CN116254102B - Molybdenum-based nano surfactant for fracturing oil displacement and preparation method thereof - Google Patents
Molybdenum-based nano surfactant for fracturing oil displacement and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of petroleum exploitation, and particularly relates to a molybdenum-based nano surfactant for fracturing oil displacement and a preparation method thereof. The preparation method comprises the following steps: sequentially adding N, N' -diallyl-L-tartaric acid diamine, 1-vinyl-3-ethylimidazole bromide, allyl alcohol polyoxyethylene ether, methacryloyl ethyl sulfobetaine and deionized water into a reactor, uniformly stirring, and transferring part of the mixture to a first high-level dropwise adding groove; adding nano molybdenum disulfide into a reactor, then adding allylpentafluorobenzene, tx-10, sodium dodecyl sulfate and buffer salt, heating and regulating pH; and adding an initiator solution into the second high-level dropwise adding groove, preserving heat, stirring to form a polymer with high viscosity, and cooling to below 40 ℃ to obtain a product. The molybdenum-based nano surfactant has the advantages of simple synthesis, high surface activity, high apparent viscosity and strong shearing force resistance.
Description
Technical Field
The invention belongs to the technical field of petroleum exploitation, and particularly relates to a molybdenum-based nano surfactant for fracturing oil displacement and a preparation method thereof.
Background
Most of domestic oil fields enter the middle and later stages of water injection development, and injected water is easy to break through along a high permeable layer and wash out due to the heterogeneity of the oil reservoirs, so that the permeability of the high permeable layer is further improved, the heterogeneity of the oil reservoirs is further enlarged, a large amount of water is discharged from the oil wells, the productivity is reduced, and the economic benefit is poor. Low-permeability and ultra-low-permeability reservoirs gradually become the main body for the output take over of oil field companies, and development has certain difficulty due to factors such as low pressure, low permeability, imperfect development of natural cracks and the like of the low-permeability reservoirs.
The fracturing oil displacement is a reservoir transformation technology widely applied in the development process of oil and gas fields, and can artificially form cracks with high diversion capacity around a shaft, improve the flowing environment of oil in the ground, slow down layers and improve the oil layer utilization condition, reduce the seepage resistance of fluid near the shaft, increase the oil drainage area of the oil and gas well and improve the oil and gas well yield. The quality of the oil displacement agent is critical to the oil displacement effect of fracturing.
The nano oil displacement agent is an emerging oil extraction technology and is a major breakthrough of the nano technology in oilfield application. The nano-material is synthesized by complex reaction, aqueous solution is used as a transmission medium, small particles of hundreds to tens or even a few nanometers are formed in water, the nano-material has good interfacial activity, the wettability of rock is reversed, capillary resistance and injection pressure are reduced, crude oil is easily peeled off and is displaced by displacement fluid, and thus the oil and gas recovery ratio is improved. The nano particles have high specific surface area and stable ultralow interfacial tension at the oil-water interface under the condition of low mass concentration. The nano particles can effectively reduce the concentration of critical glue beams, so that the solubilizing capability of the nano particles and an oil phase is increased, and the crude oil in the reservoir forms stable emulsion. The emulsification can improve the mobility of the residual oil, and the emulsion has a certain resistance coefficient and can improve the sweep coefficient of the fluid. Meanwhile, the nano oil displacement agent has a temporary blocking effect on micro pores of stratum rock, and can expand the swept volume, so that the recovery ratio can be greatly improved.
CN101857801B discloses a nano oil displacement agent and a preparation method thereof, which is prepared from 0.5-3% of alkali, 1-5% of polysilicone nano material, 1-5% of surfactant, 0.5-5% of polymer and the balance of water according to mass percent. The nano oil displacement agent has the advantages of reasonable formula, simple process, safety, environmental protection and low price, and can obviously improve the oil displacement efficiency of tertiary oil recovery. However, strong alkali such as potassium hydroxide, sodium carbonate and the like is used in the formula, and many components of the extracted crude oil are saponified, so that many difficulties are brought to subsequent crude oil smelting and processing.
CN107109203a discloses a hydraulic fracturing fluid for oilfield applications comprising a spherical bead-forming liquid composition characterized by a primary liquid precursor characterized by a micelle-forming surfactant, a bead-forming compound, and a solid-free liquid solvent; and the secondary liquid precursor is characterized by one or more curing agents and one or more co-curing agents. But the particle size of the product is between 0.1mm and 30mm, the volume is larger, the product cannot enter smaller pore throats, and the fracturing effect is limited to a certain extent.
Disclosure of Invention
The invention provides a molybdenum-based nano surfactant for fracturing oil displacement and a preparation method thereof, aiming at the defects of the prior art. The molybdenum-based nano surfactant has the advantages of simple synthesis, high surface activity, high apparent viscosity and strong shearing force resistance, the apparent viscosity reaches more than 300mPa ∙ s at 2000mg/L, and the viscosity retention rate reaches more than 96%.
The invention discloses a molybdenum-based nano surfactant for fracturing oil displacement, which comprises the following inorganic components and organic components in percentage by mass: 5-10, wherein the inorganic component is nano molybdenum disulfide, and the molecular structural formula of the organic component is as follows:
wherein:
a=500-10000；
b=2000-40000；
c=1000-20000；
d=1000-20000；
e=500-10000；
f=500-10000；
g=2000-40000；
h=1000-20000；
i=1000-20000；
j=500-10000；
m=2-50。
the organic component had a viscosity average molecular weight of 20000000-40000000.
The invention further discloses a preparation method of the molybdenum-based nano surfactant for fracturing oil displacement, which comprises the following specific steps:
(1) Purging the reactor and the pipeline for 5-8min by nitrogen, keeping nitrogen environment all the time in the later synthesis process, sequentially adding N, N' -diallyl-L-diamine tartrate, 1-vinyl-3-ethylimidazole bromide, allyl alcohol polyoxyethylene ether, methacryloyl ethyl sulfobetaine and deionized water into the reactor, uniformly stirring, adjusting pH to 7-8 by using 1mol/L sodium hydroxide solution, and transferring 70-90% of the weight of the mixed solution into a first high-level dropwise adding groove;
(2) Adding deionized water and nano molybdenum disulfide into a reactor, stirring at a high speed of 1200-1300rpm for 5-10min, reducing the rotating speed to 200-250rpm, keeping the molybdenum disulfide in a suspension state, sequentially adding allylpentafluorobenzene, tx-10 (nonylphenol polyoxyethylene ether), sodium dodecyl sulfate and buffer salt, increasing the rotating speed to 1200-1500rpm, stirring at a high speed for 20-25min, enabling substances in the reactor to be uniform and integrated, reducing the rotating speed to 200-300rpm, heating to 50-60 ℃, and adjusting the pH value to 7-8 by using 1mol/L sodium hydroxide solution;
(3) Adding an initiator solution into a second high-level dropwise adding tank, simultaneously dropwise adding liquid into the reactor in the first high-level dropwise adding tank and the second high-level dropwise adding tank in a stirring state, keeping the temperature for 20-30min after the liquid in the second high-level dropwise adding tank is delayed from the liquid in the first high-level dropwise adding tank is completely added, continuously keeping the temperature for 20-30min, then heating to 80-90 ℃, continuously stirring for 60-120min to form a high-viscosity polymer, regulating the pH value to 7-8 by using 10wt% ammonia water, and cooling to below 40 ℃ to obtain the molybdenum-based nano surfactant.
In the present invention, it is preferable that the N, N' -diallyl-L-tartaric acid diamine, 1-vinyl-3-ethylimidazole bromide, allyl alcohol polyoxyethylene ether, and methacryloyl ethyl sulfobetaine are used in an amount of 0.1 to 0.4 mole parts, 0.2 to 0.8 mole parts, and 0.1 to 0.4 mole parts, respectively, based on 1 mole part of allylpentafluorobenzene.
In the present invention, preferably, the weight ratio of deionized water to allylpentafluorobenzene in step (1) is 3 to 4:1.
in the invention, preferably, the weight ratio of deionized water, nano molybdenum disulfide, tx-10, sodium dodecyl sulfate, buffer salt and allylpentafluorobenzene in the step (2) is 5-6:0.2-0.5:0.1-0.2:0.05-0.1:0.1-0.2:1.
preferably, the buffer salt in the step (2) is one of sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate and diammonium hydrogen phosphate; more preferably, the buffer salt is one of sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium dihydrogen phosphate.
In the present invention, preferably, the initiator in step (3) is an azo compound or a redox system, and the weight ratio of the initiator to allylpentafluorobenzene is 0.15 to 0.3:1.
more preferably, the azo compound is azobisisobutyronitrile or azobisisoheptonitrile.
More preferably, the redox system is a mixture of persulfate and sulfite, wherein the mass ratio of persulfate to sulfite is 1.5-3:1.
more preferably, the persulfate is one of potassium persulfate, sodium persulfate and ammonium persulfate.
More preferably, the sulfite is one of sodium sulfite, potassium sulfite and ammonium sulfite.
The reaction equation for synthesizing the molybdenum-based nano surfactant is as follows:
the inorganic component in the molybdenum-based nano surfactant is nano molybdenum disulfide, so that on one hand, the strength of the whole system can be greatly improved, the fracturing effect is improved, and on the other hand, the organic component can be attached to the surface of the molybdenum-based nano surfactant to enter a hypotonic pore canal, and the recovery ratio is improved.
The organic component in the molybdenum-based nano surfactant is a five-membered high polymer taking N, N' -diallyl-L-tartaric acid diamine, 1-vinyl-3-ethylimidazole bromide, allyl alcohol polyoxyethylene ether, methacryloyl ethyl sulfobetaine and allyl pentafluorobenzene as monomers. The 1-vinyl-3-ethylimidazole bromine salt, the allyl alcohol polyoxyethylene ether and the methacryloyl ethyl sulfobetaine are cationic, nonionic and betaine, have higher interfacial activity, can reduce the interfacial tension of the whole system, have less damage to crack diversion, can emulsify crude oil with different components, and improve recovery ratio; the N, N' -diallyl-L-tartaric acid diamine and the allyl alcohol polyoxyethylene ether have a large number of hydroxyl groups in the molecule, have good water absorption, can greatly improve the volume of the product after water absorption, and improve the blockage wave volume of the fracturing fluid; the allyl pentafluorobenzene can increase the lipophilicity of the rock, increase the flow resistance of water and improve the fracturing effect; the allylpentafluorobenzene can also improve the rigid structure of molecules and the shearing resistance of the system; the N, N' -diallyl L-tartaric acid diamine belongs to a cross-linking agent, so that the whole molecule is changed from a one-dimensional linear structure into a two-dimensional and three-dimensional network structure, the molecular weight is greatly increased, the swept volume is increased, and the blocking capacity is improved; the tx-10 and the sodium dodecyl sulfate belong to nonionic and anionic surfactants, so that on one hand, the polymerization quality and the uniformity can be improved, the molecular weight of a polymer can be increased, on the other hand, the hydrophobic section of a soaked stratum can be facilitated to improve the blocking rate, and meanwhile, the later flowback of the fracturing fluid can be facilitated.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The molybdenum-based nano surfactant has simple synthesis process and easily obtained raw materials;
(2) The molybdenum-based nano surfactant has higher interfacial activity, the concentration of 200mg/L can reduce the surface tension to below 25mN/m, and the interfacial tension can be reduced to 0.5X10 -3 mN/m or less;
(3) The molybdenum-based nano surfactant has stronger apparent viscosity, and the concentration of 2000mg/L reaches more than 300mPa ∙ s;
(4) The molybdenum-based nano surfactant has higher shearing resistance, and the viscosity retention rate reaches more than 96%.
Drawings
FIG. 1 is a graph showing the infrared spectrum of the molybdenum-based nano surfactant G.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Example 1 (1) the reactor and the line were purged with nitrogen for 5min, and a nitrogen atmosphere was maintained throughout the post synthesis. 0.1mol of N, N' -diallyl-L-tartaric acid diamine, 0.4mol of 1-vinyl-3-ethylimidazole bromide, 0.4mol of allyl alcohol polyoxyethylene ether, 0.22mol of methacryloyl ethyl sulfobetaine and 832g of deionized water are sequentially added into a reactor, uniformly stirred, the pH value is regulated to 7-8 by using 1mol/L of sodium hydroxide solution, and 70% of the weight of the mixed solution is transferred into a first high-level dropwise adding groove.
(2) Adding 1040g of deionized water and 41.6g of nano molybdenum disulfide into a reactor, stirring at a high speed for 5min at a rotating speed of 1200rpm, reducing the rotating speed to 200rpm, keeping the molybdenum disulfide in a suspended state, sequentially adding 1mol of allylpentafluorobenzene, 20.8g tx-10, 20.8g sodium dodecyl sulfate and 32.4g sodium dihydrogen phosphate, increasing the rotating speed to 1200rpm, stirring at a high speed for 20min, enabling substances in the reactor to be uniform and integral, reducing the rotating speed to 200rpm, heating to 60 ℃, and adjusting the pH to 7-8 by using a sodium hydroxide solution of 1 mol/L;
(3) Adding an initiator solution into a second high-level dropwise adding groove, wherein the initiator is 31.2g of azodiisobutyronitrile and is dissolved in 180g of methanol, simultaneously dropwise adding liquid into the reactor in the first high-level dropwise adding groove and the second high-level dropwise adding groove in a stirring state, keeping the temperature for 30min after the second high-level dropwise adding groove is dropwise added after 20min of the liquid in the first high-level dropwise adding groove is dropwise added, heating to 83 ℃, continuously stirring for 60min to form a high-viscosity polymer, regulating the pH value to 7-8 by using 10wt% ammonia water, and cooling to below 40 ℃ to obtain the molybdenum-based nano surfactant A.
Example 2 (1) the reactor and the line were purged with nitrogen for 6min, and a nitrogen atmosphere was maintained throughout the post synthesis. 0.15mol of N, N' -diallyl-L-tartaric acid diamine, 0.35mol of 1-vinyl-3-ethylimidazole bromide, 0.38mol of allyl alcohol polyoxyethylene ether, 0.15mol of methacryloyl ethyl sulfobetaine and 724g of deionized water are sequentially added into a reactor, uniformly stirred, the pH value is regulated to 7-8 by using 1mol/L of sodium hydroxide solution, and 90% of the weight of the mixed solution is transferred into a first high-level dropwise adding groove.
(2) Adding 1180g of deionized water and 53.5g of nano molybdenum disulfide into a reactor, stirring at a high speed for 10min at a rotating speed of 1300rpm, reducing the rotating speed to 220rpm, keeping the molybdenum disulfide in a suspended state, sequentially adding 1mol of allylpentafluorobenzene, 30.3g tx-10, 10.4g sodium dodecyl sulfate and 41.6g sodium dihydrogen phosphate, increasing the rotating speed to 1500rpm, stirring at a high speed for 25min, enabling substances in the reactor to be uniform and integral, reducing the rotating speed to 300rpm, heating to 50 ℃, and adjusting the pH to 7-8 by using 1mol/L sodium hydroxide solution;
(3) Adding an initiator solution into a second high-level dropwise adding tank, wherein the initiator is 43.3g of azodiisobutyronitrile dissolved in 223g of methanol, simultaneously dropwise adding liquid into the reactor in the first high-level dropwise adding tank and the second high-level dropwise adding tank under the stirring state, keeping the temperature for 20min after the second high-level dropwise adding tank is dropwise added after the liquid in the first high-level dropwise adding tank is lagged for 30min, heating to 88 ℃, continuing stirring for 120min to form a high-viscosity polymer, regulating the pH value to 7-8 by using 10wt% ammonia water, and cooling to below 40 ℃ to obtain the molybdenum-based nano surfactant B.
Example 3 (1) the reactor and the line were purged with nitrogen for 8min, and a nitrogen atmosphere was maintained throughout the post synthesis. 0.2mol of N, N' -diallyl-L-tartaric acid diamine, 0.2mol of 1-vinyl-3-ethylimidazole bromide, 0.7mol of allyl alcohol polyoxyethylene ether, 0.1mol of methacryloyl ethyl sulfobetaine and 699g of deionized water are sequentially added into a reactor, uniformly stirred, the pH value is regulated to 7-8 by using 1mol/L of sodium hydroxide solution, and 80% of the weight of the mixed solution is transferred into a first high-level dropwise adding groove.
(2) Adding 1248g of deionized water and 61.6g of nano molybdenum disulfide into a reactor, stirring at a high speed for 6min at a rotating speed of 1250rpm, reducing the rotating speed to 210rpm, keeping the molybdenum disulfide in a suspended state, sequentially adding 1mol of allylpentafluorobenzene, 41.6g tx-10, 13.3g sodium dodecyl sulfate and 20.8g potassium dihydrogen phosphate, increasing the rotating speed to 1300rpm, stirring at a high speed for 21min, enabling substances in the reactor to be uniform and integral, reducing the rotating speed to 250rpm, heating to 58 ℃, and adjusting the pH to 7-8 by using 1mol/L sodium hydroxide solution;
(3) Adding an initiator solution into a second high-level dropwise adding tank, wherein the initiator is 52.5g of azodiisoheptanenitrile dissolved in 267g of methanol, dropwise adding liquid into the reactor simultaneously by the first high-level dropwise adding tank and the second high-level dropwise adding tank under the stirring state, keeping the temperature for 20min after the second high-level dropwise adding tank is dropwise added after the liquid is lagged by 25min from the liquid in the first high-level dropwise adding tank, heating to 86 ℃, continuing stirring for 90min to form a high-viscosity polymer, regulating the pH value to 7-8 by 10wt% ammonia water, and cooling to below 40 ℃ to obtain the molybdenum-based nano surfactant C.
Example 4 (1) the reactor and the line were purged with nitrogen for 7min, maintaining a nitrogen atmosphere throughout the post synthesis. 0.25mol of N, N' -diallyl-L-tartaric acid diamine, 0.71mol of 1-vinyl-3-ethylimidazole bromide, 0.2mol of allyl alcohol polyoxyethylene ether, 0.4mol of methacryloyl ethyl sulfobetaine and 624g of deionized water are sequentially added into a reactor, uniformly stirred, the pH value is regulated to 7-8 by using 1mol/L of sodium hydroxide solution, and 75% of the weight of the mixed solution is transferred into a first high-level dropwise adding groove.
(2) Adding 1171g of deionized water and 72.8g of nano molybdenum disulfide into a reactor, stirring at a high speed for 8min at a rotating speed of 1300rpm, reducing the rotating speed to 230rpm, keeping the molybdenum disulfide in a suspended state, sequentially adding 1mol of allylpentafluorobenzene, 37.6g tx-10, 15.8g of sodium dodecyl sulfate and 25.8g of ammonium dihydrogen phosphate, increasing the rotating speed to 1400rpm, stirring at a high speed for 23min, enabling substances in the reactor to be uniform and integral, reducing the rotating speed to 220rpm, heating to 52 ℃, and adjusting the pH to 7-8 by using a sodium hydroxide solution of 1 mol/L;
(3) Adding an initiator solution into a second high-level dropwise adding tank, wherein the initiator is 30.3g of ammonium persulfate and 20.2g of sodium sulfite, dissolving 252g of deionized water, dropwise adding liquid into the reactor simultaneously in the first high-level dropwise adding tank and the second high-level dropwise adding tank in a stirring state, keeping the temperature for 25min after the second high-level dropwise adding tank is dropwise added after the liquid in the first high-level dropwise adding tank is lagged for 20min, heating to 82 ℃, continuing stirring for 70min, forming a high-viscosity polymer, regulating pH to 7-8 by 10wt% of ammonia water, and cooling to below 40 ℃ to obtain the molybdenum-based nano surfactant D.
Example 5 (1) the reactor and piping were purged with nitrogen for 5min, maintaining a nitrogen atmosphere throughout the post synthesis. 0.3mol of N, N' -diallyl-L-tartaric acid diamine, 0.8mol of 1-vinyl-3-ethylimidazole bromide, 0.32mol of allyl alcohol polyoxyethylene ether, 0.25mol of methacryloyl ethyl sulfobetaine and 655g of deionized water are sequentially added into a reactor, uniformly stirred, the pH value is regulated to 7-8 by using 1mol/L of sodium hydroxide solution, and 85% of the weight of the mixed solution is transferred into a first high-level dropwise adding groove.
(2) Adding 1048g of deionized water and 88.6g of nano molybdenum disulfide into a reactor, stirring at a high speed for 7min at a rotating speed of 1220rpm, reducing the rotating speed to 250rpm, keeping the molybdenum disulfide in a suspended state, sequentially adding 1mol of allylpentafluorobenzene, 29.9g tx-10, 16.6g of sodium dodecyl sulfate and 33.2g of disodium hydrogen phosphate, increasing the rotating speed to 1300rpm, stirring at a high speed for 25min, enabling substances in the reactor to be uniform and integral, reducing the rotating speed to 280rpm, heating to 55 ℃, and adjusting the pH to 7-8 by using 1mol/L of sodium hydroxide solution;
(3) And adding an initiator solution into a second high-level dropwise adding tank, wherein the initiator is 35.3g of sodium persulfate and 18.4g of potassium sulfite, dissolving in 272g of deionized water, simultaneously dropwise adding liquid into the reactor in the first high-level dropwise adding tank and the second high-level dropwise adding tank in a stirring state, keeping the temperature for 22min after the second high-level dropwise adding tank is dropwise added with liquid which is delayed by 30min from the liquid in the first high-level dropwise adding tank, heating to 85 ℃, continuously stirring for 80min to form a high-viscosity polymer, regulating the pH value to 7-8 by using 10wt% of ammonia water, and cooling to below 40 ℃ to obtain the molybdenum-based nano surfactant E.
Example 6 (1) the reactor and piping were purged with nitrogen for 6min, maintaining a nitrogen atmosphere throughout the post synthesis. 0.35mol of N, N' -diallyl-L-tartaric acid diamine, 0.56mol of 1-vinyl-3-ethylimidazole bromide, 0.75mol of allyl alcohol polyoxyethylene ether, 0.3mol of methacryloyl ethyl sulfobetaine and 641g of deionized water are sequentially added into a reactor, uniformly stirred, the pH value is regulated to 7-8 by using 1mol/L of sodium hydroxide solution, and 80% of the weight of the mixed solution is transferred into a first high-level dropwise adding groove.
(2) 1075g of deionized water and 91.3g of nano molybdenum disulfide are added into a reactor, the mixture is stirred at a high speed for 9 minutes at a rotating speed of 1280rpm, the rotating speed is reduced to 240rpm, the molybdenum disulfide is kept in a suspended state, 1mol of allylpentafluorobenzene, 32.5g tx-10, 18.2g of sodium dodecyl sulfate and 37.8g of dipotassium hydrogen phosphate are sequentially added, the rotating speed is increased to 1500rpm, the mixture is stirred at a high speed for 23 minutes, the substances in the reactor are made into a uniform whole, the rotating speed is reduced to 300rpm, the mixture is heated to 50 ℃, and the pH value is regulated to 7-8 by using 1mol/L of sodium hydroxide solution;
(3) And adding an initiator solution into a second high-level dropwise adding tank, wherein the initiator is 31.2g of potassium persulfate and 10.4g of ammonium sulfite, dissolving in 262g of deionized water, simultaneously dropwise adding liquid into the reactor in the first high-level dropwise adding tank and the second high-level dropwise adding tank in a stirring state, keeping the temperature for 28min after the second high-level dropwise adding tank is dropwise added after the liquid in the first high-level dropwise adding tank is lagged for 22min, heating to 80 ℃, continuously stirring for 110min to form a high-viscosity polymer, regulating the pH value to 7-8 by 10wt% of ammonia water, and cooling to below 40 ℃ to obtain the molybdenum-based nano surfactant F.
Example 7 (1) the reactor and the line were purged with nitrogen for 8min, and a nitrogen atmosphere was maintained throughout the post synthesis. 0.4mol of N, N' -diallyl-L-tartaric acid diamine, 0.62mol of 1-vinyl-3-ethylimidazole bromide, 0.8mol of allyl alcohol polyoxyethylene ether, 0.35mol of methacryloyl ethyl sulfobetaine and 665g of deionized water are sequentially added into a reactor, uniformly stirred, the pH value is regulated to 7-8 by using 1mol/L of sodium hydroxide solution, and 78% of the weight of the mixed solution is transferred into a first high-level dropwise adding groove.
(2) 1110g of deionized water and 104g of nano molybdenum disulfide are added into a reactor, stirring is carried out for 5 minutes at a high speed at a rotating speed of 1230rpm, the rotating speed is reduced to 220rpm, the molybdenum disulfide is kept in a suspended state, 1mol of allylpentafluorobenzene, 41.6g tx-10, 14.3g of sodium dodecyl sulfate and 37.8g of diammonium hydrogen phosphate are sequentially added, the rotating speed is increased to 1300rpm, stirring is carried out for 24 minutes at a high speed, substances in the reactor become a uniform whole, the rotating speed is reduced to 260rpm, heating is carried out to 60 ℃, and pH is regulated to 7-8 by 1mol/L of sodium hydroxide solution;
(3) Adding an initiator solution into a second high-level dropwise adding tank, wherein the initiator is 41.6G of ammonium persulfate and 20.8G of sodium sulfite, dissolving 298G of deionized water, dropwise adding liquid into a reactor simultaneously in the first high-level dropwise adding tank and the second high-level dropwise adding tank in a stirring state, keeping the temperature for 26 minutes after the second high-level dropwise adding tank is dropwise added with the liquid which is lagged by 26 minutes compared with the liquid in the first high-level dropwise adding tank, heating to 90 ℃, continuously stirring for 100 minutes, forming a high-viscosity polymer, regulating pH to 7-8 by 10wt% of ammonia water, and cooling to below 40 ℃ to obtain the molybdenum-based nano surfactant G.
Example 8 testing of surface tension and interfacial tension
The present invention was prepared with tap water to a concentration of 200mg/L, and the surface tension and interfacial tension were measured with reference to SY/T5370-2018, surface and interfacial tension measurement method. The PAM for oil displacement of Shandong Dongying Bao environmental engineering Co., ltd was used as a comparative sample, and the test results are shown in Table 1.
As can be seen from table 1:
(1) The surface tension of the molybdenum-based nano surfactant A-G is lower than 25mN/m when the concentration is 200 mg/L; wherein D has a surface tension of at least 24mN/m; the surface tension of PAM for oil displacement of the Shandong Dongying Bao environmental engineering Co., ltd is 40.1mN/m;
(2) The interfacial tension of the molybdenum-based nano surfactant A-G is lower than 0.5X10 when the concentration is 200mg/L -3 mN/m; wherein G has an interfacial tension of at least 0.35×10 -5 mN/m; and the interfacial tension of PAM for oil displacement of the contrast product Shandong Dongying Bao environmental engineering Co., ltd is 5600mN/m.
Example 9 apparent viscosity test
The present invention was prepared with tap water in a 2000mg/L concentration solution and the apparent viscosity was measured with a Hark rheometer at 60 ℃. The PAM for oil displacement of Shandong Dongying Bao environmental engineering Co., ltd was used as a comparative sample, and the test results are shown in Table 1.
As can be seen from table 1: the apparent viscosity of the molybdenum-based nano surfactant A-G is more than 300mPa.s when the concentration is 2000 mg/L; wherein the apparent viscosity of C is up to 315 Pa.s; the apparent viscosity of PAM for oil displacement of the Shandong Dongying Bao environmental engineering Co., ltd is 55mPa.s, which is obviously lower than that of the invention.
Example 10 shear resistance test
The sample of example 9 was subjected to a temperature of 60℃and 170S - Continuously shearing for 2 hours under the condition of (2) and testing apparent viscosity to calculate the viscosity retention rate. The PAM for oil displacement of Shandong Dongying Bao environmental engineering Co., ltd was used as a comparative sample, and the test results are shown in Table 1.
TABLE 1 results of surface tension, interfacial tension, apparent viscosity, shear resistance test
As can be seen from table 1: the viscosity retention rate of the molybdenum-based nano surfactant A-G is greater than 96%; wherein the viscosity retention of F reaches 97.6%; the viscosity retention rate of PAM for oil displacement of the Shandong Dongying Bao environmental engineering Co., ltd is 78.2%, which is obviously lower than that of the invention.
Example 11 characterization by Infrared Spectroscopy
Product G was characterized by infrared spectroscopy and the results are shown in fig. 1.
In FIG. 1, 3480cm -1 Is the N-H bond stretching vibration absorption peak of amide in N, N' -diallyl-L-tartaric acid diamine; 2960cm -1 And 2858cm -1 Is a saturated C-H bond stretching vibration absorption peak existing in a large amount in the molecule; 1390cm -1 Is the-OH bond flexural vibration absorption peak of amide in N, N' -diallyl-L-tartaric acid diamine; 1135cm -1 Is C-O-C bond stretching vibration absorption peak of allyl alcohol polyoxyethylene ether; 980cm -1 Is the C-N bond stretching vibration absorption peak in the quaternary ammonium salt.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The molybdenum-based nano surfactant for fracturing oil displacement is characterized by comprising inorganic components and organic components according to a mass ratio of 1:5-10, wherein the inorganic component is nano molybdenum disulfide, and the molecular structural formula of the organic component is as follows:
，
wherein:
a=500-10000；
b=2000-40000；
c=1000-20000；
d=1000-20000；
e=500-10000；
f=500-10000；
g=2000-40000；
h=1000-20000；
i=1000-20000；
j=500-10000；
m=2-50。
2. the molybdenum-based nano surfactant for fracturing and flooding of claim 1, wherein the organic component has a viscosity average molecular weight of 20000000-40000000.
3. The preparation method of the molybdenum-based nano surfactant for fracturing oil displacement is characterized by comprising the following specific steps of:
(1) Purging the reactor and the pipeline for 5-8min by nitrogen, keeping nitrogen environment all the time in the later synthesis process, sequentially adding N, N' -diallyl-L-diamine tartrate, 1-vinyl-3-ethylimidazole bromide, allyl alcohol polyoxyethylene ether, methacryloyl ethyl sulfobetaine and deionized water into the reactor, uniformly stirring, adjusting pH to 7-8 by using 1mol/L sodium hydroxide solution, and transferring 70-90% of the weight of the mixed solution into a first high-level dropwise adding groove;
(2) Adding deionized water and nano molybdenum disulfide into a reactor, stirring at a high speed of 1200-1300rpm for 5-10min, reducing the rotating speed to 200-250rpm, keeping the molybdenum disulfide in a suspension state, sequentially adding allylpentafluorobenzene, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate and buffer salt, increasing the rotating speed to 1200-1500rpm, stirring at a high speed for 20-25min, enabling substances in the reactor to become a uniform whole, reducing the rotating speed to 200-300rpm, heating to 50-60 ℃, and adjusting the pH to 7-8 by using 1mol/L sodium hydroxide solution;
(3) Adding an initiator solution into a second high-level dropwise adding tank, simultaneously dropwise adding liquid into the reactor in the first high-level dropwise adding tank and the second high-level dropwise adding tank in a stirring state, keeping the temperature for 20-30min after the liquid in the second high-level dropwise adding tank is delayed from the liquid in the first high-level dropwise adding tank is completely added, continuously keeping the temperature for 20-30min, then heating to 80-90 ℃, continuously stirring for 60-120min to form a high-viscosity polymer, regulating the pH value to 7-8 by using 10wt% ammonia water, and cooling to below 40 ℃ to obtain the molybdenum-based nano surfactant.
4. The method for preparing a molybdenum-based nano surfactant for fracturing and flooding according to claim 3, wherein the dosages of the N, N' -diallyl-L-tartaric acid diamine, the 1-vinyl-3-ethylimidazole bromide, the allyl alcohol polyoxyethylene ether and the methacryloyl ethyl sulfobetaine are respectively 0.1-0.4 mole parts, 0.2-0.8 mole parts and 0.1-0.4 mole parts based on 1 mole part of allylpentafluorobenzene.
5. The method for preparing the molybdenum-based nano surfactant for fracturing and flooding, which is characterized in that the weight ratio of deionized water, nano molybdenum disulfide, polyoxyethylene nonylphenol ether, sodium dodecyl sulfate, buffer salt and allylpentafluorobenzene in the step (2) is 5-6:0.2-0.5:0.1-0.2:0.05-0.1:0.1-0.2:1.
6. the method for preparing the molybdenum-based nano surfactant for fracturing and flooding of claim 3, wherein the buffer salt in the step (2) is one of sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate and diammonium hydrogen phosphate.
7. The method for preparing the molybdenum-based nano surfactant for fracturing and flooding, according to claim 3, wherein the initiator in the step (3) is an azo compound or a redox system, and the weight ratio of the initiator to allylpentafluorobenzene is 0.15-0.3:1.
8. the preparation method of the molybdenum-based nano surfactant for fracturing and flooding, which is characterized in that the azo compound is azobisisobutyronitrile or azobisisoheptonitrile, the redox system is a mixture of persulfate and sulfite, and the mass ratio of the persulfate to the sulfite is 1.5-3:1.
9. the method for preparing the molybdenum-based nano surfactant for fracturing and flooding of claim 8, wherein the persulfate is one of potassium persulfate, sodium persulfate and ammonium persulfate.
10. The method for preparing the molybdenum-based nano surfactant for fracturing and flooding of claim 8, wherein the sulfite is one of sodium sulfite, potassium sulfite and ammonium sulfite.
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