CN108410441B - Stable strengthening foam system and preparation method thereof is cooperateed with based on graphite oxide particle - Google Patents
Stable strengthening foam system and preparation method thereof is cooperateed with based on graphite oxide particle Download PDFInfo
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
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Abstract
Stable strengthening foam system and preparation method thereof is cooperateed with based on graphite oxide particle the invention discloses a kind of, belongs to Oil-Gas Field Development Engineering technical field.It is described to cooperate with stable strengthening foam system to be made of following parts by weight of component based on graphite oxide particle: 0.3~0.7 part of cationic surfactant, 0.1~0.3 part of stabilizer, 0.2~0.5 part of graphite oxide particle, 100 parts of water；Wherein, cationic surfactant is cetyl trimethylammonium bromide.Provided by the invention that stable strengthening foam system is cooperateed with based on graphite oxide particle, stability is excellent, environment friendly and pollution-free, and preparation process is simple, can significantly improve oil recovery rate.
Description
Technical field
The present invention relates to Oil-Gas Field Development Engineering technical fields, particularly relate to a kind of based on graphite oxide particle collaboration stabilization
Strengthening foam system and preparation method thereof.
Background technique
Foam flooding is widely used as a kind of technological means for improving oil recovery factor, has there is nearly application in 60 years so far
History.Foam can cause the reduction of gas phase relative permeability, delay gas fingering.Foam quality is to determine foam flooding efficiency
Key factor, however foam, as a kind of thermodynamically unstable dispersion, this unstability applies band to foam
Tremendous influence is carried out.Scholars both domestic and external have conducted extensive research around how improving foam stability, it was also proposed that many
Method.
Researching and developing novel foaming agent is a kind of important method.Surface-active is concentrated mainly on to the research and development of foaming agent at present
The synthesis or compounding of agent.The alkyl chain appropriate that extends of research discovery before helps to increase the stability of foam.Since surface is living
The limitation of property agent itself chemical characteristic, although can produce enough foaming volumes, its stability is poor.In order to increase gas
The polymer such as polyacrylamide, albumen, polypeptide are added in the stability of bubble in foaming agent, by improving the viscosity of base fluid, reduce
Bubble mobility, to achieve the effect that foam stabilizing.
Chinese patent document ZL201210223060.0 discloses a kind of composite foam of oil gas field addition nano particle
System and preparation method thereof.Composite foam system is by anionic surfactant, modified silica nanoparticle, counter ion salt
And water composition.The foam generated using the composite foam system, the half foam life period more stable than conventional surfactants is long, blistering
Volume is big；But nano particle preparation process used is complicated in the system, involves great expense, it can not be in the big rule in oil-gas field development field
Mould application.
Chinese patent document ZL201510600689.6 discloses a kind of oil gas field novel inorganic subparticle enhanced foam
Foam system and preparation method thereof.Novel inorganic subparticle used in this method is to trap partial size≤2.5 μ screened in atmosphere
The fine particle of m, the surfactant compound formed with sasanguasaponin and sodium lauroyl glutamate form stable foam system.
Such subparticle is from a wealth of sources, mostly coal-burning power plant's solid waste, it can be realized by being applied to agent for improving oilfield recovery
Resource utilization, but such subparticle is influenced more obvious, ingredient by each batch coal kind, ingredient and burning degree
Form it is complex changeable so that its cooperateed with surfactant compound stable foam effect be difficult to control.
Summary of the invention
The technical problem to be solved in the present invention is to provide it is a kind of it is at low cost, performance is stable, preparation method is simply based on oxygen
Graphite particle cooperates with stable strengthening foam system and preparation method thereof.
In order to solve the above technical problems, present invention offer technical solution is as follows:
On the one hand, provide it is a kind of stable strengthening foam system is cooperateed with based on graphite oxide particle, by following parts by weight
Group is grouped as: 0.3~0.7 part of cationic surfactant, 0.1~0.3 part of dispersing agent, and 0.2~0.5 part of graphite oxide particle,
100 parts of water；
Wherein, cationic surfactant is cetyl trimethylammonium bromide, and graphite oxide particle is through ultrasonication point
It dissipates for the smaller oxidized graphite flake of scale, uniform and stable is dispersed in water, and surface is negatively charged, cetyl trimethylammonium bromide
It is positively charged in aqueous solution, cetyl trimethylammonium bromide is adsorbed by graphite oxide particle surface by electrostatic interaction；Ten
The hydrophobic segment of six alkyl trimethyl ammonium bromides stretches to aqueous solution, increases oxidized graphite flake hydrophobic properties of the surface.
Preferably, the dispersing agent is sodium lignin sulfonate；Sodium lignin sulfonate as a kind of high molecular polymer skeleton,
The surrounding graphene particles of tridimensional network is formed, the drain of foam is further decreased, to improve the stability of foam.
Preferably, the water is distilled water.
Preferably, the graphite oxide particle is 100 mesh flaky graphites, and partial size is 3-5 μm, and the angle of wetting to water is
30 °~50 °.
Graphite oxide particle used in the present invention can be commercial product, can also be prepared through Hummers method,
The specific method is as follows:
Step 1: being put into large beaker in ice-water bath, the 110mL concentrated sulfuric acid is added, is stirred on magnetic stirring apparatus, is put into temperature
Degree meter allows its temperature to be down to 4 DEG C or so；
Step 2: adding 100 mesh flaky graphite 5g, add 2.5g sodium nitrate, be then slowly added into 15g potassium permanganate, add
When complete postscript, 90min is stirred to react on magnetic stirring apparatus, solution changes tepidarium, temperature control into purple green, by ice-water bath
At 32 DEG C~40 DEG C, 30min is reacted, solution is in purple green；
Step 3: after reaction terminates, being slowly added to 220mL deionized water, heating is kept for 70~100 DEG C of temperature or so, is delayed
The slow mass concentration that is added is that 5% hydrogen peroxide is reacted, and reaction solution color becomes golden yellow；
Step 4: the solution after reaction is repeatedly centrifuged in centrifuge, is washed with water, until sulfate radical-free ion in solution,
Graphite oxide particle obtained by drying at a temperature of 40~50 DEG C.
On the other hand, the present invention also provides the above-mentioned preparations that stable strengthening foam system is cooperateed with based on graphite oxide particle
Method, comprising:
Step 1: graphite oxide particle being added to the water and carries out ultrasonic disperse, obtains sheet graphite oxide dispersion；
Step 2: cetyl trimethylammonium bromide and lignosulfonates are added to the graphite oxide point that step 1 obtains
In dispersion liquid, stirring obtains compounding dispersion liquid；
Step 3: compounding dispersion liquid Waring Blender method being stirred, after generation foam to obtain the final product.
Preferably, in the step 1, graphite oxide particle use 100 mesh flaky graphites, 3-5 μm of partial size, to the profit of water
Wet angle is 30 °~50 °；The mass concentration of graphite oxide is 0.2~0.5wt.%；The sheet that step 1 is prepared aoxidizes stone
Black preferable particle size is 0.5-2 μm, thickness in monolayer 1-3nm.Graphite oxide has outstanding heat resistance, so the present invention provides
Strengthening foam system have stronger temperature tolerance.
Preferably, in the step 1, the condition of ultrasonic disperse is time 2h, ultrasonic power 500-1000W.
Preferably, in the step 2, when the mass concentration of cetyl trimethylammonium bromide is 0.3~0.7wt.%, oxygen
The contact angle of fossil ink sheet and water is 80 °~90 °, and this graphite oxide thin slice with certain hydrophobic property can be irreversible
Be adsorbed on bubble interface liquid film, and by flocculation reaction, form one layer of compacted zone on interface, increase bubble film
Viscoplasticity, reduce the drain and gas diffusion of foam.
Preferably, the mass concentration of lignosulfonates is 0.1~0.3wt.%.
Preferably, in the step 2, the condition of stirring is 25 DEG C -30 DEG C of temperature, time 0.5-1h.
Preferably, in the step 2, compounding the contact angle of sheet graphite oxide and water in dispersion liquid is 80 °~90 °.
Preferably, it in the step 3, is stirred 3 minutes in Waring Blender method with the speed of 8000rpm, gas source is
Air, nitrogen or carbon dioxide gas.
The invention has the following advantages:
In above scheme, the present invention is obtained using cationic surfactant and graphite oxide particle preparation stable for the first time
Foam system increases the hydrophobic performance of graphite oxide particle, irreversible can be adsorbed on bubble interface liquid film, and lead to
Cross flocculation reaction, on interface formed one layer of compacted zone, increase the viscoplasticity of bubble film, reduce foam drain and
Gas diffusion；With the use of lignosulfonates, graphite oxide particle is set to form tridimensional network in solution phase, further
The drain for reducing foam, to improve the stability of foam；And the present invention is at low cost, preparation process is simple, indoor simulation can be shown
It writes and improves recovery ratio.
Detailed description of the invention
Fig. 1 is that graphite oxide particle ultrasonic disperse of the invention is lamella layered graphite oxide schematic diagram；
Fig. 2 is the scanning electron microscope image of graphite oxide particle used in the embodiment of the present invention 2；
Fig. 3 is the images of transmissive electron microscope of sheet graphite oxide obtained in 2 preparation method step 1 of the embodiment of the present invention.
Specific embodiment
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool
Body embodiment is described in detail.
The present invention is directed to problem at high cost in the prior art and foam system stability difference, provides a kind of based on oxygen
Graphite particle cooperates with stable strengthening foam system and preparation method thereof.
Embodiment 1
The preparation method of graphite oxide particle, comprising:
Step 1: being put into large beaker in ice-water bath, the 110mL concentrated sulfuric acid is added, is stirred on magnetic stirring apparatus, is put into temperature
Degree meter allows its temperature to be down to 4 DEG C or so；
Step 2: adding 100 mesh flaky graphite 5g, add 2.5g sodium nitrate, be then slowly added into 15g potassium permanganate, add
When complete postscript, 90min is stirred to react on magnetic stirring apparatus, solution changes tepidarium, temperature control into purple green, by ice-water bath
At 32 DEG C~40 DEG C, 30min is reacted, solution is in purple green；
Step 3: after reaction terminates, being slowly added to 220mL deionized water, heating is kept for 70~100 DEG C of temperature or so, is delayed
The slow mass concentration that is added is that 5% hydrogen peroxide is reacted, and reaction solution color becomes golden yellow；
Step 4: the solution after reaction is repeatedly centrifuged in centrifuge, is washed with water, until sulfate radical-free ion in solution,
Graphite oxide particle obtained by drying at a temperature of 40~50 DEG C.
It is 3.5 μm by the graphite oxide mean particle size that SEM is measured, its profit to water is measured based on sessile drop method
Wet angle is 35 °.
It is verified it should be noted that inventor passes through, preferred 3-5 μm of the partial size of graphite oxide particle, to the angle of wetting of water
For within the scope of 30 °~50 °, self-control graphite oxide particle and commercially available graphite oxide particle (3-5 μm of partial size, 45 ° of angle of wetting) are to strong
The influence difference for changing foam system is small, and cost, the graphite oxide particle that the present invention uses are purchased from Nanjing in order to save time
Xian Feng Nanosolutions GmbH.
Embodiment 2
Stable strengthening foam system is cooperateed with based on graphite oxide particle, is grouped as by the group of following parts by weight: hexadecane
0.7 part of base trimethylammonium bromide, 0.1 part of lignosulfonates, 0.3 part of graphite oxide particle, 100 parts of water.
The preparation method of stable strengthening foam system is cooperateed with based on graphite oxide particle, comprising:
Step 1: being 3-5 μm by partial size, the graphite oxide particle 0.3g that the angle of wetting to water is 30 °~50 ° is added to
In 100g water, ultrasonic disperse 2h, ultrasonic power 800W are carried out at 30 DEG C, obtaining partial size is 0.5-2 μm, thickness in monolayer 1-
The sheet graphite oxide dispersion of 3nm；
Step 2: by 0.7g cetyl trimethylammonium bromide and 0.1g
Lignosulfonates are added in the graphite oxide dispersion that step 1 obtains, and 1h is stirred at 30 DEG C, are stood
10min obtains compounding dispersion liquid, and compounding the contact angle of sheet graphite oxide and water in dispersion liquid is about 85 °；
Step 3: dispersion liquid will be compounded and prepared within 3 minutes surely with Waring Blender method with the speed stirring of 8000rpm
Fixed air foam to get.
Embodiment 3
Stable strengthening foam system is cooperateed with based on graphite oxide particle, is grouped as by the group of following parts by weight: hexadecane
0.7 part of base trimethylammonium bromide, 0.1 part of lignosulfonates, 0.3 part of graphite oxide particle, 100 parts of water.
The preparation method of stable strengthening foam system is cooperateed with to remove using Waring Blender based on graphite oxide particle
It is nitrogen that gas source, which uses, in method whipping process, other steps are identical with embodiment 2.
Embodiment 4
Stable strengthening foam system is cooperateed with based on graphite oxide particle, is grouped as by the group of following parts by weight: hexadecane
0.5 part of base trimethylammonium bromide, 0.3 part of lignosulfonates, 0.3 part of graphite oxide particle, 100 parts of water.
Cooperate with the preparation method of stable strengthening foam system identical with embodiment 3 based on graphite oxide particle.
Since length is limited, the beneficial effect obtained in order to further illustrate the present invention, only by taking embodiment 3 as an example, setting
Relevant comparative example carries out performance verification.Can it be led to unless otherwise specified in embodiment and comparative example using reagent and material
Commercial sources are crossed to obtain.It should be pointed out that for those skilled in the art, in the premise for not departing from principle of the present invention
Under, it can also make several improvements and retouch, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Comparative example 1
Foam system is grouped as by the group of following parts by weight: 0.7 part of cetyl trimethylammonium bromide, graphite oxide
0.3 part, 100 parts of water of grain.
The preparation method of foam system includes:
Step 1: being 3-5 μm by partial size, the graphite oxide particle 0.3g that the angle of wetting to water is 30 °~50 ° is added to
In 100g water, ultrasonic disperse 2h, ultrasonic power 800W are carried out at 30 DEG C, obtaining partial size is 0.5-2 μm, thickness in monolayer 1-
The sheet graphite oxide dispersion of 3nm；
Step 2: 0.7g cetyl trimethylammonium bromide is added in the graphite oxide dispersion that step 1 obtains,
1h is stirred at 30 DEG C, stands 10min, is obtained compounding dispersion liquid, is compounded the contact angle of sheet graphite oxide and water in dispersion liquid
About 85 °；
Step 3: dispersion liquid will be compounded and stirred 3 minutes with Waring Blender method with the speed of 8000rpm, whipping process
The middle nitrogen that is continually fed into tank body is to get stable nitrogen foam.
Comparative example 2
Foam system is grouped as by the group of following parts by weight: 0.1 part of lignosulfonates, 0.3 part of graphite oxide particle,
100 parts of water.
The preparation method of foam system includes:
Step 1: being 3-5 μm by partial size, the graphite oxide particle 0.3g that the angle of wetting to water is 30 °~50 ° is added to
In 100g water, ultrasonic disperse 2h is carried out at 30 DEG C, ultrasonic power 800W obtains graphite oxide dispersion；
Step 2: 0.1g lignosulfonates being added in the graphite oxide dispersion that step 1 obtains, stirred at 30 DEG C
1h is mixed, 10min is stood, obtains compounding dispersion liquid, compounding the contact angle of sheet graphite oxide and water in dispersion liquid is about 45 °；
Step 3: dispersion liquid will be compounded and stirred 3 minutes with Waring Blender method with the speed of 8000rpm, whipping process
The middle nitrogen that is continually fed into tank body is to get stable nitrogen foam.
Comparative example 3
Foam system is grouped as by the group of following parts by weight: 0.7 part of cetyl trimethylammonium bromide, lignin sulfonic acid
0.1 part of salt, 100 parts of water.
Step 1: 0.7g cetyl trimethylammonium bromide and 0.1g lignosulfonates being added in 100g water, 30
1h is stirred at DEG C, stands 10min；
Step 3: being stirred 3 minutes with Waring Blender method with the speed of 8000rpm, held in whipping process into tank body
It is continuous to be passed through nitrogen to get stable nitrogen foam.
Comparative example 4
Foam system is grouped as by the group of following parts by weight: 0.7 part of cetyl trimethylammonium bromide, lignin sulfonic acid
0.1 part of salt, 100 0.3 part of mesh flaky graphites, 100 parts of water.
The preparation method of foam system, it is same as Example 3.
Comparative example 5
Foam system is grouped as by the group of following parts by weight: 0.7 part of neopelex, lignosulfonates 0.1
Part, 100 0.3 part of mesh flaky graphites, 100 parts of water.
The preparation method of foam system, it is same as Example 3.
The foaming characteristic of product and estimation of stability use conventional laboratory methods Waring in embodiment and comparative example
The measurement of Blender method.
Waring Blender paddling process is one of common stirring means, frequently with the bubble of the method measurement foaming agent
Ability and the stability for forming foam, paddling process measure foaming agent performance using high speed agitator.Quantitative foaming agent solution is fallen
Enter in graduated cylinder, certain speed stirs the regular hour, and record stops foam volume V when stirring0(mL) and half is precipitated in foam
Time (becoming half-life period) t when liquid0.5(s), V is used0It indicates bubbling ability, uses t0.5Indicate foam stability.
Take 100ml foam liquid that Waring Blender method is used to stir 3 minutes with the speed of 8000rpm, stirring is completed
Foam is poured into 1000mL graduated cylinder afterwards, liquid in the initial volume and foam of foam is recorded at normal temperatures and pressures and 50mL institute is precipitated
Time, it may be verified that the stability of foam.
The foaming volume of the foam system of above-described embodiment 2-4 and comparative example 1-5 preparation and the performance number for analysing liquid half-life period
According to being shown in Table 1.
Table 1
As seen from the above table, that invents offer cooperates with stable strengthening foam system based on graphite oxide particle, has excellent
Frothing capacity and half-life it is long, bubble stability can good feature.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of cooperate with stable strengthening foam system based on graphite oxide particle, which is characterized in that by the group of following parts by weight
It is grouped as: 0.3~0.7 part of cationic surfactant, 0.1~0.3 part of dispersing agent, 0.2~0.5 part of graphite oxide particle, water
100 parts；
Wherein, cationic surfactant is cetyl trimethylammonium bromide；
The dispersing agent is sodium lignin sulfonate；The water is distilled water；
The graphite oxide particle is 100 mesh flaky graphites, and partial size is 3-5 μm, and the angle of wetting to water is 30 °~50 °.
2. the preparation method according to claim 1 that stable strengthening foam system is cooperateed with based on graphite oxide particle,
It is characterized in that, comprising:
Step 1: graphite oxide particle being added to the water and carries out ultrasonic disperse, obtains sheet graphite oxide dispersion；
Step 2: cetyl trimethylammonium bromide and sodium lignin sulfonate are added to the graphite oxide dispersion that step 1 obtains
In, stirring obtains compounding dispersion liquid；
Step 3: compounding dispersion liquid Waring Blender method being stirred, after generation foam to obtain the final product.
3. the preparation method according to claim 2 that stable strengthening foam system is cooperateed with based on graphite oxide particle,
It is characterized in that, in the step 1, the mass concentration of graphite oxide is 0.2~0.5wt.%.
4. the preparation method according to claim 2 that stable strengthening foam system is cooperateed with based on graphite oxide particle,
It is characterized in that, in the step 1, the condition of ultrasonic disperse is time 2h, ultrasonic power 500-1000W.
5. the preparation method according to claim 2 that stable strengthening foam system is cooperateed with based on graphite oxide particle,
It is characterized in that, in the step 2, the mass concentration of cetyl trimethylammonium bromide is 0.3~0.7wt.%；Lignin sulfonic acid
The mass concentration of sodium is 0.1~0.3wt.%.
6. the preparation method according to claim 2 that stable strengthening foam system is cooperateed with based on graphite oxide particle,
It is characterized in that, in the step 2, the condition of stirring is 25 DEG C -30 DEG C of temperature, time 0.5-1h.
7. the preparation method according to claim 2 that stable strengthening foam system is cooperateed with based on graphite oxide particle,
It is characterized in that, in the step 2, compounding the contact angle of sheet graphite oxide and water in dispersion liquid is 80 °~90 °.
8. the preparation method according to claim 2 that stable strengthening foam system is cooperateed with based on graphite oxide particle,
It is characterized in that, in the step 3, stirred 3 minutes in Waring Blender method with the speed of 8000rpm, gas source is air, nitrogen
Gas or carbon dioxide gas.
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| CN109456747A (en) * | 2018-10-29 | 2019-03-12 | 中国石油大学(华东) | The production system and method for the high stability foam of graphitiferous particle |
| CN109439307B (en) * | 2018-11-30 | 2020-06-16 | 中国石油大学(北京) | Graphene armor reinforced foam system for oil and gas fields and preparation method thereof |
| CN110699057A (en) * | 2019-09-27 | 2020-01-17 | 中国石油化工股份有限公司 | Temperature-resistant high-strength foam system with synergistic lamellar nano-particles and preparation method thereof |
| CN111154473B (en) * | 2020-01-14 | 2022-04-08 | 北京勃兴石油科技有限公司 | Blockage removal oil displacement agent and preparation method and application thereof |
| CN116102335B (en) * | 2023-04-13 | 2023-07-18 | 天津冶建特种材料有限公司 | Foaming composition, purple clay pug and preparation method thereof |
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| CN107556997A (en) * | 2017-08-30 | 2018-01-09 | 长江大学 | Enhanced low interfacial tension foam system of nano-particle and preparation method thereof |
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