CN101735787A - Nano material-based water-based oil field injection agent and preparation method thereof - Google Patents
Nano material-based water-based oil field injection agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nano material-based water-based oil field injection agent and a preparation method thereof. The injection agent consists of 20 to 60 weight percent of diesel oil, 30 to 70 weight percent of surfactant, 1 to 10 weight percent of nano material and 1 to 20 weight percent of auxiliary agent, wherein the nano material is one or more of nano silicon dioxide, nano titanium oxide, nano magnesium oxide and nano aluminum oxide after surface modification. The preparation method thereof comprises the following steps that: firstly, weighing the diesel oil in proportion; secondly, adding the nano material in the diesel oil; thirdly, emulsifying and dispersing the mixture in an emulsifying machine; fourthly, adding the surfactant and the auxiliary agent into the emulsified and dispersed mixture; and finally, mechanically stirring to disperse the mixture at room temperature or in a water bath to obtain stock solution of the nano water-based injection agent. The injection agent can be mixed with water at any proportion to obtain homogeneous emulsified dispersion. After the emulsified dispersion is injected in the oil field through a specific process, the water injection pressure can be obviously reduced, the amount of water injection can be increased and the oil production efficiency can be improved so as to achieve the purpose of energy conservation and injection increase.
Description
Technical field
The present invention relates to the oilfield exploitation technical field, a kind of water base oil field injection agent based on nano material that is particularly useful for low permeability oil field secondary and tertiary oil recovery and preparation method thereof.
Background technology
Utilize nanotechnology to improve the drag characteristic in duct, stratum, the purpose that can realize reducing water injection pressure, improves water injection rate, this be a kind of emerging, still be in the physics method in Exploration on mechanism stage and improve recovery efficiency technique, mainly be fit to the secondary and the tertiary recovery of low permeability oil field.2000, China Petrochemical Industry introduced the nano silicon increase water injection technology from Russia, has carried out the test in place and the application of 12 mouthfuls of wells at Shengli Oil Field and Zhongyuan Oil Field etc., has obtained success.The test-results statistics, the pressure maximum decreases by 9MPa, and the daily water-injection rate raising reaches 100m
3, step-down augmented injection effect is remarkable." long-standing " well that part is taked conventional measure weak effects such as acidifying has produced significant step-down augmented injection effect after by the well stimulation of nanometer drag reduction, and validity period is from extending to more than 6 months less than 1 month.
Nanometer step-down increase water injection technology is exactly that the hydrophobic nano powder is dispersed in the specific dispersion medium, injects zone of interest, and behind the closing well 24h, water filling drives a well.The hydrophobic nano particle is the nanometer oxide material through surface modification, and its hydrophobicity is extremely strong, and general yardstick is at 10～100nm.So far, the mechanism of nano-oxide step-down increase water injection technology does not also obtain clear understanding, and has caused the arguement in the certain limit.With oil-dissolving solvents such as diesel oil, step-down augmented injection effect gets the nod as nano material carrier's dispersion medium multiselect, but cost is higher.The present invention proposes is a kind of cheap, stable performance, the water base oil field injection agent of augmented injection obvious results nanometer and preparation method thereof, will promote the further research and development of nanometer step-down increase water injection technology.
At present some low-permeability oil deposits are faced with serious high pressure and short a difficult problem, according to incompletely statistics, mouthful water injection well surplus present domestic PetroChina Company Limited. and two major oil companies of China Petrochemical Industry nearly 4.5 ten thousand, year amount of shorting is above all places surplus 1750.The present invention is intended to utilize the property of nano material, and the flow passage of low-permeability oil deposit is carried out physically modified, forms the slippage passage with special nano-meter characteristic, and liquid flowing resistance is effectively descended, and realizes step-down augmented injection purpose.No matter this Study on Technology is that economic benefit or social benefit will be very remarkable all, simultaneously also being nanotechnology successfully combines with of petroleum engineering technology, significant.
Summary of the invention
The purpose of this invention is to provide a kind of water base oil field injection agent based on nano material and preparation method thereof, this extender can be dispersed in and form the homogeneous phase emulsified dispersed liquid in the water.After adopting special process that this emulsified dispersed liquid is injected into the oil field, can significantly reduce water injection pressure, improve water injection rate, improve produce oil efficient, reach the energy-conservation purpose that increases oil.
The technical solution used in the present invention is: this is applied to the water base extender of nanometer that low permeability oil field recovers the oil, and it is characterized in that: this extender comprises diesel oil, tensio-active agent, nano material and four kinds of components of auxiliary agent.
Each component concentration is as follows by weight percentage: diesel oil accounts for the 20wt%～60wt% of total amount, 30wt%～the 70wt% of surfactant comprise total amount, nano material accounts for the 1wt%～10wt% of total amount, and auxiliary agent accounts for the 1wt%～20wt% of total amount, and four kinds of component sums are 100wt%.
Used nano material is for through in the nano silicon of surface modification, titanium oxide, magnesium oxide, the aluminum oxide one or more in this extender, median size≤100nm, and degree of activation is greater than 95%.Nano-material surface properties-correcting agent is a kind of in lipid acid, fatty acid sodium salt, silane coupling agent, the methyl-silicone oil.
Used tensio-active agent is one or more in anion surfactant, cats product, the nonionogenic tenside in this extender.Anion surfactant is meant the alkylsulphonic acid salt anionic surfactant; Cats product is a kind of in tertiary ammonium salt, the quaternary cationic surfactant; Nonionogenic tenside is one or more in Span class, Tween class, OP class, the NP class nonionic surface active agent.
Used auxiliary agent is a kind of in ethanol, ethylene glycol, glycerol, toluene, the butyl ether in this extender.
A kind of preparation method who is used for based on the water base oil field injection agent of nano material, it is characterized in that this method has following technological process: by the proportioning of above-mentioned water base oil field injection agent based on nano material, weighing diesel oil at first, add nano material again, mulser rotating speed 3000～8000rpm, emulsification disperses 2～5min, add tensio-active agent and auxiliary agent by proportioning then, under 40～80 ℃ of room temperature or the water-baths, mechanical stirring is disperseed 10～30min, promptly obtains the water base extender stoste of nanometer.
The beneficial effect that the present invention had is: the present invention relates to a kind of water base extender of nanometer that is applicable to the low permeability oil field oil recovery and preparation method thereof, this extender emulsifying capacity is extremely strong, can mix mutually with arbitrary proportion with water, form the homogeneous phase emulsified dispersed liquid, this dispersion liquid is stable existence for a long time at room temperature.This nanometer aqueous-based dispersions has certain acid and alkali-resistance ability, can control its steady time and breakdown of emulsion time by the adjustment to prescription, reaches best result of use to cooperate different rock stratum states.The present invention utilizes the property of nano material, and the flow passage of low permeability oil field is carried out physically modified, forms the slippage passage with special nano-meter characteristic, and liquid flowing resistance is effectively descended, and realizes step-down augmented injection purpose.The water base extender of this nanometer can effectively reduce water injection pressure, improve water injection rate through shop experiment evaluation and test in place evaluation, reaches the purpose of step-down augmented injection, raising production capacity.No matter this Study on Technology is that economic benefit or social benefit will be very remarkable all, simultaneously also being nanotechnology successfully combines with of petroleum engineering technology, significant.
Description of drawings
Fig. 1 is the TEM electromicroscopic photograph of embodiment 1 described modified manometer silicon dioxide.
Fig. 2 is the TEM electromicroscopic photograph of embodiment 2 described modified manometer silicon dioxides.
Fig. 3 is the TEM electromicroscopic photograph of embodiment 4 described modified Nano titanium oxide
Fig. 4 is the contact angle photo of nano material absorption rock core sheet 4.
Fig. 5 is the SEM photo that does not pass through and pass through nano material adsorption treatment rock core sheet.
Embodiment
Below by embodiment the present invention is further specified, but protection scope of the present invention is not limited to these embodiment.
Embodiment 1
The preparation of the water base extender stoste of nanometer: take by weighing the diesel oil that accounts for total amount 40wt%, the nano silicon that adds γ-(methacryloxypropyl) propyl trimethoxy silicane modification of 2wt%, median size is about 20nm, degree of activation 〉=99%, mulser 7000rpm emulsification disperses 2min, add other tensio-active agent and auxiliary agent again, OP-10 accounts for 15wt%, Span80 and accounts for that 25wt%, sodium laurylsulfonate account for 10wt%, ethanol accounts for 8wt%, 40 ℃ of water-baths, mechanical stirring 10min promptly obtains the water base extender stoste of nanometer.
The preparation of nanometer aqueous-based dispersions: measure the 1L tap water, add the above-mentioned extender stoste of 10wt%, 15wt%, 20wt% respectively, mix, promptly obtain the nanometer aqueous-based dispersions.
The TEM electromicroscopic photograph of the nano silicon of γ-(methacryloxypropyl) propyl trimethoxy silicane modification as shown in Figure 1.
Embodiment 2
The preparation of the water base extender stoste of nanometer: take by weighing the diesel oil that accounts for total amount 40wt%, the nano silicon that adds the oleic acid modification of 2wt%, median size is about 30nm, degree of activation 〉=99.5%, mulser 7000rpm emulsification disperses 2min, adds other tensio-active agent and auxiliary agent again, petroleum sodium sulfonate accounts for 15wt%, oleic acid and accounts for that 20wt%, palmityl trimethyl ammonium chloride account for 10wt%, ethanol accounts for 13wt%, 60 ℃ of water-baths, mechanical stirring 10min promptly obtains the water base extender stoste of nanometer.
The preparation of nanometer aqueous-based dispersions is with embodiment 1.
The TEM electromicroscopic photograph of the nano silicon of oleic acid modification as shown in Figure 2.
Embodiment 3
The preparation of the water base extender stoste of nanometer: take by weighing the diesel oil that accounts for total amount 35wt%, the nano silicon that adds the dimethyl silicone oil modification of 2wt%, median size is about 50nm, degree of activation 〉=98%, mulser 4000rpm emulsification disperses 5min, adds other tensio-active agent and auxiliary agent again, and Sodium dodecylbenzene sulfonate accounts for 15wt%, oleic acid and accounts for that 15wt%, NP-10 account for 13wt%, ethylene glycol accounts for 20wt%, mechanical stirring 20min under the room temperature promptly obtains the water base extender stoste of nanometer.
The preparation of nanometer aqueous-based dispersions is with embodiment 1.
Embodiment 4
The preparation of the water base extender stoste of nanometer: take by weighing the diesel oil that accounts for total amount 35wt%, the nano-titanium oxide that adds γ-(methacryloxypropyl) propyl trimethoxy silicane modification of 5wt%, median size is about 30nm, degree of activation 〉=99.5%, mulser 4000rpm emulsification disperses 5min, add other tensio-active agent and auxiliary agent again, petroleum sodium sulfonate accounts for 15wt%, oleic acid and accounts for that 20wt%, trolamine account for 10wt%, ethylene glycol accounts for 60 ℃ of 15wt%, water-baths, mechanical stirring 20min promptly obtains the water base extender stoste of nanometer.
The preparation of nanometer aqueous-based dispersions is with embodiment 1.
The TEM electromicroscopic photograph of the nano-titanium oxide of γ-(methacryloxypropyl) propyl trimethoxy silicane modification as shown in Figure 3.
Embodiment 5
The preparation of the water base extender stoste of nanometer: take by weighing the diesel oil that accounts for total amount 40wt%, the nano magnesia that adds the oleic acid modification of 5wt%, median size is about 80nm, degree of activation 〉=98%, mulser 6000rpm emulsification disperses 3min, adds other tensio-active agent and auxiliary agent again, and Sodium dodecylbenzene sulfonate accounts for 15wt%, OP-10 and accounts for that 15wt%, Span85 account for 10wt%, butyl ether accounts for 15wt%, mechanical stirring 30min under the room temperature promptly obtains the water base extender stoste of nanometer.
The preparation of nanometer aqueous-based dispersions is with embodiment 1.
Embodiment 6
The preparation of the water base extender stoste of nanometer: take by weighing the diesel oil that accounts for total amount 35wt%, the nano-titanium oxide of the nano silicon of the dimethyl silicone oil modification of adding 2.5wt% and γ-(methacryloxypropyl) propyl trimethoxy silicane modification of 2.5wt%, median size is about 40nm, degree of activation 〉=98%, mulser 6000rpm emulsification disperses 5min, add other tensio-active agent and auxiliary agent again, petroleum sodium sulfonate accounts for 10wt%, OP-10 accounts for 15wt%, Tween60 accounts for 15wt%, butyl ether accounts for 20wt%, 40 ℃ of water-baths, mechanical stirring 30min promptly obtains the water base extender stoste of nanometer.
The preparation of nanometer aqueous-based dispersions is with embodiment 1.
The preparation of the water base extender stoste of nanometer: take by weighing the diesel oil that accounts for total amount 40wt%, add the γ-nano silicon of (methacryloxypropyl) propyl trimethoxy silicane modification of 1wt% and the nano magnesia of the oleic acid modification of 1wt%, median size is about 60nm, degree of activation 〉=98%, mulser 7000rpm emulsification disperses 2min, add other tensio-active agent and auxiliary agent again, OP-10 accounts for 15wt%, Span80 and accounts for that 25wt%, sodium laurylsulfonate account for 10wt%, ethanol accounts for 8wt%, 40 ℃ of water-baths, mechanical stirring 10min promptly obtains the water base extender stoste of nanometer.
The preparation of nanometer aqueous-based dispersions is with embodiment 1.
Embodiment 8
The preparation of the water base extender stoste of nanometer: take by weighing the diesel oil that accounts for total amount 40wt%, add the γ-nano-titanium oxide of (methacryloxypropyl) propyl trimethoxy silicane modification of 3wt% and the nano aluminium oxide of the dimethyl silicone oil modification of 2wt%, median size is about 70nm, degree of activation 〉=98%, mulser 6000rpm emulsification disperses 3min, add other tensio-active agent and auxiliary agent again, Sodium dodecylbenzene sulfonate accounts for 15wt%, OP-10 accounts for 15wt%, Span85 accounts for 10wt%, butyl ether accounts for 15wt%, mechanical stirring 30min under the room temperature promptly obtains the water base extender stoste of nanometer.
The preparation of nanometer aqueous-based dispersions is with embodiment 1.
Augmented injection effect laboratory evaluation:
The oil field rock core is to the adsorption test of the water base extender of nanometer: the nanometer aqueous-based dispersions of preparation 2g/L, the natural core of different areas is cut thin slice, and be immersed in the aqueous-based dispersions, 60 ℃, 48h.Adopt the contact angle of water droplet absorption method test nano material absorption rock core sheet, the result is as shown in table 1.The water droplet contact angle of the rock core sheet that process nanometer aqueous-based dispersions is handled is all greater than 90 °, and the maximum contact angle can reach more than 140 °, and the contact angle synoptic diagram as Fig. 4 is rock core sheet 4 shows strong-hydrophobicity.
The contact angle of table 1 rock core sheet relatively
| Numbering | Rock core 1 | Rock core 2 | Rock core 3 | Rock core 4 | Rock core 5 | Rock core 6 |
| Contact angle/° | ??126.1 | ??90.5 | ??111.8 | ??141.3 | ??104.5 | ??134.3 |
The laboratory flow test of the water base extender of nanometer: at first prepare the nanometer aqueous-based dispersions of 2g/L, under the temperature, pressure of setting, on the rock core flowing experiment instrument, measure rock core is handled front and back through the nanometer aqueous-based dispersions water phase permeability.By table 2 data as can be known, handle front and back rock core water phase permeability ratio (K through the nanometer aqueous-based dispersions
After/ K
Before) all greater than 1, illustrating that process nanometer aqueous-based dispersions processing back water phase permeability all has raising in various degree, treatment effect is tangible.Fig. 5 is the SEM photo that does not pass through and pass through the rock core sheet of nano material adsorption treatment.
The comparison of core permeability before and after table 2 nanometer aqueous-based dispersions is handled
Claims (5)
1. water base oil field injection agent based on nano material, it is characterized in that this extender comprises diesel oil, tensio-active agent, nano material and four kinds of components of auxiliary agent, wherein, diesel oil accounts for the 20wt%～60wt% of total amount, 30wt%～the 70wt% of surfactant comprise total amount, nano material accounts for the 1wt%～10wt% of total amount, and auxiliary agent accounts for the 1wt%～20wt% of total amount, and four kinds of component sums are 100wt%.
2. by the described water base oil field injection agent of claim 1 based on nano material, it is characterized in that described nano material is for through in the nano silicon of surface modification, nano-titanium oxide, nano magnesia, the nano aluminium oxide one or more, median size≤100nm, degree of activation 〉=95%; Described nano-material surface properties-correcting agent is a kind of in lipid acid, fatty acid sodium salt, silane coupling agent, the methyl-silicone oil.
3. by the described water base oil field injection agent of claim 1, it is characterized in that described tensio-active agent is one or more in anion surfactant, cats product, the nonionogenic tenside based on nano material; Described anion surfactant is the alkylsulphonic acid salt anionic surfactant, cats product is a kind of in tertiary ammonium salt, the quaternary cationic surfactant, and nonionogenic tenside is one or more in Span class, Tween class, OP class, the NP class nonionic surface active agent.
4. by the described water base oil field injection agent of claim 1, it is characterized in that described auxiliary agent is a kind of in ethanol, ethylene glycol, glycerol, toluene, the butyl ether based on nano material.
5. preparation method who is used for the described water base oil field injection agent based on nano material of claim 1, it is characterized in that this method has following technological process: by the proportioning based on the water base oil field injection agent of nano material of claim 1, weighing diesel oil at first, add nano material again, mulser rotating speed 3000～8000rpm, emulsification disperses 2～5min, add tensio-active agent and auxiliary agent by proportioning then, under 40～80 ℃ of room temperature or the water-baths, mechanical stirring is disperseed 10～30min, promptly obtains the water base extender stoste of nanometer.
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