CN111304511A - Magnesium alloy material for oil and gas exploitation and preparation method and application thereof - Google Patents
Magnesium alloy material for oil and gas exploitation and preparation method and application thereof Download PDFInfo
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- CN111304511A CN111304511A CN202010227145.0A CN202010227145A CN111304511A CN 111304511 A CN111304511 A CN 111304511A CN 202010227145 A CN202010227145 A CN 202010227145A CN 111304511 A CN111304511 A CN 111304511A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/02—Making non-ferrous alloys by melting
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
Abstract
The invention discloses a magnesium alloy material for oil and gas exploitation, and a preparation method and application thereof, and belongs to the technical field of nonferrous metals. The magnesium alloy material comprises the following components in percentage by weight: cerium-rich misch metal: 0.5-25 wt.%, Sn: 0-10 wt.%; fe: 0-10 wt.%, Ti: 0-10 wt.%; ni: 0-10 wt.%; cu: 0-10 wt.%; the balance being Mg. The tool made of the magnesium alloy material can be used for underground operation of oil and gas exploitation in oil wells, shale gas wells and oil and gas wells, and comprises a soluble bridge plug, a soluble ball seat, a fracturing ball, a plugging ball, a target dart and the like. The material can accurately control and predict the mechanical property and dissolution rate evolution of the material in the oil-gas well environment, establish an accurate prediction model, directly select the most appropriate components and preparation and deformation methods for different shale oil-gas well environments, greatly shorten the supply period, ensure the safety and efficiency of oil-gas exploitation, and reduce the risk and cost of production accidents.
Description
Technical Field
The invention belongs to the technical field of nonferrous metals, and particularly relates to a magnesium alloy material for oil and gas exploitation, and a preparation method and application thereof.
Background
Because the standard electrode potential of magnesium is as low as-2.37V, the corrosion potential is also very low in other media (such as 0.5% NaCl solution, seawater, etc.), about-1.45V to-1.6V, and the intrinsic characteristic causes the magnesium alloy to be in a humid environment and Cl-Corrosion is highly likely to occur in the presence of conditions and thus degradation can be achieved in shale gas/oil environments. The fracturing tools such as bridge plugs, ball seats, fracturing balls and the like made of magnesium alloy materials can provide reliable interlayer packing in the fracturing construction of exploiting shale oil gas and the like, can be automatically dissolved in the stratum flowback fluid environment after the construction is finished, do not need wellbore intervention operation, and realize the full-drift-diameter production of a wellbore.
The oil well environment is complex, including: the temperature is 50-180 ℃, the pressure is 30-90 Mpa, and Cl is added-Ion content (1-10%), and oil-water ratio (60-90%). The mechanical property and solubility of the fracturing tool are different when the oil well environments in different regions are different, the oil well environments in different layer depths in the same region are different, and even the well descending sequence of the fracturing tool in the same oil well is different. Therefore, due to the large variability of the service environment, the mechanical property and the degradation rate of the material for the fracturing tool in the service environment can be accurately predicted and controlled, a model is established, components can be directly selected after the service environment is determined, the fracturing tool can be provided in a targeted manner, and the engineering quality and the production efficiency can be effectively ensured.
However, the related patents of the components of magnesium alloy materials mostly used for fracturing tools at present are that alloy elements such as Ni, Cu, Fe and the like are added into the traditional Mg-Al series, Mg-Zn series and Mg-RE series magnesium alloys, so that the degradation rate is improved. There are several problems, however: 1. the strength of the non-rare earth magnesium alloy is rapidly reduced or even softened at the underground temperature, and the degradation rate cannot be accurately controlled; 2. the conventional rare earth magnesium alloy has high strength and high temperature resistance, but the production cost is high, a second phase generated by adding alloy elements has solid solubility in a matrix, and is redissolved or precipitated in the preparation and deformation processes, and the type and the quantity of the second phase cannot be accurately predicted, so that the degradation rate of the alloy cannot be accurately predicted and controlled; 3. when the need fracturing tool appears easily and provides effective interval packing at oil gas well exploitation process, because of the low softening of intensity or degradation too fast can't realize effectual packing and cause the engineering accident, perhaps when needing fracturing tool fast degradation to realize oil gas exploitation, because intensity is high, degradation is too slow again seriously influence the engineering progress. 4. The material for the fracturing tool is influenced by tissue components, cannot establish a model with accurate mechanical property and degradation rate, can only be used in a specific oil-gas environment, needs new test verification in new oil-gas field environment application, has low universality, prolongs the supply period, influences the production efficiency and increases the production cost. 5. The downhole tool is basically cylindrical or spherical, so that the degradation rate of the tool is improved, and the production efficiency is improved.
Disclosure of Invention
In order to solve the problems, the invention provides a magnesium alloy material for oil and gas exploitation, which comprises the following components in part by weight: one or more of Sn, Ni, Fe, Ti and Cu, Mg and cerium-rich misch metal;
the contents are as follows: cerium-rich misch metal: 0.5-25 wt.%, Sn: 0-10 wt.%; fe: 0-10 wt.%, Ti: 0-10 wt.%; ni: 0-10 wt.%; cu: 0-10 wt.%; the balance being Mg.
The magnesium alloy material comprises the following components in percentage by weight: cerium-rich misch metal: 0.5-25 wt.%; sn: 0-2 wt.%; fe: 0-1 wt.%, Ti: 0-1 wt.%; ni: 0-1 wt.%; cu: 0-1 wt.%, and the balance being Mg.
The cerium-rich misch metal contains Ce, La, Nd and Pr, wherein the ratio of Ce: 40-60 wt.%; la: 20-40 wt.%; nd: 10-15 wt.%; pr: 1-10 wt.%, and the balance impurities.
The mechanical property and the dissolution rate of the magnesium alloy material can be accurately predicted and controlled by changing the components and the structure of the magnesium alloy material.
A preparation method of a magnesium alloy material for oil and gas exploitation comprises the following steps:
1) uniformly mixing Ce, La, Nd and Pr according to the content proportion to obtain cerium-rich mischmetal;
preparing magnesium ingots, cerium-rich mischmetal, Sn powder, Fe powder, Ti powder, Ni powder and Cu powder as raw materials according to the content of a magnesium alloy material, and respectively preheating the cerium-rich mischmetal and metal powder;
2) melting a magnesium ingot under an anaerobic condition, and then adding preheated cerium-rich mischmetal to obtain an alloy melt;
3) adding preheated Sn powder, Fe powder, Ti powder, Ni powder and Cu powder into the alloy melt, and stirring and melting to obtain magnesium alloy melt;
4) and cooling the magnesium alloy melt, and spraying the magnesium alloy solution to the mold wall by using a spray pipe to perform ingot casting to obtain the magnesium alloy material.
The purity of the raw materials in the step 1) is more than or equal to 99.99%, the preheating temperature is 200 ℃, the preheating time is 2 hours, and the melting temperature in the step 2) is 680-800 ℃; step 3), the melting temperature is 700-800 ℃, and the melting time is 30-80 minutes; the temperature in the step 4) is 640-660 ℃, and the heat preservation time is 10 minutes.
Preheating the mold and the spray pipe before use, and additionally arranging a heat-insulating layer outside the mold; the preheating temperature is 500 ℃, and the preheating time is 5-10 hours; the heat preservation is the asbestos layer, and thickness is 5 ~ 25 mm.
The spray pipe is L-shaped, the tail end of the spray pipe is welded with a nozzle, a plurality of spray pipes are uniformly arranged in the center of the mold, the spray pipes are of a lifting structure, the bottoms of the spray pipes are parallel to the bottom of the mold, and the nozzles point to the wall of the mold; the number of the spray pipes is 4-10, the distance between the spray nozzles is 20-200 mm, and the distance between the spray nozzles and the mold wall is 40-100 mm; the bottom of the spray pipe and the liquid level of the magnesium alloy melt are kept 1-25 mm.
After the magnesium alloy material ingot casting is finished, carrying out homogenization heat treatment on the ingot blank, processing the ingot blank into a corresponding forging and carrying out aging treatment; the heat treatment temperature is 400-530 ℃, and the heat treatment time is 6-36 h.
The application of the magnesium alloy material for oil and gas exploitation is applied to the preparation of fracturing construction tools or degradable materials for oil and gas exploitation; further comprises a soluble bridge plug, a soluble ball seat, a fracturing ball, a plugging ball, a target dart and a pressure holding ball.
The invention has the beneficial effects that:
1. the magnesium alloy material has the advantages of uniform structure, controllable second phase quantity, excellent mechanical property and uniform, accurate and controllable degradation. The method can provide corresponding components and deformation methods for different oil and gas well environments, avoids researching and developing new materials for each oil and gas well, greatly shortens the supply period of tools, improves the oil and gas exploitation efficiency and safety, and reduces the production cost.
2. The tool made of the magnesium alloy material can be used for underground operation of oil and gas exploitation in oil wells, shale gas wells and oil and gas wells, and comprises a soluble bridge plug, a soluble ball seat, a fracturing ball, a plugging ball, a target dart and the like. The unique components and the structure of the magnesium alloy enable the mechanical property and the degradation property evolution of the alloy in the oil-gas well environment to be accurately controlled, an accurate prediction model can be established, the most appropriate components can be directly selected for different shale oil-gas well environments, the supply period is greatly shortened, the safety and the efficiency of oil-gas exploitation are ensured, and the risk and the cost of production accidents are reduced.
3. The magnesium alloy material can be used in various underground environments, such as temperature, pressure and Cl-The content ranges are as follows: the temperature is 50-200 ℃, the pressure is 30-120 Mpa, and Cl is-The ion content is 0.5-10%.
Drawings
FIG. 1 is a metallographic structure of an alloy according to example 1 of the present invention;
FIG. 2 is a precipitation morphology diagram of a Mg-Sn phase in a [0001] plane;
FIG. 3 is a schematic illustration of a transfer process of the present invention;
wherein, 1-melt inlet, 2-mould, 3-spray pipe, 4-nozzle.
Detailed Description
1) Preparing a raw material with the content ratio of Ce: 40-60 wt.%; la: 20-40 wt.%; nd: 10-15 wt.%; pr: 1-10 wt.% of Ce, La, Nd and Pr are uniformly mixed to obtain cerium-rich mischmetal; the cerium-rich mixed rare earth can also comprise associated ore after the purification of rare earth elements such as Gd, Y or Nd;
2) preparing raw materials of magnesium ingot, cerium-rich mixed rare earth, Sn powder, Fe powder, Ti powder, Ni powder and Cu powder according to the content of magnesium alloy materials, wherein the cerium-rich mixed rare earth: 0.5-25 wt.%, Sn: 0-10 wt.%; fe: 0-10 wt.%, Ti: 0-10 wt.%; ni: 0-10 wt.%; cu: 0-10 wt.%; the balance being Mg; the method specifically comprises the following steps: cerium-rich misch metal: 0.5-25 wt.%; sn: 0-2 wt.%; fe: 0-1 wt.%, Ti: 0-1 wt.%; ni: 0-1 wt.%; cu: 0-1 wt.%, and the balance being Mg.
Respectively preheating the cerium-rich misch metal and the metal powder raw materials at 200 ℃ for 2 hours;
3) melting a magnesium ingot under an anaerobic condition, wherein the melting temperature is 680-800 ℃, and then adding preheated cerium-rich mischmetal to obtain an alloy melt;
4) adding preheated Sn powder, Fe powder, Ti powder, Ni powder and Cu powder into the alloy melt, stirring, melting at 700-800 ℃ to obtain magnesium alloy melt, preserving heat for 30-80 minutes, and performing sufficient mechanical/electromagnetic stirring for 3-8 times to uniformly distribute all alloy elements in the magnesium solution to obtain the magnesium alloy melt.
The Mg-MM second phase formed by adding the cerium-rich misch metal and the Mg matrix is formed and uniformly distributed in the preparation and solidification process, is not dissolved in the magnesium matrix in the subsequent heat treatment and deformation processes, has controllable quantity and size, can realize a second phase strengthening mechanism, can induce dynamic recrystallization in the deformation process, and improves the mechanical property of the alloy;
and the potential difference between the Mg-MM second phase and the matrix is large, so that the Mg-MM second phase and the matrix form a galvanic cell to corrode, and the corrosion speed is higher. And the accurate control of the corrosion speed of the bridge plug can be realized by controlling the quantity of the Mg-MM second phase, an accurate prediction model is established, and the error of the model cannot be changed due to the change of alloy components. Sn, Fe, Ti, Ni, Cu and other elements are added in a powder form, are uniformly distributed in the matrix in a simple substance state, are complementary with the corrosion effect of a Mg-MM second phase and a Mg-Sn second phase in the degradation process, further promote the uniform degradation of the alloy and accelerate the degradation rate.
The Mg-MM second phase belongs to a high-temperature stable phase, so that the cerium-rich mischmetal magnesium alloy can be used in a high-temperature environment and is suitable for the conditions of 50-200 ℃, 30-120 Mpa of pressure and Cl-Under the condition that the ion content is 0.5-10%, the oil gas and other underground environments are met, meanwhile, the rich cerium mixed rare earth belongs to the rich rare earth, and the raw material cost for preparing the fracturing tool can be greatly reduced in the preparation and practical application processes.
5) In order to accurately determine the properties of the magnesium alloy material, a spectrum sample is poured into the magnesium alloy melt, the stokehole analysis is carried out, and whether the feeding adjustment is carried out or not is determined according to the components and the content of the sample until the magnesium alloy melt reaches the required components and the content of the magnesium alloy.
6) Preparing corresponding tools such as metal or graphite, a sand mold, a spray pipe and the like, wherein the spray pipe is made of copper alloy, the mold and the tools are preheated by heat preservation for 5-10 hours at 500 ℃, an asbestos layer with the thickness of 5-25 mm is additionally arranged outside the mold, a plurality of spray pipes are fixed at the center of the mold and can move up and down, the spray pipes in the mold are L-shaped, the tail ends of the spray pipes are parallel to the bottom of the mold and keep a distance of 1-25 mm from the bottom of the mold, nozzles are welded at the tail ends of the spray pipes and point to the wall of the mold, the nozzles are uniformly spread around by taking the spray pipes as the center, the interval between the nozzles is 20-200 mm;
7) reducing the temperature of the magnesium alloy melt in the step 4) to be 640-660 ℃ close to the liquidus temperature, preserving the temperature for 10 minutes, enabling the melt to be in a molten state, applying pressure, transferring the melt from a melt inlet 1 to each spray pipe 3 by using a transfer pump as shown in figure 3, and spraying out the melt by smelting through a nozzle 4, wherein the spray pipe rises along with the rise of the liquid level in the mould 2 and keeps a distance of 1-25 mm with the liquid level all the time; and after the molten liquid is transferred, performing heat preservation, covering and isolating on the top to obtain the magnesium alloy material. The mold is preheated at 500 ℃ and is kept warm for a long time, the outer side of the mold is kept warm by an asbestos layer, the molten liquid continuously collides with the mold wall and is kept in a molten state, the jet casting is a cooling process, the temperature difference between the inside and the outside of the molten liquid after flowing to the core is small, and the solidification speed is high. The melt is rapidly solidified into a solid phase after reaching the die, the temperature difference between the core part and the surface layer of the whole ingot is small, the temperature of the core part and the surface layer are synchronously reduced, and a Mg-MM second phase can be formed at the same time; the temperature gradient is small, and the formed second phase has uniform quantity and equivalent size.
8) Carrying out homogenization heat treatment on the ingot blank prepared from the magnesium alloy material in the step 7), keeping the temperature at 400-530 ℃ for 6-36 h, then processing the ingot blank into a bar, a pipe, a section or various forgings by adopting extrusion, forging, rolling and the like, so that a strong basal plane texture is formed in the processed material, carrying out aging treatment and carrying out aging treatment to obtain a magnesium alloy material casting, wherein the aging time is 100-255 ℃, the temperature is kept for 2-40 h, and the Mg-Sn phase is only precipitated on the basal plane;
9) and (3) machining the casting and various deformed processing materials in the step 8) into parts by using mechanical machining methods such as turning, milling, sawing, special control, numerical control machining and the like, and assembling or directly machining the parts into finished fracturing tool products or degradable material tools such as a soluble bridge plug, a soluble ball seat, a fracturing ball, a plugging ball, a target dart, a suppressing ball and the like.
According to the research of the invention, the cerium-rich mischmetal is found to be used as a main alloy element, and in the process of alloy smelting and cooling, the cerium-rich mischmetal and the Mg matrix form a Mg-MM second phase with a size of 1-20 um and a shape similar to that of the Mg matrix by controlling the solidification speed and the solidification direction of the ingot, and the Mg-MM second phase is uniformly distributed in the ingot; the solid solubility of the second phase in the matrix is extremely small and almost zero, and the heat treatment process has no influence on the size and quantity of the second phase and always exists in the matrix in an as-grown state. The second phase can induce dynamic recrystallization in the deformation process, refine alloy grains and improve the mechanical property of the alloy; the Mg-MM second phase belongs to a high-temperature stable phase, so that the cerium-rich mischmetal magnesium alloy can be used in a high-temperature environment and is suitable for underground environments such as oil gas and the like; the difference between the Mg-MM second phase and the matrix is large, galvanic cell corrosion is formed between the Mg-MM second phase and the matrix, the corrosion speed is higher, the accurate control of the bridge plug corrosion speed can be realized by controlling the quantity of the second phase, an accurate prediction model is established, and the error of the model cannot be changed due to the change of alloy components.
The Mg-MM second phase formed by adding the cerium-rich mixed rare earth and the Mg matrix is formed in the preparation and solidification process and is uniformly distributed in castings and ingots, and the solid solubility of the Mg-MM second phase in the matrix is extremely low and almost zero. Therefore, the second phase can not be dissolved back in the matrix in the subsequent homogenization and aging heat treatment processes, and the degradation performance and the mechanical property of the alloy can be accurately controlled. The homogenization and aging procedures in the process are respectively convenient for deformation and mechanical processing of products, and have little influence on the structure and the performance.
The tool for downhole operation is basically in a cylindrical and spherical shape, the radial corrosion rate of the tool is increased, the integral degradation rate of the tool can be accelerated, and the production efficiency is improved. The magnesium alloy forms a strong base surface texture through deformation such as extrusion, forging, rolling and the like, and the tool is obtained through machining to ensure that the base surface of the magnesium alloy matrix is parallel to the length direction of an oil-gas well and vertical to the radial direction when the tool is in service in the well; adding Sn element, fixing on the basal plane by temperature control to form a Mg-Sn second phase (belonging to a high-temperature stable phase, which can resist temperature of more than 535 ℃) and randomly distributing on the basal plane. The second phase increases the alloy basal plane erosion rate, i.e. the radial erosion rate of the tool, and greatly improves the overall degradation rate of the tool.
The invention is described in further detail below with reference to the following figures and specific examples:
example 1
Various as-cast Mg-MM-1% Sn alloys were prepared, and the components were shown in Table 1. The preparation method comprises the following steps: pure magnesium ingot, cerium-rich mixed rare earth, pure Sn powder, pure Ti powder, pure Cu powder, pure Ni powder and pure Fe powder are used as raw materials, the purity of the pure Sn powder, the purity of the pure Ti powder, the purity of the pure Cu powder, the purity of the pure Ni powder and the purity of the pure Fe powder are more than 99.99%, the granularity of the pure Fe powder is less than 10um, and the raw materials are respectively prepared according to the weight percentage of the components of the magnesium alloy in the table 1;
completely melting the magnesium ingot under the protection of protective gas, and controlling the temperature at 760 ℃; adding cerium-rich misch metal, pure Sn powder, pure Ti powder, pure Cu powder, pure Ni powder and pure Fe powder into a magnesium solution for alloying after the preheating furnace is heated at 200 ℃ for 2 hours;
controlling the temperature of the alloy melt at 800 ℃, adding cerium-rich mischmetal, pure Sn powder, pure Ti powder, pure Cu powder, pure Ni powder and pure Fe powder, preserving the heat for 60 minutes, and fully stirring to ensure that all alloy elements are uniformly distributed in the magnesium melt;
pouring a spectrum sample, and carrying out stokehole analysis and adjustment until the magnesium alloy melt reaches the magnesium alloy composition and content of the invention;
the temperature of the magnesium alloy melt is reduced to 645 ℃ near the liquidus temperature, the temperature is kept for 10 minutes,
preparing corresponding tools such as a metal mold, spray pipes and the like, wherein the spray pipes are made of copper alloy, the mold and the tools are preheated by heat preservation for 8 hours at 500 ℃, an asbestos layer with the thickness of 15mm is additionally arranged outside the mold, 4 spray pipes are fixed at the center of the mold, the spray straight line of each spray nozzle forms 90 degrees, the spray nozzles uniformly spray molten liquid towards the mold wall at equal intervals, the molten liquid is transferred into each spray pipe by a transfer pump and is sprayed out by smelting through the spray nozzles, the distance between the lower end of the mold and the liquid level of the molten magnesium alloy is always kept at 15mm along with the spraying process, and the distance between the spray nozzles and the mold wall is;
and casting the mixture into a cast ingot with the diameter phi of 400mm through a spray pipe for subsequent testing of the room-temperature tensile strength and the degradation performance, wherein the room-temperature tensile strength and the degradation performance are shown in table 1.
The Mg-MM second phase formed by adding cerium-rich mischmetal and the Mg matrix into the ingot prepared by the invention is formed in the preparation and solidification process, and is uniformly distributed in the ingot, the shape and size are not greatly different, and the typical metallographic structure of the alloy is shown in figure 1. And the solid solubility of the Mg-MM second phase in the matrix is extremely small and almost zero. As can be seen from the data in Table 1, the strength of the alloy is increased, the degradation rate is increased and the amplification is gradually reduced with the increase of the addition amount of the misch metal. In the components in the invention, the change of the content of the rare earth element in the cerium-rich mischmetal does not cause the great change of the strength and the degradation performance of the alloy, and the second phase of the Mg-MM rare earth cannot be redissolved in a matrix in the subsequent homogenization and aging heat treatment process, thereby being beneficial to accurately controlling the degradation performance and the mechanical property of the alloy.
The added Sn element and Ti, Fe, Ni and Cu alloy elements are uniformly distributed in the matrix in the form of simple substances in the ingot, and are mutually integrated with the degradation effect of the Mg-MM rare earth phase, so that the integral uniform degradation is promoted, and the degradation performance is favorably and accurately controlled.
TABLE 1 Mg-MM-1% Sn alloy composition and its mechanical properties and degradability
Example 2
According to the composition and method of the present invention, 3 kinds of ingots were prepared, which were: cerium-rich misch metal (Ce: 45 wt.%, La: 35 wt.%, Nd: 10 wt.%, Pr: 10 wt.%): 5 wt.%, Sn: 2 wt.%, 0.5 wt.% Ti, balance Mg; cerium-rich misch metal (Ce: 45 wt.%, La: 35 wt.%, Nd: 10 wt.%, Pr: 10 wt.%): 5 wt.%, Sn: 1 wt.%, 0.5 wt.% Ti, balance Mg; cerium-rich misch metal (Ce: 45 wt.%, La: 35 wt.%, Nd: 10 wt.%, Pr: 10 wt.%): 5 wt.%, 0.5 wt.% Ti, balance Mg;
pure magnesium ingot, cerium-rich mixed rare earth, pure Sn powder, pure Ti powder, pure Cu powder, pure Ni powder and pure Fe powder are used as raw materials, the purity of the pure Sn powder, the purity of the pure Ti powder, the purity of the pure Cu powder, the purity of the pure Ni powder and the purity of the pure Fe powder are more than 99.99%, the granularity of the pure Fe powder is less than 10um, and the raw materials are respectively prepared according to the weight percentage of the components of the magnesium alloy;
completely melting the magnesium ingot under the protection of protective gas, and controlling the temperature at 760 ℃;
keeping the pure Sn powder and the pure Ni powder in a preheating furnace at 200 ℃ for 2 hours, and adding cerium-rich misch metal into the magnesium melt for alloying;
controlling the temperature of the alloy melt at 800 ℃, adding pure Sn powder and pure Ti powder into the melt, keeping the temperature for 60 minutes, and fully stirring to ensure that all alloy elements are uniformly distributed in the magnesium melt; pouring a spectrum sample, carrying out stokehole analysis, and adjusting the amount until the magnesium alloy melt reaches the magnesium alloy composition and content of the invention; the method comprises the steps of reducing the temperature of magnesium alloy melt to be close to liquidus temperature 645 ℃, preserving heat for 10 minutes, preparing corresponding tools such as metal molds and spray pipes, wherein the spray pipes are made of copper alloy, the molds and the tools are preheated by preserving heat for 10 hours at 500 ℃, asbestos layers with the thickness of 20mm are additionally arranged outside the molds, 6 spray pipes are fixed in the centers of the molds, the spray straight lines of all the nozzles form 60 degrees, the nozzles uniformly spray the melt towards the mold wall at equal intervals, the melt is transferred to all the spray pipes by a transfer pump and is sprayed out through smelting, the distance between the lower end of each mold and the liquid level of the magnesium alloy melt is always kept at 20mm along with the spraying process, and the distance between each nozzle and the mold wall is kept.
Casting into a magnesium alloy material cast ingot with the diameter of 410mm through a spray pipe for subsequent deformation processing;
carrying out homogenization heat treatment on the prepared ingot blank, keeping the temperature for 24h at 480 ℃, then extruding the ingot blank into a bar with the diameter of phi 60mm to form a base surface texture, and carrying out aging treatment, wherein the aging time is 115 ℃, and keeping the temperature for 24 h; during the aging process, the alloy forms Mg-Sn phase, and the Mg-Sn phase is precipitated along the basal plane and randomly distributed in the basal plane, as shown in figure 2. Machining to obtain full-size bridge plug, and heating at 70 deg.C under 90MPa and Cl-The ion content is 2%, and the oil-water ratio is 70%, and the overall degradation rate is respectively as follows: 5340mm/a, 4635mm/a, 4230 mm/a. The overall degradation rate of the alloy containing Sn is higher than that of other alloys without Sn, and the overall degradation rate is faster as the Sn content is higher. And a Mg-Sn phase is formed on a basal plane, so that the corrosion rate of the basal plane is improved, especially, basal plane textures are formed on the alloy, the basal plane faces to corrosive liquid, and the degradation rate of the alloy is further enhanced.
Example 3
Soluble bridge plugs are needed in certain oil fields, and the oil and gas well environment is as follows: temperature 120 deg.C, pressure 70MPa, Cl-The ion content is 3 percent, the oil-water ratio is 80 percent, the time difference between before and after the bridge plug is put into the well is about 36 hours, the strength of the bridge plug is required to be higher than 250MPa, and the bridge plugs which are put into the well first and then are put into the well are synchronously degraded after the last bridge plug is put into the well for 12 hours under the environment.
Aiming at the oil field condition and the practical application requirement, ingot blanks with alloy components of three components are prepared, and the method comprises the following steps:
1) the ratio Ce: 50 wt.%; la: 30 wt.%; nd: 15 wt.%; pr: 5 wt.%; uniformly mixing metal powder to obtain cerium-rich mischmetal;
pure magnesium ingot, cerium-rich mischmetal, pure Sn powder and pure Ni powder are used as raw materials, and the cerium-rich mischmetal is prepared by the following steps: 4.5 wt.%, Sn: 0.5 wt.%, Ni: 0.5 wt.%, balance magnesium; respectively preparing materials; the purity of the raw materials is more than 99.99 percent, the granularity is less than 10um,
completely melting the magnesium ingot under the protection of protective gas, and controlling the temperature at 760 ℃;
the cerium-rich misch metal and pure metal powder are heated in a preheating furnace at 200 ℃ for 2 hours, and then the cerium-rich misch metal is added into the magnesium solution for alloying;
controlling the temperature of the alloy melt at 800 ℃, adding pure metal powder, preserving the heat for 60 minutes, and fully stirring to ensure that all alloy elements are uniformly distributed in the magnesium melt; pouring a spectrum sample, carrying out stokehole analysis, and adjusting the amount until the magnesium alloy melt reaches the magnesium alloy composition and content of the invention;
the temperature of the magnesium alloy melt is reduced to 645 ℃ which is close to the liquidus temperature, the temperature is kept for 10 minutes, the mold and the tool are preheated by keeping the temperature at 500 ℃ for 7 hours, an asbestos layer with the thickness of 20mm is additionally arranged outside the mold, 6 spray pipes are fixed at the center of the mold, the spray straight line of each spray nozzle is 60 degrees, the spray nozzles uniformly spray the melt towards the mold wall at equal intervals, the melt is transferred to each spray pipe by a transfer pump and is sprayed out by smelting through the spray nozzles, the distance between the lower end of the mold and the liquid level of the magnesium alloy melt is always kept at 20mm along with the spraying process, and the distance between the spray nozzles and the mold wall.
Casting into cast ingot with the diameter phi of 410mm through a spray pipe for subsequent deformation processing;
carrying out homogenization heat treatment on the prepared ingot blank, keeping the temperature at 480 ℃ for 24h, then extruding the ingot blank into a bar with the diameter of 100mm, carrying out aging treatment on a strong basal texture formed in a processed material, wherein the aging time is 150 ℃, and keeping the temperature for 13 h;
and machining the aged bar into a bridge plug part by using mechanical machining methods such as numerical control machining and the like to assemble the bridge plug.
2) Pure magnesium ingot, cerium-rich mischmetal, pure Sn powder and pure Ni powder are used as raw materials, and the cerium-rich mischmetal is prepared by the following steps: 6 wt.%, Sn: 1 wt.%, Ni: 0.8 wt.%, balance magnesium; respectively preparing materials; the purity of the raw materials is more than 99.99 percent, the granularity is less than 10um, and other raw material components and the processing process are not changed; and preparing the bridge plug.
3) Pure magnesium ingot, cerium-rich mischmetal, pure Sn powder, pure Ni powder and pure Fe powder are taken as raw materials, and the cerium-rich mischmetal is prepared by the following steps: 8 wt.%, Sn: 2 wt.%, Ni: 0.8 wt.%, Fe: 0.3 wt.%, balance magnesium; respectively preparing materials; the purity of the raw materials is more than 99.99 percent, the granularity is less than 10um, and other raw material components and the processing process are not changed; and preparing the bridge plug.
The tensile strength of three bridge plugs tested in the oil well environment is 260Mpa, 280Mpa and 300Mpa in sequence; the degradation rates were 4400mm/a, 5175mm/a and 5650mm/a, respectively. The packing effect is good when packing is needed in an oil-gas well, synchronous degradation is realized, and the expected effect is completely achieved;
example 4
A ball seat is needed in a certain oil field, and the oil-gas well environment is as follows: temperature 70 deg.C, pressure 90MPa, Cl-The ion content is 2 percent, the oil-water ratio is 70 percent, the time difference between the front and the back of the ball seat in the well is about 24 percent, the strength of the ball seat is required to be more than 300MPa, and the ball seats of the first well and the second well are synchronously degraded after the last ball seat is put in the well for 12 hours under the environment.
The ingot blank with alloy components of two components is prepared according to the oil field condition and the practical application requirement, and comprises the following steps:
1) the ratio Ce: 50 wt.%; la: 30 wt.%; nd: 15 wt.%; pr: 5 wt.%; uniformly mixing metal powder to obtain cerium-rich mischmetal;
pure magnesium ingot, cerium-rich mischmetal, pure Sn powder, pure Ti powder, pure Cu powder, pure Ni powder and pure Fe powder are taken as raw materials, and the cerium-rich mischmetal is prepared by the following steps: 9 wt.%, Sn: 2 wt.%, Ti: 1 wt.%, Cu: 0.5 wt.%, balance magnesium; respectively preparing materials; the purity is more than or equal to 99.99 percent, and the granularity is less than 10 um;
completely melting the magnesium ingot under the protection of protective gas, and controlling the temperature at 760 ℃;
keeping the temperature of pure Sn powder, pure Ti powder, pure Cu powder, pure Ni powder and pure Fe powder in a preheating furnace at 200 ℃ for 2 hours, and adding cerium-rich mischmetal into the magnesium solution for alloying;
controlling the temperature of the alloy melt at 800 ℃, adding pure Sn powder, pure Ti powder, pure Cu powder, pure Ni powder and pure Fe powder into the melt, preserving the heat for 60 minutes, and fully stirring to ensure that all alloy elements are uniformly distributed in the magnesium melt; pouring a spectrum sample, carrying out stokehole analysis, and adjusting the amount until the magnesium alloy melt reaches the magnesium alloy composition and content of the invention;
the temperature of the magnesium alloy melt is reduced to be near liquidus temperature 645 ℃, the temperature is kept for 10 minutes, a mold and a tool are preheated by keeping the temperature at 500 ℃ for 7 hours, an asbestos layer with the thickness of 15mm is additionally arranged outside the mold, 6 spray pipes are fixed at the center of the mold, the spray straight line of each nozzle is 60 degrees, the nozzles uniformly spray the melt towards the mold wall at equal intervals, the melt is transferred into each spray pipe by a transfer pump and is sprayed out through the nozzles, the distance between the lower end of the mold and the liquid level of the magnesium alloy melt is always kept at 15mm along with the spraying process, and the distance between the nozzles and the mold wall is kept at.
Casting into 560mm cast ingot for subsequent deformation;
carrying out homogenization heat treatment on the prepared ingot blank, wherein the homogenization temperature is 480 ℃, preserving heat for 24h, then extruding the ingot blank into a bar with the diameter of 200mm to form a basal plane texture, reheating the extruded bar for die forging, carrying out aging treatment, wherein the aging time is 120 ℃, and preserving heat for 24 h;
and machining the aged forge piece into the ball seat by using mechanical machining methods such as numerical control machining and the like.
2) Pure magnesium ingot, cerium-rich mischmetal, pure Sn powder, pure Ti powder, pure Cu powder, pure Ni powder and pure Fe powder are taken as raw materials, and the cerium-rich mischmetal is prepared by the following steps: 6 wt.%, Sn: 1 wt.%, Ti: 0.5 wt.%, Ni: 0.8 wt.%, Fe: 0.3 wt.%, balance magnesium; respectively preparing materials; the purity of the raw materials is more than 99.99 percent, the granularity is less than 10um, and other raw material components and the processing process are not changed; and preparing the ball seat.
Testing the mechanical property strength of the two alloys in the oil well environment to be 332Mpa and 315Mpa respectively; the degradation rates were 6500mm/a and 4945mm/a, respectively. The packing effect is good when the packing is needed in the oil and gas well, synchronous degradation is realized, and the expected effect is completely achieved.
Claims (10)
1. The magnesium alloy material for oil and gas exploitation is characterized by comprising the following components in parts by weight: one or more of Sn, Ni, Fe, Ti and Cu, Mg and cerium-rich misch metal;
the contents are as follows: cerium-rich misch metal: 0.5-25 wt.%, Sn: 0-10 wt.%; fe: 0-10 wt.%, Ti: 0-10 wt.%; ni: 0-10 wt.%; cu: 0-10 wt.%; the balance being Mg.
2. The magnesium alloy material according to claim 1, wherein the magnesium alloy material comprises: cerium-rich misch metal: 0.5-25 wt.%; sn: 0-2 wt.%; fe: 0-1 wt.%, Ti: 0-1 wt.%; ni: 0-1 wt.%; cu: 0-1 wt.%, and the balance being Mg.
3. The magnesium alloy material according to claim 1 or 2, wherein the cerium-rich misch metal contains Ce, La, Nd, Pr, wherein Ce: 40-60 wt.%; la: 20-40 wt.%; nd: 10-15 wt.%; pr: 1-10 wt.%, and the balance impurities.
4. The magnesium alloy material according to claim 1, wherein the mechanical properties and dissolution rate of the magnesium alloy material are precisely predicted and controlled by changing the composition and structure of the magnesium alloy material.
5. A preparation method of the magnesium alloy material for oil and gas exploitation according to any one of claims 1 to 4, which is characterized by comprising the following steps:
1) uniformly mixing Ce, La, Nd and Pr according to the content proportion to obtain cerium-rich mischmetal;
preparing magnesium ingots, cerium-rich mischmetal, Sn powder, Fe powder, Ti powder, Ni powder and Cu powder as raw materials according to the content of a magnesium alloy material, and respectively preheating the cerium-rich mischmetal and metal powder;
2) melting a magnesium ingot under an anaerobic condition, and then adding preheated cerium-rich mischmetal to obtain an alloy melt;
3) adding preheated Sn powder, Fe powder, Ti powder, Ni powder and Cu powder into the alloy melt, and stirring and melting to obtain magnesium alloy melt;
4) and cooling the magnesium alloy melt, and spraying the magnesium alloy solution to the mold wall by using a spray pipe to perform ingot casting to obtain the magnesium alloy material.
6. The preparation method according to claim 5, wherein the purity of the raw materials in the step 1) is more than or equal to 99.99%, the preheating temperature is 200-300 ℃, the preheating time is 2-3 hours, and the melting temperature in the step 2) is 680-800 ℃; step 3), the melting temperature is 700-800 ℃, and the melting time is 30-80 minutes; the temperature in the step 4) is 640-660 ℃, and the heat preservation time is 10-20 minutes.
7. The method of claim 5, wherein the mold and the nozzle are preheated before use, and the mold is externally provided with an insulating layer; the preheating temperature is 500 ℃, and the preheating time is 5-10 hours; the heat preservation is the asbestos layer, and thickness is 5 ~ 25 mm.
8. The preparation method according to claim 5, wherein the spray pipe is L-shaped, the end of the spray pipe is welded with a nozzle, the spray pipe is uniformly arranged in the center of the mold, the spray pipe is of a lifting structure, the bottom of the spray pipe is parallel to the bottom of the mold, and the nozzle points to the wall of the mold; the distance between the nozzle and the mold wall is 40-100 mm; the bottom of the spray pipe and the liquid level of the magnesium alloy melt are kept 1-25 mm.
9. The preparation method according to claim 5, characterized in that after the magnesium alloy material ingot is finished, the method further comprises the steps of carrying out homogenization heat treatment on the ingot blank, processing the ingot blank into a corresponding forging and carrying out aging treatment; the heat treatment temperature is 400-530 ℃, and the heat treatment time is 6-36 h.
10. An application of a magnesium alloy material for oil and gas exploitation is characterized in that,
the magnesium alloy material is applied to the preparation of fracturing construction tools for oil and gas exploitation or degradation materials; further comprises a soluble bridge plug, a soluble ball seat, a fracturing ball, a plugging ball, a target dart and a pressure holding ball.
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| CN116043082A (en) * | 2023-03-28 | 2023-05-02 | 有研工程技术研究院有限公司 | High-plasticity heat-resistant soluble magnesium alloy and preparation method thereof |
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