CN115059456A - Degradable radioactive isotope tracer and preparation method thereof - Google Patents

Degradable radioactive isotope tracer and preparation method thereof Download PDF

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Publication number
CN115059456A
CN115059456A CN202210884941.0A CN202210884941A CN115059456A CN 115059456 A CN115059456 A CN 115059456A CN 202210884941 A CN202210884941 A CN 202210884941A CN 115059456 A CN115059456 A CN 115059456A
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China
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degradable
tracer
solution
mixed material
prepared
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CN115059456B (en
Inventor
华成武
陈海军
邓刚
范家霖
沈超
董明静
管晖
孟闯
王晓慧
李旭照
张奕
黎振华
李甜甜
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Henan Tongxin Technology Co ltd
Isotope Institute Co ltd Of Henan Academy Of Sciences
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Henan Tongxin Technology Co ltd
Isotope Institute Co ltd Of Henan Academy Of Sciences
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    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B47/00Survey of boreholes or wells
    • E21B47/10Locating fluid leaks, intrusions or movements
    • E21B47/11Locating fluid leaks, intrusions or movements using tracers; using radioactivity
    • E21B47/111Locating fluid leaks, intrusions or movements using tracers; using radioactivity using radioactivity

Abstract

The invention provides a degradable radioisotope tracer and a preparation method thereof, aiming at the technical problems that the existing radioisotope tracer is not strong in degradability, the tracer can influence the pores of a water injection layer rock stratum and even can block the pores, the prepared degradable radioisotope tracer can be degraded under natural conditions within 1-24 months, is not easy to naturally migrate to the environment, is easy to protect in the production process, is not easy to desorb isotopes in the tracer, is mild in preparation conditions, low in equipment manufacturing difficulty and easy to realize, can distinguish tracers with different densities and purposes by utilizing colors, and the like.

Description

Degradable radioactive isotope tracer and preparation method thereof
Technical Field
The invention belongs to the field of petroleum logging, relates to an isotope tracer and a preparation method thereof, and particularly relates to a degradable radioisotope tracer and a preparation method thereof, wherein the prepared degradable radioisotope tracer has the advantages that the density can be adjusted in a large range to meet requirements of different logging conditions, the degradable radioisotope tracer can be degraded under natural conditions within 1-24 months, the natural migration to the environment is not easy, the production process is easy to protect, the isotope is not easy to desorb in the tracer, the preparation conditions are mild, the equipment manufacturing difficulty is low, the implementation is easy, the tracer with different densities and purposes can be distinguished by colors, and the like.
Background
The radioactive isotope tracer used for injecting profile logging by radioactive isotope tracer method is solid spherical particle, and its logging principle is as follows: the radioactive isotope solid tracer is injected into water from the releaser, moves along with the water, when the radioactive isotope solid tracer reaches the water-absorbing layer, the injected water enters the stratum, the tracer is remained on the surface of the water-absorbing layer, the gamma ray intensity emitted by the tracer is detected by an instrument, and the injection section condition can be obtained through calculation. It is generally believed that the radioisotope tracer is selected to have a density that is the same as or greater than the injected water when the radioisotope reaches the absorbent layer from above the absorbent layer, and to have a density that is the same as or less than the injected water when the radioisotope reaches the absorbent layer from below the absorbent layer in an upward-return manner. The degree of mineralization of the injected water also affects the selection of the tracer, wherein the tracer with a higher degree of mineralization is selected to have a higher density, and the tracer with a lower density is selected to have a lower density.
The radioactive isotope tracer used for injecting profile well logging by isotope tracer method is generally prepared by the method disclosed in Chinese patent CN201110057628.1, the carrier loaded with isotope at early stage is generally silica gel or active carbon, the two carriers have strong isotope adsorption capacity but higher density, the density of the prepared tracer is also higher, the tracer is suitable for injecting well, when logging and returning well, the tracer is required to rise to water-absorbing layer along with water, some difficulties may occur, and at this time, the density is required to be equal to or slightly lower than that of the carrier injected water. The method for the density-controllable carrier disclosed in the prior art realizes the controllable adjustment of the carrier density, so that the adjustment of the density of the radioactive isotope tracer is free from the condition of relying on a single mode of surface modification, and the density adjustment range is wider. The radioactive isotope tracer which meets different logging conditions and meets market requirements can be obtained by utilizing the prior art. With the enhancement of the awareness of society to environmental protection, some experts in the industry believe that the tracer will affect and even block the pores of the water injection layer rock stratum, and the risk can be avoided by adopting the radioactive isotope tracer which can be degraded in the water injection environment. The previous patent contains technologies such as density adjustment, isotope loading, surface modification and the like, is relatively perfect in the aspect of solid-state radioisotope tracers and is relatively effective from the perspective of popularization and application, but few attention is paid to the degradable property of the radioisotope tracers, and a plurality of logging units have generated the requirements on the degradable radioisotope tracers.
Disclosure of Invention
Technical problem to be solved by the invention
The invention provides a degradable radioisotope tracer and a preparation method thereof, aiming at the technical problems that the existing radioisotope tracer is not strong in degradability, the tracer can influence the pores of a water injection layer rock stratum and even can block the pores, the prepared degradable radioisotope tracer can be degraded under natural conditions within 1-24 months, is not easy to naturally migrate to the environment, is easy to protect in the production process, is not easy to desorb isotopes in the tracer, is mild in preparation conditions, low in equipment manufacturing difficulty and easy to realize, can distinguish tracers with different densities and purposes by utilizing colors, and the like.
(II) technical scheme adopted by invention for solving technical problem
A method for preparing a degradable radioisotope tracer, said method comprising at least the steps of:
SS1, soaking a certain amount of fine granular porous zeolite and hollow glass beads in a silane coupling agent solution for a certain time to enable the surfaces of the porous zeolite and pores to be fully soaked with the silane coupling agent, enabling the surfaces of the hollow glass beads to be fully adhered with the silane coupling agent, and then taking out the fully soaked porous zeolite and hollow glass beads to be dried for later use;
SS2, adding a certain amount of fine granular degradable materials and pigments into the porous zeolite and the hollow glass beads which are subjected to drying treatment in the step SS1, putting the porous zeolite and the hollow glass beads into rolling equipment with a heating function, uniformly spraying isotope solution on the surfaces of the materials while rolling, stirring and heating, wherein the spraying speed is controlled to avoid liquid accumulation, and completely drying the mixed materials after spraying is finished, wherein the color of the selected pigments is set according to the density of a target finished product;
SS3, uniformly mixing the dry mixed material prepared in the step SS2 with a certain amount of adhesive to prepare a viscous mixed material;
SS4, putting the viscous mixed material prepared in the step SS3 into an extruder for extrusion treatment to prepare a thin strip-shaped mixed material with the section diameter of 0.1-5 mm;
SS5, quickly transferring the thin strip-shaped mixed material prepared in the step SS4 to a rounding machine for rounding treatment to prepare a granular mixed material with a target grain size range;
SS6, putting the granular mixed material prepared in the step SS5 into rolling equipment with a heating function, uniformly spraying dilute acid on the surface of the material while rolling, stirring and heating, uniformly spraying a surfactant solution on the surface of the material after the dilute acid on the surface of the material is completely dried, and uniformly spraying an antistatic agent solution on the surface of the material after the surfactant solution on the surface of the material is completely dried until the antistatic agent solution on the surface of the material is completely dried, so that a surfactant layer and an antistatic agent layer are sequentially formed on the surface of the granular mixed material from inside to outside, wherein the grain diameter of the prepared granular mixed material subjected to surface treatment is 50-5000 microns, and the density is 0.2-1.5 g/ml;
and SS7, screening the granular mixed material subjected to surface treatment and prepared in the step SS6 to obtain a finished product of the degradable radioisotope tracer.
Preferably, in step SS1, the porous zeolite and hollow glass beads are soaked in the silane coupling agent solution for 3 hours or more.
Preferably, in steps SS1 and SS2, the fineness of the fine granular degradable material, the porous zeolite, the hollow glass beads and the pigment is 80-1000 meshes, and the mass ratio is 10-85: 5-80: 5-80: 0.05-10.
Preferably, in step SS2, the degradable material is starch, polylactic acid, poly 3-hydroxyalkanoate, polycaprolactone, polybutylene succinate, cellulose, chitosan, or a mixture thereof.
Preferably, in step SS2, the pigment is an inorganic pigment or an organic pigment.
Preferably, in step SS3, the adhesive is a starch gelatinization aqueous solution, a dextrin aqueous solution, a modified starch aqueous solution, a modified cellulose aqueous solution, a poly (ethyl lactate acetate), a polycaprolactone tetrahydrofuran solution, a chitosan acetic acid solution, or a chloroform solution of polybutylene succinate, the mass concentration of the adhesive is 3-10%, and the addition amount is 15-40%.
It is another object of the present invention to provide a degradable radioisotope tracer prepared using the above method of the present invention.
The degradable radioactive isotope tracer prepared by the invention is used for injection profile well logging by an isotope tracer method, and due to the addition of starch and other degradable materials during the preparation of the granular radioactive isotope tracer, the granular radioactive isotope tracer can be continuously disintegrated along with the degradation of the degradable materials, and under different well logging conditions, the isotope tracer has different disintegration speeds. Besides, when the granular radioactive isotope tracer is prepared, except degradable materials such as starch and the like, the composition of fine particle carriers such as porous zeolite loaded with isotopes, hollow glass microspheres and the like is similar to that of rock, and the fine particle carriers can be gradually corroded under the water flow flushing, so that the prepared degradable radioactive isotope tracer can meet the requirements of injection profile logging by an isotope tracer method, cannot cause pollution problems, and has small influence on the stratum.
(III) technical effects that the invention can achieve
Compared with the prior art, the degradable radioisotope tracer and the preparation method thereof have the following remarkable technical advantages:
(1) the density of the prepared degradable radioisotope tracer can be adjusted within a large range of 0.2-1.5g/ml, so that the requirements of different logging conditions are met;
(2) the degradable radioactive isotope tracer prepared by the invention can be degraded under natural conditions within 1-24 months, and has little influence on injection into stratum;
(3) the isotope utilization rate in the preparation process is high and can reach more than 80 percent;
(4) in the preparation method, the isotope exists in an ion form in the preparation process, is not easy to naturally migrate to the environment, has small influence on the environment, and is easy to protect in the production process;
(5) the isotope of the degradable radioactive isotope tracer prepared by the invention is not easy to desorb in the tracer;
(6) the preparation condition is mild, the equipment manufacturing difficulty is low, and the realization is easy;
(7) the invention can distinguish the tracers with different densities and purposes by utilizing the colors, is clear at a glance, is convenient for production and packaging and is convenient for users to use.
Detailed Description
In order that the invention may be better understood, the following further description is provided, taken in conjunction with the accompanying examples, so that the advantages and features of the invention will be more readily understood by those skilled in the art. It should be noted that the following description is only a preferred embodiment of the present invention, but the present invention is not limited to the following embodiment. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used with another embodiment to yield a still further embodiment. Therefore, it is intended that the present invention encompass such modifications and variations within the scope of the appended claims and their equivalents.
Examples
The invention provides a preparation method of a degradable radioisotope tracer, which is used as a preferred embodiment and mainly comprises the following steps of:
firstly, 0.3Kg of zeolite powder with the granularity of 500 meshes and 0.6Kg of hollow glass beads with the granularity of 500 meshes are soaked in a silane coupling agent solution for at least 3 hours, so that the surface and pores of porous zeolite are fully soaked with the silane coupling agent, the surface of the hollow glass beads is fully adhered with the silane coupling agent, and then the fully soaked porous zeolite and the hollow glass beads are taken out to be dried for later use.
Secondly, putting the treated zeolite powder and hollow glass beads into a device capable of heating an inclined roller, adding 0.01Kg of DPP (DPP) bright red pigment with the granularity of 600 meshes and fine granular degradable materials into the zeolite powder and the hollow glass in the process, spraying a radioisotope solution on the surface of the materials while the roller rolls, controlling the spraying speed, not accumulating liquid, uniformly spraying, and completely drying the mixed materials after the spraying is finished, wherein the degradable materials are starch, polylactic acid, poly (3-hydroxyalkanoate), polycaprolactone, polybutylene succinate, cellulose, chitosan or a mixture thereof. The mass ratio of the degradable material, the porous zeolite, the hollow glass beads and the pigment is controlled to be 10-85: 5-80: 5-80: 0.05-10.
And then, uniformly mixing the dried mixed material with an adhesive solution to prepare a viscous mixed material, wherein the adhesive solution is 300ml of 10% polybutylene succinate chloroform solution.
And thirdly, putting the viscous mixed material into an extruder for extrusion treatment, and extruding to obtain a thin strip-shaped mixed material with the cross section diameter of 1.2 mm.
Then, the thin strip-shaped mixed material is quickly put into a rounding machine for rounding treatment, and the granular mixed material with the target grain size range is prepared.
Then, the granular mixed material is transferred into a device capable of heating an inclined roller, diluted acid, a surfactant and an antistatic agent are sprayed on the surface of the material in sequence while rolling, the spraying speed is controlled without liquid accumulation, the former solution is completely dried after being sprayed, and the next solution is sprayed. The method comprises the following specific steps: firstly, uniformly spraying dilute acid on the surface of a material, uniformly spraying a surfactant solution on the surface of the material after the dilute acid on the surface of the material is completely dried, uniformly spraying an antistatic agent solution on the surface of the material after the surfactant solution on the surface of the material is completely dried, and enabling the surface of a granular mixed material to sequentially form a surfactant layer and an antistatic agent layer from inside to outside, wherein the grain diameter of the prepared granular mixed material subjected to surface treatment is 5000 microns, and the density is about 1.0 g/ml;
and finally, screening the granular mixed material subjected to surface treatment to obtain a finished product of the degradable radioactive isotope tracer.
The object of the present invention is fully effectively achieved by the above embodiments. All equivalent or simple changes of the structure, the characteristics and the principle of the invention which are described in the patent conception of the invention are included in the protection scope of the patent of the invention. Various modifications, additions and substitutions for the specific embodiments described may be made by those skilled in the art without departing from the scope of the invention as defined in the accompanying claims.
The invention has not been described in detail and is part of the common general knowledge of a person skilled in the art.

Claims (7)

1. A method for preparing a degradable radioisotope tracer, said method comprising at least the steps of:
SS1, soaking a certain amount of fine granular porous zeolite and hollow glass beads in a silane coupling agent solution for a certain time to enable the surfaces of the porous zeolite and pores to be fully soaked with the silane coupling agent, enabling the surfaces of the hollow glass beads to be fully adhered with the silane coupling agent, and then taking out the fully soaked porous zeolite and hollow glass beads to be dried for later use;
SS2, adding a certain amount of fine granular degradable materials and pigments into the porous zeolite and the hollow glass beads which are subjected to drying treatment in the step SS1, putting the porous zeolite and the hollow glass beads into rolling equipment with a heating function, uniformly spraying isotope solution on the surfaces of the materials while rolling, stirring and heating, wherein the spraying speed is controlled to avoid liquid accumulation, and completely drying the mixed materials after spraying is finished, wherein the color of the selected pigments is set according to the density of a target finished product;
SS3, uniformly mixing the dry mixed material prepared in the step SS2 with a certain amount of adhesive to prepare a viscous mixed material;
SS4, putting the viscous mixed material prepared in the step SS3 into an extruder for extrusion treatment to prepare a thin strip-shaped mixed material with the section diameter of 0.1-5 mm;
SS5, quickly transferring the thin strip-shaped mixed material prepared in the step SS4 to a rounding machine for rounding treatment to prepare a granular mixed material with a target grain size range;
SS6, putting the granular mixed material prepared in the step SS5 into rolling equipment with a heating function, uniformly spraying dilute acid on the surface of the material while rolling, stirring and heating, uniformly spraying a surfactant solution on the surface of the material after the dilute acid on the surface of the material is completely dried, and uniformly spraying an antistatic agent solution on the surface of the material after the surfactant solution on the surface of the material is completely dried until the antistatic agent solution on the surface of the material is completely dried, so that a surfactant layer and an antistatic agent layer are sequentially formed on the surface of the granular mixed material from inside to outside, wherein the grain diameter of the prepared granular mixed material subjected to surface treatment is 50-5000 microns, and the density is 0.2-1.5 g/ml;
and SS7, screening the granular mixed material subjected to surface treatment and prepared in the step SS6 to obtain a finished product of the degradable radioisotope tracer.
2. The method of claim 1, wherein the porous zeolite and the hollow glass beads are immersed in the silane coupling agent solution for 3 hours or more in step SS1.
3. The method for preparing a degradable radioisotope tracer of claim 1, wherein in steps SS1 and SS2, the fineness of the fine particulate degradable material, the porous zeolite, the hollow glass beads and the pigment is 80-1000 meshes, and the mass ratio is 10-85: 5-80: 5-80: 0.05-10.
4. The method of claim 1, wherein in step SS2, the degradable material is starch, polylactic acid, poly-3-hydroxyalkanoate, polycaprolactone, polybutylene succinate, cellulose, chitosan, or a mixture thereof.
5. The method of claim 1, wherein in step SS2, the pigment is an inorganic pigment or an organic pigment.
6. The method for preparing a degradable radioisotope tracer of claim 1, wherein in step SS3, the binder is starch gelatinization aqueous solution, dextrin aqueous solution, modified starch aqueous solution, modified cellulose aqueous solution, poly (ethyl lactate acetate) solution, polycaprolactone tetrahydrofuran solution, chitosan acetic acid solution, or poly (butylene succinate) chloroform solution, the mass concentration of the binder is 3-10%, and the addition amount is 15-40%.
7. A degradable radioisotope tracer prepared by the method of any one of claims 1 to 6.
CN202210884941.0A 2022-07-26 2022-07-26 Degradable radioisotope tracer and preparation method thereof Active CN115059456B (en)

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