CN102703050A - Tetra-polysulfonate type surfactant and preparation method thereof - Google Patents
Tetra-polysulfonate type surfactant and preparation method thereof Download PDFInfo
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- CN102703050A CN102703050A CN2012101667916A CN201210166791A CN102703050A CN 102703050 A CN102703050 A CN 102703050A CN 2012101667916 A CN2012101667916 A CN 2012101667916A CN 201210166791 A CN201210166791 A CN 201210166791A CN 102703050 A CN102703050 A CN 102703050A
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Abstract
The invention relates to a tetra-polysulfonate type surfactant which is used for tertiary oil recovery and heavy oil viscosity reduction and capable of enhancing surface activity and reducing critical micelle concentration, and a preparation method of the surfactant. The technical scheme is as follows: the surfactant is 1, 1, 1, 1-tetra (2-oxytrimethylene sodium sulfonate-3-alkylether-porpanoxy) neopentane with a code name of TTSS-4-n; the preparation method comprises steps of adding pentaerythritol, dimethyl sulfoxide and NaOH firstly, and then dropping epoxy chloropropane, reacting for 5-10h, so as to obtain pentaerythritol tetra-epoxy-propane ether; dropping the product in a reaction product of fatty alcohol and potassium or sodium hydride, reacting for 8-10h at 80 DEG C, reducing and distilling to obtain yellowish liquid; and adding the product in propane suhone dissolved into tetrahydrofuran, reacting for 12h, so as to obtain TTSS-4-n. The surfactant has the advantages of novel structure, simple manufacturing process, high surface activity, low critical micelle concentration and good temperature and salt resistance, and is used for oilfield oil extraction.
Description
Technical field
The present invention relates to a kind of displacement of reservoir oil that is used for high temperature and high salt oil deposit with four polysulfonate type tensio-active agents and preparation method thereof.
Background technology
In recent years, oligo surfactant is just becoming the research focus.These tensio-active agents are connected to form by connecting base by two above traditional surfactant molecules usually, contain many hydrophobic chains and many hydrophilic chains in the molecule.Compare with conventional surfactant; They have unique physicochemical property, and surface of good is active, lower micelle-forming concentration; Lower Krafft point; Good temperature resistance salt tolerance has confirmed and can under extremely low concentration, oil water interfacial tension have been reduced that these tensio-active agents are just becoming the novel product of field use.
Because the sandstone bottom surface of oil reservoir is generally electronegative; Use AS can reduce its electrostatic adhesion on the reservoir mineral; Thereby the reduction amount of surfactant, therefore present oil field is generally AS as the tensio-active agent of oil-displacing agent.From report, most tensio-active agent is difficult to reach stratum application requiring, particularly high temperature, high salinity and the high contents of calcium and magnesium ionic stratum of complicacy.Therefore this field presses for the sulfonate type oligo surfactant of a kind of superior performance of research and development and high temperature resistance high salt tolerance.Has a large amount of ehter bonds in the surfactant molecule of the present invention; Calcium ions and magnesium ions in the ability complexing local water; Avoided the effect of calcium ions and magnesium ions and sulfonate group to produce deposition, simultaneously, the repulsion tendency between hydrophilic base is because of being limited by chemical bonding force by weakening greatly; Reduced the effect probability of sodium ion from space conformation to hydrophilic head base; Avoid tensio-active agent in sodium at high concentration ion local water, to produce the crystalline hydrate phase, thereby improved the solvability of tensio-active agent in containing high salt high contents of calcium and magnesium ion local water, embodied good salt resistance anticalcium mg ion ability.
The research of oligo surfactant shows that " polymerization degree " is high more, and surfactivity is high more, and it is low more to reduce surface tension value, helps washing oil more; Simultaneously, the polymerization degree " high more, viscosity is high more, helps the displacement of reservoir oil more.
Summary of the invention
The object of the invention is: in order to adapt to the requirement of high temperature and high salinity bad ground, research and develop the oligomeric sulfonate surfactant of superior performance and high temperature resistance high salt tolerance, the spy provides a kind of four polysulfonate type tensio-active agents and preparation method thereof.
In order to achieve the above object, the present invention adopts following technical scheme: a kind of four polysulfonate type tensio-active agents, and chemical name is 1,1,1,1-four (2-oxygen trimethylene sodium sulfonate-3-alkyl oxide-third alkoxyl group) neopentane, code name is TTSS-4-n, its structural formula is:
Wherein, R is C
8H
17, C
10H
21, or C
12H
25, or C
14H
29, or C
16H
33A kind of, the carbonatoms among the R is the n in the code name.
The preparation method of above-mentioned four polysulfonate type tensio-active agents provided by the invention comprises the steps:
1) earlier tetramethylolmethane is dissolved in the mixing solutions of dress 150ml DMSO 99.8MIN. and basic soln, the dropping epoxy chloropropane is in the reactor drum of this mixing solutions under whipped state, and the above-mentioned raw materials mol ratio of penta tetrol and epoxy chloropropane, alkali quarterly is 1.0:6.0～8.0:4.0～6.0 consumptions; Reaction is 5～10 hours under 35 ℃ and agitation condition; In reactor drum, add methylene dichloride again, filter, remove insolubles; Methylene dichloride is removed in underpressure distillation; With 100mL saturated common salt water dissolution and with the extracted with diethyl ether twice of 150mL, merge organic phase and use anhydrous magnesium sulfate drying again, must faint yellow oily thing tetramethylolmethane Fourth Ring Ethylene Oxide base ether after the underpressure distillation;
2) earlier at 60 ℃ of sodium alkyl alcohols that make with alkyl alcohol and potassium or potassium hydride KH reaction, carbonatoms is 8～16 in the alkyl alcohol, will be dripped in the sodium alkyl alcohol solution by the above-mentioned tetramethylolmethane Fourth Ring Ethylene Oxide base ether that makes again; Tetramethylolmethane Fourth Ring Ethylene Oxide base ether and alkyl alcohol, potassium reacted 8～10 hours at 80 ℃ for 1.0:4.0～8.0:0.8～1.2 consumptions in molar ratio, and using massfraction is the pH to 7 of 10% Hydrogen chloride regulation system, joins then in the mixing solutions of volume ratio methylene dichloride: water=3:1; Volume is unit with L; Organic layer is used anhydrous magnesium sulfate drying, and methylene chloride is removed in distillation, and excessive alkyl alcohol is removed in last underpressure distillation; Promptly get light yellow solid 1; 1,1,1-four (2-hydroxyl-3-alkyl oxide-third alkoxyl group) neopentane;
3) at last will by top make 1,1,1; 1-four (2-hydroxyl-3-alkyl oxide-third alkoxyl group) neopentane is dissolved in the dry tetrahydrofuran solvent, and following to 1 50～60 ℃ of temperature of reaction, 3-propane sultone mixes; Slowly add sodium hydride while stirring, by 1,1; 1; 1-four (2-hydroxyl-3-alkyl oxide-third alkoxyl group) neopentane and THF, 1,3-propane sultone, sodium hydride mol ratio are 1.0:15.0～30.0:6.0～9.0:6.0～8.0 consumptions, finish at 50～60 ℃ of reaction 12h.Stop heating, add small amount of methanol again and remove unreacted sodium hydride, THF is removed in distillation; Be dissolved in then in the mixing solutions of volume ratio propyl carbinol: water=3:1, organic layer is used anhydrous magnesium sulfate drying, and propyl carbinol is removed in distillation; Crude product is purified also through silica gel chromatographic column, and vacuum-drying promptly gets white wax shape product 1; 1,1,1-four (2-oxygen trimethylene sodium sulfonate-3-alkyl oxide-third alkoxyl group) neopentane.
Among the above-mentioned preparation method, the basic soln described in the step 1) is sodium hydroxide or potassium hydroxide solution, and concentration is 90wt%.
Among the above-mentioned preparation method, step 2) described alkyl alcohol is a kind of in octanol or ten alcohol or lauryl alcohol or tetradecyl alcohol or the hexadecanol.
The invention has the beneficial effects as follows: (1) tensio-active agent of the present invention belongs to four polysulfonate type tensio-active agents, is a kind of tensio-active agent of novel structure; (2) preparation method of the present invention is simpler, and reaction conditions is gentle, and is easy to operate; (3) tensio-active agent of the present invention has higher surface activity and extremely low micelle-forming concentration, and its micelle-forming concentration (cmc) is all 1.6 * 10
-6～3.08 * 10
-4Mol.L
-1Between, surface tension can be used for the TOR oil-displacing agent of high temperature and high salt high contents of calcium and magnesium ion oil reservoir between 23～29mN/m.
Description of drawings
Fig. 1 is the infrared spectrogram of product TTSS-4-12 of the present invention.
Embodiment
Following combination instance is described further the present invention.
(1) preparation of tetramethylolmethane Fourth Ring Ethylene Oxide base ether:
Earlier the 1mol tetramethylolmethane is dissolved in the mixing solutions of dress 150ml DMSO 99.8MIN. and 6mol potassium hydroxide solution; Under whipped state, drip the 6mol epoxy chloropropane in the reactor drum of this mixing solutions, reacted 7 hours down, in reactor drum, add methylene dichloride again at 35 ℃ and agitation condition; Filter; Remove insolubles, methylene dichloride is removed in underpressure distillation, again with 100mL saturated common salt water dissolution and with twice of the extracted with diethyl ether of 150mL; Merge organic phase and use anhydrous magnesium sulfate drying, get faint yellow oily thing tetramethylolmethane Fourth Ring Ethylene Oxide base ether after the underpressure distillation;
(2) 1,1,1, the preparation of 1-four (2-hydroxyl-3-lauryl ether-third alkoxyl group) neopentane:
Get the 5mol lauryl alcohol in there-necked flask, 60 ℃ slowly add the 2mol potassium metal down, react to the potassium disappearance; Add the tetramethylolmethane Fourth Ring Ethylene Oxide base ether that makes above the 1mol, reacted 8 hours, after the cooling; With dilute hydrochloric acid solution regulation system pH=7, join then in the water-soluble mixed solution system of 450ml methylene dichloride and 150ml, organic layer is used anhydrous magnesium sulfate drying; Methylene chloride and excessive lauryl alcohol are removed in underpressure distillation, promptly get the light yellow solid midbody.
At 60 ℃ of sodium alkyl alcohols that make with 5mol alkyl alcohol and 2mol nak response, carbonatoms is 8～16 in the alkyl alcohol earlier, will be dripped in the sodium alkyl alcohol solution by the above-mentioned 1mol tetramethylolmethane Fourth Ring Ethylene Oxide base ether that makes again; Reacted 8 hours at 80 ℃, using massfraction is the pH to 7 of 10% Hydrogen chloride regulation system, adds then to join then in the water-soluble mixed solution system of 450ml methylene dichloride and 150ml; Organic layer is used anhydrous magnesium sulfate drying, and methylene chloride is removed in distillation, and excessive alkyl alcohol is removed in last underpressure distillation; Promptly get light yellow solid 1; 1,1,1-four (2-hydroxyl-3-alkyl oxide-third alkoxyl group) neopentane;
(3) 1,1,1, the preparation of 1-four (2-oxygen trimethylene sodium sulfonate-3-lauryl ether-third alkoxyl group) neopentane:
At last will be by the top 0.1mol that makes 1; 1,1,1-four (2-hydroxyl-3-lauryl ether-third alkoxyl group) neopentane is dissolved in the 150ml dry tetrahydrofuran solvent; At 50～60 ℃ of following and 0.8mol 1 of temperature of reaction; 3-propane sultone mixes, and slowly adds the 0.6mol sodium hydride while stirring, finishes at 50～60 ℃ of reaction 12h.Stop heating, add small amount of methanol again and remove unreacted sodium hydride, THF is removed in distillation; Be dissolved in then in 450ml propyl carbinol and the 150ml water mixed solution system, organic layer is used anhydrous magnesium sulfate drying, and propyl carbinol is removed in distillation; Crude product is purified also through silica gel chromatographic column, and vacuum-drying promptly gets white wax shape product 1; 1,1,1-four (2-oxygen trimethylene sodium sulfonate-3-lauryl ether-third alkoxyl group) neopentane.
Embodiment 2
Gained final product TTSS-4-12 structure has been made sign with ir spectra among the embodiment 1, and spectrogram is seen Figure of description, and spectrum elucidation is following: 2 923 cm
-1With 2 854 cm
-1Be respectively the asymmetrical stretching vibration absorption peak of methyl and methylene radical; 1 377 cm
-1With 922 cm
-1Be methyl flexural vibration absorption peak; 1 443 cm
-1Be methylene radical scissoring vibration absorption peak; 732cm
-1Be the continuous charateristic avsorption band of long-chain methylene radical; 1 193 cm
-1, 621 cm
-1On the sulfonate radical-SO
2-functional group charateristic avsorption band; 1 062 cm
-1With 1 110 cm
-1Be the ehter bond charateristic avsorption band.Charateristic avsorption band among the figure is corresponding one by one with the functional group in the title product, proves that the synthetic product is title product.
Embodiment 3
Micelle-forming concentration of tensio-active agent (cmc) and surface tension are the important parameters of evaluation table surface-active agent.The present invention adopts the gamut rotation to drip table/interfacial tensimeter TX-500C surface tension instrument and measures performance of products, and experimental data is listed in the table 1.
The surface property of the different four polysulfonate tensio-active agents of table 1 (50 ℃)
| Tensio-active agent | cmc/mmol.l -1 | γ cmc/ mN.m -1 |
| TTSS-4-8 | 0.308 | 28.5 |
| TTSS-4-10 | 0.072 | 26.5 |
| TTSS-4-12 | 0.051 | 26.0 |
| TTSS-4-14 | 0.0040 | 24.5 |
| TTSS-4-16 | 0.0016 | 23.6 |
| SDS | 9.7 | 34.1 |
Visible by last table, the cmc of TTSS-4-n series of surfactants like sodium laurylsulfonate (SDS), hang down the 1-3 one magnitude, and surface tension is also little than SDS, has higher surfactivity than tensio-active agent of the same type.
Claims (4)
1. polysulfonate type tensio-active agent, it is characterized in that: chemical name is 1,1,1,1-four (2-oxygen trimethylene sodium sulfonate-3-alkyl oxide-third alkoxyl group) neopentane, code name is TTSS-4-n, its structural formula is:
Wherein R is C
8H
17, C
10H
23, C
12H
25, C
14H
29Or C
16H
33A kind of, the carbonatoms among the R is the n in the code name.
2. preparation method of four polysulfonate type tensio-active agents according to claim 1; It is characterized in that: earlier tetramethylolmethane is dissolved in the mixing solutions of dress 150ml DMSO 99.8MIN. and basic soln; Under whipped state, drip epoxy chloropropane in the reactor drum of this mixing solutions; The above-mentioned raw materials mol ratio of penta tetrol and epoxy chloropropane, alkali quarterly is 1.0:6.0～8.0:4.0～6.0 consumptions; Reaction is 5～10 hours under 35 ℃ and agitation condition, through purify faint yellow oily thing tetramethylolmethane Fourth Ring Ethylene Oxide base ether; Earlier at 60 ℃ of sodium alkyl alcohols that make with alkyl alcohol and potassium or potassium hydride KH reaction; Carbonatoms is 8～16 in the alkyl alcohol, will be dripped in the sodium alkyl alcohol solution by the above-mentioned tetramethylolmethane Fourth Ring Ethylene Oxide base ether that makes again, and tetramethylolmethane Fourth Ring Ethylene Oxide base ether and alkyl alcohol, potassium reacted 8～10 hours at 80 ℃ for 1.0:4.0～8.0:0.8～1.2 consumptions in molar ratio; Again through purify light yellow solid 1; 1,1,1-four (2-hydroxyl-3-alkyl oxide-third alkoxyl group) neopentane; At last will by top make 1,1,1,1-four (2-hydroxyl-3-alkyl oxide-third alkoxyl group) neopentane is dissolved in the dry tetrahydrofuran solvent; Following to 1 50～60 ℃ of temperature of reaction, 3-propane sultone mixes, and slowly adds sodium hydride while stirring, by 1; 1,1,1-four (2-hydroxyl-3-alkyl oxide-third alkoxyl group) neopentane and THF, 1; 3-propane sultone, sodium hydride mol ratio are 1.0:15.0～30.0:6.0～9.0:6.0～8.0 consumptions, finish at 50～60 ℃ of reaction 12h, after purify white wax shape product 1; 1,1,1-four (2-oxygen trimethylene sodium sulfonate-3-alkyl oxide-third alkoxyl group) neopentane.
3. preparation method according to claim 2 is characterized in that: described basic soln is with sodium hydroxide or potassium hydroxide solution, and concentration is 90wt%.
4. preparation method according to claim 2 is characterized in that: described alkyl alcohol is a kind of with octanol or ten alcohol or lauryl alcohol or tetradecyl alcohol or hexadecanol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110357794A (en) * | 2019-08-19 | 2019-10-22 | 西南石油大学 | A kind of spy's hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation preparation method of supercritical carbon dioxide thickening agent |
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| CN102389746A (en) * | 2011-10-10 | 2012-03-28 | 西南石油大学 | Sulfonate trimeric surfactant and preparation method thereof |
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| EP1581485A1 (en) * | 2002-12-23 | 2005-10-05 | Basf Aktiengesellschaft | Methods for producing alkylaryl sulfonates by using modified dimerized olefins |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110357794A (en) * | 2019-08-19 | 2019-10-22 | 西南石油大学 | A kind of spy's hypotonic Oil in Super-low Permeability oil-gas reservoir exploitation preparation method of supercritical carbon dioxide thickening agent |
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Application publication date: 20121003 |