CN106868368B - A kind of degradable magnesium alloy downhole tool sealing ball material and preparation method thereof - Google Patents

A kind of degradable magnesium alloy downhole tool sealing ball material and preparation method thereof Download PDF

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Publication number
CN106868368B
CN106868368B CN201710089825.9A CN201710089825A CN106868368B CN 106868368 B CN106868368 B CN 106868368B CN 201710089825 A CN201710089825 A CN 201710089825A CN 106868368 B CN106868368 B CN 106868368B
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China
Prior art keywords
magnesium alloy
downhole tool
preparation
degradable
degradable magnesium
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Expired - Fee Related
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CN201710089825.9A
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CN106868368A (en
Inventor
彭庆元
周甲玉
罗浩
杨三华
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YUEYANG YUHANG NEW MATERIALS Co Ltd
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YUEYANG YUHANG NEW MATERIALS Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/04Alloys based on magnesium with zinc or cadmium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • 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
    • E21B33/00Sealing or packing boreholes or wells
    • E21B33/10Sealing or packing boreholes or wells in the borehole
    • E21B33/13Methods or devices for cementing, for plugging holes, crevices, or the like
    • E21B33/134Bridging plugs
    • 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
    • E21B34/00Valve arrangements for boreholes or wells
    • E21B34/06Valve arrangements for boreholes or wells in wells
    • E21B34/14Valve arrangements for boreholes or wells in wells operated by movement of tools, e.g. sleeve valves operated by pistons or wire line tools

Abstract

The invention belongs to degradable magnesium alloy field of material preparation, is developed for oil gas field field, specifically discloses a kind of degradable magnesium alloy downhole tool sealing ball material and preparation method thereof.According to component design ratio Zn, Mn, Ca, Mg metal is weighed prepare by technique, obtained ingot casting be processed into it is cylindric after subject alloy material, specified structure form is then processed into by the material.According to magnesium alloy made from inventive formulation and technique, crystal habit is good, mechanical strength is high, can be dissolved in the solution containing electrolyte, pressing crack construction instrument is manufactured using solvable magnesium alloy, instrument voluntarily melts after task is completed in underground, then mixes and is discharged in a liquid by the way that pipeline is counter, can be degradable, in the absence of easy bite, blocking channel problem, mill recovery process is bored so as to save, engineering difficulty is reduced, improves efficiency of construction.

Description

A kind of degradable magnesium alloy downhole tool sealing ball material and preparation method thereof
Technical field
The invention belongs to degradable magnesium alloy field of material preparation, specially a kind of degradable magnesium alloy downhole tool sealing Ball material and preparation method thereof.
Background technology
Chinese Low Permeability Oil/gas aboundresources, there is very big exploration-development potential.In recent decades, in hyposmosis sand Very big discovery is achieved in terms of rock, Marine Carbonate Rocks, volcanic rock exploration, forms world-class exploitation supporting technology. Low permeability oil and gas field exploitation mature technology has water filling, pressure break, gas injection etc..
The stable yields of following oil and gas production, volume increase will rely more heavily on these hyposmosis unconventional petroleum resourceses.Oil gas provides Source is distributed in the stratum of different depth mostly, can be realized using multilayer multistage fracturing technique and meanwhile the transformation to multiple stratum come Single well productivity is improved, so as to improve efficiency of construction.
The reservoir reconstruction technologies such as hydraulic fracturing, acid fracturing must be relied on by developing these unconventional petroleum resourceses, wherein adopting The multilayer multistage pressure break carried out with downhole tool is a technology being commonly used.
In multilayer multistage pressure break, need to use isolating tool between interval(Such as pressure break ball, bridging plug)Pressure break is successively carried out after separation Transformation, treat that isolating tool is returned into discharge pit shaft again after the completion of all interval constructions, to get through the exploitation that hoistway realizes oil, gas.
At present, commonly use isolating tool to be made by steel mostly, brill milling difficulty be present, time-consuming, powder, fragment are not easy after brill The shortcomings of row of returning.
It is difficult to there is the row of returning because than great in the ferrous materials as the first generation;Second generation composite, although solving Heavy problem, but because can not be degradable, easy bite, blocking channel problem, and raw material production be present and add Work need to rely on import, somewhat expensive;Can not be degradable during underground mining, the characteristics of easy bite be present.
And the application aims to provide third generation degradation material, field of petroleum exploitation is can be widely used for, has and surmounts second , can be degradable for material property, in the absence of easy bite, blocking channel problem, and production cost can be reduced, be used primarily in well In the submount material processing component assembly of lower instrument.
The content of the invention
The purpose of the present invention is to be directed to problem above, there is provided a kind of degradable magnesium alloy downhole tool sealing ball material and its Preparation method, pressing crack construction instrument being manufactured using solvable magnesium alloy, instrument voluntarily melts after task is completed in underground, Then mix and discharged in a liquid by the way that pipeline is counter, can be degradable, in the absence of easy bite, blocking channel problem, bored so as to save Recovery process is ground, reduces engineering difficulty, improves efficiency of construction.
To realize object above, the technical solution adopted by the present invention is:A kind of degradable magnesium alloy downhole tool ball sealer The mass fraction content of material, the degradable magnesium alloy downhole tool submount material constituent and each composition is as follows:
A kind of degradable magnesium alloy downhole tool seals ball material, it is characterised in that degradable magnesium alloy underground work The mass fraction content for having submount material constituent and each composition is as follows:
Zinc(Zn):17%-21%;
Manganese(Mn):0.6%-1.0%;
Calcium(Ca):0.6%-1.0%;
Surplus is magnesium(Mg), above each component mass fraction sum is 100%.
Preferably, the degradable magnesium alloy downhole tool submount material is used to produce the pressure break during exploitation of oil-gas field Construction use can melt ball sealer.
Another technical scheme of the present invention, formula and a kind of degradable magnesium alloy downhole tool ball sealer of component more than The preparation method of material, comprises the following steps:
(1)Melting prepares:Crucible internal washing is clean, hang in resistance furnace, open electric furnace, heated to crucible dark red Color, surface sprinkle barium fluxing agent;
(2)Charging refining:Example prepares raw material in mass ratio, and charging sequence is as follows:It is uniformly added into magnesium ingot to be allowed to melt, metal Zn materials can add with magnesium ingot, and Mn, Ca material first make MgMn, MgCa alloy material with Mg, then be placed on table pre- Heat, temperature reach 750 DEG C or so addition MgMn alloy materials, and temperature reaches 780 DEG C of addition MgCa alloy materials, and uniform stirring makes Solution alloying;
(3)Centre sampling:Sampling detection chemical composition, qualified rear seal-cover stand about one hour;
(4)Casting rod is molded:Treat step(2)After middle sampling is qualified, direct chill casting is used at 740 DEG C into casting rod;
(5)Material tests:Sampling detection chemical composition, mechanical property, metallographic structure, test corrosion rate after stove.
Preferably, in step(2)Feed in refining process, the process of haveing suffered is sufficiently stirred liquation, and sheds barium fluxing agent and go out Fire, make liquation alloying.
Preferably, in step(2)Feed in refining process, MgMn, MgCa alloy material are placed on when being preheated on table, are used Thermocouple measurement melt temperature.
Preferably, in step(3)Before the sampling of centre, temperature refines at 760 DEG C, sheds No. six flux, uniform stirring makes conjunction After golden liquid light, then it is sampled operation.
Preferably, step(2)Magnesium in charging refining(Mg), zinc(Zn), manganese(Mn), calcium(Ca)The purity of metal >= 99.9%。
Preferably, step(1)During melting prepares, the temperature control of electric furnace heating crucible is at 690-780 DEG C.
Barium fluxing agent(RJ-2)It is the eutectic that the chloride high melt such as potassium chloride, magnesium chloride, barium chloride mixes, Also a small amount of barium chloride calcination can be added by carnallite and magnesia or other methods synthesizes, closed available for magnesium alloy or magnalium The productions containing magnesium alloy such as gold.During high melt magnesium metal, block magnesium is easily aoxidized and burnt, and when coming out of the stove, adds appropriate powder Shape barium fluxing agent can prevent the burning of magnesium metal;In refined metals magnesium, add barium fluxing agent and refined, can be from fused solution Oxide impurity and nitride are settled out, therefore barium fluxing agent can be used for the refining agent and protective agent of magnesium and magnesium alloy;In addition two Number flux can be additionally used in magnesium alloy welding compound and metal fusing agent.The purposes of barium fluxing agent is different, wherein the content of each component Also it is different, and the raw material of other impurities or remained unreacted may be introduced in fusion process, therefore need to be to barium fluxing agent The content of middle magnesia is measured.
No. six flux(RJ-6)Be by the high melts such as potassium chloride, barium chloride, calcium chloride, calcirm-fluoride cast it is blocking, then It is broken to wear into powdery by ball mill, turn into product after sieving;Addition potassium chloride can significantly reduce the fusing point of flux, surface tension And viscosity, improve the stability of flux;Addition barium chloride can increase the density of flux, make flux and Serum Magnesium more easily separated;Fluorine Change calcium and can not only be used for thickening agent use, can also improve the stability and affinability of flux;Because containing calcium in this material, and chlorine Change magnesium and the compound of chemical reaction generation calcium chloride easily occurs with calcium, therefore select No. six flux of not magnesium chloride containing as refining Agent.
Beneficial effects of the present invention:The invention provides a kind of degradable magnesium alloy downhole tool sealing ball material and its system Preparation Method, pressing crack construction instrument is manufactured using solvable magnesium alloy, instrument voluntarily melts after task is completed in underground, so Mix and discharged in a liquid by the way that pipeline is counter afterwards, can be degradable, in the absence of easy bite, blocking channel problem, mill is bored so as to save Recovery process, engineering difficulty is reduced, improve efficiency of construction.
The present invention material, metal Zn materials and magnesium combination precipitation strength phase based on magnesium, improve alloy strength, improve and close The tensile property of gold;It is mainly to improve the corrosion rate of alloy to improve content.Metal Mn materials mainly play obstruction and closed in the alloy The big effect of Jin Jing's grain length, the yield strength of alloy is improved, improve alloy weldability.Metal Ca materials can improve the smelting of alloy Golden amount, mitigate the oxidation during metal bath and heat treating castings;Refining alloy crystal grain, improve alloy creep drag.
Brief description of the drawings
Fig. 1 is cylinder casting rod product diameter circle centre position(0.5D, amplify 200 times)Metallograph.
Fig. 2 is at cylinder casting rod product diameter a quarter(0.25D, amplify 200 times)Metallograph.
Fig. 3 is material corrosion curve map.Scale is defined by left side coordinate at G lines in figure;Other scales are with the right coordinate It is defined(The right coordinate value is 5 times of actual measured value, and corrosion rate is shown for amplifying).
Fig. 4 is the mechanical property stress strain curve figure of material.
Supplementary notes:
The real composition proportioning of above metallograph is embodiment 1. Mg-18.5Zn-0.7Mn-0.7Ca;Embodiment 2. Mg- 20Zn-0.9Mn-0.9Ca metallograph is similar 1., therefore omits.
The corrosion rate of embodiment 1. is 12 mg/cm2.h, the corrosion rate of embodiment 2. is 15 mg/cm2.h。
1. tensile strength is 140.2MPa to embodiment, yield strength 101.8MPa, elongation percentage 1.2, and hardness is 73.6HBW;2. tensile strength is 138.5MPa to embodiment, yield strength 102.3MPa, elongation percentage 1.0, and hardness is 75.3HBW。
Real composition proportioning is 1. Mg-18.5Zn-0.7Mn-0.7Ca;Front-end digital is represented as mass fraction, i.e. Mg- 18.5Zn-0.7Mn-0.7Ca:Represent the Zn, 0.7% Mn, 0.7% Ca that mass fraction is 18.5%, surplus Mg, gross mass Fraction is 100%.
Embodiment
In order that those skilled in the art more fully understand technical scheme, the present invention is entered below in conjunction with the accompanying drawings Row is described in detail, and the description of this part is only exemplary and explanatory, should not there is any limitation to protection scope of the present invention Effect.
Embodiment is 1.:
The present embodiment provides a kind of manufacture degradable magnesium alloy material, specific mass component:
Zn:18.5%,Mn:0.7%, Ca:0.7%, surplus Mg, above each component mass fraction add trace impurity sum For 100%.
The preparation method of formula and a kind of degradable magnesium alloy downhole tool of component sealing ball material more than, including Following steps:
(1)Melting prepares:Crucible internal washing is clean, hang in resistance furnace, open electric furnace, the temperature of electric furnace heating crucible Degree control heats kermesinus at 690-730 DEG C, to crucible, and surface sprinkles barium fluxing agent;
(2)Charging refining:Example prepares raw material in mass ratio, and charging sequence is as follows:It is uniformly added into magnesium ingot to be allowed to melt, metal Zn materials can add with magnesium ingot, and Mn, Ca material first make MgMn, MgCa alloy material with Mg, then be placed on table pre- Heat, using thermocouple measurement melt temperature, temperature reaches 750 DEG C or so addition MgMn alloy materials, and temperature reaches 780 DEG C of additions MgCa alloy materials, uniform stirring make solution alloying;The process of haveing suffered is sufficiently stirred liquation, and sheds barium fluxing agent fire extinguishing, makes Liquation alloying;
(3)Centre sampling:Sampling detection chemical composition, qualified rear seal-cover stand about one hour;Temperature refines at 760 DEG C, No. six flux are shed, after uniform stirring makes aluminium alloy light, then are sampled operation.
(4)Casting rod is molded:Treat step(2)After middle sampling is qualified, direct chill casting is used at 740 DEG C into casting rod;
(5)Material tests:Sampling detection chemical composition, mechanical property, metallographic structure, test corrosion rate after stove.
Preferably, step(2)Magnesium in charging refining(Mg), zinc(Zn), manganese(Mn), calcium(Ca)The purity of metal >= 99.9%。
The performance and detection parameters of product are shown in accompanying drawing 1-4.
Embodiment is 2.:
The present embodiment provides a kind of manufacture degradable magnesium alloy material, specific mass component:
Zn:20.0%,Mn:0.9%, Ca:0.9%, surplus Mg, above each component mass fraction add the trace impurity sum to be 100%。
The preparation method of formula and a kind of degradable magnesium alloy downhole tool of component sealing ball material more than, including Following steps:
(1)Melting prepares:Crucible internal washing is clean, hang in resistance furnace, open electric furnace, the temperature of electric furnace heating crucible Degree control heats kermesinus at 690-780 DEG C, to crucible, and surface sprinkles barium fluxing agent;
(2)Charging refining:Example prepares raw material in mass ratio, and charging sequence is as follows:It is uniformly added into magnesium ingot to be allowed to melt, metal Zn materials can add with magnesium ingot, and Mn, Ca material first make MgMn, MgCa alloy material with Mg, then be placed on table pre- Heat, using thermocouple measurement melt temperature, temperature reaches 750 DEG C or so addition MgMn alloy materials, and temperature reaches 780 DEG C of additions MgCa alloy materials, uniform stirring make solution alloying;The process of haveing suffered is sufficiently stirred liquation, and sheds barium fluxing agent fire extinguishing, makes Liquation alloying;
(3)Centre sampling:Sampling detection chemical composition, qualified rear seal-cover stand about one hour;Temperature refines at 760 DEG C, No. six flux are shed, after uniform stirring makes aluminium alloy light, then are sampled operation.
(4)Casting rod is molded:Treat step(2)After middle sampling is qualified, direct chill casting is used at 740 DEG C into casting rod;
(5)Material tests:Sampling detection chemical composition, mechanical property, metallographic structure, test corrosion rate after stove.
Preferably, step(2)Magnesium in charging refining(Mg), zinc(Zn), manganese(Mn), calcium(Ca)The purity of metal >= 99.9%。
The performance and detection parameters of product are shown in accompanying drawing 3-4.
Pass through detection, product mechanical property tensile strength:More than 135MPa, yield strength:More than 100 MPa, elongation percentage: More than 0.5%, Brinell hardness:More than 70HBW. corrosion rates:Material is in 3% Klorvess Liquid, 92 degree of constant temperature, corrodes 24 hours Tried out, reduced than second generation cost, and performance and corrosive effect all conform to by client for 8-18mg/cm2.h. materials afterwards Ask.
It should be noted that herein, term " comprising ", "comprising" or its any other variant are intended to non-row His property includes, so that process, method, article or equipment including a series of elements not only include those key elements, and And also include the other element being not expressly set out, or also include for this process, method, article or equipment institute inherently Key element.
Specific case used herein is set forth to the principle and embodiment of the present invention, the explanation of above example It is only intended to help the method and its core concept for understanding the present invention.Described above is only the preferred embodiment of the present invention, should When pointing out, due to the finiteness of literal expression, for those skilled in the art, original of the invention is not being departed from On the premise of reason, some improvement, retouching or change can also be made, above-mentioned technical characteristic can also be carried out by rights Combination;These improve retouching, change or combination, or not improved the design of invention and technical scheme are directly applied into other fields Close, be regarded as protection scope of the present invention.

Claims (7)

1. a kind of degradable magnesium alloy downhole tool seals ball material, it is characterised in that the degradable magnesium alloy downhole tool Submount material constituent and the mass fraction content of each composition are as follows:
Zinc(Zn):17%-21%;
Manganese(Mn):0.6%-1.0%;
Calcium(Ca):0.6%-1.0%;
Surplus is magnesium(Mg), above each component mass fraction sum is 100%;
The degradable magnesium alloy downhole tool submount material can disappear for the pressing crack construction use during producing exploitation of oil-gas field Melt ball sealer.
2. a kind of preparation method of degradable magnesium alloy downhole tool sealing ball material according to claim 1, its feature It is, comprises the following steps:
(1)Melting prepares:Crucible internal washing is clean, hang in resistance furnace, open electric furnace, kermesinus, table are heated to crucible Face sprinkles barium fluxing agent;
(2)Charging refining:Example prepares raw material in mass ratio, and charging sequence is as follows:It is uniformly added into magnesium ingot to be allowed to melt, metal Zn materials Material can add with magnesium ingot, and Mn, Ca material first make MgMn, MgCa alloy material with Mg, are then placed on table and preheat, temperature Degree reaches 750 DEG C or so addition MgMn alloy materials, and temperature reaches 780 DEG C of addition MgCa alloy materials, and uniform stirring makes solution Alloying;
(3)Centre sampling:Sampling detection chemical composition, qualified rear seal-cover stand about one hour;
(4)Casting rod is molded:Treat step(2)After middle sampling is qualified, direct chill casting is used at 740 DEG C into casting rod;
(5)Material tests:Sampling detection chemical composition, mechanical property, metallographic structure, test corrosion rate after stove.
3. a kind of preparation method of degradable magnesium alloy downhole tool sealing ball material according to claim 2, its feature It is, in step(2)Feed in refining process, whole process is sufficiently stirred liquation, and sheds barium fluxing agent fire extinguishing, makes liquation Alloying.
4. a kind of preparation method of degradable magnesium alloy downhole tool sealing ball material according to claim 2, its feature It is, in step(2)Feed in refining process, MgMn, MgCa alloy material are placed on when being preheated on table, using thermocouple measurement Melt temperature.
5. sealing the preparation method of ball material according to a kind of degradable magnesium alloy downhole tool described in claim 2, its feature exists In in step(3)Before the sampling of centre, temperature refines at 760 DEG C, sheds No. six flux, after uniform stirring makes aluminium alloy light, then It is sampled operation.
6. sealing the preparation method of ball material according to a kind of degradable magnesium alloy downhole tool described in claim 2, it is characterised by, Step(2)Magnesium in charging refining(Mg), zinc(Zn), manganese(Mn), calcium(Ca)Purity >=99.9% of metal.
7. sealing the preparation method of ball material according to a kind of degradable magnesium alloy downhole tool described in claim 2, it is characterised by, Step(1)During melting prepares, the temperature control of electric furnace heating crucible is at 690-780 DEG C.
CN201710089825.9A 2017-02-20 2017-02-20 A kind of degradable magnesium alloy downhole tool sealing ball material and preparation method thereof Expired - Fee Related CN106868368B (en)

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CN107956462B (en) * 2017-10-27 2020-09-08 中国石油天然气股份有限公司 Downhole soluble tool and preparation method thereof
CA3039574A1 (en) * 2018-05-10 2019-11-10 Josh Caris Degradable high-strength zinc compositions and method of manufacture
CN109406335A (en) * 2018-10-26 2019-03-01 西南石油大学 Bridge plug dissolution rate Lab-evaluation device and method under high temperature and high pressure environment
CA3174268A1 (en) * 2020-05-07 2021-11-11 Shinnosuke Yoshida Frac plug and method for manufacturing same, and method for sealing borehole

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GB201413327D0 (en) * 2014-07-28 2014-09-10 Magnesium Elektron Ltd Corrodible downhole article
CN105331863B (en) * 2015-11-20 2017-08-11 燕山大学 A kind of heat-resisting nucleocapsid hardening constituent magnesium alloy and preparation method thereof

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Inventor after: Yuan Yinghong

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