CN1189259C - Manufacture of bimetallic composite pipe - Google Patents
Manufacture of bimetallic composite pipe Download PDFInfo
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- CN1189259C CN1189259C CNB021145253A CN02114525A CN1189259C CN 1189259 C CN1189259 C CN 1189259C CN B021145253 A CNB021145253 A CN B021145253A CN 02114525 A CN02114525 A CN 02114525A CN 1189259 C CN1189259 C CN 1189259C
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- bushing pipe
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Abstract
The present invention discloses a manufacture method of a bimetallic composite pipe for industries of petroleum, chemistry, etc. The method is mainly used for solving the problems existing in bimetallic composite pipes made by the prior art that a large quantity of interlayer gaps exist between a base pipe and a lining pipe, and the base pipe and the lining pipe have unfirm combination and are easy to result in interlayer separation of large area among pipes, etc. The main steps of the present invention orderly comprise: A, cleaning the surfaces of pipes; B, coating brazing material on the external surface of the lining pipe; C, carrying out cold-drawing combination after the lining pipe and the base pipe are sheathed; D, cold-drawing the composite pipe and carrying out medium-frequency induction brazing to the composite pipe. In addition, carrying out subsequent heat treatment to the composite pipe after brazed when required. The bimetallic composite pipe manufactured by the method of the present invention forms a brazing layer between the internal surface of the base pipe and the external surface of the lining pipe; the brazing layer fills the interlayer gaps between the base pipe and the lining pipe and makes the base pipe and the lining pipe form very firm metallurgical combination of 100%. The bimetallic composite pipe manufactured by the method of the present invention is mainly used as anticorrosion pipes in industries of petroleum, chemical industry, etc.
Description
Technical field
The present invention relates to a kind of manufacture method that is used for the composite bimetal pipe of industry such as oil, chemistry.
Background technology
In recent years,, want output, want benefit, increased the weight of machine utilization greatly to equipment along with China's oil refining enterprise develops to maximization, intensification direction.And China's main oilfield crude oil becomes heavy, acid number is high, sulfur-bearing is high, salt content is big, and refines import Middle East sour crude in a large number, has all increased the weight of the corrosion of oil refining apparatus, therefore equipment and pipeline has been proposed higher anti-corrosion requirement.For a long time, petrochemical system adopts stainless steel, titanium, copper and a small amount of other precious metal seamless pipe in a large number, and is costly.Therefore, all kinds of multiple tubes (comprising composite bimetal pipe) have obtained increasing research and application.
Composite bimetal pipe is formed with the bushing pipe that is positioned at internal layer by being positioned at outer field parent tube.The at present domestic manufacture method that generally adopts is machinery applying (as processes such as hot extrusion, cold-drawn, cold spinnings); The external production technology that adopts also has the coating process of pipeline corrosion protection lining in addition to the above methods.The multiple tube of various mechanical applying manufactured, parent tube and bushing pipe do not reach firm metallurgical binding.Owing to have a large amount of interlayer gaps inevitably between parent tube and the bushing pipe, when the internal layer bushing pipe occurs between local pitting or crack, a large amount of highly corrosive medium infiltration parent tube and the bushing pipe, will form crevice corrosion, thereby quicken corrosive pipeline, and then cause pipe interlayer large tracts of land to separate.Under the temperature and pressure effect, the internal layer bushing pipe is subjected to external pressure, unstability takes place even cause the bushing pipe bulge, causes the accident of pipeline obstruction to take place.So, need to adopt a kind of composite bimetal pipe of the new more high performance metallurgical binding of method manufacturing, to replace adopting the multiple tube of existing mechanical applying method manufacturing.
At present, adopt the shooter process only to be used for the production of explosive clad plate.As metallic composite, existing explosive clad plate has been widely used in the manufacturing of petrochemical equipment.But adopt the shooter process can't produce composite bimetal pipe, corresponding multiple tube material is still blank.
In recent years, be applied to the spraying of petrochemical industry pipeline, the tubing of enamel surface modification,, have holiday, impact failure problem, do not have due anti-corrosion effect although cheap.Add that the construction requirement flange connects, and has not only increased difficulty of construction, and has improved cost.If replace, will produce huge economic benefit so, and can satisfy the requirement of industry product upgradings such as oil, chemical industry with the composite bimetal pipe material.
Summary of the invention
Technical problem to be solved by this invention is: exist a large amount of interlayer gaps and the two in conjunction with problem insecure, that in use easily cause pipe interlayer large tracts of land to separate and then make internal layer bushing pipe generation unstability even cause the bushing pipe bulge between the existing parent tube of composite bimetal pipe that adopts existing various mechanical applying manufactured and the bushing pipe.
For addressing the above problem, the technical solution used in the present invention is: a kind of manufacture method of composite bimetal pipe, being used to make caliber is that Φ is that not corrosion resistant seamless metal pipe, internal layer bushing pipe are the composite bimetal pipe of corrosion resistant seamless metal pipe to 630 millimeters of Φ, outer parent tube for 89 millimeters, and it is characterized in that: this method in turn includes the following steps:
Degreasing and oxide are removed in the surface of A, cleaning parent tube and bushing pipe;
B, at the coated solder of the outer surface of bushing pipe with corrosion resistance;
C, bushing pipe and parent tube suit are got up, it is compound to carry out cold drawing, make between the outer surface of the inner surface of parent tube and bushing pipe and obtain a capillary gap that is suitable for soldering, and the solder on the inner surface of parent tube and the bushing pipe outer surface fits tightly for coated layer;
D, under inert gas shielding, the cold drawing multiple tube is carried out the Frequency Induction Heating soldering by the heat induced circle by pipe bottom to the top vertically downward in the Frequency Induction Heating brazing device.
Adopt the present invention, has following beneficial effect: the composite bimetal pipe that adopts the inventive method to make, soldering one deck brazing layer between the outer surface of the inner surface of composite bimetal pipe parent tube and bushing pipe, brazing layer filled up the interlayer gap between parent tube and the bushing pipe and make parent tube and bushing pipe between can reach 100% metallurgical binding; Its interlayer gap is zero, and can be by the ultrasonic examination check of " Nondestructing Detection of Pressure Vessels " JB4730-94 standard code.Therefore, adopt the composite bimetal pipe of the inventive method manufacturing to eliminate existing a large amount of interlayer gap between the parent tube of the composite bimetal pipe that adopts existing various mechanical applying manufactured and the bushing pipe fully.Brazing layer forms a kind of intermediate layer of metallurgical binding between the bushing pipe of the composite bimetal pipe that the inventive method is made and parent tube; Reasonably select brazing material, can make the anti-corrosion and mechanical property of this middle close binder be higher than bushing pipe and parent tube.Therefore, the lining pipe of the composite bimetal pipe made from the inventive method to be to combine with parent tube very securely, solved effectively the existing parent tube of the composite bimetal pipe that adopts existing various mechanical applying manufactured and bushing pipe in conjunction with insecure, in use easily cause the large tracts of land of pipe interlayer to separate and then make internal layer bushing pipe generation unstability even cause series of technical such as bushing pipe bulge.
With regard to the manufacture method of composite bimetal pipe of the present invention itself, its major advantage is: the cold drawing behind the 1. coated solder is compound to be easy to obtain gratifying joint clearance of brazing between parent tube inner surface and the bushing pipe outer surface; After the Frequency Induction Heating soldering, different metal materials is easy to reach 100% metallurgical binding; 2. brazing process adopts the Frequency Induction Heating soldering, has that heating is fast, efficient is high, easily realizes characteristics such as automated production; 3. the Frequency Induction Heating soldering of different metal materials is carried out under inert gas shielding, has prevented the heated oxide of parent tube and bushing pipe; 4. in a specific embodiment of the present invention, the cold drawing multiple tube carries out the Frequency Induction Heating soldering by the heat induced circle by the pipe bottom vertically downward to the top, make full use of deadweight and the wetting principle of capillary after solder melts, in welding process, make the solder liquation constantly fill the interlayer gap between parent tube and the bushing pipe, help the two and reach 100% metallurgical binding.
With the composite bimetal pipe that the inventive method is made, be a kind of novel metallurgical brazing composite bimetal pipe; It has had both parent tube (intensity height, expense low) and both performances of bushing pipe (corrosion-resistant) and advantage.Replace the expensive all kinds of tubing of making by pure precious metal with the composite bimetal pipe of the inventive method manufacturing, but cost saving is about 20%～30%, thereby reduces material cost greatly, and save a large amount of scarce resources.Adopt argon arc welding, manual electric arc welding to tap into the requirement of capable butt welding when in addition, adopting the multiple tube of suitable solder brazing to satisfy site operation simultaneously; Can with the supporting use of existing metallic composite.In a word, the composite bimetal pipe made from the inventive method is as a kind of novel anticorrosion tubing, can satisfy in the production process requirement to dielectric corrosion and temperature, pressure; Can be widely used in high temperature, high pressure, high corrosive environment in the industries such as oil, chemical industry, pharmacy, food, and the product medium requires to prevent to have good market development potential in the device and piping engineering system of iron ion pollution.
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is the axial cross-sectional schematic of Frequency Induction Heating brazing process of the present invention and device.
Fig. 2 is the sectional drawing with the composite bimetal pipe of the inventive method manufacturing.
The specific embodiment
As shown in Figure 2, comprise the bushing pipe 103 that is positioned at outer field parent tube 101 and is positioned at internal layer, between the outer surface of the inner surface of parent tube 101 and bushing pipe 103, one deck brazing layer 102 is arranged with the composite bimetal pipe of the inventive method manufacturing.
The key step of the manufacturing process flow of composite bimetal pipe of the present invention comprises successively: A, parent tube and bushing pipe raw material clean; B, bushing pipe solder are coated; C, cold drawing are compound; D, Frequency Induction Heating soldering.Can also carry out subsequent heat treatment to the multiple tube after the soldering when needing in addition.Below above each step is described in detail.
A, parent tube and bushing pipe raw material clean
Before different tubing is compound, the inner surface of parent tube 101 and the outer surface of bushing pipe 103 are cleaned, remove lip-deep greasy dirt and oxide.
B, bushing pipe solder are coated
After the cleaning, immediately at the coated solder of the outer surface of bushing pipe 103.
C, cold drawing are compound
D, Frequency Induction Heating soldering
The Frequency Induction Heating soldering is a committed step of making composite bimetal pipe with the inventive method, belongs to the composite brazing of different metal materials.Owing to mainly be used as the pipe and the pipe fitting of the melting the implemented connection of all size of under certain temperature and pressure, carrying vapour, liquid, solid corrosive medium in the industries such as oil refining, chemical industry with the xenogenesis bimetallic material multiple tube of the inventive method manufacturing and by the various pipe fitting goods of its manufacturing, so adopt the welding method of soldering; Make full use of the uniformity and stable and the flowability under molten state, wetability of solder, under capillarity, solder is filled between the dissimilar metal, finish the welding at multiple tube different metal materials interface.
The selection of solder should be according to being decided by the performance of compound xenogenesis mother metal (bushing pipe and parent tube), is in principle and is complementary by the weldering mother metal.For example, the nickel-based solder that stainless steel one carbon steel adopts Ni-Cr-B-Si (nickel one chromium-boron-silicon) to be, copper-carbon steel adopts copper base solder, and titanium-carbon steel adopts silver-base solder.Solder itself also should have high-temperature oxidation resistance and corrosion resistance.More than to the intermediate frequency induction heating brazing method and given concentrated explanation to the selection of parent tube, bushing pipe and solder material by way of example.
Meet step C, the multiple tube soldering in intermediate frequency induction heating device with cold drawing after compound.
Fig. 1 is with the schematic diagram of a kind of Frequency Induction Heating brazing device brazed composited tube of the present invention (axially cutaway view).This Frequency Induction Heating brazing device has an annular seal space 6, in establish heat induced circle 5; Heat induced circle 5 links to each other with intermediate frequency power supply.Annular seal space inert gas conduit 9 stretches in the annular seal space 6.Multiple tube to be welded 1 usefulness suspension rod 3 vertical liftings after cold drawing is compound pass annular seal space 6 and heat induced circle 5 in intermediate frequency induction heating device.The top of suspension rod 3 is provided with suspension hook 301, links to each other with jacking equipment.Upper and lower at annular seal space 6 housings is provided with sealing flange 401 and annular seal space lower seal flange 402 on the annular seal space around multiple tube respectively.The last lower nozzle of multiple tube is provided with upper orifice sealing flange 201 and lower nozzle sealing flange 202 around suspension rod 3 respectively.Multiple tube inert gas conduit 8 stretches into the internal cavities of multiple tube through upper orifice sealing flange 201.The purpose that above-mentioned each sealing flange is set mainly is in order to prevent the inert gas effusion.
The Frequency Induction Heating brazing process as shown in Figure 1.Feed inert gas with displaced air, so that in soldering heating process, parent tube and bushing pipe are carried out protection against oxidation to the inner chamber of cold drawing multiple tube 1 and the inside of annular seal space 6 respectively through multiple tube inert gas conduit 8 and annular seal space inert gas conduit 9.Inert gas can use nitrogen, argon gas etc.; For example feed percentage by weight and be 99.999% pure argon gas, its flow-control is at 6～12 liters/minute.
Start intermediate frequency power supply then, carry out eddy-current heating by 5 pairs of cold drawing multiple tubes of heat induced circle 1.The selection of power should be decided (promptly to reach exceed the solder fusion temperature be as the criterion for 30 ℃～60 ℃) according to the tube wall temperature that is heated multiple tube.For example (the multiple tube caliber is 159 millimeters of φ to the multiple tube of 159 * (8+3) millimeters of φ, carbon steel parent tube thickness is 8 millimeters, the stainless steel lining tube thickness is 3 millimeters, solder is the nickel-based solder of Ni-Cr-B-Si system), power selects 80～160 kilowatts, heating-up temperature is between 1040 ℃～1100 ℃, to guarantee the molten solder of solder.
When above-mentioned cold drawing multiple tube 1 is heated to brazing temperature, start jacking equipment, drive it vertically downward, the speed with 100～200 mm/min is carried out the Frequency Induction Heating soldering by heating in medium frequency induction coil 5 to the top from the pipe bottom by suspension rod 3; After finishing, soldering promptly finishes the manufacture process of composite bimetal pipe of the present invention.The composite bimetal pipe of making is referring to Fig. 2, between the outer surface of the inner surface of parent tube 101 and bushing pipe 103 soldering one deck brazing layer 102.Capillary gap between the inner surface of the thickness of brazing layer 102 and the formed parent tube 101 of cold drawing compound working procedure and the outer surface of bushing pipe 103 is identical; Optimum value is 0.03～0.10 millimeter.For clarity sake, Fig. 2 has carried out exaggerative signal to the thickness of brazing layer 102.
When the multiple tube after the soldering need be heat-treated, can carry out subsequent heat treatment.For example the soldering internal lining pipe is austenitic stainless steel, when parent tube is the multiple tube of mild steel, at the multiple tube after the soldering below annular seal space 6 housings quenching water spray ring 7 is set.When multiple tube is carried out soldering; to the cooling (referring to Fig. 1) of spraying water from the outside by the pipeline section after 5 induction brazings of heat induced circle of inert gas shielding part; make the solutionizing of brazed composited tube inner liner stainless steel layer austenite, to guarantee stainless anti intercrystalline corrosion performance.
In the above-mentioned specific embodiment, cold drawing multiple tube 1 carries out the Frequency Induction Heating soldering by heat induced circle 5 by the pipe bottom vertically downward to the top, make full use of deadweight and the wetting principle of capillary after solder melts, in welding process, make the solder liquation constantly fill the interlayer gap between parent tube and the bushing pipe, help the two and reach 100% metallurgical binding.
The Frequency Induction Heating mode and the device of the invention described above can satisfy the Fast Heating soldering welding of different metal materials, and can guarantee the complete solid solution condition of stainless steel bushing pipe, satisfy the anti intercrystalline corrosion requirement.Simultaneously in heating, two processes of cooling, the different characteristics of the different metal materials coefficient of expansion have been made full use of and to useful influence that brazing process produced: promptly, when multiple tube is heated to the solder fusion temperature, the coefficient of expansion of its stainless steel bushing pipe is greater than the coefficient of expansion of carbon steel parent tube, and it is extremely useful that the solder of fusing welds under the pressure that the interlayer differences in expansion causes; And in the solder process of setting, cool by the outside water spray, the multiple tube of postwelding cools off contraction from outside to inside, can obtain fine and close brazing layer.
Adopt the composite bimetal pipe of the cited above-mentioned several parent tubes of specification of the present invention, bushing pipe and solder manufacturing, its technical target of the product is as follows:
Composite bimetal pipe caliber: 630 millimeters of Φ 89～Φ
Internal layer bushing pipe wall thickness: 1.5～4 millimeters
Scale (pipe range): 3～9 meters
Yield strength (σ
s): be not less than basic unit
Tensile strength (σ
b): be not less than basic unit
Percentage elongation (δ): be not less than basic unit
Binder course shear strength: 〉=147MPa
Bushing pipe intercrystalline corrosion (stainless steel bushing pipe): qualified (" stainless steel sulfuric acid-copper sulphate corrosion
Test method " GB4334.5-90)
Composite steel tube ultrasonic examination: by " Nondestructing Detection of Pressure Vessels "
The JB4730-94 standard is carried out
Serviceability temperature :≤450 ℃
Applicating example: ordinary decompression column bottom line, atmosphere 3rd side cut, normal four lines of refining sour crude, high-acid crude oil or high-sulfur high-acid crude oil, subtract three-way, subtract high temperature, high corroded pipelines such as four lines, catalytic fractionator bottom line, recycle oil line, service condition is: temperature is not higher than 300 ℃～400 ℃, pressure is 0.1～2.5MPa, and medium is hydrocarbon+high temperature sulphur+high temperature vulcanized hydrogen+high-temperature naphthenic acid.If tubing is selected carbon steel material for use, its corrosion rate will be above 0.5 millimeter/year, is resistant material not.If select the chrome-molybdenum steel material for use, its corrosion resistance does not have too big raising, belongs to not resistant material yet.If select stainless steel material for use, its Master Cost will increase greatly, and the danger of polythionic acid stress cracking takes place simultaneously in addition.Under these conditions, the composite bimetal pipe (parent tube is No. 20 carbon steels, and bushing pipe is 304L or 316L stainless steel) that adopts the inventive method to make is a selection preferably.
More than by the specific embodiment method that the present invention makes composite bimetal pipe is had been described in detail.The above-mentioned specific embodiment does not limit the scope of the invention.According to actual needs, can adopt the inventive method to produce the composite bimetal pipe of multiple material (material of parent tube, bushing pipe and the solder that is complementary with it) and specification.The method that those skilled in the art needs to propose according to specification of the present invention is according to specific circumstances determined concrete machined parameters, can implement the present invention fully.
Except can be used as tubing uses, can also become various elbows, threeway, big or small first-class pipe fitting, use supporting with the composite bimetal pipe of the inventive method manufacturing as the advanced composite material (ACM) processing and manufacturing with it.
Claims (3)
1, a kind of manufacture method of composite bimetal pipe, being used to make caliber is that Φ is that not corrosion resistant seamless metal pipe, internal layer bushing pipe (103) are the composite bimetal pipe of corrosion resistant seamless metal pipe to 630 millimeters of Φ, outer parent tube (101) for 89 millimeters, and it is characterized in that: this method in turn includes the following steps:
Degreasing and oxide are removed in the surface of A, cleaning parent tube (101) and bushing pipe (103);
B, at the coated solder of the outer surface of bushing pipe (103) with corrosion resistance;
C, bushing pipe (103) and parent tube (101) suit are got up, it is compound to carry out cold drawing, make between the outer surface of the inner surface of parent tube (101) and bushing pipe (103) and obtain a capillary gap that is suitable for soldering, and the solder on the inner surface of parent tube (101) and bushing pipe (103) outer surface fits tightly for coated layer;
D, under inert gas shielding, cold drawing multiple tube (1) is carried out the Frequency Induction Heating soldering by heat induced circle (5) by pipe bottom to the top vertically downward in the Frequency Induction Heating brazing device.
2, the manufacture method of composite bimetal pipe according to claim 1 is characterized in that: the capillary gap between the outer surface of the inner surface of described parent tube (101) and bushing pipe (103) is 0.03 millimeter to 0.10 millimeter.
3, the manufacture method of composite bimetal pipe according to claim 1, it is characterized in that: the material of composite bimetal pipe parent tube (101) is a mild steel, the material of bushing pipe (103) is an austenitic stainless steel, carry out in the process of soldering at multiple tube, to the cooling of spraying water from the outside of the pipeline section after heat induced circle (5) induction brazing, the water spray cooling adopts the set quenching water spray ring (7) of multiple tube after the soldering to carry out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021145253A CN1189259C (en) | 2002-04-11 | 2002-04-11 | Manufacture of bimetallic composite pipe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021145253A CN1189259C (en) | 2002-04-11 | 2002-04-11 | Manufacture of bimetallic composite pipe |
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| Publication Number | Publication Date |
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| CN1375362A CN1375362A (en) | 2002-10-23 |
| CN1189259C true CN1189259C (en) | 2005-02-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021145253A Expired - Fee Related CN1189259C (en) | 2002-04-11 | 2002-04-11 | Manufacture of bimetallic composite pipe |
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Families Citing this family (18)
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| CN1330436C (en) * | 2003-11-20 | 2007-08-08 | 吉欣（英德）热轧不锈复合钢有限公司 | Method for making soldered hot-rolled composite metal tube |
| CN100362308C (en) * | 2004-07-15 | 2008-01-16 | 浙江银轮机械股份有限公司 | Connection method for tube plate and pipe joint of tube-shell/tube-sheet type heat exchanger |
| JP4546543B2 (en) | 2004-12-21 | 2010-09-15 | ベルクローア・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ジーゲン | Multi-layer pipe manufacturing method |
| CN102128312A (en) * | 2010-12-31 | 2011-07-20 | 三一重工股份有限公司 | Taper pipe for concrete pumping device and manufacturing method thereof |
| CN103157693A (en) * | 2011-12-13 | 2013-06-19 | 洛阳希诺能源科技有限公司 | Production process of high-temperature-resistant metal composite pipe |
| CN102513401A (en) * | 2011-12-21 | 2012-06-27 | 济源豫光新材料科技有限公司 | Tubular target bonding method |
| CN102909278B (en) * | 2012-09-28 | 2014-10-15 | 北京科技大学 | Preparation method of metal composite pipe |
| CN103203598A (en) * | 2013-04-11 | 2013-07-17 | 新兴铸管股份有限公司 | Metallurgical composite bimetal seamless pipe production process |
| CN103231209A (en) * | 2013-04-11 | 2013-08-07 | 新兴铸管股份有限公司 | Method for producing vacuum-embedded metallurgical composite bimetal seamless tube |
| CN105299335A (en) * | 2014-07-31 | 2016-02-03 | 上海天阳钢管有限公司 | Manufacturing method of carbon steel stainless steel double-metal polymerization pipe |
| CN105537316B (en) * | 2016-01-15 | 2018-06-05 | 上海天阳钢管有限公司 | A kind of manufacturing method of stainless steel composite pipe |
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| CN106270905A (en) * | 2016-08-30 | 2017-01-04 | 西安向阳航天材料股份有限公司 | The induction brazing devices and methods therefor of production metallurgy formula multiple tube under atmospheric environment |
| CN108231214B (en) * | 2017-12-07 | 2020-12-08 | 广东核电合营有限公司 | Composite tube for nuclear fuel assembly and method for manufacturing same |
| CN108747214A (en) * | 2018-05-24 | 2018-11-06 | 上海天阳钢管有限公司 | A kind of process of compound oil well pipe of the manufacture with hoop |
| CN108723711A (en) * | 2018-05-24 | 2018-11-02 | 上海天阳钢管有限公司 | A kind of process of the compound oil well pipe of manufacture |
| CN113399809B (en) * | 2021-07-03 | 2022-09-23 | 天津金键航天设备有限公司 | Preparation process and equipment of dissimilar metal composite pipe and dissimilar metal composite pipe |
| CN114798802A (en) * | 2022-05-10 | 2022-07-29 | 江苏新澎复合材料有限公司 | Bimetal tube processing method |
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2002
- 2002-04-11 CN CNB021145253A patent/CN1189259C/en not_active Expired - Fee Related
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| CN1375362A (en) | 2002-10-23 |
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Owner name: SINOPEC LUOYANG ENGINEERING CO., LTD. Free format text: FORMER NAME: CHINA PETROCHEMICAL CORPORATION |
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Granted publication date: 20050216 Termination date: 20160411 |