CN105038756A - Carbon dioxide foam system added with hydrophilic nanoparticles for oil displacement and preparation method for carbon dioxide foam system - Google Patents
Carbon dioxide foam system added with hydrophilic nanoparticles for oil displacement and preparation method for carbon dioxide foam system Download PDFInfo
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Abstract
The invention relates to a carbon dioxide foam system added with hydrophilic nanoparticles for oil displacement and a preparation method for the carbon dioxide foam system. The carbon dioxide foam system is prepared from the following components in parts by mass: 0.1-0.3 part of a nonionic surfactant, 1-2 parts of hydrophilic nanoparticles, 0.01-0.2 part of inorganic salt, 0.2-0.8 part of carbon dioxide and 100 parts of water. The preparation method comprises: after preparing a foaming agent in proportion, uniformly dispersing the foaming agent by using an ultrasonic wave dispersing instrument; and introducing carbon dioxide into a stirring cup and stirring the mixture by virtue of a Waring Blender method to obtain the carbon dioxide foam system. Compared to carbon dioxide foam generated by a common surfactant, the carbon dioxide foam added with hydrophilic nanoparticles is better in temperature resistance and salt resistance, and compared to a foaming agent added with hydrophobic nanoparticles, the carbon dioxide foam system is low in cost and good in dispersing stability and is more liable to be popularized and applied in a field site.
Description
Technical field
The present invention relates to and a kind ofly with the addition of carbon dioxide foam systems of hydrophilic nano particle and preparation method thereof, belong to Oil-Gas Field Development Engineering technical field.
Background technology
The burning of fossil oil will produce a large amount of carbon dioxides, and the random discharge of carbonic acid gas will cause Greenhouse effect, endanger the weather safety of the mankind.Along with the raising day by day that people require for carbon dioxide discharge-reduction, burying of carbonic acid gas obtains increasing concern with utilizing technology.
Crude oil in carbonic acid gas and stratum can interact, play the effect reducing viscosity of crude, improve crude oil elastic energy, and compare nitrogen, air and methane gas, the miscible pressure of carbonic acid gas and crude oil is low, is a kind of ideal oil-displacing agent in oil-field development field.Therefore, carbonic acid gas is used in crude oil production process, both can play the effect of reduction of discharging, the recovery ratio of crude oil can be improved again, there is good social benefit and economic benefit.And due to carbonic acid gas, viscosity is low under formation conditions, large with the mobility ratio of crude oil, many stratum have heterogeneous feature in addition, therefore in oil displacement process, easily gas channeling phenomenon occur, cause the sweep efficiency of formation Crude Oil low, thus reduce the oil displacement efficiency of carbonic acid gas.Foam can reduce the mobility of gas, and oozes to height the effect that stratum has selectively blocking off, can overcome the above problems preferably.Conventional carbon dioxide foaming pore forming material main component is tensio-active agent, and the heatproof of conventional surfactants, salt resistant character are poor, and high temperature and high salinity condition stability inferior is in the earth formation poor, can not form the carbon dioxide foaming that quality is higher.Liu Ye, China's celebrating long oil hides CO
2drive foam system evaluation study, Xi'an Petroleum University, 2012, the impact of the factor such as temperature, salinity on the carbon dioxide foaming stability produced by tensio-active agent of this paper studies.Result shows, carbon dioxide foaming transformation period when sodium-chlor (NaCl) concentration is 1% that tensio-active agent ZY-1 produces is 9.17min, and when temperature is 60 DEG C, the transformation period is only 6.67min.
For this problem, investigator is had to propose to improve carbon dioxide foaming stability in the earth formation by adding hydrophobic nano particle.Li Zhaomin etc., SiO
2nano particle and SDS are to CO
2the synergistic stability effect of foam, Northeast Petroleum University's journal, in June, 2014, the 3rd phase, the document have studied hydrophobic type nano SiO 2 particle and aniorfic surfactant to the stabilising effect of carbon dioxide foaming.Result shows, at SiO
2the carbon dioxide foaming transformation period that mass concentration is 1.5%, SDS concentration to be obtained when being 0.25 can reach 37.2min.But hydrophobic nano particle cost is higher, and due to hydrophobicity strong, in water, disperse difficulty large, the foaming agent solution dispersion stabilization be prepared into is poor, therefore may will face many construction technology problems in Oil Field application.
Single hydrophilic nano particle dispersion cannot play the effect of stable foam, but can be adsorbed by part surface promoting agent due to its surface and produce synergy, therefore, under the proportioning suitable with part surface promoting agent, hydrophilic nano particle also can play the effect improving carbon dioxide foaming heatproof, salt resistant character.In addition, because hydrophilic nano particle cost is far below hydrophobic nano particle, and be easy to disperse in water, therefore, in Oil Field, practical value is higher, has good application prospect.
Summary of the invention
For deficiency of the prior art, the invention provides and a kind ofly add carbon dioxide foam systems of hydrophilic nano particle and preparation method thereof.
Term illustrates:
Hydrophilic nano SiO 2 particle: silica nanoparticle surface uses silanol to carry out modification, the modified nano grain surface that makes is with the silanol of different densities, thus the hydrophobic performance presented in various degree, silanol density is larger, particle hydrophilicity is stronger, and this hydrophilic nano SiO 2 particle is conventional commercial products.
Technical scheme of the present invention is as follows:
Add a carbon dioxide foam systems for hydrophilic nano particle, comprise raw materials quality part composed as follows:
Nonionogenic tenside 0.1-0.3 part, hydrophilic nano particle 1-2 part, inorganic salt 0.01-0.2 part, carbonic acid gas 0.2-0.8 part, 100 parts, water.
According to the present invention, preferably, described nonionogenic tenside is lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C
12e
9p
3).
According to the present invention, preferably, described hydrophilic nano particle is hydrophilic nano SiO 2 particle; Preferred further, described hydrophilic nano grain diameter is 15-50nm, density of surface silanol groups 1-2/nm
2, be 38-60 ° with the contact angle of water.
According to the present invention, preferably, described inorganic salt are sodium-chlor.
According to the present invention, preferably, the carbon dioxide foam systems of described interpolation hydrophilic nano particle, comprises raw materials quality part composed as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether 0.1-0.3 part, hydrophilic nano SiO 2 particle 1-2 part, sodium-chlor 0.01-0.2 part, carbonic acid gas 0.2-0.8 part, 100 parts, water.
According to the present invention, preferably, the carbon dioxide foam systems of described interpolation hydrophilic nano particle, comprises raw materials quality part composed as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether 0.1 part, hydrophilic nano SiO 2 particle 1.5 parts, 0.2 part, sodium-chlor, carbonic acid gas 0.2-0.8 part, 100 parts, water.
According to the present invention, the preparation method of the carbon dioxide foam systems of above-mentioned interpolation hydrophilic nano particle, comprises step as follows:
(1) according to proportioning hydrophilic nano particle be added to the water and stir, then adding nonionogenic tenside and inorganic salt successively, ultrasonic disperse 3-5min;
(2) continue to pass into carbonic acid gas 2-5min in the system obtained to step (1), then stir 3-5minmin with the rotating speed of 7000-9000r/min, to obtain final product.
Hydrophilic nano SiO 2 particle of the present invention, can buy in market, also can prepare by prior art.
Principle of the present invention:
Hydrophilic nano particle due to hydrophilicity excessively strong, major part is arranged in liquid phase, can not be adsorbed onto liquid-gas interface, thus cannot play the effect of stable foam.The polar group of lauryl alcohol polyethylene glycol oxide polyethenoxy ether and the silicone hydroxyl of nano grain surface are formed by hydrogen bond action and adsorb, and nano particle hydrophobic performance is strengthened, can be adsorbed onto on liquid-gas interface, thus play stabilization to foam.And when lauryl alcohol polyoxyethylene poly-oxygen propylene aether excessive concentration, under the effect of Van der Waals force, between tensio-active agent, double-deck absorption can be formed at particle surface, particle hydrophilicity is strengthened, loses the effect of steady bubble.Therefore, only under suitable proportioning, the two could play collaborative stable effect to carbon dioxide foaming.
Compare nitrogen and air, the solubleness of carbonic acid gas in water is comparatively large, and velocity of diffusion is very fast in the liquid phase, exacerbates the disproportionation of carbon dioxide foaming, causes carbon dioxide foaming to compare nitrogen and air foam is more unstable.And nano particle is because size is much larger than tensio-active agent, the contact area of carbonic acid gas and liquid phase can be reduced when it is adsorbed onto on liquid-gas interface, thus reduce disproportionation, enhance the stability of foam.In addition, nano particle add the viscosity that can increase liquid phase, thus slow down the drain age velocity of foam.And appropriate sodium-chlor add the surface potential that can reduce nano particle, reduce intergranular electrostatic repulsion, make the arrangement of particle on liquid-gas interface more tight, further increase the stability of carbon dioxide foaming.
Excellent technique effect of the present invention:
1, composite by with nonionogenic tenside, makes the hydrophilic nano particle that cannot independently surely steep obtain foam stability energy.Carbonic acid gas in the liquid phase rate of diffusion is very fast, therefore the disproportionation of carbon dioxide foaming compare other gas formed foam more obvious, and due to nano particle larger compared to the size of tensio-active agent, the contact area of carbonic acid gas and liquid phase can be reduced when it is adsorbed in liquid-gas interface, reduce the disproportionation of foam, significantly improve the stability of carbon dioxide foaming.
2, hydrophilic nano particle has the feature of solid particulate, and heatproof, salt resistant character are comparatively strong, make carbon dioxide foaming still have good stability under the formation condition of high temperature, high salt, play the advantage of its displacement of reservoir oil.
3, hydrophilic nano Particle Phase is less than stratum pore throat size, can freely migrate, and can not formation damage; In addition, hydrophilic nano particle is easy to disperse in water, and pore forming material system preparation method and site construction technology are simple, and it is with low cost to compare hydrophobic nanoparticles, is easier to apply in oil field.
Embodiment:
Be below further illustrating of in conjunction with specific embodiments the present invention being done, but the present invention's scope required for protection is not limited to the scope involved by embodiment.
Raw materials usedly in embodiment be convenient source, equipment used is conventional equipment.
Wherein: hydrophilic nano SiO 2 particle, gloomy trade Co., Ltd of Guangzhou Holley is on sale.
Embodiment 1:
Add a carbon dioxide foam systems for hydrophilic nano particle, comprise raw materials quality part composed as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C
12e
9p
3) 0.15g, hydrophilic nano SiO 2 particle (median size 16nm, surface silicon alkanol density 1.5/nm
2, be 38.8 ° with the contact angle of water) and 1.5g, sodium-chlor (NaCl) 0.2g, carbonic acid gas 0.5g, distilled water 100g.
Preparation method is as follows:
(1) hydrophilic nano SiO 2 particle to be joined in distilled water and to stir, adding lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C successively
12e
9p
3) and sodium-chlor (NaCl), use ultrasonic wave separating apparatus to carry out ultrasonic disperse 3min to mixed system;
(2) WaringBlender method is used to produce foam: to continue to pass into 3min carbonic acid gas in the system that step (1) obtains, then stir 3min with the rotating speed of 8000r/min to system, obtain carbon dioxide foam systems 315ml.
Under normal temperature, it is 29.93min that the carbon dioxide foam systems that the present embodiment obtains analyses the liquid transformation period.
Embodiment 2:
Add a carbon dioxide foam systems for hydrophilic nano particle, comprise raw materials quality part composed as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C
12e
9p
3) 0.1g, hydrophilic nano SiO 2 particle (median size 20nm, surface silicon alkanol density 1/nm
2, be 50.4 ° with the contact angle of water) and 1.5g, sodium-chlor (NaCl) 0.2g, carbonic acid gas 0.5g, distilled water 100g.
Preparation method is as follows:
(1) hydrophilic nano SiO 2 particle to be joined in distilled water and to stir, adding lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C successively
12e
9p
3) and sodium-chlor (NaCl), use ultrasonic wave separating apparatus to carry out ultrasonic disperse 3min to mixed system;
(2) WaringBlender method is used to produce foam: to continue to pass into 3min carbonic acid gas in the system that step (1) obtains, then stir 3min with the rotating speed of 8000r/min to system, obtain carbon dioxide foam systems 379ml.
Under normal temperature, it is 42.64min that the carbon dioxide foam systems that the present embodiment obtains analyses the liquid transformation period.
Embodiment 3:
Add a carbon dioxide foam systems for hydrophilic nano particle, comprise raw materials quality part composed as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C
12e
9p
3) 0.1g, hydrophilic nano SiO 2 particle (median size 20nm, surface silicon alkanol density 1/nm
2, be 50.4 ° with the contact angle of water) and 1.5g, sodium-chlor (NaCl) 0.2g, carbonic acid gas 0.5g, distilled water 100g.
Preparation method is as follows:
(1) hydrophilic nano SiO 2 particle to be joined in distilled water and to stir, adding lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C successively
12e
9p
3) and sodium-chlor (NaCl), use ultrasonic wave separating apparatus to carry out ultrasonic disperse 3min to mixed system;
(2) mixed system is placed in 80 DEG C of thermostat containers, constant temperature 3h;
(3) WaringBlender method is used to produce foam: to continue to pass into 3min carbonic acid gas in the system that step (2) obtains, then stir 3min with the rotating speed of 8000r/min to system, obtain carbon dioxide foam systems 328ml;
(4) carbon dioxide foaming obtained is moved to rapidly 80 DEG C of thermostat containers, measure its transformation period.
Heat resistance: at 80 DEG C, it is 38.77min that the carbon dioxide foam systems that the present embodiment obtains analyses the liquid transformation period.The transformation period fall compared in embodiment 2 under normal temperature is less, illustrates that the carbon dioxide foam systems heat resistance that present method obtains is stronger.
Embodiment 4:
Add a carbon dioxide foam systems for hydrophilic nano particle, comprise raw materials quality part composed as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C
12e
9p
3) 0.1g, hydrophilic nano SiO 2 particle (median size 20nm, surface silicon alkanol density 1/nm
2, be 50.4 ° with the contact angle of water) and 1.5g, sodium-chlor (NaCl) 0.2g, carbonic acid gas 0.5g, distilled water 100g.
Preparation method is as follows:
(1) hydrophilic nano SiO 2 particle to be joined in distilled water and to stir, adding lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C successively
12e
9p
3) and sodium-chlor (NaCl), use ultrasonic wave separating apparatus to carry out ultrasonic disperse 3min to mixed system;
(2) in mixed system, 0.2g calcium chloride (CaCl is added successively
2) and 0.2g magnesium chloride (MgCl
2), stir;
(3) WaringBlender method is used to produce foam: to continue to pass into 3min carbonic acid gas in the system that step (1) obtains, then stir 3min with the rotating speed of 8000r/min to system, obtain carbon dioxide foam systems 336ml.
Under normal temperature, it is 39.28min that the carbon dioxide foam systems that the present embodiment obtains analyses the liquid transformation period.
Salt resistant character: owing to adding calcium chloride (CaCl common in stratum in this embodiment
2) and magnesium chloride (MgCl
2), salinity reaches 4000mg/L, serve destruction to a certain degree, but it is still less to compare transformation period fall in embodiment 2 to froth stability, illustrates that the obtained carbon dioxide foam systems salt resistant character of present method method is stronger.
Comparative example 1:
As described in Example 1, unlike:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C
12e
9p
3) addition is 0.6g.
Under normal temperature, it is 6.24min that the carbon dioxide foam systems that this comparative example obtains analyses the liquid transformation period.
Comparing the transformation period in embodiment 1 declines to a great extent, and this is due to excessive lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C
12e
9p
3) make tensio-active agent form double-deck absorption at particle surface, cause the hydrophilicity of particle to strengthen, get back in liquid phase again, cannot be adsorbed onto on liquid-gas interface, thus the effect of stable foam can not be played.
Comparative example 2:
As described in Example 1, unlike:
Hydrophilic nano SiO 2 particle 5g.
Under normal temperature, it is 1.65min that the carbon dioxide foam systems that this comparative example obtains analyses the liquid transformation period.
Comparing the transformation period in embodiment 1 declines to a great extent, and this is owing to comparing lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C
12e
9p
3) concentration, granule density is too high, lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C
12e
9p
3) very few in the adsorptive capacity of particle surface, not obvious to the hydrophobization effect of particle, particle is still arranged in liquid phase, cannot play the effect of stable foam.
Claims (8)
1. add a carbon dioxide foam systems for hydrophilic nano particle, comprise raw materials quality part composed as follows:
Nonionogenic tenside 0.1-0.3 part, hydrophilic nano particle 1-2 part, inorganic salt 0.01-0.2 part, carbonic acid gas 0.2-0.8 part, 100 parts, water.
2. the carbon dioxide foam systems of interpolation hydrophilic nano particle according to claim 1, is characterized in that, described nonionogenic tenside is lauryl alcohol polyethylene glycol oxide polyethenoxy ether (C
12e
9p
3).
3. the carbon dioxide foam systems of interpolation hydrophilic nano particle according to claim 1, is characterized in that, described hydrophilic nano particle is hydrophilic nano SiO 2 particle.
4. the carbon dioxide foam systems of interpolation hydrophilic nano particle according to claim 3, is characterized in that, described hydrophilic nano grain diameter is 15-50nm, density of surface silanol groups 1-2/nm
2, be 38-60 ° with the contact angle of water.
5. the carbon dioxide foam systems of interpolation hydrophilic nano particle according to claim 1, is characterized in that, described inorganic salt are sodium-chlor.
6. the carbon dioxide foam systems of interpolation hydrophilic nano particle according to claim 1, is characterized in that, the carbon dioxide foam systems of described interpolation hydrophilic nano particle, comprises raw materials quality part composed as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether 0.1-0.3 part, hydrophilic nano SiO 2 particle 1-2 part, sodium-chlor 0.01-0.2 part, carbonic acid gas 0.2-0.8 part, 100 parts, water.
7. the carbon dioxide foam systems of interpolation hydrophilic nano particle according to claim 1, is characterized in that, the carbon dioxide foam systems of described interpolation hydrophilic nano particle, comprises raw materials quality part composed as follows:
Lauryl alcohol polyethylene glycol oxide polyethenoxy ether 0.1 part, hydrophilic nano SiO 2 particle 1.5 parts, 0.2 part, sodium-chlor, carbonic acid gas 0.2-0.8 part, 100 parts, water.
8. a preparation method for the carbon dioxide foam systems of the interpolation hydrophilic nano particle described in any one of claim 1-7, comprises step as follows:
(1) according to proportioning hydrophilic nano particle be added to the water and stir, then adding nonionogenic tenside and inorganic salt successively, ultrasonic disperse 3-5min;
(2) continue to pass into carbonic acid gas 2-5min in the system obtained to step (1), then stir 3-5minmin with the rotating speed of 7000-9000r/min, to obtain final product.
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Cited By (15)
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| CN106118624A (en) * | 2016-06-20 | 2016-11-16 | 中国石油大学(华东) | The method of asphaltene deposits injury during a kind of nano-fluid suppression low permeability reservoir carbon dioxide flooding |
| CN107652963A (en) * | 2017-10-13 | 2018-02-02 | 中国石油大学(华东) | A kind of gas foam foam stabilizer system and preparation method thereof |
| CN108300447A (en) * | 2018-02-09 | 2018-07-20 | 上海大学 | A kind of nano particle foam system and preparation method thereof improving oil displacement efficiency |
| CN108841368A (en) * | 2018-05-30 | 2018-11-20 | 中国石油大学(华东) | Organo-mineral complexing oil displacement agent, organo-mineral complexing oil displacement system and preparation method and application |
| CN109370551A (en) * | 2018-11-26 | 2019-02-22 | 西安石油大学 | A kind of bubbling system with high surface spreading modulus |
| CN111019622A (en) * | 2019-12-23 | 2020-04-17 | 中国石油大学(华东) | Rice hull ash particle-based reinforced foam system, preparation method and application |
| US10793763B2 (en) | 2018-11-19 | 2020-10-06 | China University Of Petroleum-Beijing | Ultra-dry three-phase flue gas foam for oil-gas fields and preparation method thereof |
| CN113117594A (en) * | 2021-05-26 | 2021-07-16 | 江南大学 | Rosin-based surfactant and silicon dioxide nanoparticle composite stabilizer and application thereof |
| CN113444509A (en) * | 2020-03-27 | 2021-09-28 | 中国石油天然气股份有限公司 | Supercritical carbon dioxide foam system, preparation method thereof and foaming liquid |
| CN113717707A (en) * | 2021-05-25 | 2021-11-30 | 西安石油大学 | Environment-friendly deep nano-drainage agent for compact gas well and preparation method thereof |
| CN113861329A (en) * | 2021-08-30 | 2021-12-31 | 苏州赫伯特电子科技有限公司 | Low-cost W/C reversed micelle and preparation method of reversed-phase Pickering emulsion polymerization thereof |
| CN113945565A (en) * | 2021-10-25 | 2022-01-18 | 青岛科技大学 | Foam performance testing device based on nanoparticle stability and testing method thereof |
| CN114316939A (en) * | 2022-01-05 | 2022-04-12 | 东北石油大学 | Carbon dioxide gas soluble foaming agent suitable for compact reservoir |
| CN114687714A (en) * | 2022-04-12 | 2022-07-01 | 中国矿业大学 | Nano-particle composite low-salinity water-enhanced CO2Method of injection capability |
| US11931708B2 (en) | 2019-04-22 | 2024-03-19 | China University Of Petroleum (East China) | Carbon dioxide fluidity control device and method |
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| CN106118624B (en) * | 2016-06-20 | 2019-02-12 | 中国石油大学(华东) | A kind of method that nano-fluid inhibits asphaltene deposits injury during low permeability reservoir carbon dioxide flooding |
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| CN108300447A (en) * | 2018-02-09 | 2018-07-20 | 上海大学 | A kind of nano particle foam system and preparation method thereof improving oil displacement efficiency |
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| CN113945565A (en) * | 2021-10-25 | 2022-01-18 | 青岛科技大学 | Foam performance testing device based on nanoparticle stability and testing method thereof |
| CN114316939A (en) * | 2022-01-05 | 2022-04-12 | 东北石油大学 | Carbon dioxide gas soluble foaming agent suitable for compact reservoir |
| CN114316939B (en) * | 2022-01-05 | 2022-07-22 | 东北石油大学 | Carbon dioxide gas soluble foaming agent suitable for compact reservoir |
| CN114687714A (en) * | 2022-04-12 | 2022-07-01 | 中国矿业大学 | Nano-particle composite low-salinity water-enhanced CO2Method of injection capability |
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