CN113149015B - Carbon-silicon composite quantum dot solution and preparation method thereof, resistance-reducing injection-increasing agent and application - Google Patents

Carbon-silicon composite quantum dot solution and preparation method thereof, resistance-reducing injection-increasing agent and application Download PDF

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CN113149015B
CN113149015B CN202110374303.XA CN202110374303A CN113149015B CN 113149015 B CN113149015 B CN 113149015B CN 202110374303 A CN202110374303 A CN 202110374303A CN 113149015 B CN113149015 B CN 113149015B
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CN113149015A (en
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戴彩丽
曹梦娇
赵青山
吴一宁
夏争争
倪万鑫
吴文婷
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China University of Petroleum East China
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Abstract

The invention provides a carbon-silicon composite quantum dot solution, a preparation method thereof, a resistance-reducing and injection-increasing agent and application thereof, and relates to the technical field of oil displacement. The carbon-silicon composite quantum dot solution is mainly prepared from a silane coupling agent, a reducing agent, water and a pH regulator, wherein the silane coupling agent and the reducing agent can perform an oxidation-reduction reaction to form the carbon-silicon composite quantum dot, the carbon-silicon composite quantum dot can utilize a silicon atom with good structural stability and can also fully exert the electron transfer characteristic and the structural regulation and control performance of the carbon atom, so that the carbon-silicon composite quantum dot is endowed with high dispersion stability, high interface activity advantage and excellent rock near-wall surface sliding function, and meanwhile, the carbon-silicon composite quantum dot solution can be used as an anti-drag injection-increasing agent due to good water dispersibility and stability in water, and a certain foundation is provided for the subsequent application to the oil displacement field. The invention provides a drag-reducing injection-increasing agent, which comprises a carbon-silicon composite quantum dot solution.

Description

Carbon-silicon composite quantum dot solution and preparation method thereof, resistance-reducing injection-increasing agent and application
Technical Field
The invention relates to the technical field of oil displacement, in particular to a carbon-silicon composite quantum dot solution and a preparation method, a drag-reducing injection-increasing agent and application thereof.
Background
With the continuous development of economic technology in China, effective development and utilization of petrochemical resources are paid more and more attention throughout the country. As a non-renewable energy source, oil exploitation is related to economic development and strategic position of China. At present, most oil fields with better development conditions enter the middle and later stages in China, and newly-explored low-permeability/extra-low-permeability reserves exceed 80 hundred million tons, account for more than 70 percent of the total explored reserves, and are quite rich. However, the low-permeability/ultra-low-permeability reservoir in China mainly adopts continental facies deposition, and the problems of large reservoir characteristic difference, small pore throat, low porosity, poor permeability, large seepage resistance, rapid displacement pressure rise in the water injection process and the like are difficult to avoid. Therefore, how to improve the development effect of the low-permeability/ultra-low-permeability oil reservoir breaks through the current technical bottleneck and is a difficult problem that people need to overcome urgently.
The conventional drag reduction, pressure reduction and injection enhancement technologies adopted by hypotonic/ultra-hypotonic oil reservoirs comprise two major types, namely reservoir transformation, wherein the reservoir porosity is changed, the resistance of injected fluid is reduced, and the water injection quantity is increased; and secondly, the resistance of formation fluid and the rock surface is reduced through rock surface modification, and the drag reduction and injection increasing modes mainly comprise a surfactant injection increasing technology, an organic molecular film drag reduction and injection increasing technology and a nano material drag reduction and injection increasing technology. The nano material drag reduction and injection enhancement technology is used as a novel low-permeability reservoir rock surface modification technology, and solves the problems which cannot be solved or are difficult to solve by a plurality of traditional technologies in the aspects of pressure reduction and injection enhancement, profile control and plugging, molecular membrane oil displacement, catalysis and viscosity reduction and the like.
Generally, the nano material drag reduction injection enhancement technology disperses nano particles in water to prepare water-based nano injection enhancement liquid to be injected into a stratum, and the nano particles are adsorbed on the surface of a pore micro channel to change the wettability and microstructure of the inner surface of the wall of a rock pore, so that the injection pressure of subsequently injected water in the stratum is effectively reduced. The technology can effectively realize resistance reduction and flow increase and effectively reduce water injection resistance, thereby solving the problems of high injection pressure, difficult water injection and the like in the water injection process and promoting the injection-production balance. Commonly used nano SiO 2 The particles are used as a non-toxic and environment-friendly material, can effectively reduce the water flow resistance of a stratum pore canal, reduce the injection pressure, increase the injection volume, obviously increase the overall flow speed and flow, and generate obvious pressure reduction and injection increase effects. However, except for the difficulty of scale-up synthesis, the granulesThe diameter is uncontrollable, the surface modification cost is high and the like, and the nano SiO 2 The dispersion has the characteristic of large specific surface area, and the dispersion is easy to agglomerate, so that the dispersion stability in a solvent is poor; and when the device is applied on site, diesel oil is mostly adopted as a carrying medium, so that the operation cost is greatly increased, the environmental pollution is easily caused, and the risks of storage and transportation are increased. Therefore, the development of an environment-friendly water-based ultra-small-size nano material with simple and convenient preparation method, strong dispersibility and good stability can effectively promote the technical breakthrough in the pressure reduction and injection increase of the oil field.
In view of the above, the present invention is proposed to solve at least one of the above technical problems.
Disclosure of Invention
The first purpose of the invention is to provide a carbon-silicon composite quantum dot solution.
The second purpose of the invention is to provide a preparation method of the carbon-silicon composite quantum dot solution.
The third purpose of the invention is to provide a drag reduction and injection enhancement agent.
The fourth purpose of the invention is to provide the application of the carbon-silicon composite quantum dot solution in the drag reduction and injection enhancement agent.
The fifth purpose of the invention is to provide the application of the carbon-silicon composite quantum dot solution or the drag reduction and injection enhancement agent in the field of oil displacement.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a carbon-silicon composite quantum dot solution, which comprises the following raw materials:
a silane coupling agent, a reducing agent, water and a pH regulator;
wherein the mass ratio of the silane coupling agent to the reducing agent to the water is 1: (2-8): (5-10);
the mass of the pH regulator accounts for 0.01-0.1% of the total mass of the silane coupling agent, the reducing agent and the water.
Further, on the basis of the above technical solution of the present invention, the silane coupling agent includes any one or a combination of at least two of N- [3- (trimethoxysilyl) propyl ] ethylenediamine, 3-aminopropyltriethoxysilane, γ -aminopropylmethyldiethoxysilane, (3-chloropropyl) trimethoxysilane, or N- (β -aminoethyl- γ -aminopropyl) methyldimethoxysilane;
preferably, the reducing agent comprises any one of sodium ascorbate, disodium ethylene diamine tetraacetate, catechol, fructose, basic fuchsin or glucose or a combination of at least two of the sodium ascorbate, the disodium ethylene diamine tetraacetate, the catechol, the fructose, the basic fuchsin and the glucose;
preferably, the pH adjuster comprises any one of sulfuric acid, hydrochloric acid, phosphoric acid, or acetic acid, or a combination of at least two thereof.
Further, on the basis of the above technical scheme of the present invention, the mass ratio of the silane coupling agent, the reducing agent and water is 1: (3-6): (6-9);
preferably, the mass of the pH regulator accounts for 0.02-0.08% of the total mass of the silane coupling agent, the reducing agent and the water.
Further, on the basis of the technical scheme, the particle size range of the carbon-silicon composite quantum dots in the carbon-silicon composite quantum dot solution is 1-10nm.
The invention also provides a preparation method of the carbon-silicon composite quantum dot solution, which comprises the following steps:
mixing a silane coupling agent, a reducing agent and water to react at the temperature of 30-80 ℃ for 6-24h to obtain a reaction solution I;
and separating the reaction liquid I, and mixing the reaction liquid II obtained by separation with a pH regulator to enable the pH value to be 6-8, thereby obtaining the composite quantum dot solution.
Further, on the basis of the technical scheme of the invention, the reaction temperature is 40-70 ℃, and the reaction time is 8-20h.
Further, on the basis of the technical scheme of the invention, dialysis separation is adopted for separation;
preferably, the dialysis separation time is 5-10h.
The invention also provides a drag-reducing injection-increasing agent, which comprises the carbon-silicon composite quantum dot solution or the carbon-silicon composite quantum dot solution prepared by the preparation method of the carbon-silicon composite quantum dot solution.
The invention also provides the application of the carbon-silicon composite quantum dot solution in the drag reduction and injection enhancement agent.
The invention also provides the application of the carbon-silicon composite quantum dot solution or the drag reduction and injection enhancement agent in the field of oil displacement.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a carbon-silicon composite quantum dot solution which is mainly prepared from silane coupling agent, reducing agent, water and pH regulator, wherein the silane coupling agent and the reducing agent can generate oxidation-reduction reaction to form the carbon-silicon composite quantum dot, and the carbon-silicon composite quantum dot can utilize silicon atoms with good structural stability and can fully exert the electron transfer characteristic and the structural regulation and control performance of the carbon atoms, so that the carbon-silicon composite quantum dot has high dispersion stability, high interface activity advantage and excellent rock near-wall surface sliding function.
(2) The preparation method of the carbon-silicon composite quantum dot solution provided by the invention is simple and convenient in process and mild in reaction conditions, and can realize convenient large-scale preparation and structural property regulation of the carbon-silicon composite quantum dot solution.
(3) The invention provides a drag reduction and injection enhancement agent, which comprises the carbon-silicon composite quantum dot solution, and the drag reduction and injection enhancement agent has good pressure reduction and injection enhancement effects and excellent performance in the field of oil displacement in view of the advantages of the carbon-silicon composite quantum dot solution.
(4) The invention provides the application of the carbon-silicon composite quantum dot solution or the anti-drag injection-increasing agent, and the carbon-silicon composite quantum dot solution or the anti-drag injection-increasing agent has good application prospect in the field of oil displacement in view of the advantages of the carbon-silicon composite quantum dot solution or the anti-drag injection-increasing agent.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a TEM image of a carbon-silicon composite quantum dot in a carbon-silicon composite quantum dot solution provided in example 1 of the present invention;
fig. 2 is a TEM image of carbon-silicon composite quantum dots in a carbon-silicon composite quantum dot solution provided in comparative example 1 of the present invention;
fig. 3 is a distribution diagram of particle sizes of carbon-silicon composite quantum dots in a carbon-silicon composite quantum dot solution provided in example 1 of the present invention;
fig. 4 is a distribution diagram of the particle size of the carbon-silicon composite quantum dots in the carbon-silicon composite quantum dot solution provided by comparative example 1 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to a first aspect of the present invention, there is provided a carbon-silicon composite quantum dot solution comprising the following raw materials:
a silane coupling agent, a reducing agent, water and a pH regulator;
wherein the mass ratio of the silane coupling agent to the reducing agent to the water is 1: (2-8): (5-10);
the mass of the pH regulator accounts for 0.01-0.1% of the total mass of the silane coupling agent, the reducing agent and the water.
Specifically, in the present invention, "to" in "carbon-silicon composite quantum dot" means "and". The carbon-silicon composite quantum dot can be understood as a quantum dot formed by silicon-carbon hybrid composite.
The silane coupling agent is mainly used for providing a silicon source, and the reducing agent is mainly used for reducing, polycondensing and crosslinking the silane coupling agent and providing a carbon source to form the carbon-silicon composite quantum dot.
The pH regulator is mainly used for controlling the pH value so as to further realize the water dispersion stability of the silicon-carbon quantum dots and inhibit the agglomeration of the carbon-silicon composite quantum dots.
The silane coupling agent, reducing agent and water are typically, but not limited to, in a mass ratio of 1:2: 5. 1:2: 6. 1:2: 8. 1:2: 10. 1:3: 5. 1:5: 5. 1:6: 5. 1:8: 5. 1:3: 6. 1:5: 6. 1:6: 6. 1:8: 6. 1:3: 8. 1:5: 8. 1:6: 8. 1:8: 8. 1:3: 10. 1:5: 10. 1:6:10 or 1:8:10.
the mass of the pH adjuster is typically, but not limited to, 0.01%, 0.02%, 0.04%, 0.05%, 0.06%, 0.08%, or 0.1% of the total mass of the silane coupling agent, the reducing agent, and water.
The term "comprising" in the present invention means that it may include other raw materials in addition to the raw materials, which give different characteristics to the carbon-silicon composite quantum dot solution. Besides, the 'including' can be replaced by a closed 'or' composed of '8230; \8230;'.
The carbon-silicon composite quantum dot solution provided by the invention is mainly prepared from a silane coupling agent, a reducing agent, water and a pH regulator, wherein the silane coupling agent and the reducing agent can generate an oxidation-reduction reaction, namely, a large number of active groups react with the reducing agent in the solution to nucleate along with the hydrolysis of the silane coupling agent, and further accumulate and condense into carbon-silicon composite quantum dots with uniform diameters.
The different types of silane coupling agents affect the reactivity in the hydrolysis process. As an alternative embodiment of the present invention, the silane coupling agent includes any one of N- [3- (trimethoxysilyl) propyl ] ethylenediamine, 3-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, (3-chloropropyl) trimethoxysilane, or N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, or a combination of at least two thereof.
The type of the reducing agent affects the reducing ability and further affects the nucleation and growth rate. In addition, the reducing agent has different functional groups, so that the type and the hydrophilic capacity of the surface functional groups for forming the composite quantum dots are influenced to a certain extent. As an alternative embodiment of the present invention, the reducing agent includes any one of sodium ascorbate, disodium edetate, catechol, fructose, basic fuchsin or glucose or a combination of at least two of them.
As an alternative embodiment of the present invention, the pH adjusting agent includes any one of sulfuric acid, hydrochloric acid, phosphoric acid, or acetic acid, or a combination of at least two thereof.
As an alternative embodiment of the present invention, the mass ratio of the silane coupling agent, the reducing agent and water is 1: (3-6): (6-9). The silane coupling agent, reducing agent and water are typically, but not limited to, in a mass ratio of 1:3: 6. 1:4: 6. 1:5: 6. 1:6: 6. 1:3: 7. 1:3: 8. 1:3: 9. 1:4: 7. 1:4: 8. 1:4: 9. 1:5: 7. 1:5: 8. 1:5: 9. 1:6: 7. 1:6:8 or 1:6:9.
as an alternative embodiment of the present invention, the pH adjusting agent accounts for 0.02 to 0.08% by mass of the total mass of the silane coupling agent, the reducing agent and water. The pH adjuster is typically, but not limited to, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, or 0.08% by mass of the total mass of the silane coupling agent, the reducing agent, and water.
Through further limiting the using amounts of the silane coupling agent, the reducing agent, water and the pH regulator, the surface charge of the carbon-silicon composite quantum dot is changed from a protonized state to a deprotonated state, and the dispersion stability of the quantum dot is facilitated.
As an alternative embodiment of the invention, the particle size of the carbon-silicon composite quantum dots in the carbon-silicon composite quantum dot solution is in the range of 1-10nm.
Typical but non-limiting particle size ranges for carbon-silicon composite quantum dots are 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, 5nm, 5.5nm, 6nm, 6.5nm, 7nm, 7.5nm, 8nm, 8.5nm, 9nm, 9.5nm, or 10nm.
The carbon-silicon composite quantum dot solution has the advantages that the capability of changing the wettability, reducing the interfacial tension and improving the fluidity ratio of the carbon-silicon composite quantum dot solution is improved by further limiting the particle size of the carbon-silicon composite quantum dot, and the carbon-silicon composite quantum dot solution has better performance as a drag reduction and injection enhancement agent.
According to the second aspect of the present invention, there is also provided a method for preparing a carbon-silicon composite quantum dot solution, comprising the steps of:
mixing a silane coupling agent, a reducing agent and water to react at the temperature of 30-80 ℃ for 6-24h to obtain a reaction solution I;
and separating the reaction liquid I, and mixing the reaction liquid II obtained by separation with a pH regulator to enable the pH value to be 6-8, thereby obtaining the composite quantum dot solution.
And (3) carrying out an oxidation-reduction reaction on a silane coupling agent and a reducing agent under certain reaction conditions in water to generate carbon-silicon composite quantum dots, and separating the reaction solution I after the reaction is finished to remove the unreacted reducing agent in the reaction solution I. And after the reaction liquid I is subjected to separation treatment, obtaining a reaction liquid II, and adjusting the pH value of the reaction liquid II by using a pH regulator to control the pH value within a certain range, so that the uniform dispersion and stable storage of the carbon-silicon composite quantum dots in water are realized.
The reaction of the silane coupling agent and the reducing agent in water is carried out under the specific reaction conditions of the reaction temperature of 30-80 ℃ and the reaction time of 6-24h, so as to effectively control the particle size of the carbon-silicon composite quantum dots. Typical but non-limiting reaction temperatures are 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C or 80 deg.C. Typical but non-limiting reaction times are 6h, 8h, 10h, 12h, 14h, 15h, 16h, 18h, 20h, 22h or 24h.
Meanwhile, the pH value of the reaction liquid II needs to be controlled to be 6-8. If the pH value is too high (higher than 8), the particle size will continue to increase, so that the performance of the carbon-silicon composite quantum dot solution will be reduced, and if the pH value is too low (lower than 6), the composite quantum dots will agglomerate, so the pH value should be controlled within a specific value range. Typical but not limiting pH values are 6, 6.5, 7, 7.5 or 8.
The preparation method of the carbon-silicon composite quantum dot solution provided by the invention has the advantages of simple and convenient process and mild reaction conditions, and can realize convenient large-scale preparation and structural property regulation of the carbon-silicon composite quantum dot solution.
As an alternative embodiment of the invention, the reaction temperature is 40-70 ℃ and the reaction time is 8-20h.
The particle size of the carbon-silicon composite quantum dots can be further controlled by further limiting the reaction temperature and the reaction time.
As an alternative embodiment of the invention, the separation is a dialysis separation.
As an alternative embodiment of the invention, the dialysis separation is carried out for a period of 5 to 10 hours. Typical but non-limiting dialysis separation times are 5h, 6h, 7h, 8h, 9h or 10h.
By further limiting the separation mode and the time, the unreacted reducing agent is separated out, and the reaction is inhibited from continuing.
According to a third aspect of the invention, the invention also provides a drag reduction and injection enhancement agent, which comprises the carbon-silicon composite quantum dot solution or the carbon-silicon composite quantum dot solution prepared by the preparation method of the carbon-silicon composite quantum dot solution.
According to the fourth aspect of the invention, the application of the carbon-silicon composite quantum dot solution in the drag reduction and injection enhancement agent is also provided.
It should be noted that the carbon-silicon composite quantum dot solution can be directly and independently used as a resistance-reducing injection-enhancing agent, and can also be used in combination with other substances in common resistance-reducing injection-enhancing agents, but on the premise of using in combination, the substances in the other common resistance-reducing injection-enhancing agents do not have adverse effects on the performance of the carbon-silicon composite quantum dot solution.
In view of the advantages of the carbon-silicon composite quantum dot solution, the anti-drag injection-increasing agent has good pressure-reducing injection-increasing effect and excellent performance in the field of oil displacement.
According to the fifth aspect of the invention, the application of the carbon-silicon composite quantum dot solution or the drag reduction and injection enhancement agent in the field of oil displacement is also provided.
In view of the advantages of the carbon-silicon composite quantum dot solution or the anti-drag injection-increasing agent, the carbon-silicon composite quantum dot solution or the anti-drag injection-increasing agent has good application prospect in the field of oil displacement.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
The embodiment provides a carbon-silicon composite quantum dot solution, which comprises the following raw materials:
silane coupling agent (N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane), reducing agent (sodium ascorbate), water and pH regulator (phosphoric acid).
The preparation method of the carbon-silicon composite quantum dot solution comprises the following steps:
uniformly mixing 8.0g of a silane coupling agent, 16.0g of a reducing agent and 40.0g of water (according to a mass ratio of 1 to 2;
the reaction solution I is placed in a dialysis bag (molecular weight 1000) for dialysis for 6h, and then 3.2 x 10 dilute sulfuric acid is used -2 And g, adjusting the pH =7 to obtain a composite quantum dot solution.
Example 2
This example provides a carbon-silicon composite quantum dot solution, and the kind, amount and preparation method of the raw materials were the same as those of example 1 except that the kind of the silane coupling agent was replaced with (3-chloropropyl) trimethoxysilane.
Example 3
This example provides a carbon-silicon composite quantum dot solution, except that the type of silane coupling agent is replaced with N- [3- (trimethoxysilyl) propyl ] ethylenediamine, and the types, amounts and preparation methods of the raw materials are the same as those of example 1.
Example 4
This example provides a carbon-silicon composite quantum dot solution, except that the kind of the reducing agent was replaced with catechol, and the kinds, amounts and preparation methods of the raw materials were the same as those of example 1.
Example 5
This example provides a carbon-silicon composite quantum dot solution, except that the kind of the reducing agent was replaced with disodium ethylenediaminetetraacetate, and the kind, amount, and preparation method of the raw materials were the same as those of example 1.
Example 6
This example provides a carbon-silicon composite quantum dot solution, and the raw materials, kinds, and preparation methods were the same as those of example 1 except that the reaction temperature in the preparation method was changed to 50 ℃.
Example 7
This example provides a carbon-silicon composite quantum dot solution, and the raw materials, kinds, and preparation methods were the same as those of example 1 except that the reaction temperature in the preparation method was changed to 80 ℃.
Example 8
This example provides a carbon-silicon composite quantum dot solution, and the raw materials, kinds, and preparation methods were the same as example 1 except that the reaction time in the preparation method was replaced with 6 hours.
Example 9
This example provides a carbon-silicon composite quantum dot solution, and the raw materials, kinds and preparation method were the same as example 1 except that the reaction time in the preparation method was replaced with 12 hours.
Example 10
The embodiment provides a carbon-silicon composite quantum dot solution, which comprises the following raw materials:
silane coupling agent (gamma-aminopropyl methyl diethoxy silane), reducing agent (fructose), water and pH regulator (sulfuric acid).
The preparation method of the carbon-silicon composite quantum dot solution comprises the following steps:
uniformly mixing 8.0g of a silane coupling agent, 64.0g of a reducing agent and 80.0g of water (according to a mass ratio of 1;
and (3) putting the reaction liquid I into a dialysis bag (with the molecular weight of 1000) for dialysis for 6h, and then adjusting the pH to be =7 by using 0.1232g of dilute sulfuric acid to obtain a composite quantum dot solution.
Example 11
The embodiment provides a carbon-silicon composite quantum dot solution, which comprises the following raw materials:
silane coupling agent (3-aminopropyltriethoxysilane), reducing agent (glucose), water and pH regulator (acetic acid).
The preparation method of the carbon-silicon composite quantum dot solution comprises the following steps:
uniformly mixing 8.0g of a silane coupling agent, 16.0g of a reducing agent and 80.0g of water (according to a mass ratio of 1 to 2);
the reaction solution I is placed in a dialysis bag (molecular weight 1000) for dialysis for 6h, and then diluted sulfuric acid is used for 2.08 x 10 -2 And g, adjusting the pH =7 to obtain a composite quantum dot solution.
Example 12 example 22
Examples 12-22 each provide a drag reducing and injection enhancing agent comprising the carbon-silicon composite quantum dot solutions provided in examples 1-11, respectively.
Comparative example 1
This comparative example provides a carbon-silicon composite quantum dot solution, except that the reaction temperature in the preparation method of the carbon-silicon composite quantum dot solution was changed from 30 ℃ to 90 ℃, and the kinds, amounts and preparation methods of the remaining raw materials were the same as those of example 1.
Comparative example 2
This comparative example provides a carbon-silicon composite quantum dot solution, and the kinds, amounts and preparation methods of the raw materials were the same as those of example 1 except that the reaction temperature in the preparation method of the carbon-silicon composite quantum dot solution was changed from 30 ℃ to 20 ℃.
Comparative example 3
This comparative example provides a carbon-silicon composite quantum dot solution, and the kinds, amounts and preparation methods of the raw materials were the same as those of example 1, except that the reaction time in the preparation method of the carbon-silicon composite quantum dot solution was changed from 24 hours to 28 hours.
Comparative example 4
This comparative example provides a carbon-silicon composite quantum dot solution, and the kinds, amounts and preparation methods of the raw materials were the same as those of example 1, except that the reaction time in the preparation method of the carbon-silicon composite quantum dot solution was changed from 24 hours to 4 hours.
Comparative example 5
This comparative example provides a carbon-silicon composite quantum dot solution, which was the same as example 1 except that no pH adjusting agent was added to the raw materials and the corresponding steps were removed from the preparation method.
Comparative example 6
This comparative example provides a carbon-silicon composite quantum dot solution except that the amount of the pH adjuster in the raw material was replaced with 9.6X 10 -2 g, kinds, amounts and preparation methods of the other raw materials are the same as those of example 1.
Comparative examples 7 to 12
Comparative examples 7 to 12 each provide a drag-reducing and injection-enhancing agent comprising the carbon-silicon composite quantum dot solutions provided in comparative example 1 and comparative example 6, respectively.
To verify the technical effects of the examples and comparative examples, the following experiments were conducted.
Experimental example 1
Taking example 1 and comparative example 1 as representatives, the morphologies of the carbon-silicon composite quantum dots in the carbon-silicon composite quantum dot solutions provided in example 1 and comparative example 1 were analyzed and tested by a Transmission Electron Microscope (TEM), as shown in fig. 1 and fig. 2. As can be seen from fig. 1, the carbon-silicon composite quantum dots of example 1 are uniformly dispersed, have uniform size, and have an average particle size of about 2 nm. As can be seen from fig. 2, the carbon-silicon composite quantum dots of comparative example 1 were significantly agglomerated, resulting in non-uniform particle size distribution.
The particle size distribution of the carbon-silicon composite quantum dots in the carbon-silicon composite quantum dot solutions provided in examples 1 to 11 and comparative examples 1 to 6 was analytically tested using a dynamic light scattering system (DLS). In order to ensure the accuracy of the detection, three groups of parallel samples are arranged in each group of examples and comparative examples for detection, and then the average value is obtained, and the specific results are shown in table 1.
TABLE 1
Figure BDA0003010550580000131
Figure BDA0003010550580000141
As can be seen from table 1, the sizes of the carbon-silicon composite quantum dots in the carbon-silicon composite quantum dot solutions provided by the embodiments of the present invention are all distributed in the range of 0.9 to 10nm, indicating that the ultra-small size carbon-silicon composite quantum dots are successfully synthesized.
Taking example 1 and comparative example 1 as representatives, the particle size distribution of the carbon-silicon composite quantum dots in the carbon-silicon composite quantum dot solutions provided in example 1 and comparative example 1 is detected, and specifically shown in fig. 3 and fig. 4. As can be seen from FIG. 3, the particle size distribution of the carbon-silicon composite quantum dots of example 1 is 1-4nm, and the average particle size is 1.93. + -. 0.01nm. As can be seen from FIG. 4, the particle size distribution of the carbon-silicon composite quantum dots in comparative example 1 is 73-95nm, and the average particle size is 78.56. + -. 0.01nm.
Experimental example 2
The rock core driving device is adopted to evaluate the oil and drag reduction performance of the drag reduction and injection enhancement agent provided by the embodiments 12-22 and the comparative examples 7-12, and the specific method comprises the following steps: (1) The method comprises the steps of vacuumizing a rock core, saturating simulated formation water, measuring the pore volume of the rock core, calculating the porosity, injecting the simulated formation water at the speed of 1mL/min, and calculating the permeability of the rock core by recording the water injection pressure when the rock core is stable; (2) Saturating the rock core with simulated oil under the condition of 0.2mL/min, weighing the mass (M) of the saturated oil in the pores of the rock core, and standing the rock core at the constant temperature of 90 ℃ for two days for aging; (3) Carrying out a core water drive experiment, injecting simulated formation water from an injection end until the water content in the produced liquid at an outlet end reaches 98%, stopping injection, and recording the stable injection pressure during water driveForce (S) 1 ) And the mass (M) of the oil produced at this point at the outlet end is weighed 0 ) (ii) a (4) Injecting the anti-drag injection-increasing agent with the concentration of 0.2 percent until the produced fluid at the outlet end does not contain oil, stopping injecting, and recording the stable injection pressure (S) of the anti-drag injection-increasing agent during driving in real time 2 ) (ii) a (5) According to the formula γ = (S) 1 -S 2 )*100％/S 1 Calculating the drag reduction ratio, wherein S 1 For stabilizing the injection pressure during water flooding, S 2 The injection pressure is stabilized during the driving of the drag reduction and injection enhancement agent, and gamma is the drag reduction rate; (6) According to the formula β = M 0 * Calculating the recovery ratio by 100%/M, wherein M is the mass of saturated oil in the pore space of the rock core, and M 0 The quality of the oil produced at the outlet end, and beta is the recovery ratio. In addition, tap water was used as a control group, and the reduction ratio and recovery ratio of tap water were calculated by the above-mentioned methods, and the specific results are shown in table 2.
TABLE 2
Experimental groups Drag reduction ratio (%) Recovery ratio (%)
Example 12 28.3 67.2
Example 13 27.6 66.3
Example 14 24.5 57.2
Example 15 25.3 58.1
Example 16 25.1 61.7
Example 17 24.6 58.2
Example 18 23.7 55.3
Example 19 17.6 45.3
Example 20 21.5 64.1
Example 21 26.3 57.1
Example 22 24.9 56.2
Comparative example 7 -183 48.4
Comparative example 8 13.3 45.1
Comparative example 9 6.8 52.1
Comparative example 10 14.6 44.9
Comparative example 11 5.7 51.7
Comparative example 12 -67.1 50.3
Tap water 0 44.9
As can be seen from the data in Table 2, the drag reduction and injection enhancement agent provided by the embodiments of the invention has good drag reduction and oil displacement performance. Wherein, the recovery ratio of the embodiment is obviously improved compared with tap water, and the drag reduction rate is basically maintained to be about 17.6-28.3%. On the contrary, the comparative example shows poor drag reduction and oil displacement performance, the recovery rate is not high, and the drag reduction rate even has negative value.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (11)

1. The drag reduction and injection enhancement agent is characterized by comprising a carbon-silicon composite quantum dot solution;
the carbon-silicon composite quantum dot solution comprises the following raw materials:
a silane coupling agent, a reducing agent, water and a pH regulator;
wherein the mass ratio of the silane coupling agent to the reducing agent to the water is 1: (2-8): (5-10);
the mass of the pH regulator accounts for 0.01-0.1% of the total mass of the silane coupling agent, the reducing agent and the water;
the preparation method of the carbon-silicon composite quantum dot solution comprises the following steps:
mixing a silane coupling agent, a reducing agent and water to react at the temperature of 30-80 ℃ for 6-24h to obtain a reaction solution I;
and separating the reaction liquid I, and mixing the reaction liquid II obtained by separation with a pH regulator to enable the pH value to be 6-8, thereby obtaining the composite quantum dot solution.
2. The drag reducing and injection enhancing agent of claim 1 wherein the silane coupling agent comprises any one or a combination of at least two of N- [3- (trimethoxysilyl) propyl ] ethylenediamine, 3-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, (3-chloropropyl) trimethoxysilane, or N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane.
3. The drag reducing and infusion enhancing agent of claim 1 wherein the reducing agent comprises any one of sodium ascorbate, disodium edetate, catechol, fructose, basic fuchsin or glucose or a combination of at least two thereof.
4. The drag reducing and injection enhancing agent of claim 1 wherein the pH adjusting agent comprises any one or a combination of at least two of sulfuric acid, hydrochloric acid, phosphoric acid or acetic acid.
5. The drag reducing and injection enhancing agent of any one of claims 1-4 wherein the mass ratio of silane coupling agent, reducing agent and water is 1: (3-6): (6-9).
6. The drag reduction and injection enhancement agent according to any one of claims 1 to 4, wherein the mass of the pH regulator is 0.02 to 0.08 percent of the total mass of the silane coupling agent, the reducing agent and the water.
7. The drag reducing and injection enhancing agent of any one of claims 1 to 4 wherein the particle size of the carbon-silicon composite quantum dots in the carbon-silicon composite quantum dot solution is in the range of 1 to 10nm.
8. The drag reducing and injection enhancing agent of claim 1 wherein the reaction temperature is 40-70 ℃ and the reaction time is 8-20h.
9. The drag reducing and infusion enhancing agent of claim 8 wherein the separation is by dialysis.
10. The drag reducing and infusion enhancing agent of claim 9 wherein the dialysis separation time is from 5 to 10 hours.
11. The use of the drag reducing and injection enhancing agent of any one of claims 1 to 10 in the field of oil displacement.
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