CN103721625B - A kind of water base foam stabilizing agent, preparation method and there is the water based foam system of ultrastability - Google Patents
A kind of water base foam stabilizing agent, preparation method and there is the water based foam system of ultrastability Download PDFInfo
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- CN103721625B CN103721625B CN201410003066.6A CN201410003066A CN103721625B CN 103721625 B CN103721625 B CN 103721625B CN 201410003066 A CN201410003066 A CN 201410003066A CN 103721625 B CN103721625 B CN 103721625B
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- 239000006260 foam Substances 0.000 title claims abstract description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000004872 foam stabilizing agent Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003546 flue gas Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000003570 air Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005261 decarburization Methods 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000002585 base Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 9
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 229960001484 edetic acid Drugs 0.000 claims description 7
- 229940059939 kayexalate Drugs 0.000 claims description 7
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 17
- 239000010779 crude oil Substances 0.000 abstract description 9
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- 239000003921 oil Substances 0.000 description 13
- 230000006641 stabilisation Effects 0.000 description 12
- 238000011105 stabilization Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004088 foaming agent Substances 0.000 description 10
- 239000003381 stabilizer Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000005187 foaming Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000009671 shengli Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 0 C*[N+]([O-])O*=* Chemical compound C*[N+]([O-])O*=* 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229940088990 ammonium stearate Drugs 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a kind of water base foam stabilizing agent, preparation method and there is the water based foam system of ultrastability.Described water base foam stabilizing agent is that water-soluble macromolecule surfactant A is soluble in water, and forming mass concentration is the clear solution of 0.1-1wt%; The present invention also provides preparation method and the application of water base foam stabilizing agent.This surfactant A can be adsorbed on gas-liquid interface stable foam, gas-liquid interface coverage is high, it is strong that the bubble film formed holds liquid ability, foam stability is high, for with nitrogen, carbon dioxide, oxygen, air, flue gas, decarburization flue gas etc. in the water based foam system of gas phase, even if adopt carbon dioxide as keeping excellent foam stability under the harsh conditions such as foamed gas or crude oil existence.
Description
Technical field
The present invention relates to a kind of water base foam stabilizing agent, preparation method and there is the water based foam system of ultrastability, belong to the technical fields such as oilfield chemistry, detergents and cosmetic and ore dressing.
Background of invention
Foam is the polydisperse system that gas and liquid mix, and wherein liquid is continuous phase, and gas is decentralized photo.Water base foam is widely used in our daily life, as cosmeticses of everyday use such as shampoo, toothpaste, mildy wash, shower creams, and all frothy application in the food and drinks such as beer, coffee, ice cream.The existence of foam improves the quality of product, improves the mouthfeel of product, skinfeel or aesthetic feeling.People also utilize foam to put out a fire, and foam can produce cover layer effect, reduce the generation of fuel gas, contribute to starvation, and can cool fuel surface.
At industrial circle, different material can be utilized to carry out the separating-purifying of material in the adsorption capacity that foam surface is different, foam is such as utilized to carry out mineral floating, ion flotation etc., the hydrophilic and hydrophobic different due to different material or different electrical, thus there is different adsorption abilities, thus effectively different separating substances is come.Foam has also been applied to oil field and has improved oil recovery factor, and main application technology comprises foam drilling, foam flooding, foam profile control water blockoff, foam acidizing, foamed cement well cementation, foam fracturing, foam sand wash well-flushing etc.In addition, foam can also in national defence for covering, be applied in building trade dust-proof etc.
Current energy source crisis is whole world facing challenges, and the application of intensified oil reduction technology quite attracts attention, and wherein foam flooding technology is because having the multiple performance such as profile control, washing oil, and raising recovery ratio is effective, Technology Potential large, causing increasing attention.Such as, CN102703052A provides a kind of foam system being applicable to oil field profile control and the displacement of reservoir oil.Foam system has liquids and gases two parts, gas is carbon dioxide, nitrogen, natural gas etc., liquid consists of: surfactant 0.1 ~ 0.5wt%, foam stabilizer (ammonium stearate, OA-12) 0.05 ~ 0.4wt%, thickener 0.08 ~ 0.4wt%, inorganic salts 0.05 ~ 1.2wt%, water is residue content.In foam profile control flooding method, under injection pressure, gas is 0.4: 1 ~ 1: 1 with liquid volume ratio.The foam system of this invention has superpower foaming properties and ultralow interfacial tension simultaneously.Postpolymer flood foam profile successful, recovery ratio improves.
In the actual application of foam, the general foam produced that needs has ultrastability.Usually adopt surfactant as blowing agent at present, the stability of the water base foam formed often can not meet the demands well, when particularly adopting carbon dioxide as foamed gas, the stability of the water base foam of surfactants stabilize is not high enough, has had a strong impact on the effect of correlation technique.Such as adopting flue gas capturing carbon dioxide to be used for foam flooding is exactly the new technology that a kind of economic benefit and social benefit are given prominence to very much, but carbon dioxide foaming poor stability then makes the effect of this technology reduce, the stability therefore how improving water base foam is the technical barrier being badly in need of solving.
Summary of the invention
Not enough for prior art, the invention provides a kind of water base foam stabilizing agent, the present invention also provides a kind of water based foam system with ultrastability.
Technical scheme of the present invention is as follows:
One, water base foam stabilizing agent
A kind of water base foam stabilizing agent, soluble in water by a kind of molecules surfactant A, forming mass concentration is the clear solution of 0.1-1wt%.Described molecules surfactant A has following general structure:
In general formula, Q is amide groups (-CONH
2), benzene sulfonic acid alkali (-C
6h
4sO
3 -), hydroxyl (-OH), carboxylic acid group (-COOH); Y is be the hydrophobic part of 8-24 hydrophobic alkane chain containing carbon number, wherein, and n=8-24, x/ (x+y)=80-95%, y/ (x+y)=5-20%, mol ratio.
Preferred according to the present invention, described molecules surfactant A molecular weight is 10,000-200,000.
Preferred further according to the present invention, described molecules surfactant A is the kayexalate of hydrophobically modified, hydrophobically modified polyacrylamide, hydrophobically modified polyvinyl alcohol or hydrophobically modified polyacrylic acid.
Two, the preparation of molecules surfactant A
According to the present invention, the preparation method of described molecules surfactant A, step is as follows:
Dissolve the ethylenediamine tetra-acetic acid (EDTA) of polymerization single polymerization monomer B and 0.1-1g of 5-20g in deionized water, then add the hydrophobically modified monomer D of surfactant C and 0.05-0.5g of 1-5g.Reactor is placed in water bath with thermostatic control, logical N
2add initator after gas 10-60 minute, keep temperature to be 40-100 DEG C of stirring reaction 10-25 hour.Product acetone precipitation is purified, and dries to constant for subsequent use after cyclic washing in vacuum desiccator, namely obtains molecules surfactant A.
Described polymerization single polymerization monomer B is acrylamide, SSS, vinyl alcohol or acrylic acid; Described hydrophobically modified monomer D is alkane chain carbon number is the acrylate of 8-24.
Described surfactant C is lauryl sodium sulfate, dodecyl sodium sulfate, neopelex, alkylpolyoxyethylene sodium sulphate.
Described initator is azodiisobutyronitrile or potassium peroxydisulfate.
Three, the preparation of water base foam stabilizing agent
The preparation of water base foam stabilizing agent of the present invention, is by molecules surfactant A under agitation, is added to the water, concentration of polymer solution is 0.1-1wt%, and when constant temperature 25-60 DEG C, Keep agitation 24-48 hour, until solution is clear.
Described water is deionized water, mineralized water or both combinations, and one of described water is preferred is deionized water, and preferred two is the combination of deionized water and mineralized water 1:1 volume ratio.
Four, the application of water base foam stabilizing agent of the present invention
For with one of nitrogen, carbon dioxide, oxygen, air, flue gas, decarburization flue gas or be combined as in the water based foam system of gas phase, join in the liquid phase of water based foam system and make stabilizing agent.
Five, a kind of water based foam system with ultrastability.
Have a water based foam system for ultrastability, the aqueous solution being 0.1-1wt% with molecules surfactant A mass concentration of the present invention in liquid phase component makes foam stabiliser; Gas phase is one of nitrogen, carbon dioxide, oxygen, air, flue gas, decarburization flue gas or combination.
Technical characterstic of the present invention and excellent results illustrate:
The present invention adopts molecules surfactant A, and its main chain is polyethylene long-chain, and side chain contains hydrophilic head base, and the side base of 5-20% contains the hydrophobic alkane chain that carbon number is 8-24, and molecular weight is 10,000-200, and 000, belong to water-soluble polymer.The present invention utilizes this water-soluble macromolecule surfactant A as the stabilizing agent of water base foam, molecules surfactant A has amphiphilic, it can be adsorbed on gas-liquid interface stable foam, and can also hydrogen bond be passed through between this large molecule, the interaction such as hydrophobic force is mutually wound around at gas-liquid interface and is cross-linked to form network structure, high to gas-liquid interface coverage, it is strong that the bubble film formed holds liquid ability, liquid holdup is large, liquid film is thicker, gas permeation rate is low, foam stability is high, even if adopt carbon dioxide can both keep excellent foam stability as under the extreme harsh conditions such as foamed gas or crude oil existence.
Through experimental verification, foam stabiliser of the present invention, be applied in water based foam system, no matter gas phase adopts the mist of nitrogen, carbon dioxide, oxygen, air, flue gas, decarburization flue gas or this several gas, all can form overstable water base foam.Exist under former oil condition, when crude oil contacts with foam, molecules surfactant A is not easy by gas-liquid interface then is adsorbed on oil-water interfaces, and crude oil is not easy to sprawl at gas-liquid interface, thus can not liquid-sheet disintegration be caused, therefore the grease resistance of foam is high.Overtemperature water based foam system of the present invention, can be applicable to the fields such as oilfield chemistry, detergents and cosmetic, mineral floating.
Accompanying drawing explanation
Fig. 1 is that the attenuation curve of the embodiment of the present invention 1 foaming agent and comparative example 1 conventional surfactant foam system foam when taking nitrogen as foamed gas compares.
Fig. 2 is that the embodiment of the present invention 2 foaming agent and comparative example 2 conventional surfactant foam system compare at the attenuation curve of the foam taking carbon dioxide as foamed gas formation.At constant temperature 30 DEG C, the conventional surfactant foaming agent being 0.3wt% with the concentration of clear water configuration and 0.2wt% foaming agent solution of the present invention, measure foam volume over time, obtain foam attenuation curve.
Fig. 3 is that the embodiment of the present invention 3 foaming agent comparative example 3 conventional surfactant foaming agent wins the comparison of foam stability when the crude oil that sticks together exists at Shengli Oil Field.
Fig. 4 is the contrast picture of bubble in the foam system of the bubble that formed of the embodiment of the present invention 4 foaming agent and conventional surfactant lauryl sodium sulfate.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described, but be not limited only to this.
Embodiment 1: hydrophobically modified polyacrylamide
1, the preparation of hydrophobically modified polyacrylamide
Dissolve the acrylamide of 10g and the EDTA of 0.5g in deionized water, then add the lauryl sodium sulfate of 3g and the acrylate (alkane chain carbon number is 16) of 0.2g.Reactor is placed in water bath with thermostatic control, logical N
2gas added initator after 30 minutes, kept temperature to be 50 DEG C of stirring reactions 20 hours.Obtain hydrophobically modified polyacrylamide, the molecular weight of products therefrom is about 150, and 000.
x/(x+y)=90%, y/(x+y)=10%, mol ratio.
2, the preparation of foam stabiliser
In deionized water, add hydrophobically modified polyacrylamide in proportion, be uniformly mixed, be mixed with the solution that concentration is 0.1wt%, stablize half an hour by constant for solution temperature 30 DEG C of stirrings.Obtain foam stabilization agent solution.
3, foam stabilization effect expedition
To in the 0.1wt% hydrophobically modified polyacrylamide foam stabilization agent solution of above-mentioned configuration, pass into nitrogen, foam is formed with air-flow method, control nitrogen flow rate degree at 75ml/min, generate 100ml foam, read foam volume at interval of the regular hour after stopping foaming, until foam attenuation is to half volume, foam attenuation curve as shown in Figure 1.
Comparative example 1: add lauryl sodium sulfate in clear water, preparation 0.3wt% solution, according to step method similarly to Example 1, measures foam attenuation curve, the results are shown in Figure 1.
As seen from Figure 1, the half foam life period that sodium dodecyl sulfate solution traditional in comparative example 1 is formed is 10 hours, and the half-life of the foam that the foam stabilization agent solution of the present embodiment is formed reaches more than 90 hour, compared with comparative example 1, foam stabilization Be very effective.
Embodiment 2: hydrophobically modified kayexalate
1, the preparation of hydrophobically modified kayexalate
Dissolve the SSS of 12g and the EDTA of 0.5g in deionized water, then add the neopelex of 3.5g and the acrylate (alkane chain carbon number is 18) of 0.25g.Reactor is placed in water bath with thermostatic control, logical N
2gas added initator after 30 minutes, kept temperature to be 50 DEG C of stirring reactions 20 hours.Obtain hydrophobically modified kayexalate, the molecular weight of products therefrom is about 180, and 000.
x/ (x+y)=85%, y/ (x+y)=15%, mol ratio.
2, the preparation of foam stabiliser
In deionized water, add hydrophobically modified kayexalate in proportion, be uniformly mixed, be mixed with the solution that concentration is 0.2wt%, by constant for solution temperature 30 DEG C of stable half an hour.Obtain foam stabilization agent solution.
3, foam stabilization effect expedition
To in the 0.2wt% hydrophobically modified kayexalate foam stabilization agent solution of above-mentioned configuration, pass into carbon dioxide, foam is formed with air-flow method, control carbon dioxide flow rate degree at 75ml/min, generate 100ml foam, read foam volume at interval of the regular hour after stopping foaming, until foam attenuation is to half volume, foam attenuation curve as shown in Figure 2.
Comparative example 2:
Preparation 0.3wt% lauryl sodium sulfate aqueous solution, passes into carbon dioxide, measures foam attenuation curve, the results are shown in Figure 2 by above-mentioned same method.As can be seen from Figure 2, the half-life of the foam that comparative example table surface-active agent is formed is only 30 minutes, and the half foam life period that the present embodiment 2 foam stabiliser is formed can reach 4 hours.
Embodiment 3: hydrophobically modified polyvinyl alcohol
1, the preparation of hydrophobically modified polyvinyl alcohol
Dissolve the vinyl alcohol of 8g and the EDTA of 0.5g in deionized water, then add the dodecyl sodium sulfate of 2g and the acrylate (alkane chain carbon number is 8) of 0.15g.Reactor is placed in water bath with thermostatic control, logical N
2gas added initator after 30 minutes, kept temperature to be 50 DEG C of stirring reactions 20 hours.Obtain hydrophobically modified polyvinyl alcohol, molecular weight of product about 80,000.
x/(x+y)=80%, y/ (x+y)=20%, mol ratio.
2, the preparation of foam stabiliser
With in Gudong oil-producing region simulated formation water (total salinity is for 7000ppm), add hydrophobically modified polyethylene glycol, at 60 DEG C, be mixed with the solution of 0.3wt%.Stir 30min.As foam stabilization agent solution.
3, foam stabilization effect expedition
When stirring, with the mass ratio of 1:10, in the 0.3wt% hydrophobically modified polyethylene glycol foam stabilization agent solution of above-mentioned configuration, add crude oil.Crude oil is that Shengli Oil Field wins the crude oil that sticks together, stir half an hour, then mixed solution is poured into glass core sparger, constant temperature 60 DEG C, control nitrogen flow rate and generate 100ml foam under 100ml/min, start immediately to record the time dependent curve of foam volume after stopping foaming, until volume becomes half, foam attenuation curve is shown in Fig. 3.
Comparative example 3:
Preparation 0.3wt% lauryl sodium sulfate aqueous solution, adds crude oil with the mass ratio of 1:10, and by carrying out foaming with the identical method of embodiment 3 and foam attenuation measures, foam attenuation curve is really shown in Fig. 3.
As can be seen from Figure 3, the conventional foams of comparative example 3 ties up to oil phase, and to there is half-life be 5min, and the foam system of the embodiment of the present invention 3 can bring up to 1 hour the half-life, therefore the foam stability of foaming agent of the present invention under oil phase existence condition is fine, namely has grease resistance.
Embodiment 4: hydrophobically modified polyacrylic acid
1, the polyacrylic preparation of hydrophobically modified
Dissolve the acrylic acid of 11g and the EDTA of 0.5g in deionized water, then add the alkylpolyoxyethylene sodium sulphate of 2.5g and the acrylate (alkane chain carbon number is 14) of 0.22g.Reactor is placed in water bath with thermostatic control, logical N
2gas added initator after 30 minutes, kept temperature to be 50 DEG C of stirring reactions 20 hours.Obtain hydrophobically modified polyacrylic acid, molecular weight of product about 100,000.
x/(x+y)=90%, y/(x+y)=10%, mol ratio.
2, the preparation of foam stabiliser
In clear water, configuration concentration is the hydrophobically modified polyacrylic acid solution of 0.5wt%, at 35 DEG C, stir 35min.As foam stabilization agent solution.
Configuration concentration be the sodium dodecyl sulfate solution of 0.5wt% as a comparison.
3, in foam, bubble regime is investigated
By the foaming processes of embodiment 1, bubble in above-mentioned hydrophobically modified polyacrylic acid solution and sodium dodecyl sulfate solution respectively, get foam respectively and be placed on slide, in the state of basis of microscopic observation bubble, and then analyze foam stability, as Fig. 4.Contrast known, thicker boundary layer (Fig. 4 b) is coated with around the bubble that foaming agent of the present invention is stable, greatly sterically hindered between bubble, prevent bubble coalescence, then light transmittance is high for the stable bubble surface of conventional surfactant (lauryl sodium sulfate), level of coverage is low, and between bubble, (Fig. 4 a) with easy coalescence.
The experimental result of comprehensive above-described embodiment, the present invention has the foaming agent system of ultrastability, thicker boundary layer can be formed at gas-liquid interface, high to interface coverage, gas permeation rate is low, therefore there is the foam stability of superelevation, even if also have good foam stability under carbon dioxide is as harsh conditions such as foamed gas and oil phase existence.
Claims (3)
1. a water base foam stabilizing agent is with one of nitrogen, carbon dioxide, oxygen, air or combination or the water based foam system that is gas phase with flue gas or decarburization flue gas, as the application of liquid phase foam stabilizing agent, described water base foam stabilizing agent is soluble in water by a kind of molecules surfactant A, and forming mass concentration is the clear solution of 0.1-1wt%; Described molecules surfactant A has following general structure:
In general formula, Q is amide groups (-CONH
2), benzene sulfonic acid alkali (-C
6h
4sO
3 -), hydroxyl (-OH), carboxylic acid group (-COOH); Y is be the hydrophobically modified part of 8-24 hydrophobic alkane chain containing carbon number, wherein, and n=8-24, x/ (x+y)=80-95%, y/ (x+y)=5-20%, mol ratio;
Described molecules surfactant A molecular weight is 10,000-200,000.
2. apply as claimed in claim 1, it is characterized in that described molecules surfactant A is the kayexalate of hydrophobically modified, hydrophobically modified polyacrylamide, hydrophobically modified polyvinyl alcohol or hydrophobically modified polyacrylic acid.
3. apply as claimed in claim 1, it is characterized in that described molecules surfactant A is prepared according to the following steps:
Dissolve the ethylenediamine tetra-acetic acid of polymerization single polymerization monomer B and 0.1-1g of 5-20g in deionized water, then add the hydrophobically modified monomer D of surfactant C and 0.05-0.5g of 1-5g; Reactor is placed in water bath with thermostatic control, logical N
2add initator after gas 10-60 minute, keep temperature to be 40-100 DEG C of stirring reaction 10-25 hour; Product acetone precipitation is purified, and dries in vacuum desiccator after cyclic washing and obtain molecules surfactant A to constant is for subsequent use;
Described polymerization single polymerization monomer B is acrylamide, SSS, vinyl alcohol or acrylic acid;
Described hydrophobically modified monomer D is alkane chain carbon number is the acrylate of 8-24;
Described surfactant C is lauryl sodium sulfate, dodecyl sodium sulfate, neopelex, alkylpolyoxyethylene sodium sulphate; Described initator is azodiisobutyronitrile or potassium peroxydisulfate.
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| CN109517592A (en) * | 2018-11-19 | 2019-03-26 | 中国石油大学(北京) | A kind of oil gas field superelevation characteristic value three-phase flue gas foam and preparation method thereof |
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