CN104910024B - Surfactant for driving oil - Google Patents
Surfactant for driving oil Download PDFInfo
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- CN104910024B CN104910024B CN201510239738.8A CN201510239738A CN104910024B CN 104910024 B CN104910024 B CN 104910024B CN 201510239738 A CN201510239738 A CN 201510239738A CN 104910024 B CN104910024 B CN 104910024B
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- China
- Prior art keywords
- myristyl
- tetramethylethylenediamine
- allyl
- surfactant
- lauryl alcohol
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 40
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 62
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims abstract description 39
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical group BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000001953 recrystallisation Methods 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 17
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 238000006073 displacement reaction Methods 0.000 claims description 15
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 12
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 8
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- -1 myristyl alkene Propyl group dibrominated tetramethylethylenediamine Chemical class 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000005187 foaming Methods 0.000 abstract description 21
- 239000006260 foam Substances 0.000 abstract description 18
- 150000003839 salts Chemical class 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 2
- SQCAYRYCRFMSHO-UHFFFAOYSA-N 1,2-dibromo-N,N,N',N'-tetramethylethane-1,2-diamine Chemical compound BrC(C(N(C)C)Br)N(C)C SQCAYRYCRFMSHO-UHFFFAOYSA-N 0.000 abstract 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 35
- 238000013329 compounding Methods 0.000 description 16
- 238000011084 recovery Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000015784 hyperosmotic salinity response Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 244000125380 Terminalia tomentosa Species 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical group C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a surfactant for driving oil. The surfactant is prepared through the following method. The method comprises steps: first, an intermediate myristyl allyl dibromo tetramethyl ethylenediamine is synthesized; second, myristyl allyl dibromo tetramethyl ethylenediamine is synthesized. The intermediate is dissolved completely in ethyl acetate, the constant temperature of 50-60 DEG C is achieved, 3-bromopropylene is added in the reaction system, after the reaction is carried out at a constant temperature with stirring for 4h, pressure reduction pumping filtration is carried out, and white solid is obtained. The white solid is subjected to recrystallization for two times by utilization of ether, drying is carried out until a constant weight is achieved, and the surfactant for driving oil is prepared. Myristyl allyl dibromo tetramethyl ethylenediamine also can be compounded with sodium phthalate of mono lauryl alcohol according to a weight ratio of 1:0.2-1, and a compound surfactant for driving oil is obtained. The synthesis technology conditions are simple, products are easy to separate, the yield is high, and industrialization is easy. Performances of the product such as salt resistance, temperature resistance, foaming property and foam stability, oil water interface tension force and the like are better than that of a traditional surfactant for driving oil.
Description
Technical field
The present invention relates to oil displacement agent, and in particular to a kind of surfactant oil displacement, belongs to exploitation technology field.
Background technology
World today's oil is still our daily life, the most important energy in commercial production, and energy problem is related to
One national lifeblood.Increase the research of DP technology technology, in the case of not finding new oil reservoir, research and development are suitable for
Raising oil recovery factor technology and invested in plantization application effectively to alleviate the nervous problem of energy resource supply.Once, two
Secondary oil recovery is physical method and recovers the oil, the recovery ratio generally only 30% about of crude oil, and intensified oil reduction measure is passed through in tertiary oil recovery,
Oil recovery factor can be made to bring up to 85% about.Surfactant plays not to increasing substantially oil recovery factor as oil displacement agent
Appreciable effect.Gemini surface active has the advantages that much to be superior to conventional surfactant, as high interface
Active and good absorption advantage etc., becomes one of relatively more active problem of current tertiary oil recovery research.Chen.H et al. studies
The interfacial tension of Gemini surface active and oily mixed solution, research finds, Gemini surface active is being used alone
Under the conditions of and concentration in ultralow scope, you can reduce oil water interfacial tension to ultralow, can be more than conventional surfactants
It is effectively reduced kerosene water interfacial tension.Shao Ruili etc. has synthesized the serial Gemini surface activity of two, anions and canons type
Agent, simulation extends the length 2 of oil field hyposmosis, chang6 oil layer sandstone has carried out flood pot test, and oil displacement efficiency is up to 63.16%, than
Water drive increased 21.05%.Compounding of research Gemini surface active and conventional surfactants, additive etc., will be
One important directions of Gemini surface active development.This respect KazuyukiTsubone etc. have studied anion Gemini
Type surfactant is compounding with conventional anion, finds that it has preferable cooperative effect.
Existing oil displacement agent shows low, the high critical micelle concentration of surface activity, high Krafft point, poorly water-soluble, profit
Moist low, rheological property is poor, compatibilization ability is low, cooperative ability is poor.Due to these shortcomings, it is undesirable to result in its oil displacement efficiency,
Relatively poor in heatproof, salt tolerant, foaming characteristic；It is easily caused oil well fouling, pump detection period shortens；Corrosive equipment.
Content of the invention
For deficiencies of the prior art, it is an object of the invention to provide a kind of surfactant oil displacement, this
More preferably, temperature tolerance, salt tolerance are higher, and foaming characteristic is more preferable for surfactant flooding effect.
The technical scheme is that and be achieved in that：
A kind of surfactant oil displacement, prepares by the following method,
1) synthesize myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate
Volume ratio is added to be 10 in synthesising container:1 acetonitrile and tetramethylethylenediamine, stir, and constant temperature is in 45 DEG C
After water-bath, it is slowly added to bromotetradecane, bromotetradecane is 1 with the mol ratio of tetramethylethylenediamine:1, after reaction 2h, first
After the unnecessary acetonitrile of distillation under pressure at 80 DEG C, then be warming up to 95 DEG C continue vacuum distillations go out unnecessary tetramethylethylenediamine, steam
Weak yellow liquid, as myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate is obtained after evaporating completely；
2) synthesize myristyl pi-allyl dibrominated tetramethylethylenediamine
With appropriate ethyl acetate by after the dissolving completely of myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate, turn
Enter in synthesising container, constant temperature to 50-60 DEG C, it is slowly added to 3- bromopropene in reaction system, 3- bromopropene consumption and the tetradecane
Base pi-allyl dibrominated tetramethylethylenediamine intermediate mol ratio is 1:1, obtain white after decompression sucking filtration after reaction constant temperature stirring 4h
Color solid, white solid Diethyl ether recrystallization twice, is dried to constant weight, obtains myristyl pi-allyl dibrominated tetramethyl second two
Amine, the surfactant oil displacement as preparing.
Described myristyl pi-allyl dibrominated tetramethylethylenediamine can also be pressed with sodium phthalate of mono lauryl alcohol
Mass ratio 1:0.2-1 compounds, and obtains compounding surfactant oil displacement.
Described sodium phthalate of mono lauryl alcohol synthetic method is as follows,
3) synthesize mono laury alcohol phthalate
Lauryl alcohol, hexamethylene, phthalic anhydride and catalyst boron is added in the synthesising container equipped with reflux condenser
Acid, wherein lauryl alcohol and phthalic anhydride mol ratio are 1:1, hexamethylene is reactant lauryl alcohol and phthalic anhydride
1.1 times of quality sum, boric acid consumption is the 0.1% of reactant lauryl alcohol and phthalic anhydride gross mass；Then in 80-
It is stirred at reflux reaction 5h at 85 DEG C, stop stirring, sucking filtration while hot, take off a layer liquid, discard the white solid in funnel, more again
Sucking filtration once, removes the phthalic anhydride of residual, using the monoesters and alcohol different solubility in hexamethylene, reactant liquor is existed
Half an hour is cooled down, monoesters separates out first, filters to obtain white fluid, as phthalic acid list lauryl alcohol in 4-11 DEG C of frozen water
Ester；
4) synthesize sodium phthalate of mono lauryl alcohol
Mono laury alcohol phthalate is heated to 60-70 DEG C, stirring is lower to add the hydroxide that concentration is 0.4mol/L
Sodium solution, adjusting PH is neutrality, then reacts 25-30 minute, obtains thick white shape liquid and is mono laury alcohol phthalate
Sodium.
The present invention has synthesized Gemini surface active myristyl pi-allyl dibrominated tetramethylethylenediamine, and with adjacent benzene
Dioctyl phthalate single lauryl alcohol ester sodium is compounded, and determines myristyl pi-allyl dibrominated tetramethylethylenediamine respectively and it is multiple
The foaming characteristic of part system, salt-resistance, temperature tolerance and Oil Displacing Capacity.Compared to existing technology, the present invention has advantages below：
(1) technique of synthesis myristyl pi-allyl dibrominated tetramethylethylenediamine and sodium phthalate of mono lauryl alcohol
Condition is simple, and product can be easily separated, yield high it is easy to industrialization.
(2) the myristyl pi-allyl dibrominated tetramethylethylenediamine system either synthesizing, or compound system is resistance to
Salt and temperature tolerance, foaming characteristic and foam stability, the performance such as oil water interfacial tension is superior to traditional surfactant oil displacement.
(3) this surfactant belongs to dissymmetrical structure, has more adjustabilitys on molecular structure.
(4) because the molecular weight of the myristyl pi-allyl dibrominated tetramethylethylenediamine system of synthesis is not high, therefore work as and be subject to
It is difficult to cut off to its strand during shear action, shows excellent anti-shear performance, lay a solid foundation for extensive application.
(5) surfactant myristyl pi-allyl dibrominated tetramethylethylenediamine passes through to compound, and can substantially reduce into
This, be tertiary oil recovery field, be with a wide range of applications.
Brief description
The impact to foaming characteristic and foam stability for Fig. 1-surfactant concentration.
The impact to foam height for the quality of Fig. 2-salt.
The impact to foam stability for the quality of Fig. 3-salt.
Fig. 4-surfactant concentration is on capillary impact.
Fig. 5-surfactant concentration is for temperature during 16g/L on capillary impact.
In Fig. 6-profit, surfactant concentration is on capillary impact.
Fig. 7-compounding the impact to foaming characteristic for the mass ratio.
The impact to salt resistant character for Fig. 8-total salinity.
The impact to foam stability for Fig. 9-salinity.
Figure 10-compounding mass ratio is on capillary impact.
Figure 11-temperature is on capillary impact.
Figure 12-compounding mass ratio capillary impact on profit.
Specific embodiment
Surfactant of the present invention has two kinds, single surfactant, i.e. myristyl pi-allyl dibrominated tetramethyl
Ethylenediamine；Compounding surfactant, i.e. myristyl pi-allyl dibrominated tetramethylethylenediamine and phthalic acid list Laurel
Alcohol ester sodium in mass ratio 1:0.2-1 is compounded.
Wherein myristyl pi-allyl dibrominated tetramethylethylenediamine prepares by the following method,
1) synthesize myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate
Volume ratio is added to be 10 in synthesising container:1 acetonitrile and tetramethylethylenediamine, stir, and constant temperature is in 45 DEG C
After water-bath, it is slowly added to bromotetradecane, bromotetradecane is 1 with the mol ratio of tetramethylethylenediamine:1, after reaction 2h, first
After the unnecessary acetonitrile of distillation under pressure at 80 DEG C, then be warming up to 95 DEG C continue vacuum distillations go out unnecessary tetramethylethylenediamine, steam
Weak yellow liquid, as myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate is obtained after evaporating completely；
2) synthesize myristyl pi-allyl dibrominated tetramethylethylenediamine
With appropriate ethyl acetate by after the dissolving completely of myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate, turn
Enter in synthesising container, constant temperature to 50-60 DEG C, it is slowly added to 3- bromopropene in reaction system, 3- bromopropene consumption and the tetradecane
Base pi-allyl dibrominated tetramethylethylenediamine intermediate mol ratio is 1:1, obtain white after decompression sucking filtration after reaction constant temperature stirring 4h
Color solid, white solid Diethyl ether recrystallization twice, is dried to constant weight, obtains myristyl pi-allyl dibrominated tetramethyl second two
Amine, the surfactant oil displacement as preparing.
Wherein sodium phthalate of mono lauryl alcohol synthetic method is as follows,
3) synthesize mono laury alcohol phthalate
Lauryl alcohol, hexamethylene, phthalic anhydride and catalyst boron is added in the synthesising container equipped with reflux condenser
Acid, wherein lauryl alcohol and phthalic anhydride mol ratio are 1:1, hexamethylene is reactant lauryl alcohol and phthalic anhydride
1.1 times of quality sum, boric acid consumption is the 0.1% of reactant lauryl alcohol and phthalic anhydride gross mass；Then at 80-85 DEG C
Under be stirred at reflux reaction 5h, stop stirring, sucking filtration while hot, take off a layer liquid, discard the white solid in funnel, then sucking filtration again
Once, remove the phthalic anhydride of residual, using the monoesters and alcohol different solubility in hexamethylene, by reactant liquor in 4-11
DEG C frozen water in cool down half an hour, monoesters separates out first, filters to obtain white fluid, as mono laury alcohol phthalate；
4) synthesize sodium phthalate of mono lauryl alcohol
Mono laury alcohol phthalate is heated to 60-70 DEG C, stirring is lower to add the hydroxide that concentration is 0.4mol/L
Sodium solution, adjusting PH is neutrality, then reacts 25-30 minute, obtains thick white shape liquid and is mono laury alcohol phthalate
Sodium.
Below in conjunction with specific embodiment and accompanying drawing, the present invention is described in further detail.
The embodiment of the present invention has synthesized single Gemini surface active myristyl pi-allyl dibrominated tetramethyl first
Base ethylenediamine, and with synthesis sodium phthalate of mono lauryl alcohol compounded, finally determine single surfactant and
The foaming characteristic of compound system, salt-resistance, temperature tolerance and Oil Displacing Capacity.
First, the synthesis of myristyl pi-allyl dibrominated tetramethylethylenediamine
1.1) synthetic method of myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate
In the three neck round bottom of 250ml, add 100mL acetonitrile and 10mL tetramethylethylenediamine, stirring, constant temperature is in 45
After DEG C water-bath, it is slowly added dropwise 0.05mol bromotetradecane with constant pressure funnel, after reaction 2h, first pressurization is steamed at 80 DEG C
After evaporating unnecessary acetonitrile, it is warming up to 95 DEG C of continuation vacuum distillations and goes out unnecessary tetramethylethylenediamine, obtain yellowish after distillation completely
Color liquid, as myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate, with infrared spectrum, qualitative analyses are carried out to it.
1.2) synthetic method of myristyl pi-allyl dibrominated tetramethylethylenediamine
To be turned after the dissolving completely of myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate with the ethyl acetate of 10mL
Enter in 250mL three neck round bottom, then plus 140mL ethyl acetate.Constant temperature to 60 DEG C in water-bath, is delayed with constant pressure funnel
Slow Deca 3- bromopropene (myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate and 3- bromopropene consumption in molar ratio 1:
1 condition), reaction constant temperature stirring 4h, obtain white solid with after buchner funnel decompression sucking filtration, by product with diethyl ether recrystallization two
Secondary, it is dried to constant weight, as myristyl pi-allyl dibrominated tetramethylethylenediamine, with infrared spectrum, qualitative point is carried out to it
Analysis.
Optimal synthetic technological condition：The myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate reaction time is 2h,
The synthesis myristyl pi-allyl dibrominated tetramethylethylenediamine response time selects 4h.
2nd, synthesize sodium phthalate of mono lauryl alcohol
2.1) method synthesizing mono laury alcohol phthalate
(alcohol acid anhydride mass ratio is 1 to add lauryl alcohol 30g in the there-necked flask equipped with reflux condenser 250ml:1.6), ring
Hexane 80g (quantity of solvent is 1.1 times of alcohol and phthalic anhydride quality), adds phthalic anhydride 38g (alcohol acid anhydride mass ratio
For 1:1.6) and catalyst boric acid 1g, boric acid consumption is the 0.1% of reactant gross mass, at 85 DEG C, is stirred at reflux reaction 5h,
Stop stirring, sucking filtration while hot, take off a layer liquid, discard the white solid in funnel, then sucking filtration once, removes the neighbour of residual again
Phthalate anhydride, liquid hexamethylene is made solvent, using the monoesters and alcohol different solubility in hexamethylene, by liquid ice
Water stands half an hour under (4-11 DEG C), and monoesters separates out first, filters to obtain white fluid, as phthalic acid list lauryl alcohol
Ester.
2.2) method synthesizing sodium phthalate of mono lauryl alcohol
Mono laury alcohol phthalate is heated to 60-70 DEG C, instills under agitation containing concentration as 0.4mol/L's
Sodium hydroxide solution, adjusting PH is neutrality, then reacts 25-30 minute, obtains thick white shape liquid, as phthalic acid
Single lauryl alcohol ester sodium, carries out qualitative analyses with infrared spectrum to it.
3rd, myristyl pi-allyl dibrominated tetramethylethylenediamine and sodium phthalate of mono lauryl alcohol are compounded
Myristyl pi-allyl dibrominated tetramethylethylenediamine and sodium phthalate of mono lauryl alcohol are pressed certain mass
Ratio is compounded.
4th, qualitative analyses：The foaming characteristic of mensure product, foam stability, salt tolerance, surface tension.
4.1) performance test of myristyl pi-allyl dibrominated tetramethylethylenediamine
4.1.1) the foaming characteristic of myristyl pi-allyl dibrominated tetramethylethylenediamine and foam stability test
Claim 5g, 4g, 3g, 2g, 1g myristyl pi-allyl dibrominated tetramethylethylenediamine respectively, existed with 250mL distilled water
After dissolving at 40 DEG C, survey its foaming characteristic and foam stability with Roche foam, parallel 3 times, measurement result is as shown in Figure 1.
As shown in Figure 1, with the increase of myristyl pi-allyl dibrominated tetramethylethylenediamine concentration, foam height is therewith
Increase, foam stability is gradually stable also with the increase of concentration, illustrate with concentration increase foaming characteristic and stability all than
Preferably, best when concentration is for 20g/L.
4.1.2) the salt tolerance test of myristyl pi-allyl dibrominated tetramethylethylenediamine
With distilled water as solvent, compound concentration is the myristyl pi-allyl dibrominated tetramethylethylenediamine solution of 20g/L,
Prepare NaCl and CaCl of different quality again2After dissolving at 40 DEG C, investigate the impact to salt resistant character for the concentration of two kinds of salt, its
Experimental result is as shown in Figure 2,3.
From Fig. 2 and 3, with NaCl and CaCl2The increase of consumption, myristyl pi-allyl dibrominated tetramethyl second two
The foaming characteristic of amine and foam stability are all gradually lowered, in NaCl and CaCl2After consumption is 3.075g, foam stability is very low and steady
Fixed, illustrate that the surfactant synthesizing is affected larger salt resistant character by salt bad.
4.1.3) investigate the temperature tolerance of myristyl pi-allyl dibrominated tetramethylethylenediamine
Prepare 20g/L, the myristyl pi-allyl dibrominated tetramethylethylenediamine of 16g/L, 12g/L, 8g/L, 4g/L is molten
Liquid, surveys surface tension with surface tension instrument after dissolving completely, the solution of the best surface tension force with recording exists at 40 DEG C respectively
Under different temperatures, carry out temperature tolerance investigation, result such as Fig. 4, shown in 5.
As shown in Figure 4, the increase surface tension with concentration first reduces and increases afterwards, this is because the increase with concentration changes
Become the surface tension of the water tension force when concentration is into 16g/L and reached minimum, the continuation with concentration has increased when reaching 20g/L,
Solution saturation so that surface tension is gone up again.As shown in Figure 5, the elevation surface tension force with temperature is gradually reduced, and this is
Due to the rising with temperature, surfactant dissolubility increases, and rises high-temperature and surfactant activity is increased so that table
Face tension force reduces.In sum, the temperature tolerance of myristyl pi-allyl dibrominated tetramethylethylenediamine is preferable.
4.1.4) the investigation of the oil water interfacial tension of myristyl pi-allyl dibrominated tetramethylethylenediamine
Compound concentration is 20g/L, the product solution 25mL of 16g/L, 12g/L, 8g/L, 4g/L respectively, then takes 20mL respectively
Diesel oil mix with the surfactant of synthesis, after dissolving completely at 40 DEG C, with surface tension instrument survey profit surface tension, such as
Fig. 6.
It will be appreciated from fig. 6 that the increase surface tension with the surfactant concentration of synthesis is being gradually reduced, to concentration it is
During 16g/L, surfactant tension force is minimum, and when concentration is for 20g/L, surface tension increases again, illustrates that concentration is system during 20g/L
It has been that saturation leads to surface tension to rise, so, surfactant concentration selects 16g/L, and oil displacement efficiency is best.
4.1.5) brief summary
In sum, the foaming characteristic of myristyl pi-allyl dibrominated tetramethylethylenediamine and foam stability are good, salt resistant character
Poor, when concentration is for 16g/L, temperature resistant capability is good, and oil water interfacial tension is minimum.
4.2) myristyl pi-allyl dibrominated tetramethylethylenediamine is compounded with sodium phthalate of mono lauryl alcohol
The performance test of system
4.2.1) the foaming test of compound system
By myristyl pi-allyl dibrominated tetramethylethylenediamine and sodium phthalate of mono lauryl alcohol in mass ratio 1:
0,5:1,1:1,1:5,0:After 1 carries out compounding, investigate its foaming characteristic, its experimental result is as shown in Figure 7.
As shown in Figure 7, compound system is with 5:1 compounding when foaming characteristic preferably, this illustrates myristyl pi-allyl dibrominated four
The bigger foaming characteristic of methyl ethylenediamine ratio is better.
4.2.2) compound system salt tolerance test
By myristyl pi-allyl dibrominated tetramethylethylenediamine and sodium phthalate of mono lauryl alcohol in mass ratio 5:1
After carrying out compounding, investigate the impact to salt resistant character for the salinity, its result is as shown in FIG. 8 and 9.
As shown in Figure 8, the increase foaming characteristic with salinity first reduces and then tends to be steady, due to total salinity in system
Increase, change the interfacial tension of surfactant so that foaming characteristic decreases, with salinity continuation increase, rise
Bubble property tends towards stability, and illustrates that compound system salt tolerance is relatively good.
As shown in Figure 9, the increase foam stability with salinity is also gradually increasing, when salinity has reached the later foam stability of 5g
Reduce, but reduce amplitude less, illustrate that the system after compounding is more stable, salt resistant character is relatively good.
4.2.3) the surface tension test of compound system
By myristyl pi-allyl dibrominated tetramethylethylenediamine and sodium phthalate of mono lauryl alcohol in mass ratio 1:
0,5:1,1:1,1:5,0:1 carry out compounding after take respectively 25mL solution dissolve at 40 DEG C complete after, measured with surface tension instrument
Measure its surface tension respectively, its result is as shown in Figure 10.
As shown in Figure 10, compounding mass ratio be 5:When 1, system surface tension is minimum, and myristyl pi-allyl two is described
The capillary ability of the bigger change of bromination tetramethylethylenediamine proportion is also stronger, and this proportioning properties of product is superior.
4.2.4) compound system temperature resistant capability test
With 5:1 compound system dissolve at 40 DEG C after respectively in 313.15K, 323.15K, 333.15K, 343.15K,
Its capillary temperature tolerance is measured under 353.15K.Its result is as shown in figure 11：
As shown in Figure 11, compound system first reduces with the elevation surface tension force of temperature and increases afterwards, then reduces again,
During 323.15K, surface tension reduces, and illustrates that the sodium phthalate of mono lauryl alcohol dissolubility in compound system is relatively good somewhat
Heating just can quickly be dissolved, and the continuation with temperature increases, and sodium phthalate of mono lauryl alcohol has dissolved completely, temperature pair
The impact of surfactant mono-layer film has become as key factor, so surface tension increased, with the continuation liter of temperature
Height, myristyl pi-allyl dibrominated tetramethylethylenediamine slowly dissolves, and is gradually lowered surface tension, compound system heatproof is described
Performance comparision is good.
4.2.5) the surface tension test of compound system profit
By myristyl pi-allyl dibrominated tetramethylethylenediamine and sodium phthalate of mono lauryl alcohol in mass ratio 1:
0,5:1,1:1,1:5,0:1 carry out compounding after dissolve completely at 40 DEG C after, be separately added into 20mL diesel oil, surveyed with surface tension instrument
Determine to measure its surface tension step respectively ibid, its result is as shown in figure 12.
As shown in Figure 12, compounding mass ratio be 1:1 and 1:When 5 oil water interfacial tension very little and the two be more or less the same,
In order to reduce dosage of surfactant, compound proportion is selected to be 1:1 compounding optimal proportion.
4.2.6) brief summary
In sum, compound system is 5:Under 1 ratio, preferably, salt resistant character is superior, and surface is opened for foaming characteristic and foam stability energy
Power is good, and temperature resistant capability is good；With 1 in the test of compound system oil water interfacial tension:The oil water interfacial tension of 1 compound system is minimum.
The above embodiment of the present invention only example to illustrate the invention, and it is not the enforcement to the present invention
The restriction of mode.For those of ordinary skill in the field, can also be made other not on the basis of the above description
Change and variation with form.Here all of embodiment cannot be exhaustive.Every belong to technical scheme
The obvious change amplified out or change the row still in protection scope of the present invention.
Claims (1)
1. a kind of surfactant oil displacement it is characterised in that：By myristyl pi-allyl dibrominated tetramethylethylenediamine and neighbour
Phthalic acid single lauryl alcohol ester sodium in mass ratio 1:0.2-1 compounds and forms；
Wherein myristyl pi-allyl dibrominated tetramethylethylenediamine prepares by the following method,
1）Synthesis myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate
Volume ratio is added to be 10 in synthesising container:1 acetonitrile and tetramethylethylenediamine, stir, and constant temperature is in 45 DEG C of water-baths
After pot, it is slowly added to bromotetradecane, bromotetradecane is 1 with the mol ratio of tetramethylethylenediamine:1, after reaction 2h, first 80
After the unnecessary acetonitrile of distillation under pressure at DEG C, then be warming up to 95 DEG C continue vacuum distillations go out unnecessary tetramethylethylenediamine, distilled
Weak yellow liquid, as myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate is obtained after complete；
2）Synthesis myristyl pi-allyl dibrominated tetramethylethylenediamine
With appropriate ethyl acetate by after the dissolving completely of myristyl pi-allyl dibrominated tetramethylethylenediamine intermediate, proceed to conjunction
Become in container, constant temperature to 50-60 DEG C, it is slowly added to 3- bromopropene in reaction system, 3- bromopropene consumption and myristyl alkene
Propyl group dibrominated tetramethylethylenediamine intermediate mol ratio is 1:1, obtain white after decompression sucking filtration after reaction constant temperature stirring 4h solid
Body, white solid Diethyl ether recrystallization twice, is dried to constant weight, obtains myristyl pi-allyl dibrominated tetramethylethylenediamine；
Described sodium phthalate of mono lauryl alcohol synthetic method is as follows,
3）Synthesis mono laury alcohol phthalate
Add lauryl alcohol, hexamethylene, phthalic anhydride and catalyst boric acid in the synthesising container equipped with reflux condenser, its
Middle lauryl alcohol and phthalic anhydride mol ratio are 1:1, hexamethylene is reactant lauryl alcohol and phthalic anhydride quality
1.1 times of sum, boric acid consumption is the 0.1% of reactant lauryl alcohol and phthalic anhydride gross mass；Then at 80-85 DEG C
Under be stirred at reflux reaction 5h, stop stirring, sucking filtration while hot, take off a layer liquid, discard the white solid in funnel, then sucking filtration again
Once, remove the phthalic anhydride of residual, using the monoesters and alcohol different solubility in hexamethylene, by reactant liquor in 4-11
DEG C frozen water in cool down half an hour, monoesters separates out first, filters to obtain white fluid, as mono laury alcohol phthalate；
4）Synthesis sodium phthalate of mono lauryl alcohol
Mono laury alcohol phthalate is heated to 60-70 DEG C, the lower sodium hydroxide adding concentration to be 0.4mol/L of stirring is molten
Liquid, adjusting PH is neutrality, then reacts 25-30 minute, obtains thick white shape liquid and is sodium phthalate of mono lauryl alcohol.
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