CN104403654B - Aryl alkyl APEO carboxyl betaine surfactant and preparation method and application - Google Patents
Aryl alkyl APEO carboxyl betaine surfactant and preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of aryl alkyl APEO carboxyl betaine surfactant and preparation method and application.The structural formula of the aryl alkyl APEO carboxyl betaine surfactant is：Wherein, R is phenyl, tolyl, xylyl or ethylbenzene；M, the integer that it is 1 30 selected from 0 15 integer and m+n=15, x that n, which is respectively,.The present invention has also passed through the preparation method of above-mentioned aryl alkyl APEO carboxyl betaine surfactant and the application in using three times.The aqueous solution of aryl alkyl APEO carboxyl betaine surfactant provided by the present invention has higher viscosity, both swept volume can be improved, and can enough reduces interfacial tension, there is good emulsifiability simultaneously, highly viscous crude viscosity reduction can be made, so as to improve recovery ratio, therefore had a good application prospect in tertiary oil recovery.
Description
Technical field
The present invention relates to a kind of aryl alkyl APEO carboxyl betaine surfactant and its preparation method and recovering the oil
In application, belong to technical field of petroleum extraction.
Background technology
High viscous, low mobility reservoir aboundresources both at home and abroad, permeability 1-200mD, viscosity 20- wherein in China's Song-liao basin
500mPas oil reservoirs, reserves reach billions of tons.Yet with wax content in crude oil, colloid, asphalt content be high and formation temperature compared with
It is low, cause viscosity of crude high, exploitation is difficult.How crude oil fluidity is effectively improved, be to increase substantially hypotonic high-viscosity oil Tibetan to adopt
The main research direction of yield.
For the exploitation of middle and high infiltration common heavy oil, chemical flooding route is used both at home and abroad, using polymer flooding, chemical combined flooding
Carry out field test research etc. mode, achieve certain effect.But middle LOW PERMEABILITY RESERVOIR chemical agent injection is adopted with raising
Yield effect is difficult to get both, and needs efficient development scheme badly.At present, chemical viscosity reduction technology is concentrated mainly on reducing viscosity by emulsifying and oil is molten
Property viscosity reduction research, it is defeated to be mainly used in the collection of viscous crude, and the problems such as viscosity break ratio is low, less economical, mechanism understanding is unclear be present, scene
Also only used as single well stimulation well stimulation.Develop nonionic (APES), anionic both at home and abroad
A variety of emulsifying pour depressors such as (polyoxyethylated alkyl alcohol sulfuric acids).But reducing viscosity by emulsification agent adaptability is poor, generally a kind of drop
Glutinous agent is only applicable to a kind of viscous crude, and need to add substantial amounts of water during exploitation, it is desirable to which the emulsion formed must have certain
Stability, the thick oil emulsion breaking dehydration difficulty increase of extraction, treating capacity is caused to increase.Therefore the exploitation of hypotonic highly viscous crude in being directed to
Need development of new thinner badly.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of aryl alkyl APEO carboxyl beet
Alkali surfactant, its aqueous solution have higher viscosity, can play the effect of good raising recovery ratio.
To reach above-mentioned purpose, the invention provides a kind of aryl alkyl APEO carboxybetaine surface-active
Agent, it is N- [aryl Steareth (x) -2- hydroxypropyls]-N, and N- dimethyl carboxybetaines amphoteric surface lives
Property agent, its structural formula are：
Wherein, R is phenyl, tolyl, xylyl or ethylbenzene；M, n is respectively integer and m+n=selected from 0-15
15, x be 1-30 integer.
According to specific embodiments of the present invention, it is preferable that above-mentioned aryl alkyl APEO carboxybetaine surface
Activating agent, wherein, R is phenyl, and m 7, n 8, x are 5-30 integer, and its structural formula is：
According to specific embodiments of the present invention, it is preferable that above-mentioned aryl alkyl APEO carboxybetaine surface
Activating agent, wherein, R is tolyl, and m 7, n 8, x are 5-30 integer, and its structural formula is：
According to specific embodiments of the present invention, it is preferable that above-mentioned aryl alkyl APEO carboxybetaine surface
Activating agent, wherein, R is xylyl, and m 7, n 8, x are 5-30 integer, and its structural formula is：
According to specific embodiments of the present invention, it is preferable that above-mentioned aryl alkyl APEO carboxybetaine surface
Activating agent, wherein, R is ethylbenzene, and m 7, n 8, x are 5-30 integer, and its structural formula is：
N- [aryl Steareth (x) -2- hydroxypropyls]-N, N- dimethyl carboxyl sweet tea provided by the present invention
The aqueous solution of dish alkali amphoteric surfactant has higher viscosity, can both improve swept volume, and and can enough reduces interface
Power, while there is good emulsifiability, highly viscous crude viscosity reduction can be made, so as to improve recovery ratio, therefore in tertiary oil recovery
Have a good application prospect.
Present invention also offers the preparation method of above-mentioned aryl alkyl APEO carboxyl betaine surfactant, its
Comprise the following steps：
(1) friedel-crafts alkylation reaction：
(2) hydrogenation reduction：
(3) ethoxylation：
(4) etherification reaction：
(5) aminating reaction：
(6) quaternary ammonium reaction：
Obtain the aryl alkyl APEO carboxyl betaine surfactant.
According to specific embodiments of the present invention, it is preferable that the above method can include step in detail below：
(1) friedel-crafts alkylation reaction：
Using methanesulfonic acid as catalyst, 3.4-3.6mol benzene or toluene or dimethylbenzene or ethylbenzene are added, is warming up to 100-120
DEG C, start that 1-1.1mol methyl oleates are added dropwise, time for adding controls in 6-7h, after being added dropwise, continues to react 3-4h, be cooled to
Room temperature, stratification, being flushed three times with frozen water, separate the aqueous solution of lower catalyst agent, supernatant liquid continues to be washed three times with frozen water,
Dry successively, at 20-30Pa, 220-230 DEG C, molecular distillation obtains aryl Methyl Stearate；
(2) hydrogenation reduction：
Under conditions of 200-350 DEG C, 25-30MPa, make aryl Methyl Stearate in hydrogenation catalyst CuO-ZnO-Cr2O3
The lower hydrogenating reduction of effect obtains aryl octadecyl alcolol；
(3) ethoxylation：
By aryl octadecyl alcolol and KOH according to 1:1 mol ratio is added in potheater, after closed, is added by nitrogen
0.01mol oxirane, nitrogen displacement is carried out to potheater, then evacuates 30 points under 60-80 DEG C, 30mmHg under agitation
Clock, then release and add appropriate second catalyst (mol ratio of aryl octadecyl alcolol and second catalyst be 1:0.1 to 1:
0.05) above-mentioned nitrogen displacement, the operation evacuated, are then repeated；
When temperature rises to 140-180 DEG C of reaction temperature, under 0.3-0.4MPa pressure, epoxy second is added dropwise in continuous-stable
Alkane, insulation cool down after 1 hour, and unreacted oxirane, release in elimination reaction material, obtain aryl alkane under rough vacuum
Base alcohol APEO；
(4) etherification reaction：
0.10mol aryl alkyl alcohol polyvinylether, 0.005mol TBABs, 0.20mol solids NaOH are mixed
Close, add n-hexane and make solvent, be heated to 60 DEG C, 0.11mol epoxychloropropane is added dropwise, time for adding 5h, then heats up
To 80-100 DEG C, after isothermal reaction 5-10h, neutrality is washed to, obtains etherification reaction product；
(5) aminating reaction：
0.05mol etherification reactions product is mixed with the dimethylamine agueous solution that 10.0g mass concentrations are 30-33%, added
Ethanol as solvent, in 50-80 DEG C of stirring reaction 5-10h, rotary evaporation removes ethanol, obtains aminating reaction product；
(6) quaternary ammonium reaction：
By sodium chloroacetate dissolved in appropriate water and absolute ethyl alcohol, then mixed with aminating reaction product, the amination
Reaction product and the mol ratio of sodium chloroacetate are 1:1.1,60-80 DEG C of reaction 6-10h is warming up to, obtains aryl alkyl polyoxyethylene
Ether carboxyl betaine surfactant.
In the above-mentioned methods, it is preferable that hydrogenation catalyst CuO-ZnO-Cr2O3, it is by CuO, ZnO and Cr2O3 group
Into the mass ratio of three is 7.5：2.5：50.
In the above-mentioned methods, it is preferable that the second catalyst is Ca (OEt)2/H3PO4。
The synthesis step of aryl alkyl APEO carboxyl betaine surfactant provided by the invention can be according to
In the following manner is carried out：
(1) friedel-crafts alkylation reaction：
In reactor is sealed, using methanesulfonic acid as catalyst, 3.4-3.6mol benzene,toluene,xylenes or ethylbenzene are added, is risen
Temperature starts that 1-1.1mol methyl oleates are added dropwise, time for adding controls in 6-7h, after being added dropwise, continues to react to 100-120 DEG C
3-4h, room temperature is cooled to, stratification, is flushed three times with frozen water, separate the aqueous solution of lower catalyst agent, supernatant liquid continues to use
Frozen water is washed three times, is dried successively, and at 20-30Pa, 220-230 DEG C, molecular distillation obtains aryl Methyl Stearate；
(2) hydrogenation reduction：
Under 200-350 DEG C, 25-30MPa reaction condition, make the reaction product aryl Methyl Stearate of step (1)
In hydrogenation catalyst CuO-ZnO-Cr2O3(CuO, ZnO and Cr2O3 mass ratio are 7.5：2.5：50) lower hydrogenating reduction, is acted on to obtain
To aryl octadecyl alcolol；
(3) ethoxylation：
The reaction product aryl octadecyl alcolol and KOH of step (2) will be made, according to 1:1 mol ratio is added in potheater；It is close
After closing, 0.01mol oxirane is added by nitrogen, nitrogen displacement is carried out to potheater；In 60-80 under stirring
DEG C, evacuate 30 minutes under 30mmHg, with the water in elimination reaction system and other low-boiling point materials, then release and add appropriate
Second catalyst Ca (OEt)2/H3PO4(mol ratio of aryl octadecyl alcolol and second catalyst is 1:0.1 to 1:0.05), then
Repeat above-mentioned nitrogen displacement, the operation evacuated；
When kettle temperature rises to 140-180 DEG C of reaction temperature, under conditions of pressure is 0.3-0.4MPa, continuous-stable is added dropwise
Oxirane to required amount, insulation cools down after 1 hour, the unreacted epoxy second in elimination reaction material under rough vacuum
Alkane, release, weighing products, and calculate apparent average adduction number；Average adduction number is computed as 5,7,10,15,20,25 or 30
(in each reaction, by controlling the proportioning of reaction raw materials aryl octadecyl alcolol and oxirane, respectively obtain the production of different adduction numbers
Thing) because ethyleneoxide addition characteristic determines that the reaction product is that possess certain distribution, the present invention has been principally obtaining tool
The aryl alkyl alcohol polyoxyethylene ether products of standby narrow ditribution；
(4) etherification reaction：
According to 1:1.1 mol ratio weighs above-mentioned aryl alkyl alcohol APEO and epoxychloropropane, equipped with electronic
0.10mol aryl alkyl alcohol polyvinylether, the fourths of 0.005mol tetra- are added in the three-necked flask of stirring, thermometer and reflux condensing tube
Base ammonium bromide, 0.20mol solid NaOH, add n-hexane and make solvent, be heated to 60 DEG C, 0.11mol epoxy chloropropionates are added dropwise
Alkane, time for adding 5h then heat to 80-100 DEG C, after isothermal reaction 5-10h, are washed to neutrality, obtain etherification reaction product；
(5) aminating reaction：
The above-mentioned etherification reaction products of 0.05mol are added in three-necked flask, it is 30-33% to add 10.0g mass concentrations
Dimethylamine agueous solution, add ethanol as solvent, 50-80 DEG C of stirring reaction 5-10h, rotary evaporation remove ethanol, obtain amination
Reaction product.
(6) quaternary ammonium reaction：
According to 1:1.1 mol ratio, above-mentioned aminating reaction product and sodium chloroacetate are added in three-necked flask, wherein chlorine
Sodium acetate is initially dissolved in appropriate water and absolute ethyl alcohol, is being added drop-wise to after being uniformly dissolved in there-necked flask, is being warming up to 60-80 DEG C
After reacting 6-10h, final product N- [aryl Steareth (x) -2- hydroxypropyls]-N, N- dimethyl carboxyls are obtained
Beet alkali ampholytic surface active agent.
Present invention also offers above-mentioned aryl alkyl APEO carboxyl betaine surfactant in using three times
Application.
Provided by the present invention is that the alkyl polyoxyethylene ether carboxybetaine surface that a kind of side chain contains aromatic group is lived
Property agent, not only the prices of raw materials are cheap, and route matured product high income, and the beet alkali surface activator being prepared is also
Containing aromatic group necessary to surface active agent for tertiary oil recovery, this is due to have in oil containing substantial amounts of aromatic compound
Presence, therefore to improve with the compatibility of crude oil, it is necessary to introduce aromatic group on carbon atom skeleton.
The aqueous solution of aryl alkyl APEO carboxyl betaine surfactant provided by the present invention has higher
Viscosity, can both improve swept volume, and can enough reduces interfacial tension；Higher emulsifiability is just obtained under low concentration
And interfacial activity；Its heat endurance is good, possesses higher temperature-resistant anti-salt performance.
Aryl alkyl APEO carboxyl betaine surfactant provided by the present invention has good interface, breast
Change performance, the series of surfactants has a good application prospect in tertiary oil recovery, available for chemical combined flooding, also thick
Oil and the exploitation of highly viscous crude viscosity reduction and the value that is widely used in collecting defeated, it is harsh that heat and salt resistance can be applied to reservoir condition well
High temperature and high salt oil deposit, the small injection of molecular dimension can be used for well low-permeability oil deposit.
Brief description of the drawings
Fig. 1 is the interface performance test result of the solution for the various concentrations that the glycine betaine of embodiment 3 is made into；
Fig. 2 is the influence test result of the interface performance for the solution that temperature is made into for the glycine betaine of embodiment 3；
Fig. 3 is the anti-absorption test result for the solution that the glycine betaine of embodiment 3 is made into；
Fig. 4 is the infrared spectrum of X=20 prepared by embodiment 1 carboxy betaine type surfactant.
Embodiment
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
Present embodiments provide N- [phenyl Steareth (x) -2- hydroxypropyls]-N, N- dimethyl carboxyl sweet tea
Dish alkali amphoteric surfactant, its synthetic method comprise the following steps：
(1) friedel-crafts alkylation reaction：
In reactor is sealed, using methanesulfonic acid as catalyst, 3.5mol benzene is added, after being warming up to 100 DEG C, starts to be added dropwise
1mol methyl oleates, time for adding control in 6h, after being added dropwise, continue to react 3h, be cooled at room temperature, stratification, use
Frozen water flushes three times, and separates the aqueous solution of lower catalyst agent, and recovery preserves, and supernatant liquid continues to be washed three times with frozen water, done successively
Dry, under conditions of 20Pa, 220 DEG C, molecular distillation obtains phenyl Methyl Stearate.
(2) hydrogenation reduction：
Under 200 DEG C, 25-30MPa reaction condition, adding the reaction product phenyl Methyl Stearate of step (1)
Hydrogen catalyst CuO-ZnO-Cr2O3(CuO, ZnO and Cr2O3Mass ratio be 7.5：2.5：50), act on lower hydrogenating reduction and obtain benzene
Base octadecyl alcolol.
(3) ethoxylation：
The reaction product phenyl octadecyl alcolol of step (2) will be made with KOH according to 1:1 mol ratio is added in potheater, close
After closing, 0.01mol oxirane is added by nitrogen, nitrogen displacement is carried out to reaction system；Under stirring in 60 DEG C,
Evacuate 30 minutes under 30mmHg, with the water in elimination reaction system and other low-boiling point materials, then release and add appropriate
Second catalyst Ca (OEt)2/H3PO4(mol ratio of aryl octadecyl alcolol and second catalyst is 1:0.1 to 1:0.05) it is, then heavy
Multiple above-mentioned nitrogen displacement, the operation evacuated；
When kettle temperature rises to 140 DEG C of reaction temperature, under conditions of pressure is 0.3-0.4MPa, epoxy is added dropwise in continuous-stable
Ethane to required amount (is 1 according to the mol ratio of reaction raw materials aryl octadecyl alcolol and oxirane:1.1X ratio addition ring
Oxidative ethane, wherein X=5,7,10,15,20,25 or 30), insulation cools down after 1 hour, under rough vacuum in elimination reaction material
Unreacted oxirane, release, weighing products, and calculate apparent average adduction number.Be computed average adduction number 5,7,10,
15th, 20,25 or 30 (proportioning of reaction raw materials aryl octadecyl alcolol and oxirane is controlled, respectively obtains the production of different adduction numbers
Thing).
(4) etherification reaction：
According to 1:1.1 mol ratio weighs above-mentioned phenylalkyl alcohol APEO and epoxychloropropane, equipped with electronic
0.10mol phenylalkyl alcohol polyvinylether, the fourths of 0.005mol tetra- are added in the three-necked flask of stirring, thermometer and reflux condensing tube
Base ammonium bromide, 0.20mol solid NaOH, add n-hexane and make solvent, be heated to 60 DEG C, 0.11mol epoxy chloropropionates are added dropwise
Alkane, time for adding 5h then heat to 80 DEG C, after isothermal reaction 5h, are washed to neutrality, obtain etherification reaction product.
(5) aminating reaction：
The above-mentioned etherification reaction products of 0.05mol are added in three-necked flask, it is 30-33% to add 10.0g mass concentrations
Dimethylamine agueous solution, add ethanol as solvent, 50 DEG C of stirring reaction 5h, rotary evaporation remove ethanol, obtain aminating reaction production
Thing；
(6) quaternary ammonium reaction：
Above-mentioned aminating reaction product is added into there-necked flask, it is molten by sodium chloroacetate dissolved in suitable quantity of water and absolute ethyl alcohol
It is added drop-wise to after solution is uniform in there-necked flask, the mol ratio of aminating reaction product and sodium chloroacetate is 1:1.1；
After being warming up to 60 DEG C of reaction 6h, final product N- [phenyl Steareth (x) -2- hydroxypropyls are obtained
Base]-N, N- dimethyl carboxybetaine amphoteric surfactantes, its structural formula is：
Infrared analysis is carried out to X=20 carboxy betaine type surfactant, its infrared spectrum is as shown in Figure 4.
As seen from Figure 4,3060cm-1Left and right is=weaker CH vibration performance peak, 1625cm-1And 1475cm-1For C
=C vibration performance peak, 781cm-1And 704cm-1It is the vibration performance of phenyl ring for=CH flexural vibrations characteristic peaks, at above-mentioned three
Peak, it was demonstrated that phenyl ring in molecular structure be present；2920cm-1Left and right is-CH2Antisymmetry stretching vibration peak；1460cm-1Left and right is-CH2
Scissoring vibration peak or-CH3Antisymmetric vibration peak；1380-1370cm-1For-CH3Symmetric curvature characteristic peak；Polyoxyethylene ether
The characteristic absorption peak of group has：1350cm-1It is nearby-CH2Wagging vibration peak, C-O-C strong absworption peaks appear in 1120cm-1
Near, 950cm-1Weaker symmetrical stretching vibration peak nearby, 885cm-1It is nearby end group-CH2CH2OH CH2Plane, which is waved, shakes
Dynamic peak, 845cm-1It is nearby polyoxyethylene groups rocking vibration peak.The lipophilic group for illustrating surfactant be containing phenyl ring and
The Long carbon chain saturated hydrocarbons of polyoxyethylene ether group.3400cm-1Neighbouring peak is O-H stretching vibration characteristic peaks.1620cm-1、
1466cm-1、1395cm-1Neighbouring spike is carboxylate ion antisymmetric stretching vibration characteristic absorption peak.In summary, it is infrared
Spectrogram proves that synthetic product is the carboxybetaine containing phenyl ring and polyoxyethylene ether group.
Elementary analysis (being calculated value in bracket) is carried out to above-mentioned X=20 carboxy betaine type surfactant：C
61.85% (61.52%)；H 9.91% (9.75%)；N 1.05% (1.01%).Theoretical value and test value approach, it was demonstrated that close
It is consistent with design surface activating agent into product.
Embodiment 2
Present embodiments provide N- [tolyl Steareth (x) -2- hydroxypropyls]-N, N- dimethyl carboxyls
Beet alkali ampholytic surface active agent, its synthetic method comprise the following steps：
(1) friedel-crafts alkylation reaction：
In reactor is sealed, using methanesulfonic acid as catalyst, 3.5mol toluene is added, after being warming up to 110 DEG C, starts to drip
Add 1.1mol methyl oleates, time for adding controls in 7h, after being added dropwise, continues to react 3h, be cooled at room temperature, stand and divide
Layer, is flushed three times with frozen water, separates the aqueous solution of lower catalyst agent, and recovery preserves, supernatant liquid continue with frozen water wash three times, according to
Secondary drying, at 20Pa, 220 DEG C, molecular distillation obtains tolyl Methyl Stearate.
(2) hydrogenation reduction：
Under 250 DEG C, 25-30MPa reaction condition, the reaction product tolyl Methyl Stearate of step (1) is set to exist
Hydrogenation catalyst CuO-ZnO-Cr2O3(CuO, ZnO and Cr2O3Mass ratio be 7.5：2.5：50) lower hydrogenating reduction, is acted on to obtain
Tolyl octadecyl alcolol.
(3) ethoxylation：
By the reaction product tolyl octadecyl alcolol of step (2) and KOH according to 1:1 mol ratio is added in potheater；It is close
After closing, 0.01mol oxirane is added by nitrogen, nitrogen displacement is carried out to reaction system；Under stirring in 70 DEG C,
Evacuate 30 minutes under 30mmHg, with the water in elimination reaction system and other low-boiling point materials, then release and add appropriate
Second catalyst Ca (OEt)2/H3PO4(it is 1 according to aryl octadecyl alcolol and second catalyst:0.1 to 1:0.05 mol ratio), with
Above-mentioned nitrogen displacement, the operation evacuated are repeated afterwards；When kettle temperature rises to 150 DEG C of reaction temperature, in the case where pressure is 0.3-0.4MPa,
It (is 1 according to the proportioning of reaction raw materials aryl octadecyl alcolol and oxirane that oxirane to required amount, which is added dropwise, in continuous-stable:1.1X
Ratio addition oxirane, wherein X=5,7,10,15,20,25 or 30)；Insulation cools down after 1 hour, is taken off under rough vacuum
Except unreacted oxirane, release, weighing products in reaction mass, apparent average adduction number is calculated；It is computed average adduction
Number 5,7,10,15,20,25 or 30 (in each reaction, by controlling the proportioning of reaction raw materials aryl octadecyl alcolol and oxirane, point
The product of different adduction numbers is not obtained) because ethyleneoxide addition characteristic determines that the reaction product is that possess certain distribution,
The present invention has been principally obtaining the tolyl alkyl alcohol ethoxylates product for possessing narrow ditribution.
(4) etherification reaction：
According to 1:1.1 mol ratio weighs above-mentioned tolyl alkyl alcohol ethoxylates and epoxychloropropane, equipped with electricity
0.10mol tolyl alkylols polyvinylether, 0.005mol are added in the three-necked flask of dynamic stirring, thermometer and reflux condensing tube
TBAB, 0.20mol solid NaOH, add n-hexane and make solvent, be heated to 60 DEG C, 0.11mol epoxies are added dropwise
Chloropropane, time for adding 5h then heat to 90 DEG C, after isothermal reaction 70h, are washed to neutrality, obtain etherification reaction product.
(5) aminating reaction：
The above-mentioned etherification reaction products of 0.05mol are added in three-necked flask, it is 30-33% to add 10.0g mass concentrations
Dimethylamine agueous solution, add ethanol as solvent, 60 DEG C of stirring reaction 8h, rotary evaporation remove ethanol, obtain aminating reaction production
Thing.
(6) quaternary ammonium reaction：
Above-mentioned aminating reaction product is added into there-necked flask, it is molten by sodium chloroacetate dissolved in suitable quantity of water and absolute ethyl alcohol
It is added drop-wise to after solution is uniform in there-necked flask, the mol ratio of aminating reaction product and sodium chloroacetate is 1:1.1；
After being warming up to 65 DEG C of reaction 8h, final product N- [tolyl Steareth (x) -2- hydroxypropyls are obtained
Base]-N, N- dimethyl carboxybetaine amphoteric surfactantes, its structural formula is：
Elementary analysis (being calculated value in bracket) is carried out to above-mentioned X=20 carboxy betaine type surfactant：C
61.93% (61.76%)；H 9.95% (9.79%)；N 1.02% (1.00%).Theoretical value and test value approach, it was demonstrated that close
It is consistent with design surface activating agent into product.
Embodiment 3
Present embodiments provide N- [meta-xylene base Steareth (x) -2- hydroxypropyls]-N, N- dimethyl
Carboxybetaine amphoteric surfactant, its synthetic method comprise the following steps：
(1) friedel-crafts alkylation reaction：
In reactor is sealed, using methanesulfonic acid as catalyst, 3.5mol meta-xylenes are added, after being warming up to 120 DEG C, are opened
Begin that 1.05mol methyl oleates are added dropwise, time for adding controls in 7h, after being added dropwise, continues to react 4h, be cooled at room temperature, quiet
Layering is put, is flushed three times with frozen water, separates the aqueous solution of lower catalyst agent, recovery preserves, and supernatant liquid continues to wash three with frozen water
It is secondary, dry successively, at 30Pa, 230 DEG C, molecular distillation obtains meta-xylene base Methyl Stearate.
(2) hydrogenation reduction：
Under 200-350 DEG C, 25-30MPa reaction condition, make the reaction product meta-xylene base 18 of step (1)
Sour methyl esters is in hydrogenation catalyst CuO-ZnO-Cr2O3(CuO, ZnO and Cr2O3Mass ratio be 7.5：2.5：50), effect is lower is hydrogenated with
Reduction obtains meta-xylene base octadecyl alcolol.
(3) ethoxylation：
The reaction product meta-xylene base octadecyl alcolol of step (2) will be made with KOH according to 1:1 mol ratio adds potheater
In；After closed, 0.01mol oxirane is added by nitrogen, nitrogen displacement is carried out to reaction system；In 70 under stirring
DEG C, evacuate 30 minutes under 30mmHg, with the water in elimination reaction system and other low-boiling point materials, then release and add appropriate
Second catalyst Ca (OEt)2/H3PO4(mol ratio of aryl octadecyl alcolol and second catalyst is 1:0.1 to 1:0.05), then
Repeat above-mentioned nitrogen displacement, the operation evacuated；When kettle temperature rises to 160 DEG C of reaction temperature, in the case where pressure is 0.3-0.4MPa, even
Continuous stable oxirane to the required amount that is added dropwise (is 1 according to the proportioning of reaction raw materials aryl octadecyl alcolol and oxirane:1.1X
Ratio adds oxirane, wherein X=5,7,10,15,20,25 or 30), and insulation is cooled down after 1 hour, removed under rough vacuum
Unreacted oxirane, release, weighing products in reaction mass, and calculate apparent average adduction number；It is computed average adduction
Number 5,7,10,15,20,25 or 30 (in each reaction, by controlling the proportioning of reaction raw materials aryl octadecyl alcolol and oxirane, point
The product of different adduction numbers is not obtained) because ethyleneoxide addition characteristic determines that the reaction product is that possess certain distribution,
The present invention has been principally obtaining the meta-xylene base alkyl alcohol ethoxylates product for possessing narrow ditribution.
(4) etherification reaction：
According to 1:1.1 mol ratio weighs above-mentioned xylyl alkyl alcohol ethoxylates and epoxychloropropane, equipped with
0.10mol aryl alkyl alcohol polyvinylether, 0.005mol are added in the three-necked flask of electric stirring, thermometer and reflux condensing tube
TBAB, 0.20mol solid NaOH, add n-hexane and make solvent, be heated to 60 DEG C, 0.11mol epoxies are added dropwise
Chloropropane, time for adding 5h then heat to 100 DEG C, after isothermal reaction 10h, are washed to neutrality, obtain etherification reaction product.
(5) aminating reaction：
The above-mentioned etherification reaction products of 0.05mol are added in three-necked flask, it is 30-33% to add 10.0g mass concentrations
Dimethylamine agueous solution, add ethanol as solvent, 80 DEG C of stirring reaction 10h, rotary evaporation remove ethanol, obtain aminating reaction production
Thing.
(6) quaternary ammonium reaction：
Above-mentioned aminating reaction product is added into there-necked flask, it is molten by sodium chloroacetate dissolved in suitable quantity of water and absolute ethyl alcohol
It is added drop-wise to after solution is uniform in there-necked flask, the mol ratio of aminating reaction product and sodium chloroacetate is 1:1.1；
70 DEG C of reaction 10h are warming up to, obtain final product N- [meta-xylene base Steareth (x) -2- hydroxyls
Propyl group]-N, N- dimethyl carboxybetaine amphoteric surfactantes, its structural formula is：
Elementary analysis (being calculated value in bracket) is carried out to above-mentioned X=20 carboxy betaine type surfactant：C
62.24% (62.00%)；H 9.96% (9.84%)；N 1.01% (0.99%).Theoretical value and test value approach, it was demonstrated that close
It is consistent with design surface activating agent into product.
Embodiment 4
Present embodiments provide N- [ethylbenzene Steareth (x) -2- hydroxypropyls]-N, N- dimethyl carboxyls
Beet alkali ampholytic surface active agent, its synthetic method comprise the following steps：
(1) friedel-crafts alkylation reaction：
In reactor is sealed, using methanesulfonic acid as catalyst, ethylbenzene between 3.6mol is added, after being warming up to 110 DEG C, is started
1.1mol methyl oleates are added dropwise, time for adding controls in 6h, after being added dropwise, continues to react 4h, be cooled at room temperature, stand and divide
Layer, is flushed three times with frozen water, separates the aqueous solution of lower catalyst agent, and recovery preserves, supernatant liquid continue with frozen water wash three times, according to
Secondary drying, at 30Pa, 230 DEG C, molecular distillation obtains ethylbenzene Methyl Stearate.
(2) hydrogenation reduction：
Under 200-350 DEG C, 25-30MPa reaction condition, make the reaction product ethylbenzene stearic acid first of step (1)
Ester is in hydrogenation catalyst CuO-ZnO-Cr2O3(CuO, ZnO and Cr2O3Mass ratio be 7.5：2.5：50) lower hydrogenating reduction, is acted on
Obtain ethylbenzene octadecyl alcolol.
(3) ethoxylation：
By the reaction product ethylbenzene octadecyl alcolol of step (2) and KOH according to 1:1 mol ratio is added in potheater；It is close
After closing, 0.01mol oxirane is added by nitrogen, nitrogen displacement is carried out to reaction system；Under stirring in 70 DEG C,
Evacuate 30 minutes under 30mmHg, with the water in elimination reaction system and other low-boiling point materials, then release and add appropriate
Second catalyst Ca (OEt)2/H3PO4(mol ratio of aryl octadecyl alcolol and second catalyst is 1:0.1 to 1:0.05) it is, then heavy
Multiple above-mentioned nitrogen displacement, the operation evacuated；When kettle temperature rises to 180 DEG C of reaction temperature, in the case where pressure is 0.3-0.4MPa, continuously
Stable oxirane to the required amount that is added dropwise (is 1 according to the proportioning of reaction raw materials aryl octadecyl alcolol and oxirane:1.1X ratio
Example addition oxirane, wherein X=5,7,10,15,20,25 or 30), insulation cool down after 1 hour, are removed under rough vacuum anti-
Unreacted oxirane, release, weighing products in material are answered, and calculate apparent average adduction number；It is computed average adduction number
5th, 7,10,15,20,25 or 30 (in each reaction, by controlling the proportioning of reaction raw materials aryl octadecyl alcolol and oxirane, respectively
Obtain the product of different adduction numbers) because ethyleneoxide addition characteristic determines that the reaction product is that possess certain distribution, this
Invention has been principally obtaining the ethylbenzene alkyl alcohol ethoxylates product for possessing narrow ditribution.
(4) etherification reaction：
According to 1:1.1 mol ratio weighs above-mentioned ethylbenzene alkyl alcohol ethoxylates and epoxychloropropane, equipped with electricity
0.10mol aryl alkyl alcohol polyvinylether, 0.005mol tetra- are added in the three-necked flask of dynamic stirring, thermometer and reflux condensing tube
Butylammonium bromide, 0.20mol solid NaOH, add n-hexane and make solvent, be heated to 60 DEG C, 0.11mol epoxy chlorine is added dropwise
Propane, time for adding 5h then heat to 100 DEG C, after isothermal reaction 10h, are washed to neutrality, obtain etherification reaction product.
(5) aminating reaction：
The above-mentioned etherification reaction products of 0.05mol are added in three-necked flask, it is 30-33% to add 10.0g mass concentrations
Dimethylamine agueous solution, add ethanol as solvent, 80 DEG C of stirring reaction 10h, rotary evaporation remove ethanol, obtain aminating reaction production
Thing.
(6) quaternary ammonium reaction：
Above-mentioned aminating reaction product is added into there-necked flask, it is molten by sodium chloroacetate dissolved in suitable quantity of water and absolute ethyl alcohol
It is added drop-wise to after solution is uniform in there-necked flask, the mol ratio of aminating reaction product and sodium chloroacetate is 1:1.1；
80 DEG C of reaction 10h are warming up to, obtain final product N- [ethylbenzene Steareth (x) -2- hydroxypropyls
Base]-N, N- dimethyl carboxybetaine amphoteric surfactantes, its structural formula is：
Elementary analysis (being calculated value in bracket) is carried out to above-mentioned X=20 carboxy betaine type surfactant：C
62.27% (62.00%)；H 9.94% (9.84%)；N 0.98% (0.99%).Theoretical value and test value approach, it was demonstrated that close
It is consistent with design surface activating agent into product.
Embodiment 5
Present embodiments provide four kinds of N- [aryl Steareth (x) -2- hydroxypropyls for embodiment 1-4
Base]-N, N- dimethyl carboxybetaines amphoteric surfactant (aromatic yl group be respectively phenyl, tolyl, meta-xylene base,
Ethyl) performance test, mainly include interface performance and viscosity reducing effect and evaluate.
Using TX500C interface tension test instruments, using the interfacial tension of rotation drop method test surfactant solution, test temperature
Spend for 30 DEG C, rotating speed 5000RPM.Viscosity reducing effect evaluation is carried out in such a way：According to 1：1 oil-water ratio is by crude oil and table
Face activator solution mixing, uses mulser (rotating speed 104R/min) disperse, take middle level emulsion measurement system to glue after 5min
Degree；Viscosity test uses U.S.'s Brookfield LVDVII rotation viscometers, 0# rotors, rotating speed 6rpm, test temperature 30
℃。
Wherein, water (TDS=476mg/L), configuration embodiment 1-4 N- [aryl 18 are injected using Fuyu oil fields in Jilin
Alkyl polyoxyethylene ether (10) -2- hydroxypropyls]-N, the solution of N- dimethyl carboxyl betaine surfactants, concentration is
0.3wt%.Crude oil initial viscosity is 64.4mPas.Test result is listed in table 1.
The glycine betaine the performance test results of table 1
The solution of four kinds of glycine betaines of embodiment 1-4 offers is can be seen that from the content in table 1 can reach ultralow boundary
Face tension force, there is preferable interface performance；The viscosity break ratio of four kinds of glycine betaines has good viscosity reducing effect more than 80%；
Contrast N- [the meta-xylene base Steareths of the interfacial tension and viscosity break ratio, wherein embodiment 3 of four kinds of glycine betaines
(10) -2- hydroxypropyls]-N, the performance of N- dimethyl carboxybetaines is optimal.
Change N- [meta-xylene base Steareth (x) -2- hydroxypropyls]-N of embodiment 3, N- dimethyl
APEO (x) number of carboxybetaine, investigates the interface performance of glycine betaine, and test result is as shown in table 2.
The glycine betaine interface performance test result of table 2
It can be seen from the content of table 2 in the range of APEO number is 5-30, above-mentioned glycine betaine can reach
Ultralow interfacial tension；And when APEO number is 20, above-mentioned beet alkali surface activator interface performance is optimal.
Change N- [meta-xylene base Steareth (20) -2- hydroxypropyls]-N of embodiment 3, N- dimethyl
The concentration of the solution of carboxybetaine, its oil-water interfaces the performance test results are as shown in Figure 1.
As seen from Figure 1, in 0.05wt% to 0.3wt% concentration range, the solution could in 30 minutes
Reach ultralow interfacial tension, and ultralow interfacial tension was always maintained within 2 hours, interface performance is excellent.
Embodiment 6
Present embodiments provide N- [meta-xylene base Steareth (20) -2- hydroxypropyls]-N, N- diformazans
The temperature-resistant anti-salt performance and emulsifiability test result of base carboxybetaine amphoteric surfactant.
The interfacial tension of above-mentioned solution is tested using rotation drop method using TX500C interface tension test instruments, test temperature is
30-80 DEG C, rotating speed 5000RPM.Emulsifiability is evaluated, according to 1：1 oil-water ratio is by crude oil and above-mentioned surfactant solution
Mixing, using the reciprocating isothermal vibration device of HZ-8812S water-baths, shaken 6 hours with 90rpm speed, after 80 DEG C stand 72 hours
The delamination of observation system.
Reservoir temperature is 80 DEG C, formation water salinity 84000mg/L, configures N- [the meta-xylene bases 18 of embodiment 3
Alkyl polyoxyethylene ether (20) -2- hydroxypropyls]-N, the solution of N- dimethyl carboxybetaines, concentration range arrives for 0.05wt%
0.3wt%.Test result is as shown in table 3.
The glycine betaine Evaluation results of table 3
| The concentration of surfactant solution, wt% | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension, mN/m | 5.43×10-3 | 3.71×10-3 | 1.92×10-3 | 2.35×10-3 |
| Middle microemulsion phase volume content, % | 1 | 3 | 7 | 12 |
It can be seen that by the content of table 3：Under the conditions of high temperature and high salt, (0.05wt% is arrived in wider concentration range
0.3wt%), above-mentioned glycine betaine has preferable interface and emulsifiability.Middle microemulsion phase be present in the solution of surfactant, and
Middle Emulsion Phase proportion gradually increases with the increase of surfactant concentration, now profit System forming bicontinuous
Microemulsion, microemulsion type are the types of Winsor III.Middle microemulsion phase has not only can be with solubilisation oils but also can be with the uniqueness of Solubilization of Water
Matter, and the interfacial tension between oil phase and aqueous phase is extremely low, therefore, the presence of middle microemulsion phase shows that surfactant has necessarily
Emulsifying capacity.
Formation water salinity is used as 84000mg/L, configures N- [the meta-xylene base octadecyl polyoxy second of embodiment 3
Alkene ether (20) -2- hydroxypropyls]-N, the solution of N- dimethyl carboxybetaines, concentration 0.2wt%.Test at different temperatures,
The interfacial tension of the solution, test result are as shown in Figure 2.As seen from Figure 2 (30 DEG C to 90 within the scope of wider temperature
DEG C), above-mentioned glycine betaine has a preferable interface performance, and temperature-resistant anti-salt performance is good.
Embodiment 7
N- [meta-xylene base Steareth (20) -2- the hydroxypropyls]-N, N- of the present embodiment to embodiment 3
Dimethyl carboxyl betaine surfactant has carried out viscosity and anti-adsorption research.
Using the area stratum water (salinity 24270ppm) of Changqing oilfields horse Ling Bei tri-, a N- [diformazan for various concentrations is configured
Phenyl Steareth (20) -2- hydroxypropyls]-N, the solution of N- dimethyl carboxybetaines, and carry out viscosity survey
Examination.Viscosity test uses U.S.'s Brookfield LVDVII rotation viscometers, 0# rotors, rotating speed 6rpm, test temperature 50
℃。
Experimental result is as shown in table 4, it can be seen that the apparent viscosity of solution is with the increasing of the concentration of surfactant solution
Add and gradually step up, and N- [meta-xylene base Steareth (20) -2- hydroxypropyls]-N, N- dimethyl carboxyl sweet teas
Dish alkali soluble fluid viscosity is higher, and when concentration is 0.3wt%, the apparent viscosity of solution can reach 39.8mPas, much larger than ground
The viscosity (5mPas) of layer crude oil, this illustrates that above-mentioned surfactant can be used as oil displacement agent, its with alkali/surfactant/gather
The composite oil-displacing system of compound (ASP) or Surfactant/Polymer (SP) is the same, possesses and preferably expands swept volume energy
Power, also illustrate N- [aryl Steareth (x) -2- hydroxypropyls]-N of the present invention, N- dimethyl carboxybetaines
Amphoteric surfactant can substitute polymer as the mobility control agent in oil displacement system, low for permeability and polymer is difficult
With the oil reservoir of injection (molecular dimension is small, is readily injected into).
The viscosity test results of the alkali solution of beet of table 4
| Surfactant concentration | 0.05wt% | 0.1wt% | 0.2wt% | 0.3wt% | 0.5wt% |
| Viscosity, mPas | 6.1 | 13.2 | 23.9 | 39.8 | 57.9 |
Using the area stratum water (salinity 24270ppm) of Changqing oilfields horse Ling Bei tri-, configuration concentration is 0.3wt% implementation
N- [meta-xylene base Steareth (20) -2- hydroxypropyls]-N of example 3, N- dimethyl carboxybetaine solution.
By solid-to-liquid ratio 1：9 mix the natural oil-sand of the surfactant solution configured and Changqing oilfields (60-100 mesh)
And be added in air-tight bottle, after being adsorbed 6 hours with 90rpm rotating speed concussion in 50 DEG C of thermostatic control oscillator vibration, test oil
Water interfacial tension, remaining solution continue to be adsorbed with new oil-sand by said process, are so repeated 6 times.
Using TX500C interface tension test instruments, using the interfacial tension of solution after rotation drop method test absorption, test temperature
Spend for 50 DEG C, rotating speed 5000rpm, as a result as shown in Figure 3.As seen from Figure 3, above-mentioned beet alkali surface activator solution
Anti-adsorption is good, and system oil water interfacial tension can also reach ultralow after adsorbing 6 times, it is not easy to inactivate, suitable for hyposmosis
Oil reservoir.
Claims (1)
1. a kind of surfactant for development of low-permeability oil reservoir, it is characterised in that the surfactant is a N- [diformazan
Phenyl Steareth (20) -2- hydroxypropyls]-N, N- dimethyl carboxybetaines；Its structural formula is：
In structure above, m=7, n=8, x=20.
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| CN111533664A (en) * | 2020-05-09 | 2020-08-14 | 东营宝莫环境工程有限公司 | Ester-based polyether betaine surfactant and synthesis method thereof |
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| CN102775976A (en) * | 2012-08-02 | 2012-11-14 | 中国石油天然气股份有限公司 | Non-alkali composite flooding compound based on straight-chain fatty alcohol ether carboxylic betaine |
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| CN102775976A (en) * | 2012-08-02 | 2012-11-14 | 中国石油天然气股份有限公司 | Non-alkali composite flooding compound based on straight-chain fatty alcohol ether carboxylic betaine |
| CN103992247A (en) * | 2014-05-15 | 2014-08-20 | 中国石油天然气股份有限公司 | Fatty alcohol polyoxypropylene ether sulphobetaine and alkali-free composite combination for displacing oil |
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