CN109628091B - Synthesis method and application of BYC tracer - Google Patents

Synthesis method and application of BYC tracer Download PDF

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Publication number
CN109628091B
CN109628091B CN201811587565.9A CN201811587565A CN109628091B CN 109628091 B CN109628091 B CN 109628091B CN 201811587565 A CN201811587565 A CN 201811587565A CN 109628091 B CN109628091 B CN 109628091B
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tracer
byc
fluorescence intensity
libif
deionized water
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CN109628091A (en
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熊金平
蔡冠宇
翟保林
张军
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Tianjin Dongfang Huaze Energy Technology Co ltd
Beijing University of Chemical Technology
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Tianjin Dongfang Huaze Energy Technology Co ltd
Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7772—Halogenides
    • C09K11/7773—Halogenides with alkali or alkaline earth metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B47/00—Survey of boreholes or wells
    • E21B47/10—Locating fluid leaks, intrusions or movements
    • E21B47/11—Locating fluid leaks, intrusions or movements using tracers; using radioactivity
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material

Abstract

The invention relates to a synthesis method of a BYC tracer and application thereof. The rare earth element tracing method becomes one of effective means for detecting oil reservoirs in oil fields. The invention synthesizes a fluorescent nano material with a core-shell structure, which can be used as an oil field tracer and is named as a BYC tracer. This tracer has numerous advantages: good water solubility, small using amount, small water sample required sampling amount, simple and convenient analysis method and high analysis sensitivity; no radioactivity, low toxicity and little influence on the environment; does not affect the mineralization degree, has good compatibility with the polymer and does not affect the polymer flooding. The invention creatively realizes the application of the BYC tracer which is a fluorescent nano material in the field of oilfield detection, and provides a feasible operation scheme.

Description

Synthesis method and application of BYC tracer
Technical Field
The invention relates to a synthesis method and an application method of a novel tracer, namely a BYC tracer. The BYC tracer is successfully synthesized by newly utilizing a multiphase ion alternate transfer method in the synthesis process, is a fluorescent nano material with a core-shell structure, has good effect particularly as an oilfield inter-well tracer, and plays an important role in the process of detecting an oil reservoir and testing the distribution and movement of oil reservoir fluid.
Background
In the water injection development of complex block oil fields, high permeability zones or large pore canals are gradually formed among oil wells due to the heterogeneity of oil layers, the oil-water displacement efficiency is reduced, the water content of oil wells is rapidly increased, and the development effect is obviously deteriorated. The tracer can qualitatively judge the existence of high permeability zone or large pore canal, and the interwell tracer is an important means for detecting the distribution and movement of oil layer fluid and the heterogeneity of oil layer. The currently used tracers have the following problems:
first, there are few types of tracers that can be widely used in oil fields, due to limitations on the nature of the tracers themselves and the types and physicochemical properties of the mineral in the formation.
Secondly, common tracers are anions, dyes, low molecular alcohols and the like which are easy to detect, and the tracers have the defects of large use amount (up to several tons), high toxicity, large water sample required sampling amount, low analysis sensitivity, long measurement period and the like, and are not beneficial to environmental friendliness.
Thirdly, the use of ammonium thiocyanate, sodium bromide and potassium iodide can also increase the mineralization degree, which affects the viscosity of the polymer solution, and due to the influence of the polymer, the error of the detection of sodium bromide and potassium iodide is larger, and the cost of potassium iodide is higher, so that the use of the ammonium thiocyanate, the sodium bromide and the potassium iodide is limited.
Fourthly, artificial radioactive substance-60Co、3H、82Br, etc., which are difficult to detect on site due to high detection difficulty and are limited in use; with the increasing demand for environmental protection, this substance will be gradually eliminated.
Fifthly, the titration method is one of the most commonly used methods for measuring the content of the rare earth element at present, but the method has various steps, is subjected to multiple times of extraction, has larger error of separation operation and has long measuring period; meanwhile, because the error caused by human difference factors is larger, under the condition that the analysis condition is not changed, increasing the concentration of the rare earth element is one of effective schemes for improving the analysis precision, but the increase of the concentration of the rare earth element causes the improvement of the use cost of the rare earth element, so that the rare earth tracer is not commonly used for controlling the cost in the practical application of detecting the oil deposit in the oil field.
Sixthly, the prior fluorescent tracer has large using amount, high cost and unstable chemical and physical properties in the stratum, and the inorganic fluorescent material is easily adsorbed on silt and other small molecules or small-particle-size particles in an underground oil layer; the organic fluorescent material has poor chemical stability in a complex underground environment, and is easy to react with other substances to cause the failure of the tracer.
Disclosure of Invention
Aiming at the problems, the invention provides a novel tracer which is free from polymer interference, low in price, small in dosage, easy to operate and convenient to detect, is a rare earth ion double-doped bismuth tetrafluoride physical @ sodium tartrate nanomaterial with good water solubility and a core-shell structure, is named as 'BYC tracer', and the structural schematic diagram and the fluorescence spectrum schematic diagram of the tracer are respectively shown in figure 1 and figure 2.
The present invention relates to an innovative method suitable for the synthesis of BYC tracers, named "multiphase ion transfer method" or MIAT (Multi-phase ion exchange transfer method) method.
A method for synthesizing a BYC tracer, characterized by comprising the steps of:
1) preparation of LiBiF4
Anhydrous ethylene glycol was placed in a beaker and BiCl was weighed3Dissolving LiF solid in anhydrous glycol, uniformly mixing, placing in a reaction kettle, and reacting for 24h at 150 ℃; cooling, adding deionized water, and vacuum filtering to obtain LiBiF4Powder;
2) preparation of LiBiF4:Yb3+,Ce3+
[a]Preparing a rare earth solution: placing deionized water in a beaker, CeCl3And YbCl3Dissolving the solid in deionized water;
[b]doping: mixing the LiBiF in the step 1)4The powder is uniformly dispersed in the [ a ] in the step 2)]The rare earth solution is evenly mixed and then placed in a reaction kettle to react for 12 hours at the temperature of 220 ℃; cooling, washing with deionized water, and vacuum filtering to obtain LiBiF4:Yb3+,Ce3+Powder;
3) preparation of BYC
[a] Preparing a sodium tartrate aqueous solution: putting deionized water into a conical flask, weighing sodium tartrate solid, dissolving the sodium tartrate solid in the deionized water in the conical flask, and stirring until the sodium tartrate solid is completely dissolved;
[b]coating: mixing the LiBiF in the step 2)4:Yb3+,Ce3+The powder is uniformly dispersed in the [ a ] of the step 3)]Continuously stirring the solution for 10 hours at the temperature of 80 ℃; stopping heating, and naturally cooling to room temperature.
4) Purification, namely adding acetone into the conical flask in the step 3) b, and after white precipitates are completely separated out, carrying out vacuum filtration to obtain white powder; and (3) drying the white powder in vacuum to obtain a final product, namely the BYC tracer with the core-shell structure.
The raw materials meet the following mixture ratio, and the total of the raw materials takes 100 percent as a calculation criterion;
Figure BDA0001919480940000031
use of a "BYC tracer", characterized in that: firstly adding a tracer into liquid to be detected to prepare a plurality of solutions with different concentrations of less than 10.0ppm, then detecting fluorescence intensities under a plurality of concentrations by using an excitation light spectrophotometer under the condition that an excitation wavelength EX/emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration; uniformly dispersing the fluorescent tracer with unknown quantity in the solution to be detected, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the solution to be detected according to a standard curve corresponding to the fluorescence intensity.
The invention has the following characteristics
1. Low adsorptivity. The surface energy of the BYC nanocrystals is reduced by the coating of the sodium tartrate, so that the tracer is not easy to adsorb underground inorganic mineral substances in the complex environment of an oil well, but is fully dissolved in water, so that the tracer can be better dispersed among wells and in pore channels, and the detection precision of the tracer is favorably improved.
2. High efficiency. On the oil well site, the water solution of the tracer can be rapidly prepared, the injection mode is the same as that of the conventional tracer, the water sample can be rapidly obtained due to the low adsorptivity and fast diffusion between wells and in a pore channel, the content of the tracer can be qualitatively and quantitatively determined by a fluorescence spectrum, the oil mass distribution between wells of an oil field is calculated, and the efficiency is improved.
3. The detection is convenient, the detection limit is low, and the precision is high. The content of the tracer is detected by a fluorescence spectrometer, the excitation wavelength is 980nm, and the emission wavelength is 650 nm. Calculating the content of the tracer agent by matching with a standard curve, wherein the error range is 1-20%. The minimum detectable concentration of this tracer was 0.1 ppm.
4. Low consumption and low cost. The tracer is easy to dissolve in water, has good dispersibility in the stratum, and simultaneously has excellent fluorescence performance and low detection limit, so compared with the traditional tracer, the tracer does not need large dosage, and the use cost is reduced.
5. Good compatibility with polymer and no environmental pollution. The tracer has a core-shell structure, and the sodium tartrate of the shell layer has good water solubility, so that the tracer has the essential characteristics of organic matters, thereby obtaining good compatibility with polymers; the tracer is non-toxic, non-radioactive and has very small dosage, so it does not pollute environment.
Drawings
FIG. 1 schematic of the structure of the BYC tracer
FIG. 2 fluorescent spectrogram of BYC tracer
FIG. 3 is a standard curve of fluorescence intensity versus concentration of 5) tracer in tap water in example 1-B.
FIG. 4 is a standard curve of fluorescence intensity versus concentration for the injected water of the oilfield of 6) tracer in example 1-B.
FIG. 5 is a standard curve of fluorescence intensity versus concentration of 7) tracer in tap water containing a rock sample in example 1-B.
FIG. 6 is a standard curve of fluorescence intensity versus concentration of 8) tracer in oilfield injection water containing a rock sample in example 1-B.
Detailed Description
(divided into two parts of preparation and application, taking the preparation of 2g of tracer as an example, the invention is not limited by the following examples, and specific implementation scheme can be determined according to the technical scheme and practical situation of the invention.)
Example 1:
preparation of BYC tracer
1) Preparation of LiBiF4:
The measuring cylinder accurately measures 60mL of anhydrous ethylene glycol, the anhydrous ethylene glycol is placed in a beaker, and 4.018g of BiCl is accurately weighed by an analytical balance3And 1.038g of LiF solid are dissolved in anhydrous glycol, mixed uniformly and then placed in a reaction kettle to react for 24 hours at the temperature of 150 ℃. After cooling, 100mL of deionized water was added thereto and a white precipitate was obtainedAfter complete precipitation, carrying out vacuum filtration to obtain LiBiF4And (3) powder.
2) Preparation of LiBiF4:Yb3+,Ce3+
[a]Preparing a rare earth solution: the measuring cylinder is used for accurately measuring 60mL of deionized water, the deionized water is placed in a beaker, and 0.192g of YbCl is accurately weighed by an analytical balance3And 0.004g of CeCl3Dissolving the solid in deionized water;
[b]doping: mixing the LiBiF in the step 1)4The powder is uniformly dispersed in the [ a ] in the step 2)]The rare earth solution is evenly mixed and then placed in a reaction kettle to react for 12 hours at the temperature of 220 ℃. Cooling, washing with deionized water for 3 times, and vacuum filtering to obtain LiBiF4:Yb3+,Ce3+And (3) powder.
3) Preparation of BYC
[a] Preparing a sodium tartrate aqueous solution: accurately measuring 100mL of deionized water by using a measuring cylinder, placing the deionized water in a 250mL conical flask, accurately weighing 3.720g of sodium tartrate solid dissolved in the deionized water in the conical flask by using an analytical balance, and stirring until the sodium tartrate solid is completely dissolved;
[b]coating: mixing the LiBiF in the step 2)4:Yb3+,Ce3+The powder is uniformly dispersed in the [ a ] of the step 3)]Continuously stirring the solution for 10 hours at the temperature of 80 ℃; stopping heating, and naturally cooling to room temperature.
4) Purification, namely adding 100mL of acetone into the conical flask in the step 3) b, and after white precipitates are completely separated out, carrying out vacuum filtration to obtain white powder; and (3) drying the white powder in vacuum to obtain a final product, namely the BYC tracer with the core-shell structure.
Application of B tracer
5) Experiment of tracer in tap water
[a] Firstly, adding a tracer into tap water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, then detecting the fluorescence intensity at seven concentrations by using an excitation spectrophotometer under the condition that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[b] And secondly, uniformly dispersing an unknown amount of the fluorescent tracer in 1L of tap water, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the tap water according to a standard curve corresponding to the fluorescence intensity.
6) Experiment of tracer in oil field injection water
[a] Firstly adding a tracer into oilfield injection water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, then detecting fluorescence intensities at the seven concentrations by using an excitation light spectrophotometer under the condition that an excitation wavelength EX/emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[b] And secondly, uniformly dispersing the fluorescent tracer with unknown quantity in 1L of oilfield injection water, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the oilfield injection water according to a standard curve corresponding to the fluorescence intensity.
7) Experiment of tracer in tap water containing rock sample
[a] And preparing the tap water containing the rock sample according to the mass ratio of the tap water to the rock sample with the natural particle size of 1: 2.
[b] Adding different amounts of tracer into the tap water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, taking a supernatant after standing, detecting fluorescence intensities at the seven concentrations by using an excitation spectrophotometer under the conditions that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[c] And adding the fluorescent tracer into 1L of tap water containing the rock sample, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer according to a standard curve corresponding to the fluorescence intensity.
8) Experiment of tracer in injected water of oil field containing rock sample
[a] Preparing the oilfield injection water containing the rock sample according to the mass ratio of the oilfield injection water to the rock sample with the natural particle size of 1: 2.
[b] Adding different amounts of tracer into the oilfield injection water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, taking a supernatant after standing, detecting fluorescence intensities at the seven concentrations by using an excitation spectrophotometer under the condition that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of the fluorescence intensities-concentrations.
[c] And adding the fluorescent tracer into 1L of oilfield injection water containing the rock sample, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer according to a standard curve corresponding to the fluorescence intensity.
Example 2:
preparation of BYC tracer
1) Preparation of LiBiF4
The measuring cylinder accurately measures 60mL of anhydrous ethylene glycol, the anhydrous ethylene glycol is placed in a beaker, and 3.789g of BiCl is accurately weighed by an analytical balance3And 1.038g of LiF solid are dissolved in anhydrous glycol, mixed uniformly and then placed in a reaction kettle to react for 24 hours at the temperature of 150 ℃. Cooling, adding 100mL of deionized water, and after white precipitates are completely separated out, carrying out vacuum filtration to obtain LiBiF4And (3) powder.
2) Preparation of LiBiF4:Yb3+,Ce3+
[a]Preparing a rare earth solution: the measuring cylinder is used for accurately measuring 60mL of deionized water, the deionized water is placed in a beaker, and 0.018g of CeCl is accurately weighed by an analytical balance3And 0.384g YbCl3Dissolving the solid in deionized water;
[b]doping: mixing the LiBiF in the step 1)4The powder is uniformly dispersed in the [ a ] in the step 2)]The rare earth solution is evenly mixed and then placed in a reaction kettle to react for 12 hours at the temperature of 220 ℃. Cooling, washing with deionized water for 3 times, and vacuum filtering to obtain LiBiF4:Yb3+,Ce3+And (3) powder.
3) Preparation of BYC
[a] Preparing a sodium tartrate aqueous solution: 100mL of deionized water is accurately measured by a measuring cylinder and placed in a 250mL conical flask, 3.720g of sodium tartrate solid is accurately weighed by an analytical balance and dissolved in the deionized water in the conical flask, and the mixture is stirred until the sodium tartrate solid is completely dissolved.
[b]Coating: mixing the LiBiF in the step 2)4:Yb3+,Ce3+The powder is uniformly dispersed in the [ a ] of the step 3)]Continuously stirring the solution for 10 hours at the temperature of 80 ℃; stopping heating, and naturally cooling to room temperature;
4) and (3) purification: adding 100mL of acetone into the conical flask in the step 3) [ b ], and after white precipitates are completely separated out, carrying out vacuum filtration to obtain white powder; and (3) drying the white powder in vacuum to obtain a final product, namely the BYC tracer with the core-shell structure.
Application of B tracer
5) Experiment of tracer in tap water
[a] Firstly, adding a tracer into tap water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, then detecting the fluorescence intensity at seven concentrations by using an excitation spectrophotometer under the condition that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[b] And secondly, uniformly dispersing an unknown amount of the fluorescent tracer in 1L of tap water, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the tap water according to a standard curve corresponding to the fluorescence intensity.
6) Experiment of tracer in oil field injection water
[a] Firstly adding a tracer into oilfield injection water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, then detecting fluorescence intensities at the seven concentrations by using an excitation light spectrophotometer under the condition that an excitation wavelength EX/emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[b] And secondly, uniformly dispersing the fluorescent tracer with unknown quantity in 1L of oilfield injection water, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the oilfield injection water according to a standard curve corresponding to the fluorescence intensity.
7) Experiment of tracer in tap water containing rock sample
[a] And preparing the tap water containing the rock sample according to the mass ratio of the tap water to the rock sample with the natural particle size of 1: 2.
[b] Adding different amounts of tracer into the tap water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, taking a supernatant after standing, detecting fluorescence intensities at the seven concentrations by using an excitation spectrophotometer under the conditions that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[c] And adding the fluorescent tracer into 1L of tap water containing the rock sample, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer according to a standard curve corresponding to the fluorescence intensity.
8) Experiment of tracer in injected water of oil field containing rock sample
[a] Preparing the oilfield injection water containing the rock sample according to the mass ratio of the oilfield injection water to the rock sample with the natural particle size of 1: 2.
[b] Adding different amounts of tracer into the oilfield injection water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, taking a supernatant after standing, detecting fluorescence intensities at the seven concentrations by using an excitation spectrophotometer under the condition that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of the fluorescence intensities-concentrations.
[c] And adding the fluorescent tracer into 1L of oilfield injection water containing the rock sample, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer according to a standard curve corresponding to the fluorescence intensity.
Example 3:
preparation of BYC tracer
1) Preparation of LiBiF4
The measuring cylinder accurately measures 60mL of anhydrous ethylene glycol, the anhydrous ethylene glycol is placed in a beaker, and 3.260g of BiCl is accurately weighed by an analytical balance3And 1.038g of LiF solid are dissolved in anhydrous glycol, mixed uniformly and then placed in a reaction kettle to react for 24 hours at the temperature of 150 ℃. Cooling, adding 100mL of deionized water, and after white precipitates are completely separated out, carrying out vacuum filtration to obtain LiBiF4And (3) powder.
2) Preparation of LiBiF4:Yb3+,Ce3+
[a]Preparing a rare earth solution: the measuring cylinder accurately measures 60mL of deionized water, the deionized water is placed in a beaker, and 0.106g of CeCl is accurately weighed by an analytical balance3And 0.767g YbCl3Dissolving the solid in deionized water;
[b]doping: mixing the LiBiF in the step 1)4The powder is uniformly dispersed in the [ a ] in the step 2)]Of rare earth elementThe solution is evenly mixed and then placed in a reaction kettle to react for 12 hours at the temperature of 220 ℃. Cooling, washing with deionized water for 3 times, and vacuum filtering to obtain LiBiF4:Yb3+,Ce3+And (3) powder.
3) Preparation of BYC
[a] Preparing a sodium tartrate aqueous solution: accurately weighing 100mL of deionized water by using a measuring cylinder, placing the deionized water into a 250mL conical flask, accurately weighing 3.720g of sodium tartrate solid by using an analytical balance, dissolving the sodium tartrate solid in the deionized water in the conical flask, and stirring until the sodium tartrate solid is completely dissolved;
[b]coating: mixing the LiBiF in the step 2)4:Yb3+,Ce3+The powder is uniformly dispersed in the [ a ] of the step 3)]Continuously stirring the solution for 10 hours at the temperature of 80 ℃; stopping heating, and naturally cooling to room temperature.
4) Purification, namely adding 100mL of acetone into the conical flask in the step 3) b, and after white precipitates are completely separated out, carrying out vacuum filtration to obtain white powder; and (3) drying the white powder in vacuum to obtain a final product, namely the BYC tracer with the core-shell structure.
Application of B tracer
5) Experiment of tracer in tap water
[a] Firstly, adding a tracer into tap water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, then detecting the fluorescence intensity at seven concentrations by using an excitation spectrophotometer under the condition that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[b] And secondly, uniformly dispersing an unknown amount of the fluorescent tracer in 1L of tap water, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the tap water according to a standard curve corresponding to the fluorescence intensity.
6) Experiment of tracer in oil field injection water
[a] Firstly adding a tracer into oilfield injection water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, then detecting fluorescence intensities at the seven concentrations by using an excitation light spectrophotometer under the condition that an excitation wavelength EX/emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[b] And secondly, uniformly dispersing the fluorescent tracer with unknown quantity in 1L of oilfield injection water, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the oilfield injection water according to a standard curve corresponding to the fluorescence intensity.
7) Experiment of tracer in tap water containing rock sample
[a] And preparing the tap water containing the rock sample according to the mass ratio of the tap water to the rock sample with the natural particle size of 1: 2.
[b] Adding different amounts of tracer into the tap water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, taking a supernatant after standing, detecting fluorescence intensities at the seven concentrations by using an excitation spectrophotometer under the conditions that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[c] And adding the fluorescent tracer into 1L of tap water containing the rock sample, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer according to a standard curve corresponding to the fluorescence intensity.
8) Experiment of tracer in injected water of oil field containing rock sample
[a] Preparing the oilfield injection water containing the rock sample according to the mass ratio of the oilfield injection water to the rock sample with the natural particle size of 1: 2.
[b] Adding tracer agents with different amounts into the oilfield injection water, configuring the tracer agents into the oilfield injection water to be 0.1, 0.5 and 1.0,
1.5, 2.0, 5.0, 10.0ppm seven concentrations of solution, after standing, taking the supernatant, using an excitation spectrophotometer under the excitation wavelength EX/emission wavelength EM equal to 980nm/650nm, detecting the fluorescence intensity under seven concentrations, and drawing a fluorescence intensity-concentration standard curve.
[c] And adding the fluorescent tracer into 1L of oilfield injection water containing the rock sample, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer according to a standard curve corresponding to the fluorescence intensity.
Example 4:
preparation of BYC tracer
1) Preparation of LiBiF4
The measuring cylinder accurately measures 60mL of anhydrous ethylene glycol, the anhydrous ethylene glycol is placed in a beaker, and 2.117g of BiCl is accurately weighed by an analytical balance3And 1.038g of LiF solid are dissolved in anhydrous glycol, mixed uniformly and then placed in a reaction kettle to react for 24 hours at the temperature of 150 ℃. Cooling, adding 100mL of deionized water, and after white precipitates are completely separated out, carrying out vacuum filtration to obtain LiBiF4And (3) powder.
2) Preparation of LiBiF4:Yb3+,Ce3+
[a]Preparing a rare earth solution: the measuring cylinder accurately measures 60mL of deionized water, the deionized water is placed in a beaker, and 0.355g of CeCl is accurately weighed by an analytical balance3And 1.534g YbCl3Dissolving the solid in deionized water;
[b]doping: mixing the LiBiF in the step 1)4The powder is uniformly dispersed in the [ a ] in the step 2)]The rare earth solution is evenly mixed and then placed in a reaction kettle to react for 12 hours at the temperature of 220 ℃. Cooling, washing with deionized water for 3 times, and vacuum filtering to obtain LiBiF4:Yb3+,Ce3+And (3) powder.
3) Preparation of BYC
[a] Preparing a sodium tartrate aqueous solution: accurately weighing 100mL of deionized water by using a measuring cylinder, placing the deionized water into a 250mL conical flask, accurately weighing 3.720g of sodium tartrate solid by using an analytical balance, dissolving the sodium tartrate solid in the deionized water in the conical flask, and stirring until the sodium tartrate solid is completely dissolved;
[b]coating: mixing the LiBiF in the step 2)4:Yb3+,Ce3+The powder is uniformly dispersed in the [ a ] of the step 3)]Continuously stirring the solution for 10 hours at the temperature of 80 ℃; stopping heating, and naturally cooling to room temperature.
4) Purification, namely adding 100mL of acetone into the conical flask in the step 3) b, and after white precipitates are completely separated out, carrying out vacuum filtration to obtain white powder; and (3) drying the white powder in vacuum to obtain a final product, namely the BYC tracer with the core-shell structure.
Application of B tracer
5) Experiment of tracer in tap water
[a] Firstly, adding a tracer into tap water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, then detecting the fluorescence intensity at seven concentrations by using an excitation spectrophotometer under the condition that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[b] And secondly, uniformly dispersing an unknown amount of the fluorescent tracer in 1L of tap water, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the tap water according to a standard curve corresponding to the fluorescence intensity.
6) Experiment of tracer in oil field injection water
[a] Firstly adding a tracer into oilfield injection water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, then detecting fluorescence intensities at the seven concentrations by using an excitation light spectrophotometer under the condition that an excitation wavelength EX/emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[b] And secondly, uniformly dispersing the fluorescent tracer with unknown quantity in 1L of oilfield injection water, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the oilfield injection water according to a standard curve corresponding to the fluorescence intensity.
7) Experiment of tracer in tap water containing rock sample
[a] And preparing the tap water containing the rock sample according to the mass ratio of the tap water to the rock sample with the natural particle size of 1: 2.
[b] Adding different amounts of tracer into the tap water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, taking a supernatant after standing, detecting fluorescence intensities at the seven concentrations by using an excitation spectrophotometer under the conditions that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[c] And adding the fluorescent tracer into 1L of tap water containing the rock sample, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer according to a standard curve corresponding to the fluorescence intensity.
8) Experiment of tracer in injected water of oil field containing rock sample
[a] Preparing the oilfield injection water containing the rock sample according to the mass ratio of the oilfield injection water to the rock sample with the natural particle size of 1: 2.
[b] Adding different amounts of tracer into the oilfield injection water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, taking a supernatant after standing, detecting fluorescence intensities at the seven concentrations by using an excitation spectrophotometer under the condition that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of the fluorescence intensities-concentrations.
[c] And adding the fluorescent tracer into 1L of oilfield injection water containing the rock sample, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer according to a standard curve corresponding to the fluorescence intensity.
Example 5:
preparation of BYC tracer
1) Preparation of LiBiF4
The measuring cylinder is used for accurately measuring 60mL of anhydrous ethylene glycol, and the analytical balance is used for accurately weighing 0.423g of BiCl3And 1.038g of LiF solid are dissolved in anhydrous glycol, mixed uniformly and then placed in a reaction kettle to react for 24 hours at the temperature of 150 ℃. After cooling, adding 100mL of deionized water into the mixture, and performing vacuum filtration to obtain LiBiF after white precipitates are completely separated out4And (3) powder.
2) Preparation of LiBiF4:Yb3+,Ce3+
[a]Preparing a rare earth solution: the measuring cylinder is used for accurately measuring 60mL of deionized water, the deionized water is placed in a beaker, and 0.709g of CeCl is accurately weighed by an analytical balance3And 0.306g YbCl3Dissolving the solid in deionized water;
[b]doping: mixing the LiBiF in the step 1)4The powder is uniformly dispersed in the [ a ] in the step 2)]The rare earth solution is evenly mixed and then placed in a reaction kettle to react for 12 hours at the temperature of 220 ℃. Cooling, washing with deionized water for 3 times, and vacuum filtering to obtain LiBiF4:Yb3+,Ce3+And (3) powder.
3) Preparation of BYC
[a] Preparing a sodium tartrate aqueous solution: accurately weighing 100mL of deionized water by using a measuring cylinder, placing the deionized water into a 250mL conical flask, accurately weighing 3.720g of sodium tartrate solid by using an analytical balance, dissolving the sodium tartrate solid in the deionized water in the conical flask, and stirring until the sodium tartrate solid is completely dissolved;
[b]coating: mixing the LiBiF in the step 2)4:Yb3+,Ce3+The powder is uniformly dispersed in the [ a ] of the step 3)]Continuously stirring the solution for 10 hours at the temperature of 80 ℃; stopping heating, and naturally cooling to room temperature.
4) Purification, namely adding 100mL of acetone into the conical flask in the step 3) b, and after white precipitates are completely separated out, carrying out vacuum filtration to obtain white powder; and (3) drying the white powder in vacuum to obtain a final product, namely the BYC tracer with the core-shell structure.
Application of B tracer
5) Experiment of tracer in tap water
[a] Firstly, adding a tracer into tap water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, then detecting the fluorescence intensity at seven concentrations by using an excitation spectrophotometer under the condition that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[b] And secondly, uniformly dispersing an unknown amount of the fluorescent tracer in 1L of tap water, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the tap water according to a standard curve corresponding to the fluorescence intensity.
6) Experiment of tracer in oil field injection water
[a] Firstly adding a tracer into oilfield injection water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, then detecting fluorescence intensities at the seven concentrations by using an excitation light spectrophotometer under the condition that an excitation wavelength EX/emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[b] And secondly, uniformly dispersing the fluorescent tracer with unknown quantity in 1L of oilfield injection water, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the oilfield injection water according to a standard curve corresponding to the fluorescence intensity.
7) Experiment of tracer in tap water containing rock sample
[a] And preparing the tap water containing the rock sample according to the mass ratio of the tap water to the rock sample with the natural particle size of 1: 2.
[b] Adding different amounts of tracer into the tap water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, taking a supernatant after standing, detecting fluorescence intensities at the seven concentrations by using an excitation spectrophotometer under the conditions that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration.
[c] And adding the fluorescent tracer into 1L of tap water containing the rock sample, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer according to a standard curve corresponding to the fluorescence intensity.
8) Experiment of tracer in injected water of oil field containing rock sample
[a] Preparing the oilfield injection water containing the rock sample according to the mass ratio of the oilfield injection water to the rock sample with the natural particle size of 1: 2.
[b] Adding different amounts of tracer into the oilfield injection water to prepare solutions with seven concentrations of 0.1, 0.5, 1.0, 1.5, 2.0, 5.0 and 10.0ppm, taking a supernatant after standing, detecting fluorescence intensities at the seven concentrations by using an excitation spectrophotometer under the condition that an excitation wavelength EX/an emission wavelength EM is 980nm/650nm, and drawing a standard curve of the fluorescence intensities-concentrations.
[c] And adding the fluorescent tracer into 1L of oilfield injection water containing the rock sample, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer according to a standard curve corresponding to the fluorescence intensity.
TABLE 1 weight percentages of the raw materials in the above examples
Examples BiCl3 CeCl3 YbCl3 LiF Tartaric acid sodium salt
1 44.79％ 0.04％ 2.14％ 11.57％ 41.46％
2 42.35％ 0.20％ 4.29％ 11.60％ 41.56％
3 36.67％ 1.20％ 8.63％ 11.67％ 41.83％
4 24.16％ 4.05％ 17.51％ 11.84％ 42.44％
5 4.73％ 7.92％ 34.25％ 11.58％ 41.52％

Claims (2)

  1. A method for synthesizing a BYC tracer, characterized by comprising the steps of:
    1) preparation of LiBiF4
    Anhydrous ethylene glycol was placed in a beaker and BiCl was weighed3Dissolving LiF solid in anhydrous glycol, uniformly mixing, placing in a reaction kettle, and reacting for 24h at 150 ℃; cooling, adding deionized water, and vacuum filtering to obtain LiBiF4Powder;
    2) preparation of LiBiF4:Yb3+,Ce3+
    [a]Preparing a rare earth solution: placing deionized water in a beaker, CeCl3And YbCl3Dissolving the solid in deionized water;
    [b]doping: mixing the LiBiF in the step 1)4The powder is uniformly dispersed in the [ a ] in the step 2)]The rare earth solution is evenly mixed and then placed in a reaction kettle to react for 12 hours at the temperature of 220 ℃; cooling, washing with deionized water, and vacuum filtering to obtain LiBiF4:Yb3+,Ce3+Powder;
    3) preparation of BYC
    [a] Preparing a sodium tartrate aqueous solution: putting deionized water into a conical flask, weighing sodium tartrate solid, dissolving the sodium tartrate solid in the deionized water in the conical flask, and stirring until the sodium tartrate solid is completely dissolved;
    [b]coating: mixing the LiBiF in the step 2)4:Yb3+,Ce3+The powder is uniformly dispersed in the [ a ] of the step 3)]Continuously stirring the solution for 10 hours at the temperature of 80 ℃; stopping heating, and cooling to room temperature;
    4) purification, namely adding acetone into the conical flask in the step 3) b, and after white precipitates are completely separated out, carrying out vacuum filtration to obtain white powder; drying the white powder in vacuum to obtain a final product, namely the BYC tracer with the core-shell structure;
    the raw materials meet the following mixture ratio, and the total of the raw materials takes 100 percent as a calculation criterion;
    Figure FDA0002654905420000011
  2. 2. use of a "BYC tracer" synthesized according to the synthesis method of claim 1, characterized in that: firstly adding a tracer into liquid to be detected to prepare a plurality of solutions with different concentrations of less than 10.0ppm, then detecting fluorescence intensities under a plurality of concentrations by using an excitation light spectrophotometer under the condition that an excitation wavelength EX/emission wavelength EM is 980nm/650nm, and drawing a standard curve of fluorescence intensity-concentration; uniformly dispersing the fluorescent tracer with unknown quantity in the solution to be detected, measuring the fluorescence intensity of the fluorescent tracer, and obtaining the concentration of the fluorescent tracer in the solution to be detected according to a standard curve corresponding to the fluorescence intensity.
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