alkyl polyoxyethylene ether Gemini anionic surface active agent, this method generates alkyl diphenyl ether or generates alkylphenol oxygen Vinyl Ether with alkylphenol and oxygen Vinyl Ether with bromoalkane and phenyl ether, carries out sulfonation, neutralization again.But this method tensio-active agent preparation cost is higher, and the alkylphenol degradation property is relatively poor.It is raw material with ditane, phenyl ether, diphenylethane, lipid acid, thionyl chloride, sulfuric acid that patent CN101104794A provides a kind of, the method for the two benzene tensio-active agents of the two alkyl disulfonates of preparation, but this method complicated process of preparation, and cost is higher.
Summary of the invention
The object of the present invention is to provide a kind of Gemini surface active agent and preparation and application that activity is high, working concentration is low, be suitable for used for tertiary oil recovery that have.This Gemini surface active agent is raw material with the alkylbenzene, is the two alkylbenzene intermediates of link base preparation with the halogenated alkane, prepares used for tertiary oil recovery double type tensio-active agent through acidylate again; technology is simple; need not to purify and separate, tensio-active agent is applicable to that the weak base prescription uses, and working concentration is low.
The preparation method of used for tertiary oil recovery Gemini surface active agent of the present invention, its required starting material are alkylbenzene, halogenated alkane, acid anhydrides, catalyzer, organic solvent, alkali, mineral acid; The ratio of reactant species amount is: alkylbenzene and halogenated alkane (2～5): 1, and alkylbenzene and acid anhydrides 1: (1～1.5), catalyzer and halogenated alkane (1～4): 10;
Concrete grammar is:
1. in reactor 1, add alkylbenzene and alkylation catalyst, mix, and be preheating to 20 ℃～50 ℃; Under agitation in reactant, drip halogenated alkane, be added dropwise to complete the back and continue to stir 30min; Heat up 40～80 ℃ then, reaction 2h～5h;
2. in reactor 2, add acid anhydrides and solvent, be stirred to dissolving; Stir cooling and slowly add acylation catalyst down, drip 1. reaction product behind the 30min, be added dropwise to complete the back and continue to stir 30min; 20 ℃～30 ℃ reaction 0.5h～3h;
3. add dilute acid soln and trash ice in the beaker, stir down 2. product and slowly pour beaker into, mix the back standing demix, tell organic layer to wash again 2 times with diluted acid;
4. organic layer is neutralized to pH=7～9 with alkali lye, and decompression is sloughed solvent and namely got Gemini surface active agent.
Used alkylbenzene is the alkylbenzene of C10～C24.
Used halogenated alkane is a kind of in dichloro (bromine, iodine) ethane, dichloro (bromine, iodine) propane, dichloro (bromine, the iodine) butane.
Used acid anhydrides is a kind of in malonic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, Pyroglutaric acid, the adipic anhydride.
Used catalyzer is anhydrous AlCl
3, FeCl
3, SbCl
5, BF
3, TiCl
4, ZnCl
2, perhaps HF, H
2SO
4, P
2O
5, H
3PO
4, perhaps acidic oxide SiO
2-Al
2O
3, a kind of in the ionic liquid, storng-acid cation exchange resin.
Used organic solvent is a kind of in methylene dichloride, ethylene dichloride, trichloromethane, tetracol phenixin, the hexanaphthene.
Used alkali is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor, thanomin, diethanolamine, the trolamine.
Used acid is hydrochloric acid or sulfuric acid.
This Gemini surface active agent and Na
2CO
3, water is composite as the tertiary oil recovery oil-displacing agent, using prescription to be tensio-active agent 0.002%～0.005% weight, Na
2CO
30.6%～2.0% weight, surplus are distilled water or mineralized water.
The present invention has following characteristics:
1. surfactant activity height of the present invention: at present, the working concentration of sulfonated petro-leum or heavy alkylbenzene sulfonate is generally more than 0.2%, and the minimum working concentration of tensio-active agent of the present invention can reach 0.002%～0.005%.
2. surfactant product yield height of the present invention: the present invention has good production repeatability, and product yield is more than 70%.
3. preparation method of the present invention is ripe classical: reaction involved in the present invention is alkylation and acylation reaction, and the reaction process maturation is easy to realize industrialization.
4. the present invention is basic raw material with the alkylbenzene, and the tensio-active agent cost is low, is beneficial to and applies.
5. tensio-active agent of the present invention is suitable for and weak base Na
2CO
3Composite use.
Description of drawings
Fig. 1 CMC of surfactant.
Fig. 2 surfactant interface tension force performance.
Embodiment
Embodiment 1:
The preparation of Gemini surface active agent of the present invention
1. add 36.0g heavy alkyl benzene and 12g hexanaphthene in the reactor of drying, the control temperature is not higher than 30 ℃, under agitation slowly adds the anhydrous AlCl of 1.07g
3, continue in reactant, slowly to drip the 7.5g ethylene dibromide behind the stirring 30min, be added dropwise to complete the back and continue stirring 30min, be warming up to 80 ℃ of reaction 2h then, stopped reaction cooling cooling.
2. in another dry reactor, add 12.5g maleic anhydride and 30g ethylene dichloride, be stirred to dissolving; The control temperature is not higher than 30 ℃, stirs slowly to add the anhydrous AlCl of 31.2g down
3, drip 1. reaction product behind the 30min, be added dropwise to complete and be warming up to 30 ℃ of reaction 2h after 30min is continued to stir in the back.
3. add 5% dilute hydrochloric acid solution and trash ice in the beaker, stir down 2. product and slowly pour beaker into, mix the back standing demix, tell organic layer and wash again 2 times with 5% dilute hydrochloric acid.Organic layer is neutralized to pH=7～9 with 20%NaOH solution, and solvent is sloughed in decompression and water namely gets Gemini surface active agent.
Embodiment 2:
The preparation of Gemini surface active agent of the present invention
1. add 72.0g heavy alkyl benzene and 24g hexanaphthene in the reactor of drying, the control temperature is not higher than 30 ℃, under agitation slowly adds the anhydrous AlCl of 2.14g
3, continue in reactant, slowly to drip the 15g ethylene dibromide behind the stirring 30min, be added dropwise to complete the back and continue stirring 30min, be warming up to 70 ℃ of reaction 5h then, stopped reaction cooling cooling, pressure reducing and steaming solvent.
2. in another dry reactor, add 21g Succinic anhydried and 30g ethylene dichloride, be stirred to dissolving; The control temperature is not higher than 30 ℃, stirs slowly to add the anhydrous AlCl of 48.0g down
3, drip 1. reaction product behind the 30min, be added dropwise to complete and be warming up to 30 ℃ of reaction 0.5h after 30min is continued to stir in the back.
3. add 5% dilute hydrochloric acid solution and trash ice in the beaker, stir down 2. product and slowly pour beaker into, mix the back standing demix, tell organic layer and wash again 2 times with 5% dilute hydrochloric acid.Organic layer is neutralized to pH=7～9 with 20%NaOH solution, and solvent is sloughed in decompression and water namely gets Gemini surface active agent.
Embodiment 3:
The preparation of Gemini surface active agent of the present invention
1. add 36.0g heavy alkyl benzene and 20g hexanaphthene in the reactor of drying, the control temperature is not higher than 30 ℃, under agitation slowly adds the anhydrous AlCl of 1.1g
3, continue in reactant, slowly to drip the 8.2g dibromopropane behind the stirring 30min, be added dropwise to complete the back and continue stirring 30min, be warming up to 70 ℃ of reaction 4h then, stopped reaction cooling cooling, pressure reducing and steaming solvent.
2. in another dry reactor, add 11.5g maleic anhydride and 20g ethylene dichloride, be stirred to dissolving; The control temperature is not higher than 30 ℃, stirs slowly to add the anhydrous AlCl of 30.0g down
3, drip 1. reaction product behind the 30min, be added dropwise to complete and be warming up to 25 ℃ of reaction 1.0h after 30min is continued to stir in the back.
3. add 5% dilution heat of sulfuric acid and trash ice in the beaker, stir down 2. product and slowly pour beaker into, mix the back standing demix, tell organic layer and wash again 2 times with 5% dilute sulphuric acid.Organic layer is neutralized to pH=7～9 with 20%NaOH solution, and solvent is sloughed in decompression and water namely gets Gemini surface active agent.
Embodiment 4:
The preparation of Gemini surface active agent of the present invention
1. in the reactor of drying, add the anhydrous AlCl of 1.0g
3With the 0.8g Triethylammonium chloride, be stirred to dissolving, add the 36.0g heavy alkyl benzene, continue in reactant, slowly to drip the 3.5ml ethylene dibromide behind the stirring 30min, be added dropwise to complete the back and continue stirring 30min, be warming up to 40 ℃ of reaction 4h then, stopped reaction cooling cooling.
2. in another dry reactor, add 11.5g maleic anhydride and 20g ethylene dichloride, be stirred to dissolving; The control temperature is not higher than 30 ℃, stirs slowly to add the anhydrous AlCl of 30.0g down
3, drip 1. reaction product behind the 30min, be added dropwise to complete and be warming up to 30 ℃ of reaction 3.0h after 30min is continued to stir in the back.
3. add 5% dilute hydrochloric acid solution and trash ice in the beaker, stir down 2. product and slowly pour beaker into, mix the back standing demix, tell organic layer and wash again 2 times with 5% dilute hydrochloric acid.Organic layer is neutralized to pH=7～9 with 20%NaOH solution, and solvent is sloughed in decompression and water namely gets Gemini surface active agent.
Embodiment 5:
The preparation of Gemini surface active agent of the present invention
1. in the reactor of drying, add the anhydrous AlCl of 1.0g
3With the 0.8g Triethylammonium chloride, be stirred to dissolving, add the 36.0g heavy alkyl benzene, continue in reactant, slowly to drip the 3.5ml ethylene dibromide behind the stirring 30min, be added dropwise to complete the back and continue stirring 30min, be warming up to 40 ℃ of reaction 5h then, stopped reaction cooling cooling.
2. in another dry reactor, add 11.5g maleic anhydride and 20g ethylene dichloride, be stirred to dissolving; The control temperature is not higher than 30 ℃, stirs slowly to add the anhydrous AlCl of 30.0g down
3, drip 1. reaction product behind the 30min, be added dropwise to complete and be warming up to 30 ℃ of reaction 1.0h after 30min is continued to stir in the back.
3. add 5% dilute hydrochloric acid solution and trash ice in the beaker, stir down 2. product and slowly pour beaker into, mix the back standing demix, tell organic layer and wash again 2 times with 5% dilute hydrochloric acid.
4. above-mentioned organic layer is dissolved in the 50g Virahol, the sodium sulfite solution of slow Dropwise 5 0.0g10% under 40 ℃ of agitation conditions drips the back at 60 ℃ of reaction 1h.
5. above-mentioned product standing demix divides the sub-cloud inorganic salt, and solvent is sloughed in the upper strata decompression and water namely gets Gemini surface active agent.
Embodiment 6
The performance of Gemini surface active agent of the present invention
Get 10.0g embodiment 1 prepared Gemini surface active agent, be dissolved in the 40ml volume ratio and be in 1: 1 the isopropanol mixed solvent, with n-hexane extraction 3 times, solvent evaporated obtains pure tensio-active agent.Measure the CMC value of this tensio-active agent with conductometric titration, as Fig. 1.The micelle-forming concentration that can obtain tensio-active agent of the present invention from figure is 40mg/L.
Embodiment 7:
The application of Gemini surface active agent of the present invention
With distilled water preparation different concns tensio-active agent of the present invention, add 1.2%Na
2CO
3, the interfacial tension of mensuration alkali/surfactant system and Karamay oilfield Qi Zhong district crude oil, surfactant concentration interfacial tension when 20mg/L is above all can reach 10
-3MN/m is as Fig. 2.
Claims (10)
1. the preparation method of a used for tertiary oil recovery Gemini surface active agent, it is characterized in that: required starting material are alkylbenzene, halogenated alkane, acid anhydrides, catalyzer, organic solvent, alkali, mineral acid; The ratio of reactant species amount is: alkylbenzene and halogenated alkane (2～5): 1, and alkylbenzene and acid anhydrides 1: (1～1.5), catalyzer and halogenated alkane (1～4): 10; Concrete grammar is:
1. in reactor 1, add alkylbenzene and alkylation catalyst, mix, and be preheating to 20 ℃～50 ℃; Under agitation in reactant, drip halogenated alkane, be added dropwise to complete the back and continue to stir 30min; Reaction 2h～5h; Heat up 40～80 ℃ then, reaction 2h～5h;
2. in reactor 2, add acid anhydrides and solvent, be stirred to dissolving; Stir cooling and slowly add acylation catalyst down, drip 1. reaction product behind the 30min, be added dropwise to complete the back and continue to stir 30min; 20 ℃～30 ℃ reaction 0.5h～3h;
3. add dilute acid soln and trash ice in the beaker, stir down 2. product and slowly pour beaker into, mix the back standing demix, tell organic layer to wash again 2 times with diluted acid;
4. above-mentioned organic layer is neutralized to pH=7～9 with alkali lye, and decompression is sloughed solvent and namely got Gemini surface active agent.
2. the preparation method of a kind of used for tertiary oil recovery Gemini surface active agent according to claim 1, it is characterized in that: used alkylbenzene is the alkylbenzene of C10～C24.
3. the preparation method of a kind of used for tertiary oil recovery Gemini surface active agent according to claim 1 is characterized in that: used halogenated alkane is a kind of in dichloro (bromine, iodine) ethane, dichloro (bromine, iodine) propane, dichloro (bromine, the iodine) butane.
4. the preparation method of a kind of used for tertiary oil recovery Gemini surface active agent according to claim 1 is characterized in that: used acid anhydrides is a kind of in malonic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, Pyroglutaric acid, the adipic anhydride.
5. the preparation method of a kind of used for tertiary oil recovery Gemini surface active agent according to claim 1, it is characterized in that: used catalyzer is anhydrous AlCl
3, FeCl
3, SbCl
5, BF
3, TiCl
4, ZnCl
2, perhaps HF, H
2SO
4, P
2O
5, H
3PO
4, perhaps acidic oxide SiO
2-Al
2O
3, a kind of in the ionic liquid, storng-acid cation exchange resin.
6. the preparation method of a kind of used for tertiary oil recovery Gemini surface active agent according to claim 1 is characterized in that: used organic solvent is a kind of in methylene dichloride, ethylene dichloride, trichloromethane, tetracol phenixin, the hexanaphthene.
7. the preparation method of a kind of used for tertiary oil recovery Gemini surface active agent according to claim 1 is characterized in that: used alkali is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor, thanomin, diethanolamine, the trolamine.
8. the preparation method of a kind of used for tertiary oil recovery Gemini surface active agent according to claim 1, it is characterized in that: used mineral acid is hydrochloric acid or sulfuric acid.
9. used for tertiary oil recovery Gemini surface active agent is characterized in that: this tensio-active agent is the preparation method preparation of used for tertiary oil recovery Gemini surface active agent according to claim 1.
10. the application of the described used for tertiary oil recovery Gemini surface active agent of claim 9 is characterized in that: with Na
2CO
3, water is composite as the tertiary oil recovery oil-displacing agent, using prescription to be tensio-active agent 0.002%～0.005% weight, Na
2CO
30.6%～2.0% weight, surplus are distilled water or mineralized water.
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| CN104830301A (en) * | 2015-04-13 | 2015-08-12 | 山东大学 | Vesicle oil displacement agent formed from gemini surfactant, and applications of vesicle oil displacement agent in crude oil recovery rate increase |
| CN106947455A (en) * | 2017-03-21 | 2017-07-14 | 四川格鑫拓科技有限公司 | New how sub- viscoelastic surfactant and its preparation method and application |
| CN110903912A (en) * | 2019-11-29 | 2020-03-24 | 华东理工大学 | Aryl grease and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104830301A (en) * | 2015-04-13 | 2015-08-12 | 山东大学 | Vesicle oil displacement agent formed from gemini surfactant, and applications of vesicle oil displacement agent in crude oil recovery rate increase |
| CN106947455A (en) * | 2017-03-21 | 2017-07-14 | 四川格鑫拓科技有限公司 | New how sub- viscoelastic surfactant and its preparation method and application |
| CN106947455B (en) * | 2017-03-21 | 2019-11-05 | 四川格鑫拓科技有限公司 | Novel how sub- viscoelastic surfactant and its preparation method and application |
| CN110903912A (en) * | 2019-11-29 | 2020-03-24 | 华东理工大学 | Aryl grease and preparation method and application thereof |
| CN110903912B (en) * | 2019-11-29 | 2022-01-28 | 华东理工大学 | Aryl grease and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN103184042B (en) | 2015-02-25 |
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