CN106636742A - ZSA-3 titanium alloy pipe, and preparation method and application thereof - Google Patents

ZSA-3 titanium alloy pipe, and preparation method and application thereof Download PDF

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Publication number
CN106636742A
CN106636742A CN201611019842.7A CN201611019842A CN106636742A CN 106636742 A CN106636742 A CN 106636742A CN 201611019842 A CN201611019842 A CN 201611019842A CN 106636742 A CN106636742 A CN 106636742A
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titanium alloy
zsa
temperature
carried out
alloy tubes
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CN106636742B (en
Inventor
张忠世
郭淑君
张政伟
张桂艳
莫喜刚
于晓玲
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World Titanium Industry Co Ltd
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World Titanium Industry Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
    • 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

Abstract

The invention discloses a ZSA-3 titanium alloy pipe, and a preparation method and application thereof. The ZSA-3 titanium alloy pipe is composed of the following components in percentage by mass: 4.6-5.4% of Al, 3.6-4.4% of V, 0.4-1.3% of Mo, 1.6-2.4% of Zr, at most 0.12% of Fe, at most 0.08% of C, at most 0.05% of N, at most 0.015% of H, at most 0.2% of O and the balance of Ti. The preparation method comprises the following steps: smelting a cast ingot according to the proportion, perforating the forged bar, rolling to obtain the finished pipe, and carrying out heat treatment, thereby obtaining the ZSA-3 titanium alloy pipe. The titanium alloy pipe has the characteristic of corrosion resistance at high temperature, and especially has very high resistance to corrosion of H2S and CO2 at 150-260 DEG C under petroleum working conditions; and the corrosion rate is lowered to 0.0006 mm/a or below. The ZSA-3 titanium alloy pipe has excellent room-temperature mechanical properties: the tensile strength is 830-1200 MPa, the yield strength is 750-1120 MPa, and the elongation percentage is 10-20%; and thus, the ZSA-3 titanium alloy pipe is a high-strength material capable of resisting corrosion of H2S and CO2 at high temperature. The ZSA-3 titanium alloy pipe has long service life, fills up the blank in China, and thus, has wide application prospects.

Description

A kind of ZSA-3 titanium alloy tubes, preparation method and applications
Technical field
The present invention relates to titanium alloy preparing technical field, and in particular to a kind of ZSA-3 titanium alloy tubes, preparation method and its should With.
Background technology
As the world is to the growing of petroleum resources demand, the exploitation for promoting oil gas field gradually develops in depth.Ultra-deep Superelevation kill-job Oil/gas Well becomes very common.Investigation shows, in following 3-5, the well in marine drilling more than 11%, and bottom hole temperature (BHT) Will be above 175 DEG C.Drilling well under all high temperature of various degrees, the hyperbaric environment such as land many oil fields of China with it is complete Well problem, such as Tarim Basin storehouse car newly developed block in front of the mountains, bottom pressure is up to 183-204 DEG C more than 130MPa, bottom hole temperature (BHT).It is high Super pressure-high temperature, continuing to bring out for high pressure high temperature well cause exploration and development difficulty gradually to increase, and its key problem is the material of tubing string Select permeability.Because high pressure-temperature, high pressure high temperature well typically contain H2S and CO2, CO under hot conditions2And H2The corrosivity of S It is extremely strong, in the development process of petroleum gas, CO2And H2The gases such as S and medium are to the corrosion of tubing into the main corruption in oil field Erosion problem, therefore in the urgent need to developing the anti-corrosion OCTG of high temperature of high intensity.
CN103643082A discloses a kind of high strength petroleum and covers effective titanium alloy and its side for manufacturing petroleum casing pipe Method, by controlling its component for Fe<0.3%;C<0.08%;N<0.05%;H<0.015%;0<0.2%;Al5.5-6.8%; V3.5-4.5%;Mo2.5-3.5%;Surplus Ti, has prepared the petroleum casing pipe with good mechanical properties and longer life.
CN103341520A discloses a kind of TB9 square-sections and admires alloy wire preparation technology, many by special-shaped wire-drawing die High intensity is prepared in passage cold drawing, TB9 (Ti-3Al-8V-6Cr-4Zr-4Mo) square-section of high tenacity is admired alloy cold silk Material, makes silk material have the cold technique for coiling performance of preferable spring, and after ageing strengthening heat treatment, the intensity of silk material is 1240- 1380MPa, elongation percentage and reduction of area are respectively greater than 10% and 20%.
Baoju Titanium Industry Co., Ltd. solves etching problem to meet continent oil-gas mining demand, realizes that oil well is permanent Property exploitation, Ti-6Al-4V is retrofited, TC4S alloy extrusion pipes are developed, to meet high yield and high impact property Require.The extruding tubing has been produced in batches, and the extruding tubing mechanical performance data see the table below.
Although above-mentioned titanium alloy tube all has good mechanical performance, its high temperature corrosion resistance still has deficiency.TC4 alloys Pipe is only at 60 DEG C -80 DEG C to H2S、CO2Corrosion has resistance, once temperature is higher than 80 DEG C, it is difficult to meet present oil well harshness Bottom hole temperature (BHT), pressure and corrosive conditions condition, therefore in the urgent need to developing the new anti-corrosion petroleum pipeline of high temperature.
The content of the invention
Not enough for prior art, the present invention provides a kind of ZSA-3 titanium alloy tubes, possesses resistance to H at high temperature2S and CO2It is rotten The characteristics of erosion, at 150 DEG C -260 DEG C of oil operating mode, H2S、CO2Below 0.0006mm/a is fallen below to its corrosion rate, should Titanium alloy tube is provided simultaneously with excellent room-temperature mechanical property, and its tensile strength is 830-1200MPa, and yield strength is 760- 1120MPa, elongation is 10-20%, is a kind of resistance to H of high temperature resistant2S、CO2The material of corrosion, has replenished domestic blank, there is wide Wealthy application prospect.
For achieving the above object, the present invention is employed the following technical solutions:
In a first aspect, the present invention provides a kind of ZSA-3 titanium alloy tubes, the ZSA-3 titanium alloy tubes press weight/mass percentage composition It is composed of the following components:
The present invention by the mating reaction between above-mentioned Al, V, Mo, Zr and Ti each component with certain content, in each group On the basis of dividing the effect having respectively, the performance of titanium alloy is further increased, especially in tetra- kinds of elements of Al, V, Mo, Zr On the basis of specific components content, specific adding proportion, obtains the ZSA-3 titanium alloy tubes for preparing between control each element Obtained the anti-CO at 150-260 DEG C2And H2The ability of S corrosion, is provided simultaneously with good mechanical property.
Although Mo elements and Zr elements all have some excellent performances, it is simple by it with first with Al elements and V Element prepares titanium alloy, is merely capable of increasing the mechanical performance and part resistance to corrosion of titanium alloy, and it does not have at high temperature Anti- CO2And H2The ability of S corrosion, only in the content range of above-mentioned Mo and Zr, controls the adding proportion of the two, Mo and Zr phases Synergy can be just produced between mutually, resistance to CO under titanium alloy high-temperature can be greatly improved2And H2The ability of S corrosion.
Above-mentioned Fe, C, N, H and O are the impurity unavoidably brought in actual production, and its content is controlled in above range Within can't produce impact to the performance of ZSA-3 titanium alloy tubes for finally preparing, therefore it is repeated no more.
The content of Al is 4.6-5.4% in ZSA-3 titanium alloy tubes of the present invention, for example can be 4.6%, 4.7%, 4.8%th, the concrete point value between 4.9%, 5.0%, 5.1%, 5.2%, 5.3% or 5.4%, and above-mentioned numerical value, is limited to a piece Width and for simple and clear consideration, the present invention concrete point value that no longer scope described in exclusive list includes.
Al is modal addition element in titanium alloy, adds Al to primarily serve the effect of solution strengthening in titanium alloy, There is positive effect for putting forward heavy alloyed normal temperature and elevated temperature strength, reducing proportion, increase elastic modelling quantity.Appropriate Al elements can Effectively increase the tensile strength of titanium alloy, but addition meeting the moulding of alloy of the Al of excess, toughness and stress corrosion are not Profit.
The content of V is 3.6-4.4% in ZSA-3 titanium alloy tubes of the present invention, for example can be 3.6%, 3.7%, 3.8%th, the concrete point value between 3.9%, 4.0%, 4.1%, 4.2%, 4.3% or 4.4%, and above-mentioned numerical value, is limited to a piece Width and for simple and clear consideration, the present invention concrete point value that no longer scope described in exclusive list includes.
V element can play a part of solution strengthening β phases, and significantly reduce transformation temperature, increase quenching degree, carry heavy alloyed Intensity, toughness and wearability.When V element is very few, low-alloyed heat endurance can significantly drop.
For the present invention, in the range of above-mentioned Al and V content, the ratio of Al elements and V element is not in titanium alloy It is preferably too low or too high, if the ratio of the two is less than 1.1:1 or higher than 1.5:When 1, it can be caused with the follow-up Mo elements for adding and Synergy weakens or disappears between Zr, does not reach the effect of the present invention.
The content of Mo is 0.4-1.3% in ZSA-3 titanium alloy tubes of the present invention, for example can be 0.4%, 0.5%, 0.6%th, the concrete point value between 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2% or 1.3%, and above-mentioned numerical value, As space is limited and for simple and clear consideration, the present invention concrete point value that no longer scope described in exclusive list includes.
Mo elements have the effect for improving creep resistance, can effectively improve the corrosion resistance of alloy, especially anti-gap The ability of corrosion.Mo elements cross that I haven't seen you for ages causes the corrosion resisting property of alloy not enough.
The content of Zr is 1.6-2.4% in ZSA-3 titanium alloy tubes of the present invention, for example can be 1.6%, 1.7%, 1.8%th, the concrete point value between 1.9%, 2.0%, 2.1%, 2.2%, 2.3% or 2.4%, and above-mentioned numerical value, is limited to a piece Width and for simple and clear consideration, the present invention concrete point value that no longer scope described in exclusive list includes.
Zr elements have corrosion resistance, and the generally appropriate Zr elements that add in titanium alloy can improve the anti-corrosion of titanium alloy Property and heat resistance.
In the present invention, on the basis of above-mentioned Mo and Zr contents, the addition ratio of Mo and Zr in the ZSA-3 titanium alloy tubes Example is (0.2-0.75):1, for example can be 0.2:1、0.3:1、0.4:1、0.5:1、0.6:1、0.7:1 or 0.75:1st, and Concrete point value between above-mentioned numerical value, as space is limited and for simple and clear consideration, scope bag no longer described in exclusive list of the invention The concrete point value for including.
In the content range of above-mentioned Mo and Zr, above proportion is selected to be added so that Mo and Zr are each other Synergy is produced, together with same Al and V with special ratios, resistance to CO under titanium alloy high-temperature is greatly improved2And H2S corrodes Ability.
In ZSA-3 titanium alloy tubes of the present invention in addition to containing Al, Mo, V and Zr, also containing Fe, C, O, H and N etc. A little impurity elements, " the balance of Ti " is it is meant that in addition to above-mentioned alloy compositions Al, Mo, V, Zr and Impurity Fe, C, O, H, N Component be Ti.
Preferably, to press weight/mass percentage composition composed of the following components for ZSA-3 titanium alloy tubes of the present invention:
Preferably, to press weight/mass percentage composition composed of the following components for ZSA-3 titanium alloy tubes of the present invention:
It is improved can the mechanical strength of ZSA-3 titanium alloy tubes from above-mentioned preferably constituent content, under its high temperature To CO2、H2The resistance of S corrosion also can be lifted further.
Second aspect, the present invention provides a kind of preparation method of ZSA-3 titanium alloy tubes, the method comprising the steps of:
(1) Ti, Al, V, Mo and Zr are carried out into dispensing, melting is carried out after dispensing, obtain alloy cast ingot;
(2) step (1) alloy cast ingot is forged, the bar obtained after forging is processed into into optical wand, to optical wand Heated, be incubated laggard eleven punch 11;
(3) by the bar after step (2) perforation Jing pipe repairing after rolled, after obtain production tube;
(4) step (3) production tube is carried out into normalized treatment, temper is carried out after cooling, tempering is cooled down after terminating, Obtain ZSA-3 titanium alloy tubes.
According to the present invention, the temperature of step (1) melting is 1680-3000 DEG C, for example, can be 1680 DEG C, 1700 ℃、1800℃、1900℃、2000℃、2100℃、2200℃、2300℃、2400℃、2500℃、2600℃、2700℃、2800 DEG C, the concrete point value between 2900 DEG C or 3000 DEG C, and above-mentioned numerical value, as space is limited and for simple and clear consideration, the present invention The concrete point value that no longer scope described in exclusive list includes.
According to the present invention, the time cooled down after step (1) melting is 90-180min, for example can be 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 180min, and above-mentioned numerical value Between concrete point value, as space is limited and for simple and clear consideration, it is concrete that the present invention no longer scope described in exclusive list includes Point value.
According to the present invention, step (2) temperature to optical wand heating is 890-1000 DEG C, for example can be 890 DEG C, 900 DEG C, 910 DEG C, 920 DEG C, 930 DEG C, 940 DEG C, 950 DEG C, 960 DEG C, 970 DEG C, 980 DEG C, 990 DEG C or 1000 DEG C, and it is above-mentioned Concrete point value between numerical value, as space is limited and for simple and clear consideration, the present invention no longer scope described in exclusive list includes Concrete point value.
According to the present invention, the speed of step (2) perforation is 15-60mm/s, for example, can be 15mm/s, 20mm/s, Concrete point value between 25mm/s, 30mm/s, 35mm/s, 40mm/s, 45mm/s, 55mm/s or 60mm/s, and above-mentioned numerical value, As space is limited and for simple and clear consideration, the present invention concrete point value that no longer scope described in exclusive list includes.
Optical wand described in step (2) of the present invention means:The bar lathe obtained after forging pulls down oxide skin and crackle etc. Optical wand is obtained after defect.
The time of step (2) the of the present invention insulation calculates as follows:
Temperature retention time (min)=(diameter of rod/2) min+ (30-60) min;The unit of wherein diameter of rod is mm.
According to the present invention, the speed of step (3) rolling is 20-50 time/min, for example can be 20 times/min, 25 Secondary/min, 30 times/min, 35 times/min, 40 times/min, 45 times/specific between min or 50 time/min, and above-mentioned numerical value Value, as space is limited and for simple and clear consideration, the present invention concrete point value that no longer scope described in exclusive list includes.
According to the present invention, the feed of step (3) rolling is 3-6mm/ time, for example, can be 3mm/ time, 3.5mm/ Concrete point value secondary, between 4mm/ time, 4.5mm/ time, 5mm/ time, 5.5mm/ time or 6mm/ time, and above-mentioned numerical value, is limited to a piece Width and for simple and clear consideration, the present invention concrete point value that no longer scope described in exclusive list includes.
According to the present invention, the passage of step (3) rolling is 2-5 time, for example, can be 2 times, 3 times, 4 times or 5 times.
Passage described in step (3) of the present invention means:Rolled by milling train, rolling once occurs once to deform, claimed For rolling pass, every time rolling reduction 20%-50%.
According to the present invention, the temperature of step (4) normalized treatment is 750 DEG C -850 DEG C, for example, can be 750 DEG C, 760 DEG C, between 770 DEG C, 780 DEG C, 790 DEG C, 800 DEG C, 810 DEG C, 820 DEG C, 830 DEG C, 840 DEG C or 850 DEG C, and above-mentioned numerical value Concrete point value, as space is limited and for simple and clear consideration, the present invention concrete point value that no longer scope described in exclusive list includes.
According to the present invention, the temperature retention time of step (4) normalized treatment is 45-90min, for example can be 45min, It is concrete between 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min or 90min, and above-mentioned numerical value Point value, as space is limited and for simple and clear consideration, the present invention concrete point value that no longer scope described in exclusive list includes.
According to the present invention, the temperature of step (4) temper is 450 DEG C -650 DEG C, for example, can be 450 DEG C, 470 DEG C, it is specific between 490 DEG C, 500 DEG C, 530 DEG C, 550 DEG C, 570 DEG C, 600 DEG C, 620 DEG C or 650 DEG C, and above-mentioned numerical value Value, as space is limited and for simple and clear consideration, the present invention concrete point value that no longer scope described in exclusive list includes.
According to the present invention, the temperature retention time of step (4) temper is 120-240min, for example, can be 120min、130min、140min、150min、160min、170min、180min、190min、200min、210min、220min、 Concrete point value between 230min or 240min, and above-mentioned numerical value, as space is limited and for simple and clear consideration, the present invention is no longer The concrete point value that scope described in exclusive list includes.
In the preparation method of ZSA-3 titanium alloy tubes described in second aspect present invention, various equipment and technological means are adopted Equipment generally in the art and conventional method, do not limit this.
Exemplary, the preparation method of ZSA-3 titanium alloy tubes of the present invention is comprised the following steps:
(1) Ti, Al, V, Mo and Zr are carried out into dispensing, melting is carried out in vaccum consumable electrode electric arc furnace, smelting temperature is 1680-3000 DEG C, cooled down by cooling circulating water in fusing, cooling 90-180min, obtains alloy cast ingot after melting is complete;
(2) step (1) alloy cast ingot is forged, the bar obtained after forging is machined to into optical wand, then will Heated at 890-1000 DEG C in optical wand loading electric furnace, come out of the stove after insulation, with Mannesmann piercing mill with 15-60mm/s's Punching rate to coming out of the stove after bar enter eleven punch 11;
(3) bar after step (2) perforation is rolled Jing after pipe repairing with the mill speed of 20-50 time/min System, feed is 3-6mm/ time, and after rolling 2-5 passages production tube is obtained;
(4) step (3) production tube is carried out into normalized treatment, normalizing temperature is 750 DEG C -850 DEG C, and temperature retention time is 45-90min, then cools down in atmosphere;Then the production tube after normalized treatment is carried out into temper, temperature is 450 DEG C -650 DEG C, temperature retention time is 120-240min, and tempering is cooled down in atmosphere after terminating, that is, obtain ZSA-3 titanium alloy tubes.
The third aspect, the present invention provides a kind of application of ZSA-3 titanium alloy tubes in exploitation of oil-gas field, the ZSA-3 titaniums Compo pipe due to good mechanical property, and to H at 150 DEG C -260 DEG C2S、CO2There is high resistance to corrosion, Meet bottom hole temperature (BHT) harsh in Oil/gas Well, pressure and corrosive conditions condition, can be used as a kind of new corrosion-and high-temp-resistant Oil and gas pipes and be widely used in exploitation of oil-gas field field.
Compared with prior art, the present invention at least has the advantages that:
(1) the ZSA-3 titanium alloy tubes that the present invention is prepared, possess resistance to H at high temperature2S and CO2The characteristics of corrosion, At 150 DEG C -260 DEG C of oil operating mode, H2S、CO2Below 0.0006mm/a is fallen below to its corrosion rate, is that a kind of high temperature resistant is resistance to The material of corrosion, the life-span used in high temperature oil well is significantly larger than other tubing.
(2) the ZSA-3 titanium alloy tubes that the present invention is prepared have good room-temperature mechanical property, and tensile strength is 830- 1200MPa, yield strength is 750-1120MPa, and elongation is 10-20%, meets the requirement to compo pipe intensity in industry, is fitted For oil exploitation under HTHP.
(3) the ZSA-3 titanium alloy tubes that the present invention is prepared have replenished domestic blank, have broad application prospects.
Specific embodiment
For ease of understanding, it is as follows that the present invention enumerates embodiment.It will be understood to those of skill in the art that following examples are only The preferred embodiments of the present invention, are only used for help and understand the present invention, thus should not be taken as limiting the scope of the invention.
Embodiment 1
Dispensing is carried out by following components:Al 4.6%, V 3.6%, Mo 0.4%, Zr 1.6%, Fe 0.05%, C 0.03%, N 0.01%, H 0.008%, O 0.07%, balance of Ti;Carry out in vaccum consumable electrode electric arc furnace after dispensing Melting, smelting temperature is 1680 DEG C, is cooled down by cooling circulating water in fusing, and cooling 90min after melting is complete obtains alloy casting Ingot;Alloy cast ingot is carried out to be machined to optical wand after forging bar, then will be heated in its optical wand loading electric furnace, heated up To 890 DEG C, bar enters eleven punch 11 after coming out of the stove with Mannesmann piercing mill, and punching rate is 15mm per second;Pipe enters rolling after repairing, Mill speed is per minute 20 times, each 3mm of feed, is 5 passages by billet production to production tube rolling pass, obtains finished product Pipe;Normalized treatment is carried out to production tube, normalizing temperature is 850 DEG C, temperature retention time is 90min, after air cooling, is carried out at tempering Reason, 650 DEG C of temperature, temperature retention time is 240min, after air cooling, has prepared ZSA-3 titanium alloy tubes.
Embodiment 2
Dispensing is carried out by following components:Al 5.2%, V 4%, Mo 1%, Zr 2%, Fe 0.085%, C 0.055%, N 0.03%, H 0.011%, O 0.13%, balance of Ti;Melting is carried out in vaccum consumable electrode electric arc furnace after dispensing, is melted Refining temperature is 2300 DEG C, is cooled down by cooling circulating water in fusing, and cooling 135min, obtains alloy cast ingot after melting is complete;To close Golden ingot casting carries out being machined to optical wand after forging bar, then will be heated in its optical wand loading electric furnace, is warming up to 950 DEG C, bar enters eleven punch 11 after coming out of the stove with Mannesmann piercing mill, and punching rate is 40mm per second;Pipe enters rolling, rolling after repairing Speed is per minute 35 times, each 4mm of feed, is 3 passages by billet production to production tube rolling pass, obtains production tube;It is right Production tube carries out normalized treatment, and normalizing temperature is 800 DEG C, and temperature retention time is 60min, after air cooling, carries out temper, is returned 500 DEG C of fiery temperature, temperature retention time is 180min, after air cooling, has prepared ZSA-3 titanium alloy tubes.
Embodiment 3
Dispensing is carried out by following components:Al 5.4%, V 4.4%, Mo 1.3%, Zr 2.4%, Fe 0.12%, C 0.08%, N 0.05%, H 0.015%, O 0.2%, balance of Ti;Melted in vaccum consumable electrode electric arc furnace after dispensing Refining, smelting temperature is 3000 DEG C, is cooled down by cooling circulating water in fusing, and cooling 180min, obtains alloy cast ingot after melting is complete; Alloy cast ingot is carried out to be machined to optical wand after forging bar, then will be heated in its optical wand loading electric furnace, be warming up to 1000 DEG C, bar enters eleven punch 11 after coming out of the stove with Mannesmann piercing mill, and punching rate is 60mm per second;Pipe enters rolling after repairing, Mill speed is per minute 50 times, each 6mm of feed, is 2 passages by billet production to production tube rolling pass, obtains finished product Pipe;Normalized treatment is carried out to production tube, normalizing temperature is 750 DEG C, temperature retention time is 45min, after air cooling, is carried out at tempering Reason, 450 DEG C of temperature, temperature retention time is 120min, after air cooling, has prepared ZSA-3 titanium alloy tubes.
Embodiment 4
Compared with Example 2, be changed to except the addition " Mo1%, Zr2% " by Mo in dispensing and Zr " Mo0.4%, (adding proportion of Mo and Zr is 0.17 to Zr2.4% ":1), other conditions and all same of embodiment 2.
Embodiment 5
Compared with Example 2, be changed to except the addition " Mo1%, Zr2% " by Mo in dispensing and Zr " Mo1.3%, (adding proportion of Mo and Zr is 0.81 to Zr1.6% ":1), other conditions and all same of embodiment 2.
Comparative example 1
Compared with Example 2, except no Mo, other conditions and all same of embodiment 2 in raw material.
Comparative example 2
Compared with Example 2, except no Zr, other conditions and all same of embodiment 2 in raw material.
Comparative example 3
Compared with Example 2, except no V, other conditions and all same of embodiment 2 in raw material.
Comparative example 4
Compared with Example 2, except no Al, other conditions and all same of embodiment 2 in raw material.
Comparative example 5
Compared with Example 2, in addition to dispensing " Mo 1% " is changed to into " Mo 0.3% ", other conditions and embodiment 2 All same.
Comparative example 6
Compared with Example 2, in addition to dispensing " Mo 1% " is changed to into " Mo 1.4% ", other conditions are equal with embodiment 2 It is identical.
Comparative example 7
Compared with Example 2, in addition to dispensing " Zr 2% " is changed to into " Zr 1.5% ", other conditions are equal with embodiment 2 It is identical.
Comparative example 8
Compared with Example 2, in addition to dispensing " Zr 2% " is changed to into " Zr 2.5% ", other conditions are equal with embodiment 2 It is identical.
Comparative example 9
Compared with Example 2, except dispensing " Al 5.2%, V 4%, Mo 1%, Zr 2% " is changed to into " Al3%, V 8%, Cr 6%, Mo 4%, Zr 4% " outward, other conditions and all same of embodiment 2.
Comparative example 10
Compared with comparative example 9, except removing component in " Cr 6% ", other conditions are identical with comparative example 9.
Corrosion resistance is tested:The ZSA-3 titanium alloy samples for preparing are placed in into H2S、CO2Under partial pressure, at 150-260 DEG C Temperature range build-in test its corrosion weight loss.Test evaluation standard calculates a year corrosion rate according to sample mass difference before and after corrosion, The extent of corrosion of sample is judged according to NACE standards RP-0775-91.
Mechanics Performance Testing
Test tensile strength, yield strength and the elongation percentage of ZSA-3 titanium alloy samples, testing standard:GB/T 228.1: 2010;ASTM E8/E8M-11;JIS Z2241-2011.
Experiment condition is as follows:
Test stagnation pressure:25MPa;Temperature:150-260℃;H2S partial pressures:7MPa;CO2Partial pressure:11MPa test periods:720 is little When.
Titanium alloy sample prepared by embodiment 1-5 and comparative example 1-10 is surveyed using above-mentioned corrosion resistance method of testing Examination, experimental temperature wherein set in embodiment 1 as 150 DEG C, experimental temperature is set in embodiment 3 as 205 DEG C, other embodiment with Comparative example experimental temperature is 260 DEG C, to weighing before and after sample corrosion, calculates its year corrosion rate;Test at room temperature The tensile strength of titanium alloy sample, yield strength and elongation percentage obtained in embodiment and comparative example, the experimental result such as institute of table 1 Show.
Table 1
As seen from the above table:Mass change is minimum before and after the corrosion of ZSA-3 titanium alloy tubes sample in embodiment 1-3, its year corrosion Speed falls below below 0.0006mm/a, and wherein preferably, its annual corrosion rate is the corrosion stability of the sample that embodiment 2 is obtained 0.0002mm/a, the titanium alloy tube for illustrating present invention preparation has excellent resistance to H at 150-260 DEG C2S、CO2The ability of corrosion.This Outward, not within the scope of the present invention, the titanium alloy sample that it is prepared exists the ratio of component, constituent content and Mo and Zr H is subject at 150-260 DEG C2S、CO2The corrosion of faster rate, it is impossible to reach the effect acquired by the present invention.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as it is without prejudice to this The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (10)

1. a kind of ZSA-3 titanium alloy tubes, it is characterised in that the ZSA-3 titanium alloy tubes press weight/mass percentage composition by following components Composition:
2. ZSA-3 titanium alloy tubes as claimed in claim 1, it is characterised in that the ZSA-3 titanium alloy tubes are contained by quality percentage Amount is composed of the following components:
3. ZSA-3 titanium alloy tubes as claimed in claim 1, it is characterised in that the ZSA-3 titanium alloy tubes are contained by quality percentage Amount is composed of the following components:
4. a kind of preparation method of the ZSA-3 titanium alloy tubes as described in any one of claim 1-3, it is characterised in that the side Method is comprised the following steps:
(1) Ti, Al, V, Mo and Zr are carried out into dispensing, melting is carried out after dispensing, obtain alloy cast ingot;
(2) step (1) alloy cast ingot is forged, the bar obtained after forging is processed into into optical wand, optical wand is carried out Heating, is incubated laggard eleven punch 11;
(3) bar after step (2) perforation is rolled Jing after pipe repairing, production tube is obtained after rolling;
(4) step (3) production tube is carried out into normalized treatment, temper is carried out after cooling, tempering is cooled down after terminating, obtained final product To ZSA-3 titanium alloy tubes.
5. method as claimed in claim 4, it is characterised in that the temperature of step (1) melting is 1680-3000 DEG C;
Preferably, the time for cooling down after step (1) melting is 90-180min.
6. the method as described in claim 4 or 5, it is characterised in that step (2) temperature to optical wand heating is 890- 1000℃;
Preferably, the speed of step (2) perforation is 15-60mm/s.
7. the method as described in any one of claim 4-6, it is characterised in that the speed of step (3) rolling is 20-50 Secondary/min;
Preferably, the feed of step (3) rolling is 3-6mm/ time;
Preferably, the passage of step (3) rolling is 2-5 time.
8. the method as described in any one of claim 4-7, it is characterised in that the temperature of step (4) normalized treatment is 750 ℃-850℃;
Preferably, the temperature retention time of step (4) normalized treatment is 45-90min;
Preferably, the temperature of step (4) temper is 450 DEG C -650 DEG C;
Preferably, the temperature retention time of step (4) temper is 120-240min.
9. the preparation method of the ZSA-3 titanium alloy tubes as described in any one of claim 4-8, it is characterised in that methods described bag Include following steps:
(1) Ti, Al, V, Mo and Zr are carried out into dispensing, melting is carried out in vaccum consumable electrode electric arc furnace, smelting temperature is 1680-3000 DEG C, cooled down by cooling circulating water in fusing, cooling 90-180min, obtains alloy cast ingot after melting is complete;
(2) step (1) alloy cast ingot is forged, the bar obtained after forging is machined to into optical wand, then by optical wand Load and heated at 890-1000 DEG C in electric furnace, come out of the stove after insulation, with Mannesmann piercing mill with the perforation of 15-60mm/s Speed to coming out of the stove after bar enter eleven punch 11;
(3) bar after step (2) perforation is rolled Jing after pipe repairing with the mill speed of 20-50 time/min, Feed is 3-6mm/ time, and after rolling 2-5 passages production tube is obtained;
(4) step (3) production tube is carried out into normalized treatment, normalizing temperature is 750 DEG C -850 DEG C, and temperature retention time is 45- 90min, then cools down in atmosphere;Then the production tube after normalized treatment being carried out into temper, temperature is 450 DEG C- 650 DEG C, temperature retention time is 120-240min, and tempering is cooled down in atmosphere after terminating, that is, obtain ZSA-3 titanium alloy tubes.
10. application of a kind of ZSA-3 titanium alloy tubes as described in any one of claim 1-3 in exploitation of oil-gas field.
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CN107779670A (en) * 2017-11-23 2018-03-09 中国航发北京航空材料研究院 A kind of high precision titanium sheet alloy and preparation method thereof
CN109161727A (en) * 2018-10-19 2019-01-08 中国航发北京航空材料研究院 A kind of electric arc/electron beam fuse increasing material manufacturing titanium alloy and preparation method thereof
CN109622659A (en) * 2018-12-17 2019-04-16 安徽宝泰特种材料有限公司 A kind of manufacturing method of heavy caliber TC4 titanium alloy thick-wall seamless material
CN111349817A (en) * 2020-04-27 2020-06-30 中世钛业有限公司 Titanium alloy drill rod, preparation method and application thereof
CN111593230A (en) * 2020-04-30 2020-08-28 中国石油天然气集团有限公司 Pipe for 930 MPa-level ultrahigh-strength titanium alloy drill rod and manufacturing method thereof
CN112442613A (en) * 2020-11-09 2021-03-05 中国石油天然气集团有限公司 105ksi titanium alloy pipe for petroleum drill pipe and manufacturing method thereof
CN113369811A (en) * 2021-06-04 2021-09-10 成都日进冶金锻造有限公司 Production process of hydrogen sulfide corrosion resistant forge piece

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107779670A (en) * 2017-11-23 2018-03-09 中国航发北京航空材料研究院 A kind of high precision titanium sheet alloy and preparation method thereof
CN109161727A (en) * 2018-10-19 2019-01-08 中国航发北京航空材料研究院 A kind of electric arc/electron beam fuse increasing material manufacturing titanium alloy and preparation method thereof
CN109622659A (en) * 2018-12-17 2019-04-16 安徽宝泰特种材料有限公司 A kind of manufacturing method of heavy caliber TC4 titanium alloy thick-wall seamless material
CN111349817A (en) * 2020-04-27 2020-06-30 中世钛业有限公司 Titanium alloy drill rod, preparation method and application thereof
CN111593230A (en) * 2020-04-30 2020-08-28 中国石油天然气集团有限公司 Pipe for 930 MPa-level ultrahigh-strength titanium alloy drill rod and manufacturing method thereof
CN111593230B (en) * 2020-04-30 2021-08-31 中国石油天然气集团有限公司 Pipe for 930 MPa-level ultrahigh-strength titanium alloy drill rod and manufacturing method thereof
CN112442613A (en) * 2020-11-09 2021-03-05 中国石油天然气集团有限公司 105ksi titanium alloy pipe for petroleum drill pipe and manufacturing method thereof
CN113369811A (en) * 2021-06-04 2021-09-10 成都日进冶金锻造有限公司 Production process of hydrogen sulfide corrosion resistant forge piece

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