CN113980675B - Petroleum tracer, application thereof and oilfield tracing method - Google Patents
Petroleum tracer, application thereof and oilfield tracing method Download PDFInfo
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Abstract
The invention discloses a petroleum tracer, which is a phosphorescent carbon quantum dot, wherein the phosphorescent carbon quantum dot comprises a carbon quantum dot body and a loading agent, and the phosphorescent carbon quantum dot has phosphorescence characteristic. The petroleum tracer has phosphorescence property, the phosphorescence service life is as long as millisecond level, and the detection limit can reach 0.3ppm; the petroleum tracer with phosphorescence performance is used, so that the interference of petroleum autofluorescence can be effectively avoided, the detection sensitivity is improved, and the method is environment-friendly; the phosphorescent carbon quantum dots with different phosphorescent lives are simultaneously applied to the petroleum tracing field, so that the luminous peak positions of the phosphorescent carbon quantum dots can be conveniently distinguished, and the detection efficiency and accuracy are greatly improved; the oil field tracing method can accurately detect the oil well communication condition and provide detection basis for oil well investigation.
Description
Technical Field
The invention belongs to the field of detection and analysis, and particularly relates to a petroleum tracer, application thereof and an oilfield tracing method.
Background
The tracer has great significance for exploitation, design, crosslinking condition and later adjustment of oil fields and water wells, and the common tracer in the prior art mainly comprises dye-type tracer, chemical-type tracer, radioisotope, trace substances and the like, but has a plurality of defects respectively, so that the application of the tracer is limited. For example, dye tracers have strong adsorptivity and large dosage; chemical tracers, such as ammonium nitrate, ammonium thiocyanate and the like, have high cost, are easy to be adsorbed by rocks, have large detection error, have low test resolution, have poor adaptability and selectivity, and have environmental and safety problems; the radioactivity of the radioisotope is strong, the analysis and test means are complex, the cost is high, and the large-scale popularization and application are not facilitated; the trace substances such as gadolinium are adopted, the detection requirement is high, high-end analysis equipment such as inductively coupled plasma mass spectrometry is needed, and the cost is high.
In summary, there is a need to find a petroleum tracer and an oil field tracing method which are simple in preparation method, long in service life, strong in anti-interference capability and environment-friendly.
Disclosure of Invention
In view of the above, the invention aims to provide an oil tracer, application thereof and an oil field tracing method, wherein the oil tracer has long service life and strong anti-interference capability, is environment-friendly, and is simple and easy to operate.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a first object of the present invention is to provide a petroleum tracer, which is a phosphorescent carbon quantum dot, wherein the phosphorescent carbon quantum dot comprises a carbon quantum dot body and a loading agent, and the phosphorescent carbon quantum dot has phosphorescence property.
Specifically, the loading agent is a porous material, and the carbon quantum dot body is dispersed in the porous material through physical adsorption.
Preferably, the porous material comprises at least one of a polymer and an inorganic substance;
preferably, the polymer is at least one selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylene oxide, polysiloxane, polyphenylene, polythiophene, polystyrene, polysilane, polyethylene terephthalate and polyphenylacetylethynyl, polymethyl methacrylate, polydodecyl methacrylate, polycarbonate and epoxy resin;
preferably, the inorganic substance is at least one selected from the group consisting of silicon oxide, boron-containing inorganic substance, aluminum-containing oxide, zirconium-containing oxide, titanium-containing oxide, hafnium-containing oxide, and yttrium-containing oxide.
Preferably, the loading agent is an intercalation element connected with the carbon quantum dot body through a covalent bond, and the intercalation element comprises at least one of N, P, F;
preferably, the intercalation element is at least one selected from phosphoric acid, nitric acid, hydrofluoric acid, ammonium fluoride, ammonium citrate, triethylamine and hydrogen trifluoride.
Specifically, the petroleum tracer comprises at least one of red phosphorescent carbon quantum dots, green phosphorescent carbon quantum dots and blue phosphorescent carbon quantum dots;
preferably, the petroleum tracer is a mixture of red phosphorescent carbon quantum dots, green phosphorescent carbon quantum dots and blue phosphorescent carbon quantum dots.
In particular, the solubility of the petroleum tracer in water at 10-100 ℃ is less than 1X 10 -5 g/L, solubility in petroleum is greater than 1X 10 2 g/L。
The characteristic mode of the solubility of the phosphorescent carbon quantum dots in petroleum is similar to the mode of dispersion degree, namely the phosphorescent carbon quantum dots are gradually added into petroleum with a certain volume at normal temperature and normal pressure while stirring is continuously carried out, when the phosphorescent carbon quantum dots in petroleum can not be dispersed just and precipitation occurs, the adding mass of the phosphorescent carbon quantum dots is stopped at the moment and divided by the volume of the petroleum, and the solubility of the phosphorescent carbon quantum dots in the petroleum under the condition can be obtained.
In particular, the phosphorescent carbon quantum dots of the petroleum tracer may be excited at 350 nm or more and 450nm or less.
The second object of the invention is to provide an application of the petroleum tracer, wherein the petroleum tracer is used for petroleum tracing detection, oil pipe leakage detection and oil well communication condition detection.
A third object of the present invention is to provide a method of oilfield tracking comprising the steps of:
s1, adding the phosphorescent carbon quantum dots into an oilfield injection well;
s2, obtaining an oil-water mixture at an oilfield produced well, and extracting an oil phase in the oil-water mixture;
s3, detecting whether the oil phase has phosphorescence signals or phosphorescence service life, so as to judge whether the oil phase has the phosphorescence carbon quantum dots.
Specifically, the method further comprises the following steps:
s4, establishing a phosphorescent carbon quantum dot concentration-phosphorescent intensity standard curve in petroleum;
s5, detecting the phosphorescence intensity in the oil phase, and obtaining the phosphorescence carbon quantum dot concentration in the oil field well according to the phosphorescence carbon quantum dot concentration-phosphorescence intensity standard curve.
Compared with the prior art, the petroleum tracer and the application thereof and the oilfield tracing method have the following advantages:
(1) The petroleum tracer has phosphorescence property, the phosphorescence service life is as long as millisecond level, and the detection limit can reach 0.3ppm;
(2) The petroleum tracer with phosphorescence performance is used, so that the interference of petroleum autofluorescence can be effectively avoided, the detection sensitivity is improved, and the method is environment-friendly;
(3) The phosphorescent carbon quantum dots with different phosphorescent lives are simultaneously applied to the petroleum tracing field, so that the luminous peak positions of the phosphorescent carbon quantum dots can be conveniently distinguished, and the detection efficiency and accuracy are greatly improved;
(4) The oil field tracing method can accurately detect the oil well communication condition and provide detection basis for oil well investigation.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram related to embodiment 1:
(a) A graph of the phosphorescence intensity of the phosphorescent carbon quantum dots over time;
(b) A change chart of phosphorescence intensity of the phosphorescence carbon quantum dots along with irradiation time of the ultraviolet lamp;
(c) A change chart of phosphorescence intensity of the phosphorescence carbon quantum dots mixed with petroleum along with heating time;
(d) A standard curve of phosphorescent carbon quantum dot concentration value and phosphorescent intensity value;
(e) Phosphorescent lifetime diagram of phosphorescent carbon quantum dots;
fig. 2 is a schematic diagram related to embodiment 2:
(a) A graph of the phosphorescence intensity of the phosphorescent carbon quantum dots over time;
(b) A change chart of phosphorescence intensity of the phosphorescence carbon quantum dots along with irradiation time of the ultraviolet lamp;
(c) A change chart of phosphorescence intensity of the phosphorescence carbon quantum dots mixed with petroleum along with heating time;
(d) A standard curve of phosphorescent carbon quantum dot concentration value and phosphorescent intensity value;
(e) Phosphorescent lifetime diagram of phosphorescent carbon quantum dots;
fig. 3 is a schematic diagram related to embodiment 3:
(a) A graph of the phosphorescence intensity of the phosphorescent carbon quantum dots over time;
(b) A change chart of phosphorescence intensity of the phosphorescence carbon quantum dots along with irradiation time of the ultraviolet lamp;
(c) A change chart of phosphorescence intensity of the phosphorescence carbon quantum dots mixed with petroleum along with heating time;
(d) A standard curve of phosphorescent carbon quantum dot concentration value and phosphorescent intensity value;
(e) Phosphorescent lifetime diagram of phosphorescent carbon quantum dots;
fig. 4 is a schematic diagram related to example 4:
(a) A graph of the phosphorescence intensity of the phosphorescent carbon quantum dots over time;
(b) A change chart of phosphorescence intensity of the phosphorescence carbon quantum dots along with irradiation time of the ultraviolet lamp;
(c) A change chart of phosphorescence intensity of the phosphorescence carbon quantum dots mixed with petroleum along with heating time;
(d) A standard curve of phosphorescent carbon quantum dot concentration value and phosphorescent intensity value;
FIG. 5-a is a graph showing the change of petroleum fluorescence signals before and after adding fluorescent carbon quantum dots in comparative example 1;
FIG. 5-b is a graph of phosphorescent signals of any phosphorescent carbon quantum dot of the invention mixed with petroleum.
Detailed Description
The technical solutions in the examples will be described in detail below in connection with the implementation of the present application. It should be noted that this embodiment is only a partial way, not an entire way.
At least one of the "when preceding or following a list of elements" as for example "is described herein modifies the entire list of elements without modifying individual elements of the list. Unless otherwise defined, all terms (including technical and scientific terms) in the specification can be defined as commonly understood by one of ordinary skill in the art. Terms defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Furthermore, unless expressly stated to the contrary, the words "comprise" and the words "comprising" when used in this specification mean the presence of stated features, regions, integers, steps, operations, elements, and/or components, but does not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof. Accordingly, the above phraseology is to be understood as meaning to include the stated elements, but not to exclude any other elements.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. The term "or" means "and/or".
It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms.
As used herein, "about" or "approximately" includes the stated values and is meant to be within an acceptable range of deviation from the particular values as determined by one of ordinary skill in the art in view of the measurements in question and the errors associated with the measurement of the particular quantities (i.e., limitations of the measurement system). For example, "about" may mean that the deviation from the stated value is within one or more standard deviations, or within + -10%, + -5%.
The invention researches a petroleum tracer in order to solve the problems that the petroleum tracer in the prior art has poor anti-interference capability, high cost, complex preparation method, unfriendly environment, incapability of eliminating petroleum autofluorescence interference and the like.
A petroleum tracer is a phosphorescent carbon quantum dot, and the phosphorescent carbon quantum dot has phosphorescence characteristic. The petroleum tracer has phosphorescence property, namely, after the phosphorescent carbon quantum dots are excited by radiation, an excited triplet state (or excited triplet state) is formed, and when the excited triplet state with high energy is transited to a ground state with low energy, energy is released and phosphorescence is emitted, wherein the phosphorescence still has macroscopic afterglow after the radiation is finished. The aromatic carbonyl compound on the surface of the carbon quantum dot is an origin of a triplet excited state, but is susceptible to non-radiative decay caused by heat and collision processes, and is extremely sensitive to oxygen in the air, and needs to exhibit phosphorescent properties in the presence of a supporting agent.
In order to prevent the quenching effect of the phosphorescent material, the phosphorescent carbon quantum dot comprises a carbon quantum dot body and a loading agent, and the carbon quantum dot can effectively prevent the quenching effect of the petroleum tracer by means of the action of the loading agent.
The supporting agent may be a porous material or an intercalating element that is covalently linked to the bulk of the carbon quantum dot.
When the loading agent is a porous material, the carbon quantum dot body is dispersed in the porous material through physical adsorption. The porous material comprises at least one of a polymer and an inorganic substance.
The polymer is one or more selected from polyethylene, polypropylene, polystyrene, polyethylene oxide, polysiloxane, polyphenylene, polythiophene, polystyrene, polysilane, polyethylene terephthalate and polyphenylacetylethynyl, polymethyl methacrylate, polydodecyl methacrylate, polycarbonate and epoxy resin; the inorganic material is one or more selected from silicon oxide, boron-containing inorganic material, aluminum-containing oxide, zirconium-containing oxide, titanium-containing oxide, hafnium-containing oxide or yttrium-containing oxide.
When the loading agent is an embedded element connected with the carbon quantum dot body through a covalent bond, the embedded element comprises at least one of N, P, F; the intercalation element is at least one selected from phosphoric acid, nitric acid, hydrofluoric acid, ammonium fluoride, ammonium citrate and triethylamine hydrogen trifluoride. The embedding of the embedded element is helpful to regulate and control the triplet energy level structure of the carbon quantum dot body, so that the phosphorescent carbon quantum dot with stable phosphorescence characteristic is formed.
The solubility of petroleum tracer in water at 10-100deg.C is less than 1×10 -5 g/L, solubility in petroleum is greater than 1X 10 2 g/L. The characteristic mode of the solubility of the phosphorescent carbon quantum dots in petroleum is similar to the mode of dispersion degree, namely the phosphorescent carbon quantum dots are gradually added into petroleum with a certain volume at normal temperature and normal pressure while stirring is continuously carried out, when the phosphorescent carbon quantum dots in petroleum can not be dispersed just and precipitation occurs, the adding mass of the phosphorescent carbon quantum dots is stopped at the moment and divided by the volume of the petroleum, and the solubility of the phosphorescent carbon quantum dots in the petroleum under the condition can be obtained.
The petroleum tracer is favorable for being used in an oil phase, can effectively avoid water adsorption interference and improves the accuracy of tracing detection. The petroleum tracer in the application can be used for petroleum tracing detection or oil pipe leakage detection or oil well communication detection.
In a specific embodiment, the petroleum tracer disclosed herein can be used for oil phase tracing, oil pipe leak detection or oil well communication detection, and the oil phase disclosed herein refers to the liquid to be detected as petroleum. When the petroleum tracer is used for oil pipe leak detection, phosphorescent carbon quantum dots are gathered at the leaking oil position, and at the moment, two obvious points can be seen by illumination, so that the leaking oil position is detected; when the petroleum tracer is used for oil well communication detection, the petroleum tracer is put into any oil well, and after a certain time, samples are taken in other oil wells to carry out phosphorescence detection of phosphorescence carbon quantum dots, so that the communication condition among the oil wells is judged.
The petroleum tracer is easy to disperse in petroleum, can detect phosphorescence service life and phosphorescence intensity in a phosphorescence carbon quantum dot flowing region along with the flowing of petroleum, and detects the flowing direction and flow of petroleum by means of the movement track and content of the phosphorescence carbon quantum dot.
In one embodiment of the present application, phosphorescent carbon quantum dots may be excited at 350 nm or more and 450nm or less. The wavelength band which can be excited in the application can be used for judging whether a phosphor optical signal exists or not or the phosphor service life by an instrument. When the fluorescent carbon quantum dots are blue light phosphorescent carbon quantum dots, the phosphorescent lifetime is longer than the identification time of human eyes, phosphorescent signals can be observed by naked eyes, and the operation is more convenient.
The preparation of the carbon quantum dots can adopt a microwave method or a solvothermal method; the preparation of the carbon quantum dots is carried out by adopting a conventional preparation method in the prior art.
The phosphorescent carbon quantum dots include at least one of red light phosphorescent carbon quantum dots, green light phosphorescent carbon quantum dots, and blue light phosphorescent carbon quantum dots. The phosphorescence materials with different colors are excited at different wavelengths, so that the problem of spectrum superposition can be effectively eliminated, and the detection efficiency is improved. Red light phosphorescence carbon quantum dots, green light phosphorescence carbon quantum dots and blue light phosphorescence carbon quantum dots are simultaneously applied to the petroleum tracing field, and phosphorescence carbon quantum dots with different phosphorescence service lives are simultaneously applied to the petroleum tracing field, so that the light-emitting peak positions of the phosphorescence carbon quantum dots can be distinguished conveniently, and the detection efficiency and accuracy are greatly improved.
In addition, the use of phosphorescent materials prolongs the light-emitting time window and avoids the influence of fluorescent materials or petroleum autofluorescence; the phosphorescent lifetime value of the phosphorescent material is substantially longer than the fluorescent lifetime value of the fluorescent material. The two characteristics lead the application of the phosphorescent carbon quantum dot to have wider application fields than the fluorescent carbon quantum dot.
The invention also provides application of the petroleum tracer, which is used for petroleum tracing detection, oil pipe leakage detection and oil well communication condition detection.
The invention provides an oilfield tracing method, which comprises the following steps:
s1, adding the phosphorescent carbon quantum dots into an oilfield injection well;
s2, obtaining an oil-water mixture at an oilfield produced well, and extracting an oil phase in the oil-water mixture;
s3, detecting whether the oil phase has phosphorescence signals or phosphorescence service life, so as to judge whether the oil phase has the phosphorescence carbon quantum dots.
The method can be used for oil phase tracing, oil pipe leakage detection and oil well communication condition detection. This is a very simple method as a qualitative characterization of petroleum.
In another embodiment of the present application, the method of oilfield tracking further comprises the steps of:
s4, establishing a phosphorescent carbon quantum dot concentration-phosphorescent intensity standard curve in petroleum;
s5, detecting the phosphorescence intensity in the oil phase, and obtaining the phosphorescence carbon quantum dot concentration in the oil field well according to the phosphorescence carbon quantum dot concentration-phosphorescence intensity standard curve.
The present application will be described in detail with reference to specific examples and comparative examples below:
example 1
1. Preparation of blue phosphorescent carbon quantum dots (petroleum tracers):
and (3) ultrasonically dissolving 1.5g of urea, 0.5g of citric acid, 0.2mL of phosphoric acid and 10mL of water to obtain a mixed solution, then placing the mixed solution into a microwave oven, setting the power of microwaves to be 800W, reacting for 5min, centrifuging the obtained liquid at the rotating speed for 10min after the reaction is finished, centrifugally washing for 3 times under the same condition to obtain white solid, placing the white solid into a freezer, and finally freeze-drying by a freeze dryer to obtain the blue light carbon quantum dots of white solid powder.
Dispersing the obtained blue light carbon quantum dots in ethanol again, then adding 2mL of polyethylene glycol 600 and 1.0g of boric acid, then carrying out solution thermal reaction at 180 ℃ for 6 hours, naturally cooling to room temperature after the reaction is finished, centrifuging the obtained solution, removing supernatant, collecting bottom sediment, washing the sediment with distilled water, and finally freeze-drying the obtained substrate to obtain the blue light phosphorescence carbon quantum dots, namely the petroleum tracer.
2. Stability test of petroleum tracer:
2.1 air stability
The phosphorescent carbon quantum dots are placed in the air, the change of the phosphorescence intensity of the phosphorescent carbon quantum dots along with the placement time is tested under the condition of room temperature and normal pressure, and the phosphorescence intensity of the phosphorescent carbon quantum dots is tested at different times respectively, and the result is shown in figure 1-a. After the phosphorescent carbon quantum dots are placed for 400min, the phosphorescent intensity still keeps more than 98% of the initial value.
2.2 UV stability
Ultraviolet stability of phosphorescent carbon quantum dots was tested. And placing the phosphorescent carbon quantum dots under an ultraviolet lamp with the power of 20W, continuously irradiating the phosphorescent carbon quantum dots, and testing and recording the phosphorescent intensity at different moments to obtain a change chart of the luminous intensity of the phosphorus along with the irradiation time of the ultraviolet lamp, as shown in the figure 1-b. And respectively testing the phosphorescence intensity of the phosphorescence carbon quantum dots at different times, wherein the phosphorescence intensity still keeps more than 96% of the initial value after the phosphorescence carbon quantum dots are irradiated by an ultraviolet lamp for 400 min.
2.3 internal Petroleum stability
0.5g of phosphorescent carbon quantum dots was mixed with 50mL of petroleum, stirred at 65℃and the change in phosphorescence intensity with heating time was tested, and the results are shown in FIG. 1-c. From the stability test results, the phosphorescence intensity can still be maintained to be more than 95% of the initial value after 168 hours.
3. Standard curve
To determine the concentration value of specific phosphorescent carbon quantum dots in petroleum, a standard curve is measured on petroleum in advance, namely, a petroleum solution of the phosphorescent carbon quantum dots with known concentration is prepared, and then the phosphorescent intensity value is measured to obtain the relationship between the concentration value of the phosphorescent carbon quantum dots and the phosphorescent intensity value, as shown in table 1, and the obtained standard curve is shown in fig. 1-d. Test conditions: excitation wavelength: 370nm, the test procedure was carried out with 3mL of the as-received reagent for phosphorescence spectrum.
TABLE 1
From the above, it can be seen thatThe petroleum tracer standard curve of this example has good linear relationship, R 2 The value was 0.999, the phosphorescence intensity of the petroleum tracer solution remained substantially unchanged over a longer period of time, the detection limit was as low as 0.36mg/L, and as seen in FIG. 1-e, the phosphorescence lifetime of this example was 40ms.
4. The method for oil field tracing by the petroleum tracer is as follows, at this time, the flow rate and the flow rate are consistent when the injection well flows to the extraction well, and the concentration of the tracer in the extraction well is stable and does not change any more when the extraction well is sampled:
the petroleum tracer of the embodiment is used for measuring connectivity among oil wells, and the specific method comprises the following steps: weighing 5kg of petroleum tracer to prepare petroleum solution with certain concentration, adding the petroleum solution into an injection well, sampling in the injection well, and measuring phosphorescence intensity to obtain the concentration of the tracer of 10ppm; after petroleum tracer is injected for a period of time, sampling is carried out on the 1# extraction well, the 2# extraction well and the 3# extraction well respectively, the phosphorescence intensity of sample liquid in the three extraction wells is measured at fixed time, the concentration of the tracer in the 1# is finally measured to be 2ppm, the tracer is not detected in the 2#, the concentration of the tracer in the 3# is 1ppm, the injection well is known to be communicated with the 1# extraction well and the 3# extraction well respectively, and is not communicated with the 2# extraction well, so that the use of the injection well can be reasonably planned according to the requirement.
Example 2
1. Preparation of green phosphorescent carbon quantum dots (petroleum tracers):
0.3g of pseudo-boehmite, 0.17g of manganese acetate tetrahydrate and 0.2g of boric acid were taken and dissolved in 20mL of deionized water, and 0.56mL of phosphoric acid and 1.5g of triethylenetetramine were added, followed by putting the mixed solution into a high-temperature reaction kettle and reacting at 180℃for 10 hours. And after the reaction is finished, carrying out centrifugal treatment on the obtained solution, washing a substrate by using distilled water, and drying at 80 ℃ to obtain the green phosphorescent carbon quantum dot powder.
2. Stability test of petroleum tracer:
2.1 air stability
The phosphorescent carbon quantum dots were placed in air, and the change of the phosphorescent intensity of the phosphorescent carbon quantum dots with the time of placement was tested under the conditions of room temperature and normal pressure, and the results are shown in fig. 2-a. The test of phosphorescence intensity of the phosphorescence carbon quantum dots shows that after 400 minutes of standing, the phosphorescence intensity still keeps more than 94% of the initial value.
2.2 UV stability
And (5) testing ultraviolet stability of the phosphorescent carbon quantum dots. And placing the phosphorescent carbon quantum dots under an ultraviolet lamp with the power of 20W, continuously irradiating the phosphorescent carbon quantum dots, and recording the phosphorescent intensity at different times to obtain a change chart of the phosphorescent intensity value along with the irradiation time of the ultraviolet lamp, as shown in fig. 2-b. After the phosphorescent carbon quantum dots are irradiated by an ultraviolet lamp for 400min, the phosphorescence intensity still keeps more than 92% of the initial value.
2.3 internal Petroleum stability
0.5g of phosphorescent carbon quantum dot is mixed with 50mL of petroleum, stirred at 65 ℃ and tested for the change of the phosphorescent signal intensity value at different heating times, and the result is shown in fig. 2-c. From the stability test results, the phosphorescence intensity can be maintained to be more than 94% of the initial value after 168 hours
3. Standard curve
To determine the concentration value of specific phosphorescent carbon quantum dots in petroleum, a standard curve is measured on petroleum in advance, namely, a petroleum solution of the phosphorescent carbon quantum dots with known concentration is prepared, and then the phosphorescent intensity value is measured to obtain the relationship between the concentration value of the phosphorescent carbon quantum dots and the phosphorescent intensity value, as shown in table 2, and the obtained standard curve is shown in fig. 2-d. Test conditions: excitation wavelength: 450nm, test procedure phosphorescence spectrum was measured with 3mL of as-received reagent.
TABLE 2
| Concentration ppm | 0.7 | 14 | 70 | 140 | 280 |
| Phosphorescent intensity a.u. | 15 | 70 | 385 | 763 | 1442 |
From the above, the linear relationship of the standard curve of the petroleum tracer of the embodiment is good, R 2 The value was 0.999, the phosphorescence intensity of the petroleum tracer solution remained substantially unchanged over a longer period of time, the detection limit was as low as 0.3mg/L, and as seen in FIG. 2-e, the phosphorescence lifetime of this example was 5.6ms.
4. The method for oil tracing by using the petroleum tracer is as follows:
the connectivity between oil wells is measured by using the petroleum tracer of the embodiment, at the moment, the flow rate and the flow rate of the injection well when flowing to the extraction well are assumed to be consistent, and the concentration of the tracer in the extraction well is stable and does not change any more when the extraction well is used for sampling, and the specific method is as follows: weighing 5kg of petroleum tracer to prepare petroleum solution with a certain concentration, adding the petroleum solution into an injection well, sampling in the injection well, and measuring the phosphorescence intensity to obtain the concentration of the tracer of 5ppm; after petroleum tracer is injected for a period of time, sampling is carried out in the 1# extraction well, the 2# extraction well and the 3# extraction well respectively, the phosphorescence intensity of the sample liquid in the three extraction wells is measured at fixed time, the concentration of the tracer in the 1# is finally measured to be 1ppm, the tracer is not detected in the 2#, the tracer is not detected in the 3#, and the injection well is only communicated with the 1# extraction well.
Example 3
1. Preparation of red light phosphorescence carbon quantum dots (petroleum tracer):
0.3g of pseudo-boehmite, 0.17g of manganese acetate tetrahydrate and 0.2g of boric acid were dissolved in 20mL of deionized water, 0.56mL of phosphoric acid and 0.8mL of 2,2- (ethylenedioxy) bis (ethylamine) were added, and then the mixed solution was put into a high temperature reaction vessel to react for 12 hours at 160 ℃. And after the reaction is finished, carrying out centrifugal treatment on the obtained solution, washing a substrate by using distilled water, and drying at 80 ℃ to obtain red phosphorescent carbon quantum dot powder.
2. Stability test of petroleum tracer:
2.1 air stability
The phosphorescent carbon quantum dots were placed in air, and the change of the phosphorescent intensity of the phosphorescent carbon quantum dots with the time of placement was tested under the conditions of room temperature and normal pressure, and the results are shown in fig. 3-a. The test of phosphorescence intensity of the phosphorescence carbon quantum dot shows that after 400 minutes of standing, the phosphorescence intensity still keeps more than 86% of the initial value.
2.2 UV stability
And (5) testing ultraviolet stability of the phosphorescent carbon quantum dots. And (3) placing the phosphorescent carbon quantum dots under an ultraviolet lamp with the power of 20W, continuously irradiating the phosphorescent carbon quantum dots, and recording the phosphorescent intensity at different times to obtain a change chart of the phosphorescent intensity value along with the irradiation time of the ultraviolet lamp, wherein the result is shown in the figure 3-b. After the phosphorescent carbon quantum dots are irradiated by an ultraviolet lamp for 400min, the phosphorescence intensity still keeps more than 81% of the initial value.
2.3 internal Petroleum stability
0.5g of phosphorescent carbon quantum dot is mixed with 50mL of petroleum, stirred at 65 ℃ and tested for the change of the phosphorescent signal intensity value at different heating times, and the result is shown in figure 3-c. From the stability test results, the phosphorescence intensity can still keep more than 86% of the initial value after 168 hours.
3. Standard curve
To determine the concentration value of specific phosphorescent carbon quantum dots in petroleum, a standard curve is measured on petroleum in advance, namely, a petroleum solution of the phosphorescent carbon quantum dots with known concentration is prepared, and then the phosphorescent intensity value is measured to obtain the relationship between the concentration value of the phosphorescent carbon quantum dots and the phosphorescent intensity value, as shown in table 3, and the obtained standard curve is shown in fig. 3-d. Test conditions: excitation wavelength: 520nm, the test procedure was carried out with 3mL of the as-received reagent for phosphorescence spectrum.
TABLE 3 Table 3
| Concentration ppm | 1 | 10 | 50 | 100 | 500 |
| Phosphorescent intensity a.u. | 18 | 60 | 225 | 403 | 1631 |
From the above, the linear relationship of the standard curve of the petroleum tracer of the embodiment is good, R 2 The value was 0.998, the phosphorescence intensity of the petroleum tracer solution remained substantially unchanged over a longer period of time, and the detection limit was as low as 0.32mg/L as seen in FIG. 3-e, and the phosphorescence lifetime of this example was 5.2ms.
4. The method for oil tracing by using the petroleum tracer is as follows:
the petroleum tracer of the embodiment is utilized to measure the connectivity between oil wells, at this time, the flow rate and the flow rate are consistent when the injection well flows to the production well, and the concentration of the tracer in the production well is stable and does not change when the production well is sampled, and the specific method is as follows: weighing 5kg of petroleum tracer to prepare petroleum solution with certain concentration, adding the petroleum solution into an injection well, sampling in the injection well, and measuring phosphorescence intensity to obtain the concentration of the tracer of 15ppm; after the petroleum tracer is injected for a period of time, sampling is carried out on the 1# extraction well, the 2# extraction well and the 3# extraction well respectively, the phosphorescence intensity of the sample liquid in the three extraction wells is measured at fixed time, the concentration of the petroleum tracer in the 1# is measured to be 1ppm, the concentration of the petroleum tracer in the 2# is measured to be 2ppm, the concentration of the petroleum tracer in the 3# is measured to be 3ppm, the injection well is communicated with the 1# extraction well, the 2# extraction well and the 3# extraction well, and further the use of the injection well can be reasonably planned according to the requirement.
Example 4
1. Ordinary carbon quantum dots (without N, P, F) were prepared and loaded in the pores of inorganic boric acid.
2g of citric acid is dissolved in 10mL of deionized water, then the solution is put into a reaction kettle for hydrothermal reaction, wherein the reaction temperature is 180 ℃ and the reaction time is 5 hours, the obtained solution is centrifugally separated after the reaction is finished, the supernatant is collected to obtain a carbon quantum dot solution, and then water in the solution is removed by a rotary evaporation or freeze drying mode to obtain carbon quantum dot powder.
2g of boric acid is taken and dissolved in 20mL of deionized water, then 3mg of carbon quantum dots synthesized by the method are added, the mixture is stirred and then the solution is placed into a reaction kettle again for reaction, wherein the reaction temperature is 180 ℃, the reaction time is 6 hours, and then the phosphorescent carbon quantum dots are obtained after natural cooling to room temperature.
2. Stability test of petroleum tracer:
2.1 air stability
The phosphorescent carbon quantum dots were placed in air, and the change of the phosphorescent intensity of the phosphorescent carbon quantum dots with the time of the placement was tested under the conditions of room temperature and normal pressure, and the results are shown in fig. 4-a. The test of phosphorescence intensity of the phosphorescence carbon quantum dot shows that after 420min of standing, the phosphorescence intensity still keeps more than 90% of the initial value.
2.2 UV stability
And (5) testing ultraviolet stability of the phosphorescent carbon quantum dots. And (3) placing the phosphorescent carbon quantum dots under an ultraviolet lamp with the power of 20W, continuously irradiating the phosphorescent carbon quantum dots, and recording the phosphorescent intensity at different times to obtain a change chart of the phosphorescent intensity value along with the irradiation time of the ultraviolet lamp, wherein the result is shown in fig. 4-b. After the phosphorescent carbon quantum dots are irradiated by an ultraviolet lamp for 420min, the phosphorescence intensity still keeps more than 89% of the initial value.
2.3 internal Petroleum stability
0.5g of phosphorescent carbon quantum dot is mixed with 50mL of petroleum, stirred at 65 ℃ and tested for the change of the phosphorescent signal intensity value at different heating times, and the result is shown in fig. 4-c. From the stability test results, the phosphorescence intensity can still be maintained to be more than 91% of the initial value after 168 hours.
3. Standard curve
To determine the concentration value of specific phosphorescent carbon quantum dots in petroleum, a standard curve is measured on petroleum in advance, namely, a petroleum solution of the phosphorescent carbon quantum dots with known concentration is prepared, and then the phosphorescent intensity value is measured to obtain the relationship between the concentration value of the phosphorescent carbon quantum dots and the phosphorescent intensity value, as shown in table 4, and the obtained standard curve is shown in fig. 4-d. Test conditions: excitation wavelength: 450nm, test procedure phosphorescence spectrum was measured with 3mL of as-received reagent.
TABLE 3 Table 3
| Concentration ppm | 0.5 | 5 | 50 | 250 | 500 |
| Phosphorescent intensity a.u. | 13 | 61 | 260 | 738 | 1331 |
From the above, the linear relationship of the standard curve of the petroleum tracer of the embodiment is good, R 2 The value is 99.2%, the phosphorescence intensity of the petroleum tracer solution is basically maintained unchanged for a long time, and the detection limit is as low as 0.3mg/L.
4. The method for oil tracing by using the petroleum tracer is as follows:
the petroleum tracer of the embodiment is used for measuring connectivity among oil wells, and the specific method comprises the following steps: weighing 5kg of petroleum tracer to prepare petroleum solution with certain concentration, adding the petroleum solution into an injection well, sampling in the injection well, and measuring phosphorescence intensity to obtain the concentration of the tracer of 8ppm; after the petroleum tracer is injected for a period of time, sampling is carried out on the 1# extraction well, the 2# extraction well and the 3# extraction well respectively, the phosphorescence intensity of the sample liquid in the three extraction wells is measured at fixed time, the concentration of the petroleum tracer in the 1# is 2ppm, the concentration of the petroleum tracer in the 2# is 2ppm, the petroleum tracer in the 3# is not present, the injection well is communicated with the 1# extraction well and the 2# extraction well, the injection well is not communicated with the 3# extraction well, and the use of the injection well can be reasonably planned according to the requirement.
Example 5 phosphorescent carbon quantum dots of three different lights prepared in the above examples 1 to 3 were mixed and used.
The measurement of phosphorescent signals was performed by adding a certain mass of a (blue light prepared in example 1), B (green light prepared in example 2), C (red light prepared in example 3) petroleum tracers to injection wells # 1, # 2 and # 3 (not communicating with each other) respectively, and sampling in different monitoring wells # 4 and # 5 (not communicating with each other). Monitoring the phosphorescent signals of the A tracer, the B tracer and the C tracer in the monitoring well 4#; the B tracer, the C tracer, and no phosphorescent signal of the a tracer were monitored in monitor well 5 #.
The following information can be obtained from this:
1. injection well 1# and injection well 2# are simultaneously communicated with monitoring well 4# and injection well 3# is not communicated with monitoring well 4 #;
2. injection well 2# and injection well 3# are simultaneously communicated with monitoring well 5 #; injection well # 1 is not in communication with monitoring well # 5.
In embodiment 5, because the phosphorescent carbon quantum dots of different types have different service lives, the monitoring time of the phosphorescent signal of each phosphorescent carbon quantum dot is different, and the peak positions of the phosphorescent carbon quantum dots of different types are conveniently distinguished, so that the communication condition of different injection wells and the same monitoring well is judged.
Comparative example 1 this comparative example provides a conventional preparation method of fluorescent carbon quantum dots, specifically as follows: dissolving 1.2g of citric acid and 0.5g of cysteine in 15mL of deionized water, after the two reagents are completely dissolved, placing the solution into a reaction kettle for hydrothermal reaction, wherein the reaction temperature is 150 ℃, the reaction time is 6 hours, centrifuging the obtained solution after the reaction is finished, collecting supernatant to obtain a fluorescent carbon quantum dot solution, purifying the fluorescent carbon quantum dot solution by using a silica gel chromatographic column, and performing rotary evaporation or freeze drying to obtain fluorescent carbon quantum dot powder.
The fluorescent carbon quantum dots obtained by the method are mixed with petroleum, and the change condition of petroleum fluorescent signals before and after the fluorescent carbon quantum dots are added is measured, as shown in a figure 5-a, a petroleum sample without the fluorescent carbon quantum dots has a fluorescent emission peak with certain intensity at a wavelength of 430nm, the fluorescent signals in the petroleum sample after the fluorescent carbon quantum dots are added have certain similarity with the fluorescent signals in pure petroleum, and the fluorescent emission peak at a wavelength of 440nm, so that the emission peak of the fluorescent carbon quantum dots is greatly disturbed due to the interference of the petroleum autofluorescence signals, and errors are easily caused in the actual petroleum use detection process.
FIG. 5-b is a graph of phosphorescent signals of the mixture of the phosphorescent carbon quantum dots and petroleum, which is arbitrarily prepared in the application, wherein the difference of the phosphorescent signals of the phosphorescent carbon quantum dots and the petroleum is very large, so that the influence of fluorescent materials or the autofluorescence of petroleum is avoided, and the application range of the fluorescent materials is widened.
Compared with the prior art, the qualitative and quantitative method for petroleum tracer and petroleum tracer has the following advantages:
(1) The petroleum tracer has phosphorescence property, the phosphorescence service life is as long as millisecond level, and the detection limit can reach 0.3ppm;
(2) The petroleum tracer with phosphorescence performance is used, so that the interference of petroleum autofluorescence can be effectively avoided, the detection sensitivity is improved, and the method is environment-friendly;
(3) The phosphorescent carbon quantum dots with different phosphorescent lives are simultaneously applied to the petroleum tracing field, so that the luminous peak positions of the phosphorescent carbon quantum dots can be conveniently distinguished, and the detection efficiency and accuracy are greatly improved;
(4) The oil field tracing method can accurately detect the oil well communication condition and provide detection basis for oil well investigation.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (11)
1. An oil tracer, characterized in that: the petroleum tracer is a phosphorescent carbon quantum dot, the phosphorescent carbon quantum dot comprises a carbon quantum dot body and a loading agent, the phosphorescent carbon quantum dot has phosphorescence, the loading agent is an embedded element, the embedded element is connected with the carbon quantum dot body through a covalent bond, or the loading agent is a porous material, and the carbon quantum dot body is dispersed in the porous material through physical adsorption; the embedded element includes at least one of N, P, F; the porous material comprises at least one of a polymer and an inorganic substance.
2. A petroleum tracer according to claim 1, characterised in that: the polymer is at least one selected from polyethylene, polypropylene, polystyrene, polyethylene oxide, polysiloxane, polyphenylene, polythiophene, polystyrene, polysilane, polyethylene terephthalate, polyphenylacetylethynyl, polymethyl methacrylate, polydodecyl methacrylate, polycarbonate and epoxy resin.
3. A petroleum tracer according to claim 1, characterised in that: the inorganic substance is at least one selected from the group consisting of silicon oxide, boron-containing inorganic substance, aluminum-containing oxide, zirconium-containing oxide, titanium-containing oxide, hafnium-containing oxide and yttrium-containing oxide.
4. A petroleum tracer according to claim 1, characterised in that: the intercalation element is at least one selected from phosphoric acid, nitric acid, hydrofluoric acid, ammonium fluoride, ammonium citrate and triethylamine hydrogen trifluoride.
5. A petroleum tracer according to claim 1, characterised in that: the petroleum tracer comprises at least one of red phosphorescent carbon quantum dots, green phosphorescent carbon quantum dots and blue phosphorescent carbon quantum dots.
6. A petroleum tracer according to claim 1, characterised in that: the petroleum tracer is a mixture of red phosphorescent carbon quantum dots, green phosphorescent carbon quantum dots and blue phosphorescent carbon quantum dots.
7. A petroleum tracer according to claim 1, characterised in that: the solubility of the petroleum tracer in water at 10-100deg.C is less than 1×10 -5 g/L, solubility in petroleum is greater than 1X 10 2 g/L。
8. A petroleum tracer according to claim 1, characterised in that: the phosphorescent carbon quantum dots of the petroleum tracer are excited at 350 nm or more and 450nm or less.
9. An application of a petroleum tracer, which is characterized in that: use of the petroleum tracer of any of claims 1-8 for petroleum tracer detection, oil pipe leak detection, oil well communication detection.
10. A method of oilfield tracking comprising the steps of:
s1, adding the petroleum tracer according to any one of claims 1-8 into an oilfield injection well;
s2, obtaining an oil-water mixture at an oilfield produced well, and extracting an oil phase in the oil-water mixture;
s3, detecting whether the oil phase has phosphorescence signals or phosphorescence service life, so as to judge whether the oil phase has the phosphorescence carbon quantum dots.
11. The method of oilfield tracking of claim 10, further comprising the step of:
s4, establishing a standard curve of the concentration-phosphorescence intensity of the petroleum tracer in petroleum;
s5, detecting the phosphorescence intensity in the oil phase, and obtaining the concentration of the petroleum tracer in the oil field well according to the concentration-phosphorescence intensity standard curve of the petroleum tracer.
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