Stock material or miscellaneous articles – All metal or with adjacent metals – Composite; i.e. – plural – adjacent – spatially distinct metal...
Reexamination Certificate
2001-06-11
2003-06-17
Zimmerman, John J. (Department: 1775)
Stock material or miscellaneous articles
All metal or with adjacent metals
Composite; i.e., plural, adjacent, spatially distinct metal...
C428S679000, C138S142000, C138S143000, C138S145000, C219S076160
Reexamination Certificate
active
06579628
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a multi-layered heat resistant metal tube having excellent anti-coking characteristics and a method for manufacturing thereof. The multi-layered heat resistant metal tube is suitable for those tubes which are used in a high temperature and in a high carbonization potential environment as components of apparatus.
2. Description of the Related Art
High resistance to coking and carbonization, in addition to heat resistance, is required to some parts such as heat radiant tube of carburization-hardening furnaces, cracking tubes of thermal decomposition furnaces, particularly, ethylene cracking furnace tube or oil refinery cracking tube or all the other petrochemical thermal cracking furnace tube applications. Coking is a phenomenon of deposition and accumulation of carbon generated by thermal decomposition of hydrocarbons onto the surfaces of the metal tubes. This causes trouble of decrease in cross sectional area of furnace tubes, which may finally lead to blocking of the furnace tubes. Carbonization of metal is a carburization phenomenon of intrusion of carbon through the surface of the metal and diffusion of carbon into the inner part of the metal. This may either cause the coking or directly be processed by intrusion of carbon from the atmosphere. In any way, corrosion of the tubes due to decreased corrosion resistance caused by the carburization, decrease in the area of inner diameter of the tubes due to coke deposit, and possible embrittlement subsequently caused is fatal to the furnace tube units.
There exists a single layer solid tube of Cr—Ni base heat resistant alloy in application for the above listed use. A group of the conventionally known materials are composed of 40-50 wt % Cr—Ni alloys disclosed in Unexamined Japanese Patent Publication (kokai) Nos. 05-93240, 07-113139, 07-258782 and 07-258783. The alloys were designed to contain, in order to provide high temperature strength, 0.1-0.5 wt % of C and not more than 0.2 wt % of N, and additionally contain, as the components to enhance the high temperature strength, at least one element of Al, Nb, Ti, Zr or W. Another group is represented by an alloy steel disclosed in Unexamined Japanese Patent Publication (kokai) No. 05-1344. This alloy steel has alloy compositions containing 0.05-0.3 wt % of C and 0.1-0.6 wt % of N with the purpose of providing high temperature strength, not more than 5.0 wt % of Si as the component of giving resistance to carburization, and not more than 0.4 wt % of Mn and 0.001-0.02 wt % of Mg for improvement of the ductility.
These alloy compositions are, on one hand, effective for the purpose of providing high temperature strength and improving ductility, and on the other hand, could be rather harmful in anti-coking and/or anti-carburizing characteristics, and thus, the conventional materials are not satisfactory from these points of view.
Then dual layered cast tube was developed so that base layer might function for high temperature resistance while the surface layer would work for anti-coking or anti-carburizing. “Insert casting” is a typical method for producing the double layered tubes. Unexamined Japanese Patent Publication (kokai) No. 60-170564 discloses a technology to produce bent tubes by using a previously heated insert in a shape of a bent tube and a sand mold as the outer mold and casting molten metal therebetween to obtain a cast product in which the bent tube is inserted. The drawback of this technology is that the surface of the insert which contacts with the molten metal melts and contaminates the molten metal. Further, in case where the cast product is thin, distribution of the molten metal will be insufficient, and defects such as incomplete surface fusion and blow holes often occur.
Another method for producing double layered tubes is centrifugal casting. Unexamined Japanese Patent Publication (kokai) Nos. 05-93238 and 05-93249 propose sequential casting which is composed of the first charging molten metal of high nickel Fe—Ni—Cr heat resistant steel in a centrifugal casting machine to case the other layer, and then charging a molten metal of Cr—Ni alloy to cast and form the inner layer. In order to operate a centrifugal casting machine with high productivity, however, it is forced to charge the molten metal for inner layer before complete solidification of the outer layer. It has been known that, as far as coking is concerned, Fe acts as a catalyst for coke depositing, and therefore, is harmful. In case of combining the above alloy compositions, it is inevitable that Fe contained in the outer tube material diffuses into the inner layer material to reach the surface of the inner layer, and thus, it is not possible to produce multi-layered tube having excellent anti-coking characteristics. On the other hand, casting the inner layer after solidification of the outer layer results in cracking due to thermal expansion-contraction during solidification, and thus, it is quite difficult to produce desired tubes with practical yield.
Possible further way of producing double layered tubes is hot extrusion to form cladded tubes. Unexamined Japanese Patent Publication (kokai) No. 07-150556 proposes tube forming by hot rolling of a blank prepared by inserting a hollow billet of alloy having a suitable alloy composition into a hollow billet of a Ni—Fe—Cr heat resistant alloy. At present, however, the costs for production is so high that this kind of cladded tubes have not practical use in this field.
“Inchromizing” method is a technology to form a high chromium layer on the surface of a heat resistant metal tube. Thickness of the chromium rich layer formed by this technology is, however, 30 &mgr;m to 50 &mgr;m at highest, and thus, there is limitation in application to the parts of apparatus from which surface layer as a consumable will be lost by oxidation or carbonization.
Ethylene cracking reactor furnace (or ETHYLENE TUBE) produces ethylene by cracking naphtha at the toughest conditions where high temperature heat resisting and anti-coking material were critically demanded. Naphtha, as the feed steam mixture, passes through the ETHYLENE TUBE of the radiant section where thermal cracking takes place. The heat of conversion is provided by burners on the side wall or in the bottom of the radiant section, called fire box. During the very short residence time in the radiant coil (tenth of a second) at around 1000° C., the hydrocarbons including naphtha are cracked to ethylene, butadiene, butanes and aromatics. Since the tube material temperature in the fire box can often exceed 1100° C. (2021° F.), centrifugal cast high temperature, creep resistant alloys such as HK-40, HP-40 or HP Mod. are in use. While these conventional materials are good for creep rapture at 1100° C., precipitation and depositing of carbon and/or embrittlement of ETHYLENE TUBE accompanied with carbonization are inevitable. Built-up carbon coke needs a cyclical removal of coke which is accompanied with interrupting the operation (anti-coking). Embrittlement by carbonizing in a serious case needs replacement of the whole tube unit. Because of gas stream inside the tube being of hydrocarbon at high temperature the gas atmosphere will be origin for building carbon deposition on the surface of the tube metal. This will reduce run-length and also leads to subsequent diffusion into the tube material. The diffusion process or carbonization will cause many detrimental effects in the physical properties of the tube. The ductility, toughness, rupture time and melting will deduce the original grade progressively as the carbonization process goes on. This can eventually lead to prematured failure of the tubes by a set of attacks of thermal shock, stress rupture, thermal fatigue, or carbonization-induced cracking. In fact carbonization is the major cause of ethylene furnace failure in industry wide.
At the 11
th
Conference of Ethylene Makers held in Houston in March of 1999 there was a presentation for improvement of the ethylene tubes to give dou
Asari Seiya
Kato Yoshihisa
Shimizu Takao
Takeuchi Yuko
Tanaka Isao
Bacon & Thomas
Daido Tokushuko Kabushiki Kaisha
Zimmerman John J.
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