CN108467969A - A kind of high corrosion resistant Ti alloy pipe and preparation method thereof for oil and gas development - Google Patents
A kind of high corrosion resistant Ti alloy pipe and preparation method thereof for oil and gas development Download PDFInfo
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- CN108467969A CN108467969A CN201810245394.5A CN201810245394A CN108467969A CN 108467969 A CN108467969 A CN 108467969A CN 201810245394 A CN201810245394 A CN 201810245394A CN 108467969 A CN108467969 A CN 108467969A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/06—Manufacture 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- 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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- 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
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
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Abstract
The high corrosion resistant Ti alloy pipe and preparation method thereof that the present invention relates to a kind of for oil and gas development mainly solves existing titanium alloy tube corrosion resistance in high corrosion environment insufficient, high cost, manufacturing complexity, has the problems such as larger gap in performance.Titanium alloy tube is mainly made of following component, Al by mass percentage in addition to Ti：3.6~4.1%, V：2.1~2.6%, Fe：0.7~1.6%, O：0.15~0.26%, Ru：0.01~1.1%, Ni：0.05~1.5%, 0 ＜ C≤0.07%, 0 ＜ N≤0.05%, 0 ＜ H≤0.0155%.Meanwhile the present invention also provides a kind of methods preparing above-mentioned titanium alloy tube.The usage amount that titanium alloy tube material of the present invention uses rational design of alloy, reduces noble metal Ru and V etc. in original composition, and the supplement of β phase stable elements is carried out using rational Fe elements and O elements proportioning, improve alloy strength and toughness, it is acted synergistically using elements such as Ru, V, Fe, Ni, W, Mo, the densification of holding surface oxidation film improves corrosion resisting property with stablizing.
Description
Technical field
The present invention relates to industrial gas oil oil and gas development tubing fields, and in particular to a kind of for oil and gas development
High corrosion resistant Ti alloy pipe and preparation method thereof, to ensure that oil/gas well is safely and effectively exploited.
Background technology
With further going deep into for natural petroleum gas field, many western and Southwest Oils exploitations of China are with high temperature
(being more than 140 DEG C), high pressure (being more than 100MPa), well depth (being more than 5000m), (CO of medium containing high corrosion2、H2S、CL) etc. harsh ring
Border, in order to adapt to requirement of the oil-gas field development to tubing and casing corrosion resistance, it is contemplated that titanium alloy material has intensity height, corrosion resistance
The excellent, good characteristics such as elasticity modulus is low, be easy to cold forming, sea water resistance washes away, have been used for manufacturing tubing and casing and with very
Excellent performance.
Developing operating mode and other countries due to Chinese Petroliferous has larger difference, the gross pressure of many oil gas fields, CO2Partial pressure
And H2The etching conditions such as S partial pressures are all far more than foreign countries, therefore not every titanium alloy material is suitable for the harsh oil of China
Gas develops operating mode, and serious etching problem (such as stress can occur under such operating mode in conventional titanium alloy such as TA18, TC4
Corrosion cracking, crevice corrosion etc.) to constrain use of the titanium alloy material in oil development industry, have at present in the world
And the alloys such as the corrosion resistant Ti alloy used such as Ti-0.15Pd, Ti-Ru, it is added to a large amount of noble metal such as palladium, ruthenium etc., greatly
The cost and manufacturing complexity of alloy are improved, while also having larger gap in performance, to limit the application of titanium alloy
And popularization, it is therefore desirable to keep some strength and it is corrosion proof under the conditions of, drop low-alloyed cost, develop inexpensive high resistance to
The titanium alloy tube material and its preparation processing technology of erosion, realize that industrialization of the titanium alloy oil well pipe product in oil-gas mining field is answered
With.
Invention content
Present invention aim to address existing titanium alloy tube, there are have larger gap etc. in high cost, processing complexity, performance
Problem provides a kind of high corrosion resistant Ti alloy pipe and preparation method thereof for oil and gas development, and the titanium alloy material is except so that the pipe
Except material meets the harsh oil and gas development operating mode of China using mechanical property and corrosion resistance, also there is lower cost, it can be with
Meet the use needs in Chinese Petroliferous exploitation field.
Technical proposal that the invention solves the above-mentioned problems is,
A kind of high corrosion resistant Ti alloy pipe for oil and gas development, in addition to Ti, mainly by mass percentage by following component
Composition, Al：3.6~4.1%, V：2.1~2.6%, Fe：0.7~1.6%, O：0.15~0.26%, Ru：0.01~1.1%,
Ni：0.05~1.5%, 0 ＜ C≤0.07%, 0 ＜ N≤0.05%, 0 ＜ H≤0.0155%.
Further, the above-mentioned high corrosion resistant Ti alloy pipe for oil and gas development is made of by mass percentage following component,
Al：4.05%, V：2.15%, Fe：0.92%, O：0.25%, Ru：0.01%, Ni：0.97%, C：0.05%, N：0.03%,
H：0.0131%, surplus Ti.
Further, it is following component that the above-mentioned high corrosion resistant Ti alloy pipe for oil and gas development, which is also added with mass percent,
One or more of alloying element, Cr：0.1~0.7%, W：0.02~0.55%, Mo：0.01~0.12%.In titanium
Mo elements are added in alloy not only can improve the intensity and plasticity of alloy, and addition is appropriate micro in titanium with crystal grain thinning
Mo elements allow Ru-Mo element mating reactions to improve the corrosion resistance of titanium alloy, Cr elements are added in titanium can make titanium
FLADE current potentials (passivation potential) moved to active region, the passivation of titanium alloy can be promoted by being used cooperatively with Ru elements, Ru-W members
Element cooperation addition will greatly enhance the corrosion resistance of titanium alloy, while less element additive amount reduces cost of alloy.
Further, the above-mentioned high corrosion resistant Ti alloy pipe for oil and gas development is made of by mass percentage following component,
Al：3.6%, V：2.55%, Fe：1.38%, O：0.17%, Ru：1.0%, Ni：0.12%, C：0.06%, N：0.03%, H：
0.0142%, W：0.35%, Mo：0.08%, surplus Ti.
Further, the above-mentioned high corrosion resistant Ti alloy pipe for oil and gas development is made of by mass percentage following component,
Al：3.95%, V：2.45%, Fe：1.48%, O：0.21%, Ru：0.05%, Ni：1.21%, C：0.06%, N：0.04%,
H：0.0149%, Cr：0.6%, W：0.35%, surplus Ti.
Meanwhile the present invention also provides a kind of method preparing the above-mentioned high corrosion resistant Ti alloy pipe for oil and gas development, packets
Include following steps：
1) proportioned titanium alloy component is smelted into ingot casting through consumable electrode vacuum furnace, Surface Oxygen is removed using machine-tooled method vehicle
Change layer, ingot casting is heated to 1050~1150 DEG C of forgings to intermediate billet state；
2) intermediate base is heated to 1000~1050 DEG C of homogenizing annealings, intermediate base is carried out at 940~1000 DEG C secondary
Forging, drafts are 50%~70%, and extruded bar stock is made；
3) titanium alloy extruded bar stock is heated to 870~955 DEG C of progress hot extrusions, deflection is 75~90%, and titanium is made
After the extrusion tube blank of alloy, carries out checking surfaces externally and internally state after soda acid is washed, surface defect is handled；
4) vacuum stress relief annealing is carried out between 600~800 DEG C of temperature to extrusion tube blank, is annealed 1~2 hour, it is right
Pipe is straightened, and is carried out soda acid to the pipe after alignment and washed, check surface state and remove defect；
5) pipe that step 4) obtains is further processed using cold-rolling process at room temperature, then cold rolled tube is gone
Production tube is made in stress annealing processing, and ultrasonic examination and eddy current inspection are carried out to the tubing after annealing；
6) both ends of qualified titanium alloy tube numerically-controlled machine tool is processed into API standard screw thread or special thread, completes the titanium
The preparation of alloy petroleum pipeline is processed.
Further, it is to carry out school to pipe using vacuum creep sizing machine to carry out alignment to pipe described in step 4)
Directly.
Beneficial effects of the present invention are：
1. titanium alloy tube material of the present invention using rational design of alloy, reduce in original composition noble metal Ru and
The usage amount of V etc., and using the supplement of rational Fe elements and O elements proportioning progress β phase stable elements, improve the strong of alloy
Degree and toughness, while being acted synergistically using elements such as Ru, V, Fe, Ni, W, Mo, titanium alloy surface evolving hydrogen reaction rate is improved,
The formation speed for accelerating hydrogen makes titanium alloy surface passivating film (titanium oxide) keep higher steady in severe acidic environment
It is fixed and complete, to improve the corrosion resistance of the alloy, make the titanium alloy tube with higher-strength and excellent in toughness
Meanwhile still there is higher corrosion resistance.
2. the precious metal element dosage of titanium alloy tube of the present invention is less, cost is relatively low, while to Fe elements and O members in ingredient
The requirement of element is more wide in range, the lower titanium sponge of grade can be used to carry out melting processing, pure titanium or TC4 can also be used in the later stage
It returns to material and carries out remelting preparation, can significantly reduce the cost of titanium alloy tube.
3. the high anti-corrosion low-cost titanium alloy petroleum pipeline of oil and gas development prepared by preparation method of the present invention have primary alpha phase and
The tissue of β phases is regenerated, ingredient is uniform, and crystal grain is tiny, and without apparent segregation, entire titanium alloy tube has excellent mechanical property, bends
Take intensity >=758MPa, tensile strength >=860MPa, elongation percentage >=20%, full-scale Charpy V-type impact energy >=50J.
4. the year homogeneous corrosion speed of titanium alloy petroleum pipeline prepared by the present invention in the typical environment of Southwest China oil gas field
Rate≤0.25mm/y, with excellent anticorrosive performance and while mechanical performance, of low cost that preparation is facilitated to process, Ke Yiman
Demand under the harsh oil and gas development operating mode of foot China to low cost and high corrosion resistance capability titanium alloy petroleum pipeline.
Description of the drawings
Fig. 1 is titanium alloy tube metallographic structure figure prepared by the embodiment of the present invention one；
Fig. 2 is titanium alloy tube metallographic structure figure prepared by the embodiment of the present invention two；
Fig. 3 is titanium alloy tube metallographic structure figure prepared by the embodiment of the present invention three；
Fig. 4 is the lattice diffraction pattern figure of Ti-Ru-Fe compounds.
Specific implementation mode
Present disclosure is described in further detail below in conjunction with specific embodiment：
The present invention is used for the high corrosion resistant Ti alloy pipe of oil and gas development, in addition to Ti, mainly presses quality percentage by following component
Than composition, Al：3.6~4.1%, V：2.1~2.6%, Fe：0.7~1.6%, O：0.15~0.26%, Ru：0.01~
1.1%, Ni：0.05~1.5%, 0 ＜ C≤0.07%, 0 ＜ N≤0.05%, 0 ＜ H≤0.0155%；May be used also on this basis
Add mass percent Cr：0.1~0.7%, W：0.02~0.55%, Mo：One or more of 0.01~0.12%
Alloying element.
Mo elements are a kind of isomorphism β phase stable elements, and Mo can be infinitely dissolved in β phases, and Mo members are added in titanium alloy
Element not only can improve the intensity and plasticity of alloy with crystal grain thinning, and appropriate micro Mo elements are added in titanium and make Ru-
The mating reaction of Mo elements can improve the corrosion resistance of titanium alloy, but addition is further continued for when Mo elements are added to a certain amount of instead
Corrosion proof decline can be brought.
Cr elements can form unlimited solid solution with the β phases in titanium alloy and stablize β phases, the Cr of 05%wt. when 667 DEG C
With titanium eutectoid reaction can occur for element, generate α phases and TiCr2 phases, and Cr elements are added in titanium can make the FLADE current potentials of titanium
(passivation potential) is moved to active region, and the passivation that can promote titanium alloy is used cooperatively with Ru elements.
W elements are also a kind of eutectoid type β phase stable elements, and W is similar with Cr, and continuous solid solution is formed with β phases.Add in titanium
The corrosion resistance in hydrochloric acid and sulfuric acid of titanium can also be improved by entering W elements, especially with palladium race metal combination in use, can phase
Anti-corrosion capability is greatly improved in interaction；But in reproducibility acid, the corrosion resistance of titanium can be reduced by only adding W elements, but Ru-W is first
Element cooperation addition will greatly enhance the corrosion resistance of titanium alloy, while less element additive amount reduces cost of alloy.
The preparation processing method of titanium alloy tube provided by the invention, includes the following steps：
1) the good titanium alloy component of said ratio is smelted into ingot casting by consumable electrode vacuum furnace, is removed using mach method vehicle
After surface oxide layer, ingot casting is heated to 1050~1150 DEG C and is forged to intermediate billet state；
2) 1000~1050 DEG C or more homogenizing annealings and then by intermediate base are heated to improve segregation, keep tissue more equal
It is even, secondary forging then is carried out to intermediate base between 940~1000 DEG C, drafts is 50%~70%, and extruded bar stock is made；
3) the titanium alloy extruded bar stock is heated to 870~955 DEG C of progress hot extrusions, deflection is 75~90%, is made
After the extrusion tube blank of the titanium alloy, carries out checking surfaces externally and internally state after soda acid is washed, surface defect is disposed；
4) vacuum stress relief annealing and then to extrusion tube blank is carried out between 600~800 DEG C, is annealed 1~2 hour, and
Pipe is straightened using vacuum creep sizing machine, and soda acid is carried out to the pipe after alignment and is washed, check surface state and is gone
Except defect；
5) by above-mentioned steps 4) pipe of state is further processed using cold-rolling process to required petroleum pipeline ruler at room temperature
Then very little and precision carries out stress relief annealing process to cold rolled tube and production tube is made, ultrasound is carried out to the tubing after annealing
Wave inspection and eddy current inspection；
6) API standard screw thread or special thread are processed in the both ends numerically-controlled machine tool of every qualified titanium alloy, you can complete
It is processed at the preparation of the titanium alloy petroleum pipeline.
Embodiment one
Oil and gas development of the present invention is organized by mass percentage with high anti-corrosion low-cost titanium alloy petroleum pipeline ingredient to be become, Al：
4.05%, V：2.15%, Fe：0.92%, O：0.25%, Ru：0.01%, Ni：0.97%, C：0.05%, N：0.03%, H：
0.0131%；Ti：91.5569%.
The preparation processing method of titanium alloy tube:
The good titanium alloy component of said ratio is smelted into ingot casting by consumable electrode vacuum furnace, surface porosity is removed using lathe car
After layer, ingot casting is heated to 1080~1100 DEG C and is forged to intermediate billet state, intermediate base is then heated to 1020 DEG C
Annealing is homogenized to improve segregation, keeps tissue more uniform, secondary forging, pressure then are carried out to intermediate base at 940 DEG C~960 DEG C
Amount is 70%, and extruded bar stock is made；
The titanium alloy extruded bar stock is heated to 870~900 DEG C of progress hot extrusions, deflection 85% is made the titanium and closes
After the extrusion tube blank of gold, carries out checking surfaces externally and internally state after soda acid is washed, surface defect is disposed, is then existed to extrusion tube blank
Vacuum stress relief annealing is carried out between 650~700 DEG C, is annealed 1 hour, and school is carried out to pipe using vacuum creep sizing machine
Directly, it and carries out soda acid to the pipe after alignment to wash, checks surface state and remove defect；
Pipe after above-mentioned extruding is straightened is further processed using cold-rolling process to outer diameter 88.9mm, wall thickness at room temperature
The petroleum pipeline of 7.03mm, then to cold rolled tube carry out stress relief annealing process production tube is made, to the tubing after annealing into
Row ultrasonic examination and eddy current inspection process API standard screw thread in the both ends numerically-controlled machine tool of every qualified titanium alloy, and completing should
The preparation of size titanium alloy oil pipe is processed.
As shown in Figure 1, the titanium alloy petroleum pipeline prepared to the ingredient and technique is tested for the property, tubing is organized as coming into being
α phases+regeneration β phases, ingredient is uniformly without apparent segregation, and grain size is 5~15 μm, yield strength 798MPa, tensile strength
895MPa, is laterally extended rate 24%, full-scale Charpy V-type impact energy 51J, and flattening test and the equal flawless of flaring test generate.
To titanium alloy petroleum pipeline sampling prepared by the present invention, sample is made in the present embodiment titanium alloy petroleum pipe, under
High temperature pressure corrosion experiment is carried out in 1 environmental condition of table, Dynamic Speed is 300 revs/min, and test period 96 hours is pressed after experiment
Average year corrosion rate is calculated in the quasi- NACE RP0775-2005 of sighting target, by result as it can be seen that the titanium alloy material is with excellent
Corrosion resistance.
1 embodiment of table, one corrosion test condition and test result
| Experimental enviroment medium | Corrosion rate, mm/y | Test period, day |
| 25% nitric acid environment at 98 DEG C | 3 | 7 |
| 100% acetic acid | 0 | 7 |
| 50% formic acid | 5 | 1 |
| 5%HCl is at 75 DEG C | 0.57 | 1 |
| 10%HCl is at 75 DEG C | 6.9 | 1 |
| 10%HCl+0.1%FeCl3 is at 101 DEG C | 3.5 | 7 |
| 21 DEG C of seawater, crevice corrosion sample | 0 | 21 |
| 160℃+9MPa H2S+6MPaCO2The Cl of+150000mg/L- | 0.021 | 6 |
Embodiment two
Oil and gas development of the present invention is organized by mass percentage with high anti-corrosion low-cost titanium alloy petroleum pipeline ingredient to be become, Al：
3.95%, V：2.45%, Fe：1.48%, O：0.21%, Ru：0.05%, Ni：1.21%, C：0.06%, N：0.04%, H：
0.0149%, Cr：0.6%, W：0.35%, Ti：89.5851%.
The preparation processing method of titanium alloy tube:
The good titanium alloy component of said ratio is smelted into ingot casting by consumable electrode vacuum furnace, surface porosity is removed using lathe car
After layer, ingot casting is heated to 1100~1130 DEG C and is forged to intermediate billet state, intermediate base is then heated to 1050 DEG C
Annealing is homogenized to improve segregation, keeps tissue more uniform, secondary forging, pressure then are carried out to intermediate base at 960 DEG C~1000 DEG C
Lower amount is 60%, and extruded bar stock is made；
The titanium alloy extruded bar stock is heated to 930~955 DEG C of progress hot extrusions, deflection 90% is made the titanium and closes
After the extrusion tube blank of gold, carries out checking surfaces externally and internally state after soda acid is washed, surface defect is disposed, is then existed to extrusion tube blank
Vacuum stress relief annealing is carried out between 730~750 DEG C, is annealed 1.5 hours, and pipe is carried out using vacuum creep sizing machine
Alignment, and soda acid is carried out to the pipe after alignment and is washed, check surface state and removes defect；
Pipe after above-mentioned extruding is straightened is further processed using cold-rolling process to outer diameter 88.9mm, wall thickness at room temperature
The petroleum pipeline of 7.03mm, then to cold rolled tube carry out stress relief annealing process production tube is made, to the tubing after annealing into
Row ultrasonic examination and eddy current inspection process API standard screw thread in the both ends numerically-controlled machine tool of every qualified titanium alloy, and completing should
The preparation of size titanium alloy oil pipe is processed.
As shown in Fig. 2, the titanium alloy petroleum pipeline prepared to the ingredient and technique is tested for the property, tubing is organized as coming into being
α phases+regeneration β phases, ingredient is uniformly without apparent segregation, and grain size is 10~15 μm, yield strength 825MPa, tensile strength
920MPa, is laterally extended rate 20%, full-scale Charpy V-type impact energy 52J, and flattening test and the equal flawless of flaring test generate.
To titanium alloy petroleum pipeline sampling prepared by the present invention, sample is made in the present embodiment titanium alloy petroleum pipe, under
High temperature pressure corrosion experiment is carried out in 1 environmental condition of table, Dynamic Speed is 300 revs/min, and test period 96 hours is pressed after experiment
Average year corrosion rate is calculated in the quasi- NACE RP0775-2005 of sighting target, by result as it can be seen that the titanium alloy material is with excellent
Corrosion resistance.
2 embodiment of table, two corrosion test condition and test result
Embodiment three
Oil and gas development of the present invention is organized by mass percentage with high anti-corrosion low-cost titanium alloy petroleum pipeline ingredient to be become：Al：
3.6%, V：2.55%, Fe：1.38%, O：0.17%, Ru：1.0%, Ni：0.12%, C：0.06%, N：0.03%, H：
0.0142%, W：0.35%, Mo：0.08%, Ti：90.6458%.
The preparation processing method of titanium alloy tube：
The good titanium alloy component of said ratio is smelted into ingot casting by consumable electrode vacuum furnace, using lathe car except surface is dredged
After loose layer, ingot casting is heated to 1100~1150 DEG C and is forged to intermediate billet state, intermediate base is then heated to 1050 DEG C
Homogenizing annealing keeps tissue more uniform to improve segregation, then carries out secondary forging to intermediate base at 980 DEG C~1000 DEG C,
Drafts is 55%, and extruded bar stock is made；
The titanium alloy extruded bar stock is heated to 920~940 DEG C of progress hot extrusions, deflection 80% is made the titanium and closes
After the extrusion tube blank of gold, carries out checking surfaces externally and internally state after soda acid is washed, surface defect is disposed, is then existed to extrusion tube blank
Vacuum stress relief annealing is carried out between 760~800 DEG C, is annealed 2 hours, and school is carried out to pipe using vacuum creep sizing machine
Directly, it and carries out soda acid to the pipe after alignment to wash, checks surface state and remove defect；
Pipe after above-mentioned extruding is straightened is further processed using cold-rolling process to outer diameter 73.02mm, wall at room temperature
Then the petroleum pipeline of thick 6.45mm carries out stress relief annealing process to cold rolled tube and production tube is made, to the tubing after annealing
Ultrasonic examination and eddy current inspection are carried out, hermetic seal screw thread is processed in the both ends numerically-controlled machine tool of every qualified titanium alloy, completes
The preparation of the size titanium alloy oil pipe is processed.
The titanium alloy petroleum pipeline prepared to the ingredient and technique is tested for the property, and tubing is organized as primary alpha phase+regeneration β
Phase+a little Ti-Ru-Fe compounds, ingredient is uniformly without apparent segregation, and grain size is 3~15 μm, and the tiny reason of crystal grain is Ru
There is crystal grain thinning, as shown in Fig. 2, wherein the lattice diffraction pattern of Ti-Ru-Fe compounds is as shown in figure 3, vertical for body-centered
Square structure, tubing yield strength 827MPa, tensile strength 955MPa are laterally extended rate 22%, full-scale Charpy V-type impact energy
53J, flattening test and the equal flawless of flaring test generate.
To titanium alloy petroleum pipeline sampling prepared by the present invention, sample is made in the present embodiment titanium alloy pipe, in the following table 2 ring
High temperature pressure corrosion experiment is carried out in the condition of border, Dynamic Speed is 300 revs/min, test period 96 hours, according to standard after experiment
Average year corrosion rate is calculated in NACE RP0775-2005, by result as it can be seen that the titanium alloy material has excellent corrosion resistant
Corrosion energy.
3 embodiment of table, three corrosion test condition and test result
| Experimental enviroment medium | Corrosion rate, mm/y | Test period, day |
| 25% nitric acid environment at 98 DEG C | 2.1 | 7 |
| 100% acetic acid | 0 | 7 |
| 50% formic acid | 3.61 | 1 |
| 5%HCl is at 75 DEG C | 0.38 | 1 |
| 10%HCl is at 75 DEG C | 5.7 | 1 |
| 10%HCl+0.1%FeCl3 is at 101 DEG C | 2.57 | 7 |
| 21 DEG C of seawater, crevice corrosion sample | 0 | 21 |
| 160℃+9MPa H2S+6MPaCO2The Cl of+150000mg/L- | 0.009 | 6 |
Claims (7)
1. a kind of high corrosion resistant Ti alloy pipe for oil and gas development, it is characterised in that：In addition to Ti, matter is mainly pressed by following component
Measure percentage composition, Al：3.6~4.1%, V：2.1~2.6%, Fe：0.7~1.6%, O：0.15~0.26%, Ru：0.01
~1.1%, Ni：0.05~1.5%, 0 ＜ C≤0.07%, 0 ＜ N≤0.05%, 0 ＜ H≤0.0155%.
2. the high corrosion resistant Ti alloy pipe according to claim 1 for oil and gas development, it is characterised in that：It is pressed by following component
Mass percentage composition, Al：4.05%, V：2.15%, Fe：0.92%, O：0.25%, Ru：0.01%, Ni：0.97%, C：
0.05%, N：0.03%, H：0.0131%, surplus Ti.
3. the high corrosion resistant Ti alloy pipe according to claim 1 for oil and gas development, it is characterised in that：Also it is added with quality
Percentage is one or more of following component alloying element, Cr：0.1~0.7%, W：0.02~0.55%, Mo：
0.01~0.12%.
4. the high corrosion resistant Ti alloy pipe according to claim 3 for oil and gas development, it is characterised in that：It is pressed by following component
Mass percentage composition, Al：3.6%, V：2.55%, Fe：1.38%, O：0.17%, Ru：1.0%, Ni：0.12%, C：
0.06%, N：0.03%, H：0.0142%, W：0.35%, Mo：0.08%, surplus Ti.
5. the high corrosion resistant Ti alloy pipe according to claim 3 for oil and gas development, it is characterised in that：It is pressed by following component
Mass percentage composition, Al：3.95%, V：2.45%, Fe：1.48%, O：0.21%, Ru：0.05%, Ni：1.21%, C：
0.06%, N：0.04%, H：0.0149%, Cr：0.6%, W：0.35%, surplus Ti.
6. a kind of method preparing any high corrosion resistant Ti alloy pipe for oil and gas development of claim 1 to 5, feature exist
In including the following steps：
1) proportioned titanium alloy component is smelted into ingot casting through consumable electrode vacuum furnace, surface oxidation is removed using machine-tooled method vehicle
Ingot casting is heated to 1050~1150 DEG C of forgings to intermediate billet state by layer；
2) intermediate base is heated to 1000~1050 DEG C of homogenizing annealings, secondary forging is carried out to intermediate base at 940~1000 DEG C,
Drafts is 50%~70%, and extruded bar stock is made；
3) titanium alloy extruded bar stock is heated to 870~955 DEG C of progress hot extrusions, deflection is 75~90%, and titanium alloy is made
Extrusion tube blank after, carry out soda acid wash after check surfaces externally and internally state, surface defect is handled；
4) vacuum stress relief annealing is carried out between 600~800 DEG C of temperature to extrusion tube blank, is annealed 1~2 hour, to pipe
It is straightened, and soda acid is carried out to the pipe after alignment and is washed, check surface state and removes defect；
5) pipe that step 4) obtains is further processed using cold-rolling process at room temperature, destressing then is carried out to cold rolled tube
Production tube is made in annealing, and ultrasonic examination and eddy current inspection are carried out to the tubing after annealing；
6) both ends of qualified titanium alloy tube numerically-controlled machine tool is processed into API standard screw thread or special thread, completes the titanium alloy
The preparation of petroleum pipeline is processed.
7. the method for preparing the high corrosion resistant Ti alloy pipe for oil and gas development according to claim 6, it is characterised in that：Step
4) carrying out alignment to pipe described in is straightened to pipe using vacuum creep sizing machine.
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| CN111471891A (en) * | 2020-04-30 | 2020-07-31 | 中国石油天然气集团有限公司 | 720 MPa-grade high-strength corrosion-resistant titanium alloy pipe for drill rod and manufacturing method thereof |
| CN111485135A (en) * | 2020-04-30 | 2020-08-04 | 中国石油天然气集团有限公司 | 930 MPa-grade Ti-Al-V-Zr-Ru corrosion-resistant titanium alloy pipe and preparation method thereof |
| CN112813299A (en) * | 2019-11-12 | 2021-05-18 | 新疆大学 | High-strength low-cost corrosion-resistant titanium alloy |
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| CN111471891A (en) * | 2020-04-30 | 2020-07-31 | 中国石油天然气集团有限公司 | 720 MPa-grade high-strength corrosion-resistant titanium alloy pipe for drill rod and manufacturing method thereof |
| CN111485135A (en) * | 2020-04-30 | 2020-08-04 | 中国石油天然气集团有限公司 | 930 MPa-grade Ti-Al-V-Zr-Ru corrosion-resistant titanium alloy pipe and preparation method thereof |
| CN111471891B (en) * | 2020-04-30 | 2022-07-05 | 中国石油天然气集团有限公司 | 720 MPa-grade high-strength corrosion-resistant titanium alloy pipe for drill rod and manufacturing method thereof |
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Address after: 710065, No. two, No. 32, Xi'an, Shaanxi Patentee after: CNPC TUBULAR GOODS Research Institute Patentee after: Xi'an Sanhuan Petroleum Pipe Technology Co.,Ltd. Address before: 710065, No. two, No. 32, Xi'an, Shaanxi Patentee before: CNPC TUBULAR GOODS Research Institute Patentee before: XI'AN TRI-CIRCLE TECHNOLOGY DEVELOPMENT Corp. |
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