EP0576571B1 - Procedes de reformage en presence de faibles quantites de soufre - Google Patents

Procedes de reformage en presence de faibles quantites de soufre Download PDF

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Publication number
EP0576571B1
EP0576571B1 EP92908806A EP92908806A EP0576571B1 EP 0576571 B1 EP0576571 B1 EP 0576571B1 EP 92908806 A EP92908806 A EP 92908806A EP 92908806 A EP92908806 A EP 92908806A EP 0576571 B1 EP0576571 B1 EP 0576571B1
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Prior art keywords
reforming
reactor system
tin
sulfur
carburization
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EP92908806A
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German (de)
English (en)
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EP0576571A4 (fr
EP0576571A1 (fr
Inventor
John V. Heyse
Bernard F. Mulaskey
Robert A. Innes
Daniel P. Hagewiesche
Gale L. Hubred
Steven C. Moore
Paul F. Bryan
Robert L. Hise
Steven E. Trumbull
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Chevron Phillips Chemical Co LP
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Chevron Chemical Co LLC
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Priority to EP97110024A priority Critical patent/EP0798363B1/fr
Priority to EP98100396A priority patent/EP0845521B1/fr
Publication of EP0576571A1 publication Critical patent/EP0576571A1/fr
Publication of EP0576571A4 publication Critical patent/EP0576571A4/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • the present invention relates to improved techniques for catalytic reforming under low-sulfur, and low-sulfur and low-water conditions. More specifically, the invention relates to the discovery and control of problems particularly acute with low-sulfur, and low-sulfur and low-water reforming processes.
  • Catalytic reforming is well known in the petroleum industry and involves the treatment of naphtha fractions to improve octane rating by the production of aromatics.
  • the more important hydrocarbon reactions which occur during the reforming operation include the dehydrogenation of cyclohexanes to aromatics, dehydroisomerization of alkylcyclopentanes to aromatics, and dehydrocyclization of acyclic hydrocarbons to aromatics.
  • a number of other reactions also occur, including the dealkylation of alkylbenzenes, isomerization of paraffins, and hydrocracking reactions which produce light gaseous hydrocarbons, e.g., methane, ethane, propane and butane. It is important to minimize hydrocracking reactions during reforming as they decrease the yield of gasoline boiling products and hydrogen.
  • Catalysts for successful reforming processes must possess good selectivity. That is, they should be effective for producing high yields of liquid products in the gasoline boiling range containing large concentrations of high octane number aromatic hydrocarbons. Likewise, there should be a low yield of light gaseous hydrocarbons.
  • the catalysts should possess good activity to minimize excessively high temperatures for producing a certain quality of products. It is also necessary for the catalysts to either possess good stability in order that the activity and selectivity characteristics can be retained during prolonged periods of operation; or be sufficiently regenerable to allow frequent regeneration without loss of performance.
  • Catalytic reforming is also an important process for the chemical industry.
  • aromatic hydrocarbons for use in the manufacture of various chemical products such as synthetic fibers, insecticides, adhesives, detergents, plastics, synthetic rubbers, pharmaceutical products, high octane gasoline, perfumes, drying oils, ion-exchange resins, and various other products well known to those skilled in the art.
  • Water sensitivity was found to be a serious drawback which was difficult to effectively address. Water is produced at the beginning of each process cycle when the catalyst is reduced with hydrogen. And, water can be produced during process upsets when water leaks into the reformer feed, or when the feed becomes contaminated with an oxygen-containing compound. Eventually, technologies were also developed to protect the catalysts from water.
  • Figure 1A is a photomicrograph of a portion of the inside (process side) of a mild steel furnace tube from a commercial reformer. The tube had been exposed to conventional reforming conditions for about 19 years. This photograph shows that the surface of the tube has remained essentially unaltered with the texture of the tube remaining normal after long exposure to hydrocarbons at high temperatures (the black portion of the photograph is background).
  • Figure 1B is a photomicrograph of a portion of a mild steel coupon sample which was placed inside a reactor of a low-sulfur/low-water demonstration plant for only 13 weeks. The photograph shows the eroded surface of the sample (contrasted against a black background) from which metal dusting has occurred. The dark grey-like veins indicate the environmental carburization of the steel, which was carburized and embrittled more than 1 mm in depth.
  • the active metal particulates provide additional sites for coke formation in the system. While catalyst deactivation from coking is generally a problem which must be addressed in reforming, this new significant source of coke formation leads to a new problem of coke plugs which excessively aggravates the problem. In fact, it was found that the mobile active metal particulates and coke particles metastasize coking generally throughout the system. The active metal particulates actually induce coke formation on themselves and anywhere that the particles accumulate in the system resulting in coke plugs and hot regions of exothermic demethanation reactions. As a result, an unmanageable and premature coke-plugging of the reactor system occurs which can lead to a system shut-down within weeks of start-up. Use of the process and reactor system of the present invention, however, overcomes these problems.
  • a method for the catalytic reforming of a hydrocarbon feed to produce aromatics over a prolonged period of operation without coke-plugging of the reactor system, using a sulfur sensitive reforming catalyst charged with one or more Group VIII metals comprising:
  • the reforming reactor system has a resistance to carburization and metal dusting which is an improvement over conventional mild steel reactor systems under conditions of low sulfur and often low sulfur and low water, and upon reforming the resistance is such that embrittlement from carburization will be less than about 2.5 mm/year, preferably less than 1.5 mm/year, more preferably less than 1 mm/year, and most preferably less than 0.1 mm/year. Preventing embrittlement to such an extent will significantly reduce metal dusting and coking in the reactor.
  • the present invention is based on the discovery that in low-sulfur, and low-sulfur and low-water reforming processes there exist significant carburization, metal dusting and coking problems, which problems do not exist to any significant extent in conventional reforming processes where higher levels of sulfur are present.
  • This discovery has led to intensive work and development of solutions to the problems, which solutions are novel to low-sulfur reforming and are directed to the identification and selection of resistant materials for low-sulfur reforming systems, ways to effectively utilize and apply the resistant materials, additives (other than sulfur) for reducing carburization, metal dusting and coking, various process modifications and configurations, and combinations thereof, which effectively address the problems.
  • the discovery has led to the search for, identification of, and selection of resistant materials for low-sulfur reforming systems, preferably the reactor walls, furnace tubes and screens thereof, which were previously unnecessary in conventional reforming systems such as certain alloy and stainless steels, aluminized and chromized materials, and certain ceramic materials.
  • other specific materials applied as a plating, cladding, paint, for example, can be effectively resistant. These materials include copper, tin, arsenic, antimony, brass, lead bismuth chromium, intermetallic compounds thereof, and alloys thereof, as well as silica and silicon based coatings.
  • anticarburizing and anticoking agents which out of necessity are essentially sulfur free, preferably completely sulfur free, which are novel to reforming.
  • additives include organo-tin compounds, organo-antimony compounds, organo-bismuth compounds, organo-arsenic compounds and organo-lead compounds.
  • Figure 1A is a photomicrograph of a portion of the inside (process side) of a mild steel furnace tube from a commercial reformer which had been in use about 19 years; and as also noted above,
  • Figure 1B is a photomicrograph of a portion of a mild steel coupon sample which was placed inside a reactor of a low-sulfur/low-water demonstration plant for only 13 weeks.
  • Figure 2 is an illustration of a suitable reforming reactor system for use in the present invention.
  • alloy steels are those steels having no specified minimum quantity for any alloying element (other than the commonly accepted amounts of manganese, silicon and copper) and containing only an incidental amount of any element other than carbon, silicon, manganese, copper, sulfur and phosphorus.
  • Metal steels are those carbon steels with a maximum of about 0.25% carbon. Alloy steels are those steels containing specified quantities of alloying elements (other than carbon and the commonly accepted amounts of manganese, copper, silicon, sulfur and phosphorus) within the limits recognized for constructional alloy steels, added to effect changes in mechanical or physical properties. Alloy steels will contain less than 10% chromium.
  • Stainless steels are any of several steels containing at least 10, preferably 12 to 30%, chromium as the principal alloying element.
  • one focus of the invention is to provide an improved method for reforming hydrocarbons using a sulfur sensitive reforming catalyst, particularly a large pore zeolite catalyst including an alkali or alkaline earth metal and charged with one or more Group VIII metals, under conditions of low sulfur.
  • a sulfur sensitive reforming catalyst particularly a large pore zeolite catalyst including an alkali or alkaline earth metal and charged with one or more Group VIII metals, under conditions of low sulfur.
  • Such a process must demonstrate better resistance to carburization than conventional low-sulfur reforming techniques.
  • the reforming reactor system has an improved resistance to carburization and metal dusting upon reforming using a feed containing less than 50ppb sulfur, said system including at least one furnace to heat said feed to catalytic reforming temperatures, said furnace comprising, in contact with said feed, a plurality of furnace tubes having a resistance to carburization and metal dusting at least as great as that of 347 stainless steel when assessed as weight percent carbon gain compared to said 347 stainless steel upon exposure to a carburizing gas at a temperature between 1100 and 1200°F (593-649°C).
  • reactor system as used herein there is intended at least one reforming reactor and its corresponding furnace means and piping.
  • Figure 2 illustrates a typical reforming reactor system suitable for practice of the present invention. It can include a plurality of reforming reactors (10), (20) and (30). Each reactor contains a catalyst bed. The system also includes a plurality of furnaces (11), (21) and (31); heat exchanger (12); and separator (13).
  • reforming reactor systems have been constructed of mild steels, or alloy steels such as typical chromium steels, with insignificant carburization and dusting.
  • mild steels or alloy steels such as typical chromium steels, with insignificant carburization and dusting.
  • 21 ⁇ 4 Cr furnace tubes can last twenty years.
  • these steels are unsuitable under low-sulfur reforming conditions. They rapidly become embrittled by carburization within about one year. For example, it was found that 21 ⁇ 2 Cr 1 Mo steel carburized and embrittled more than 1 mm/year.
  • stainless steels specifically those having a resistance to carburization and metal dusting at least as great as that of 347 stainless steel are acceptable. They have been found to have a resistance to carburization greater than mild steels and nickel-rich alloys.
  • Alonized Steels aluminized materials such as those sold by Alon Corporation
  • Alonized Steels aluminized materials
  • the application of thin aluminum or alumina films to metal surfaces of the reforming reactor system, or simply the use of Alonized Steels during construction can provide surfaces which are sufficiently resistant to carburization and metal dusting under the low-sulfur reforming conditions.
  • such materials are relatively expensive, and while resistant to carburization and metal dusting, tend to crack, and show substantial reductions in tensile strengths. Cracks expose the underlying base metal rendering it susceptible to carburization and metal dusting under low sulfur reforming conditions.
  • the film When applying an aluminum or alumina film, it is preferable that the film have a thermal expansivity that is similar to that of the metal surface to which it is applied (such as a mild steel) in order to withstand thermal shocks and repeated temperature cycling which occur during reforming. This prevents cracking or spalling of the film which could expose the underlying metal surface to the carburization inducing hydrocarbon environment.
  • the film should have a thermal conductivity similar to that of, or exceeding, those of metals conventionally used in the construction of reforming reactor systems. Furthermore, the aluminum or alumina film should not degrade in the reforming environment, or in the oxidizing environment associated with catalyst regeneration, nor should it result in the degradation of the hydrocarbons in the reactor system.
  • Suitable methods for applying aluminum or alumina films to metal surfaces such as mild steels include well known deposition techniques.
  • Preferred processes include powder and vapor diffusion processes such as the "Alonizing" process, which has been commercialized by Alon Processing, Inc., Terrytown, Pa.
  • Alonizing is a high temperature diffusion process which alloys aluminum into the surface of a treated metal, such as e.g., a commercial grade mild steel.
  • the metal e.g., a mild steel
  • the retort is then hermetically sealed and placed in an atmosphere-controlled furnace.
  • the aluminum deeply diffuses into the treated metal resulting in an alloy.
  • the substrate is taken out of the retort and excess powder is removed. Straightening, trimming, beveling and other secondary operations can then be performed as required.
  • This process can render the treated ("alonized") metal resistant to carburization and metal dusting under low-sulfur reforming conditions according to the invention.
  • Thin chromium or chromium oxide films can also be applied to metal surfaces of the furnace tubes of the reactor system to render the surfaces resistant to carburization and metal dusting under low-sulfur reforming conditions. Like the use of alumina and aluminum films, and aluminized materials, chromium or chromium oxide coated metal surfaces have not been used to address carburization problems under low-sulfur reforming conditions.
  • the chromium or chromium oxide can also be applied to other carburization and metal dusting susceptible metal surfaces such as the reactor walls and furnace liners. However, any surface in the system which would show signs of carburization and metal dusting under low-sulfur reforming conditions would benefit from the application of a thin chromium or chromium oxide film.
  • the chromium or chromium oxide film When applying the chromium or chromium oxide film, it is preferable that the chromium or chromium oxide film have a thermal expansivity similar to that of the metal to which it is applied. Additionally, the chromium or chromium oxide film should be able to withstand thermal shocks and repeated temperature cycling which are common during reforming. This avoids cracking or spalling of the chromium or chromium oxide film which could potentially expose the underlying metal surfaces to carburization inducing environments. Furthermore, the chromium or chromium oxide film should have a thermal conductivity similar to or exceeding those materials conventionally used in reforming reactor systems (in particular mild steels) in order to maintain efficient heat transfer. The chromium or chromium oxide film also should not degrade in the reforming environment or in the oxidizing environment associated with catalyst regeneration, nor should it induce degradation of the hydrocarbons in the reactor system.
  • Suitable methods for applying chromium or chromium oxide films to surfaces include well known deposition techniques.
  • Preferred processes include powder-pack and vapor diffusion processes such as the "chromizing" process, which is commercialized by Alloy Surfaces, Inc., of Wilmington, Delaware.
  • the "chromizing” process is essentially a vapor diffusion process for application of chromium to a metal surface (similar to the above described “Alonizing process”).
  • the process involves contacting the metal to be coated with a powder of chromium, followed by a thermal diffusion step. This, in effect, creates an alloy of the chromium with the treated metal and renders the surface extremely resistant to carburization and metal dusting under low-sulfur reforming conditions.
  • Chromium-rich stainless steels such as 446 and 430 are even more resistant to carburization than 300 series stainless steels. However, these steels are not as desirable for heat resisting properties (they tend to become brittle).
  • Resistant materials which are preferred over stainless steels for use in the present invention include copper, tin, arsenic, antimony, bismuth, chromium and brass, and intermetallic compounds and alloys thereof (e.g., Cu-Sn alloys, Cu-Sb alloys, stannides, antimonides or bismuthides). Steels and even nickel-rich alloys containing these metals can also show reduced carburization. In a preferred embodiment, these materials are provided as a plating, cladding, paint (e.g., oxide paints) or other coating to a base construction material. This is particularly advantageous since conventional construction materials such as mild steels can still be used with only the surface contacting the hydrocarbons being treated.
  • paint e.g., oxide paints
  • tin is especially preferred as it reacts with the surface to provide a coating having excellent carburization resistance at higher temperatures, and which resists peeling and flaking of the coating. Also, it is believed that a tin containing layer can be as thin as 1/10 micron and still prevent carburization.
  • the resistant materials be applied in a paint-like formulation (hereinafter "paint") to a new or existing reactor system.
  • a paint can be sprayed, brushed or pigged, for example, on reactor system surfaces such as mild steels or stainless steels.
  • a paint be a decomposable, reactive, tin-containing paint which reduces to a reactive tin and forms metallic stannides (e.g., iron stannides and nickel/iron stannides) upon heating in a reducing atmosphere.
  • the aforementioned paint contain at least four components (or their functional equivalents); (i) a hydrogen decomposable tin compound, (ii) a solvent system, (iii) a finely divided tin metal and (iv) tin oxide as a reducible sponge/dispersing/binding agent.
  • the paint should contain finely divided solids to minimize settling, and should not contain non-reactive materials which will prevent reaction of reactive tin with surfaces of the reactor system.
  • tin octanoate As the hydrogen decomposable tin compound, tin octanoate is particularly useful. Commercial formulations of this compound itself are available and will partially dry to an almost chewing-gum-like layer on a steel surface; a layer which will not crack and/or split. This property is necessary for any coating composition used in this context because it is conceivable that the coated material will be stored for months prior to treatment with hydrogen. Also, if parts are coated prior to assembly they must be resistant to chipping during construction. As noted above, tin octanoate is available commercially. It is reasonably priced, and will decompose smoothly to a reactive tin layer which forms iron stannide in hydrogen at temperatures as low as 600°F (316°C).
  • Tin octanoate should not be used alone in a paint, however. It is not sufficiently viscous. Even when the solvent is evaporated therefrom, the remaining liquid will drip and run on the coated surface. In practice, for example, if such were used to coat a horizontal furnace tube, it would pool at the bottom of the tube.
  • Component (iv) is a porous tin-containing compound which can sponge-up an organo-metallic tin compound, yet still be reduced to active tin in the reducing atmosphere.
  • tin oxide can be processed through a colloid mill to produce very fine particles which resist rapid settling. The addition of tin oxide will provide a paint which becomes dry to the touch, and resists running.
  • component (iv) is selected such that it becomes a reactive part of the coating when reduced. It is not inert like formed silica; a typical paint thickener which would leave an unreactive surface coating after treatment.
  • Finely divided tin metal, component (iii), is added to insure that metallic tin is available to react with the surface to be coated at as low a temperature as possible, even in a non-reducing atmosphere.
  • the particle size of the tin is preferably one to five microns which allows excellent coverage of the surface to be coated with tin metal. Non-reducing conditions can occur during drying of the paint and welding of pipe joints. The presence of metallic tin ensures that even when part of the coating is not completely reduced, tin metal will be present to react and form the desired stannide layer.
  • the solvent should be non-toxic, and effective for rendering the paint sprayable and spreadable when desired. It should also evaporate quickly and have compatible solvent properties for the hydrogen decomposable tin compound. Isopropyl alcohol is most preferred, while hexane and pentane can be useful, if necessary. Acetone, however, tends to precipitate organic tin compounds.
  • tin paint of 20 percent Tin Ten-Cem (stannous octanoate in octanoic acid), stannic oxide, tin metal powder and isopropyl alcohol.
  • furnace tubes of the reactor system can be painted individually or as modules.
  • a reforming reactor system according to the present invention can contain various numbers of furnace tube modules (e.g., about 24 furnace tube modules) of suitable width, length and height (e.g., about 10 feet (3.05m) long, about 4 feet (1.22m) wide, and about 40 feet (12.2m) in height).
  • each module will include two headers of suitable diameter, preferably about 2 feet (0.61m) in diameter, which are connected by about four to ten u-tubes of suitable length (e.g., about 42 feet (12.8m) long). Therefore, the total surface area to be painted in the modules can vary widely; for example, in one embodiment it can be about 16,500 ft 2 (1530m 2 ).
  • Painting modules rather than the tubes individually can be advantageous in at least four respects; (i) painting modules rather than individual tubes should avoid heat destruction of the tin paint as the components of the modules are usually heat treated at extremely elevated temperatures during production; (ii) painting modules will likely be quicker and less expensive than painting tubes individually; (iii) painting modules should be more efficient during production scheduling; and (iv) painting of the modules should enable painting of welds.
  • painting the modules may not enable the tubes to be as completely coated with paint as if the tubes were painted individually. If coating is insufficient, the tubes can be coated individually.
  • the paint be sprayed into the tubes and headers. Sufficient paint should be applied to fully coat the tubes and headers. After a module is sprayed, it should be left to dry for about 24 hours followed by application of a slow stream of heated nitrogen (e.g., about 150°F (60°C) for about 24 hours). Thereafter, it is preferable that a second coat of paint be applied and also dried by the procedure described above. After the paint has been applied, the modules should preferably be kept under a slight nitrogen pressure and should not be exposed to temperatures exceeding about 200°F (34°C) prior to installation, nor should they be exposed to water except during hydrotesting.
  • a slow stream of heated nitrogen e.g., about 150°F (60°C) for about 24 hours.
  • a second coat of paint be applied and also dried by the procedure described above.
  • the modules should preferably be kept under a slight nitrogen pressure and should not be exposed to temperatures exceeding about 200°F (34°C) prior to installation, nor should they be exposed to water except during hydrotesting
  • Iron bearing reactive paints are also useful in the present invention.
  • Such an iron bearing reactive paint will preferably contain various tin compounds to which iron has been added in amounts up to one third Fe/Sn by weight.
  • iron can, for example, be in the form of Fe 2 O 3 .
  • the addition of iron to a tin containing paint should afford noteworthy advantages; in particular: (i) it should facilitate the reaction of the paint to form iron stannides thereby acting as a flux; (ii) it should dilute the nickel concentration in the stannide layer thereby providing better protection against coking; and (iii) it should result in a paint which affords the anti-coking protection of iron stannides even if the underlying surface does not react well.
  • Yet another means for preventing carburization, coking, and metal dusting in the low-sulfur reactor system comprises the application of a metal coating or cladding to chromium rich steels contained in the reactor system.
  • These metal coatings or claddings may be comprised of tin, antimony, bismuth or arsenic. Tin is especially preferred.
  • These coatings or claddings may be applied by methods including electroplating, vapor depositing, and soaking of the chromium rich steel in a molten metal bath.
  • the thickness of the metal coating or cladding it may be desirable to vary the thickness of the metal coating or cladding to achieve the desired resistance against carburization, coking, and metal dusting. This can be done by, e.g., adjusting the amount of time the chromium rich steel is soaked in a molten tin bath. This will also affect the thickness of the resulting chromium rich steel layer. It may also be desirable to vary the operating temperature, or to vary the composition of the chromium rich steel which is coated which in order to control the chromium concentration in the chromium rich steel layer produced.
  • tin-coated steels can be further protected from carburization, metal dusting, and coking by a post-treatment process which involves application of a thin oxide coating, preferably a chromium oxide, such as Cr 2 O 3 .
  • a thin oxide coating preferably a chromium oxide, such as Cr 2 O 3 .
  • This coating will be thin, as thin as a few ⁇ m.
  • Application of such a chromium oxide will protect aluminum as well as tin coated steels, such as Alonized steels, under low-sulfur reforming conditions.
  • the chromium oxide layer can be applied by various methods including: application of a chromate or dichromate paint followed by a reduction process; vapor treatment with an organo-chromium compound; or application of a chromium metal plating followed by oxidation of the resulting chromium plated steel.
  • aluminized, e.g., "Alonized" steels which are resistant to carburization under the present reforming conditions of low sulfur can be rendered further resistant by post-treatment of the aluminum coated steel with a coating of tin.
  • such a post-treatment should result in a lower cost since a thinner aluminum coating can be applied to the steel surface which is to be post-treated with the tin coating.
  • this post-treatment will protect the underlying steel layer exposed by bending of aluminized steels, which can introduce cracks in the aluminum layer, and expose the steel to carburization induced under reforming conditions. Also, this post-treatment process can prevent coke formation on the treated steel surfaces and also prevent coke formation that occurs on the bottom of cracks which appear on steels which have been aluminized, but not additionally coated with tin.
  • iron, cobalt, and nickel form relatively unstable carbides which will subsequently carburize, coke and dust.
  • Elements such as chromium, niobium, vanadium, tungsten, molybdenum, tantalum and zirconium, will form stable carbides which are more resistant to carburization coking and dusting.
  • Elements such as tin, antimony and bismuth do not form carbides or coke. And, these compounds can form stable compounds with many metals such as iron, nickel and copper under reforming conditions.
  • Stannides, antimonides and bismuthides, and compounds of lead, mercury, arsenic, germanium, indium, tellurium, selenium, thallium, sulfur and oxygen are also resistant.
  • a final category of materials include elements such as silver, copper, gold, platinum and refractory oxides such as silica and alumina. These materials are resistant and do not form carbides, or react with other metals in a carburizing environment unde reforming conditions.
  • the selection of appropriate metals which are resistant to carburization and metal dusting, and their use as coating materials for metal surfaces in the reactor system is one means for preventing the carburization and metal dusting problem.
  • carburization and metal dusting can be prevalent in a wide variety of metals; and carburization resistant metals can be more costly or exotic than conventional materials (e.g., mild steels) used in the construction of reforming reactor systems.
  • at least a portion of the furnace liners may be constructed of ceramic materials.
  • the ceramic material In choosing the ceramic materials for use in the present invention, it is preferable that the ceramic material have thermal conductivities about that or exceeding those of materials conventionally used in the construction of reforming reactor systems. Additionally, the ceramic materials should have sufficient structural strengths at the temperatures which occur within the reforming reactor system. Further, the ceramic materials should be able to withstand thermal shocks and repeated temperature cycling which occur during operation of the reactor system. When the ceramic materials are used for constructing the furnace liners, the ceramic materials should have thermal expansivities about that of the metal outer surfaces with which the liner is in intimate contact. This avoids undue stress at the juncture during temperature cycling that occurs during start-up and shut-down. Additionally, the ceramic surface should not be susceptible to degradation in the hydrocarbon environment or in the oxidizing environment which occurs during catalyst regeneration. The selected ceramic material also should not promote the degradation of the hydrocarbons in the reactor system.
  • Suitable ceramic materials include, but are not restricted to, materials such as silicon carbides, silicon oxides, silicon nitrides and aluminum nitrides. Of these, silicon carbides and silicon nitrides are particularly preferred as they appear capable of providing complete protection for the reactor system under low-sulfur reforming conditions.
  • At least a portion of the metal surfaces in the reactor system can also be coated with a silicon or silica film.
  • the metal surfaces which can be coated include, but are not limited to the reactor walls, furnace tubes, and furnace liners.
  • any metal surface in the reactor system which shows signs of carburization and metal dusting under low-sulfur reforming conditions would benefit from the application of a thin silicon or silica film.
  • Silica or silicon can be applied by electroplating and chemical vapor deposition of an alkoxysilane in a steam carrier gas. It is preferable that the silicon or silica film have a thermal expansivity about that of the metal surface which it coats. Additionally, the silicon or silica film should be able to withstand thermal shocks and repeated temperature cycling that occur during reforming. This avoids cracking or spalling of the silicon or silica film, and potential exposure of the underlying metal surface to the carburization inducing hydrocarbon environment. Also, the silica or silicon film should have a thermal conductivity approximate to or exceeding that of metals conventionally used in reforming reactor systems so as to maintain efficient heat transfer. The silicon or silica film also should not degrade in the reforming environment or in the oxidizing environment associated with catalyst regeneration; nor should it cause degradation of the hydrocarbons themselves.
  • the material selection can be staged, such that those materials providing better carburization resistances are used in those areas of the system experiencing the highest temperatures.
  • oxidized Group VIII metal surfaces such as iron, nickel and cobalt are more active in terms of coking and carburization than their unoxidized counterparts.
  • an air roasted sample of 347 stainless steel was significantly more active than an unoxidized sample of the same steel. This is believed to be due to a re-reduction of oxidized steels which produces very fine-grained iron and/or nickel metals. Such metals are especially active for carburization and coking.
  • an air roasted 300 series stainless steel coated with tin can provide similar resistances to coking and carburization as unroasted samples of the same tin coated 300 series stainless steel.
  • these agents interact with the surfaces of the reactor system by decomposition and surface attack to form iron and/or nickel intermetallic compounds, such as stannides, antimonides, bismuthides, plumbides, arsenides, for example.
  • intermetallic compounds are resistant to carburization, coking and dusting and can protect the underlying metallurgy.
  • intermetallic compounds are also believed to be more stable than the metal sulfides which were formed in systems where H 2 S was used to passivate the metal. These compounds are not reduced by hydrogen as are metal sulfides. As a result, they are less likely to leave the system than metal sulfides. Therefore, the continuous addition of a carburization inhibitor with the feed can be minimized.
  • Preferred non-sulfur anti-carburizing and anti-coking agents include organo-metallic compounds such as organo-tin compounds, organo-antimony compounds, organo-bismuth compounds, organo-arsenic compounds, and organo-lead compounds.
  • organo-lead compounds include tetraethyl and tetramethyl lead.
  • Organo-tin compounds such as tetrabutyl tin and trimethyl tin hydride are especially preferred.
  • organo-metallic compounds include bismuth neodecanoate, chromium octoate, copper naphthenate, manganese carboxylate, palladium neodecanoate, silver neodecanoate, tetrabutylgermanium, tributylantimony, triphenylantimony, triphenylarsine, and zirconium octoate.
  • adding the agents to the feed is not preferred as they would tend to accumulate in the initial portions of the reactor system. This may not provide adequate protection in the other areas of the system.
  • the agents be provided as a coating prior to construction, prior to start-up, or in-situ (i.e., in an existing system). If added in-situ, it should be done right after catalyst regeneration. Very thin coatings can be applied. For example, it is believed that when using organo-tin compounds, iron stannide coatings as thin as 0.1 micron can be effective.
  • a preferred method of coating the agents on an existing or new reactor surface, or a new or existing furnace tube is to decompose an organometallic compound in a hydrogen atmosphere at temperatures of about 900°F (482°C). For organo-tin compounds, for example, this produces reactive metallic tin on the tube surface. At these temperatures the tin will further react with the surface metal to passivate it.
  • Optimum coating temperatures will depend on the particular organometallic compound, or the mixtures of compounds if alloys are desired.
  • an excess of the organometallic coating agent can be pulsed into the tubes at a high hydrogen flow rate so as to carry the coating agent throughout the system in a mist. The flow rate can then be reduced to permit the coating metal mist to coat and react with the furnace tube or reactor surface.
  • the compound can be introduced as a vapor which decomposes and reacts with the hot walls of the tube or reactor in a reducing atmosphere.
  • Another aspect of the invention is a process which avoids such deposition in reforming reactor systems where temperatures are not closely controlled and exhibit areas of high temperature hot spots.
  • Such a process involves preheating the entire reactor system to a temperature of from 750 to 1150°F (399-621°C) preferably 900 to 1100°F (482-593°C), and most preferably about 1050°F (566°C), with a hot stream of hydrogen gas.
  • a colder gas stream at a temperature of 400 to 800°F (204-427°C), preferably 500 to 700°F (260-371°C), and most preferably about 550°F (288°C), containing a vaporized organometallic tin compound and hydrogen gas is introduced into the preheated reactor system.
  • This gas mixture is introduced upstream and can provide a decomposition "wave" which travels throughout the entire reactor system.
  • the hot hydrogen gas produces a uniformly heated surface which will decompose the colder organometallic gas as it travels as a wave throughout the reactor system.
  • the colder gas containing the organometallic tin compound will decompose on the hot surface and coat the surface.
  • the organometallic tin vapor will continue to move as a wave to treat the hotter surfaces downstream in the reactor system.
  • the entire reactor system can have a uniform coating of the organometallic tin compound. It may also be desirable to conduct several of these hot-cold temperature cycles to ensure that the entire reactor system has been uniformly coated with the organometallic tin compound.
  • naphtha will be reformed to form aromatics.
  • the naphtha feed is a light hydrocarbon, preferably boiling in the range of about 70°F (21°C) to 450°F (232°C), more preferably about 100°F (37.8°C) to 350°F (177°C).
  • the naphtha feed will contain aliphatic or paraffinic hydrocarbons. These aliphatics are converted, at least in part, to aromatics in the reforming reaction zone.
  • the feed will preferably contain less than 100 ppb sulfur, and more preferably, less than 50 ppb sulfur. If necessary, a sulfur sorber unit can be employed to remove small excesses of sulfur.
  • Preferred reforming process conditions include a temperature between 700 and 1050°F (371-565°C), more preferably between 850 and 1025°F (454-552°C); and a pressure between 0 and 400 psig (101-2860KPa (abs)), more preferably between 15 and 150 psig (136-1140Kpa (abs)); a recycle hydrogen rate sufficient to yield a hydrogen to hydrocarbon mole ratio for the feed to the reforming reaction zone between 0.1 and 20, more preferably between 0.5 and 10; and a liquid hourly space velocity for the hydrocarbon feed over the reforming catalyst of between 0.1 and 10, more preferably between 0.5 and 5.
  • furnace tubes can often range from 600 to 1800°F (320-980°C), usually from 850 and 1250°F (450-680°C), and more often from 900 and 1200°F (480-650°C).
  • an additional feature of the invention is also to lower the temperatures of the metal surfaces inside the furnace tubes, transfer-lines and/or reactors of the reforming system below the aforementioned levels.
  • temperatures can be monitored using thermocouples attached at various locations in the reactor system.
  • thermocouples can be attached to the outer walls thereof, preferably at the hottest point of the furnace (usually near the furnace outlet). When necessary, adjustments in process operation can be made to maintain the temperatures at desired levels.
  • heat transfer areas can be used with resistant (and usually more costly) tubing in the final stage where temperatures are usually the highest.
  • superheated hydrogen can be added between reactors of the reforming system.
  • a larger catalyst charge can be used.
  • the catalyst can be regenerated more frequently. In the case of catalyst regeneration, it is best accomplished using a moving bed process where the catalyst is withdrawn from the final bed, regenerated, and charged to the first bed.
  • Carburization and metal dusting can also be minimized in the low-sulfur reforming reactor system of the invention by using certain other novel equipment configurations and process conditions.
  • the reactor system can be constructed with staged heaters and/or tubes.
  • the heaters or tubes which are subjected to the most extreme temperature conditions in the reactor system can be constructed of materials more resistant to carburization than materials conventionally used in the construction of reforming reactor systems; materials such as those described above. Heaters or tubes which are not subjected to extreme temperatures can continue to be constructed of conventional materials.
  • the reactor system can also be operated using at least two temperature zones; at least one of higher and one of lower temperature.
  • This approach is based on the observation that metal dusting has a temperature maximum and minimum, above and below which dusting is minimized. Therefore, by “higher” temperatures, it is meant that the temperatures are higher than those conventionally used in reforming reactor systems and higher than the temperature maximum for dusting. By “lower” temperatures it is meant that the temperature is at or about the temperatures which reforming processes are conventionally conducted, and falls below that in which dusting becomes a problem.
  • Operation of portions of the reactor system in different temperature zones should reduce metal dusting as less of the reactor system is at a temperature conducive for metal dusting.
  • other advantages of such a design include improved heat transfer efficiencies and the ability to reduce equipment size because of the operation of portions of the system at higher temperatures.
  • operating portions of the reactor system at levels below and above that conducive for metal dusting would only minimize, not completely avoid, the temperature range at which metal dusting occurs. This is unavoidable because of temperature fluctuations which will occur during day to day operation of the reforming reactor system; particularly fluctuations during shut-down and start-up of the system, temperature fluctuations during cycling, and temperature fluctuations which will occur as the process fluids are heated in the reactor system.
  • Another approach to minimizing metal dusting relates to providing heat to the system using superheated raw materials (such as e.g., hydrogen), thereby minimizing the need to heat the hydrocarbons through furnace walls.
  • superheated raw materials such as e.g., hydrogen
  • Yet another process design approach involves providing a pre-existing reforming reactor system with larger tube diameters and/or higher tube velocities. Using larger tube diameters and/or higher tube velocities will minimize the exposure of the heating surfaces in the reactor system to the hydrocarbons.
  • catalytic reforming is well known in the petroleum industry and involves the treatment of naphtha fractions to improve octane rating by the production of aromatics.
  • the more important hydrocarbon reactions which occur during the reforming operation include the dehydrogenation of cyclohexanes to aromatics, dehydroisomerization of alkycyclopentanes to aromatics, and dehydrocyclization of acyclic hydrocarbons to aromatics.
  • reaction refers to the treatment of a hydrocarbon feed through the use of one or more aromatics producing reactions in order to provide an aromatics enriched product (i.e., a product whose aromatics content is greater than in the feed).
  • feedstocks such as paraffin hydrocarbons, olefin hydrocarbons, acetylene hydrocarbons, cyclic paraffin hydrocarbons, cyclic olefin hydrocarbons, and mixtures thereof, and particularly saturated hydrocarbons.
  • paraffin hydrocarbons examples include those having 6 to 10 carbons such as n-hexane, methylpentane, n-haptane, methylhexane, dimethylpentane and n-octane.
  • acetylene hydrocarbons examples include those having 6 to 10 carbon atoms such as hexyne, heptyne and octyne.
  • acyclic paraffin hydrocarbons are those having 6 to 10 carbon atoms such as methylcyclopentane, cyclohexane, methylcyclohexane and dimethylcyclohexane.
  • Typical examples of cyclic olefin hydrocarbons are those having 6 to 10 carbon atoms such as methylcyclopentene, cyclohexene, methylcyclohexene, and dimethylcyclohexene.
  • the present invention will also be useful for reforming under low-sulfur conditions using a variety of different reforming catalysts.
  • Such catalyst include, but are not limited to Noble Group VIII metals on refractory inorganic oxides such as platinum on alumina, Pt/SN on alumina and Pt/Re on alumina; Noble Group VIII metals on a zeolite such as Pt, Pt/SN and Pt/Re on zeolites such as L-zeolites, ZSM-5, silicalite and beta; and Nobel Group VIII metals on alkali- and alkaline-earth exchanged L-zeolites.
  • a preferred embodiment of the invention involves the use of a large-pore zeolite catalyst including an alkali or alkaline earth metal and charged with one or more Group VIII metals. Most preferred is the embodiment where such a catalyst is used in reforming a naphtha feed.
  • large-pore zeolite is indicative generally of a zeolite having an effective pore diameter of 6 to 15 Angstroms.
  • Preferable large pore crystalline zeolites which are useful in the present invention include the type L zeolite, zeolite X, zeolite Y and faujasite. These have apparent pore sizes on the order to 7 to 9 Angstroms. Most preferably the zeolite is a type L zeolite.
  • the composition of type L zeolite expressed in terms of mole ratios of oxides may be represented by the following formula: (0.9-1.3)M 2 / n O:AL 2 O 3 (5.2-6.9)SiO 2 :yH 2 O
  • M represents a cation
  • n represents the valence of M
  • y may be any value from 0 to about 9.
  • Zeolite L, its X-ray diffraction pattern, its properties, and method for its preparation are described in detail in, for example, U.S. Patent No. 3,216,789.
  • the actual formula may vary without changing the crystalline structure.
  • the mole ratio of silicon to aluminum (Si/Al) may vary from 1.0 to 3.5.
  • the chemical formula for zeolite Y expressed in terms of mole ratios of oxides may be written as: (0.7-1.1)Na 2 O:Al 2 O 3 :xSiO 2 :yH 2 O
  • x is a value greater than 3 and up to about 6.
  • y may be a value up to about 9.
  • Zeolite Y has a characteristic X-ray powder diffraction pattern which may be employed with the above formula for identification. Zeolite Y is described in more detail in U.S.Patent No. 3,130,007.
  • Zeolite X is a synthetic crystalline zeolitic molecular sieve which may be represented by the formula: (0.7-1.1)M 2/n O:Al 2 O 3 :(2.0-3.0)SiO 2 :yH 2 O
  • M represents a metal, particularly alkali and alkaline earth metals
  • n is the valence of M
  • y may have any value up to about 8 depending on the identity of M and the degree of hydration of the crystalline zeolite.
  • Zeolite X, its X-ray diffraction pattern, its properties, and method for its preparation are described in detail in U.S. Patent No. 2,882,244.
  • alkali or alkaline earth metal is preferably present in the large-pore zeolite.
  • That alkaline earth metal may be either barium, strontium or calcium, preferably barium.
  • the alkaline earth metal can be incorporated into the zeolite by synthesis, impregnation or ion exchange. Barium is preferred to the other alkaline earths because it results in a somewhat less acidic catalyst. Strong acidity is undesirable in the catalyst because it promotes cracking, resulting in lower selectivity.
  • At least part of the alkali metal can be exchanged with barium using known techniques for ion exchange of zeolites. This involves contacting the zeolite with a solution containing excess Ba ++ ions.
  • the barium should preferably constitute from 0.1% to 35% by weight of the zeolite.
  • the large-pore zeolitic catalysts used in the invention are charged with one or more Group VIII metals, e.g., nickel, ruthenium, rhodium, palladium, iridium or platinum.
  • the preferred Group VIII metals are iridium and particularly platinum. These are more selective with regard to dehydrocyclization and are also more stable under the dehydrocyclization reaction conditions than other Group VIII metals. If used, the preferred weight percentage of platinum in the catalyst is between 0.1% and 5%.
  • Group VIII metals are introduced into large-pore zeolites by synthesis, impregnation or exchange in an aqueous solution of appropriate salt. When it is desired to introduce two Group VIII metals into the zeolite, the operation may be carried out simultaneously or sequentially.
  • a control run was made using essentially pure hexane containing less than 0.2 ppm sulfur.
  • the tube was found to be completely filled with carbon after only three hours. This not only stopped the flow of the hydrogen and hexane feeds, the growth of carbon actually split the tube and produced a bulge in the reactor. Methane in the product effluent was approaching 60-80 wt% before plugging.
  • Tests were conducted to determine suitable materials for use in low-sulfur reforming reactor systems; materials which would exhibit better resistance to carburization than the mild steels conventionally used in low-sulfur reforming techniques.
  • thermocouple placed on the exterior of the tube in the heated zone.
  • the furnace tube had an internal diameter of 5/8 inches (15.9mm).
  • Several runs were conducted at an applied temperature of 1200°F (650°C) using a thermocouple suspended within the hot zone ( ⁇ 2 inches) of the tube.
  • the internal thermocouple constantly measured temperatures from 0 to 10°F (0-5.6°C) lower than the external thermocouple.
  • Samples of mild steels (C steel and 21 ⁇ 4 Cr) and samples of 300 series stainless steels were tested at 1100°F (593°C), 1150°F (621°C) and 1200°F (650°C) for twenty-four hours, and 1100°F (593°C) for ninety hours, under conditions which simulate the exposure of the materials under conditions of low-sulfur reforming.
  • the samples of various materials were placed in an open quartz boat within the hot zone of the furnace tube.
  • the boats were one inch (25.4mm) long and 1 ⁇ 2 inch (12.7mm) wide and fit well within the two-inch (50.8 mm) hot zone of the tube.
  • the boats were attached to silica glass rods for each placement and removal. No internal thermocouple was used when the boats were placed inside the tube.
  • the apparatus After exposing the materials to the carburizing gas for the desired period at the desired temperature, the apparatus was quenched with an air stream applied to the exterior of the tube. When the apparatus was sufficiently cool, the hydrocarbon gas was swept out with nitrogen and the boat was removed for inspection and analysis.
  • test materials Prior to start up the test materials were cut to a size and shape suitable for ready-visual identification. After any pretreatment, such as cleaning or roasting, the samples were weighed. Most samples were less than 300 mg. Typically, each run was conducted with three to five samples in a boat. A sample of 347 stainless steel was present with each run as an internal standard.
  • each material was carefully noted. Typically the boat was photographed. Then, each material was weighed to determine changes while taking care to keep any coke deposits with the appropriate substrate material. The samples were then mounted in an epoxy resin, ground and polished in preparation for petrographic and scanning electron microscopy analysis to determine the coking, metal dusting and carburization responses of each material.
  • the residence time of the carburizing gas used in these tests were considerably higher than in typical commercial operation.
  • the experimental conditions may have been more severe than commercial conditions.
  • Some of the materials which failed in these tests may actually be commercially reliable. Nevertheless, the test provides a reliable indication of the relative resistances of the materials to coking, carburization and metal dusting.
  • Samples of 446 stainless steel and 347 stainless steel were placed in a sample boat and tested simultaneously in the carburization apparatus at 1100°F for a total of two weeks.
  • the 446 stainless steel had a thin coating of coke, but no other alteration was detected.
  • the 347 stainless steel on the other hand, had massive localized coke deposits, and pits more than 4 mils (0.102 mm) deep from which coke and metal dust had erupted.
  • Samples were tested of a 304 stainless steel screen; each sample being electroplated with one of tin, silver, copper and chromium.
  • the samples had coatings with thicknesses of approximately 0.5 mil (0.0127mm) After 16-hour carburization screening tests at 1200°F (649°C), no coke had formed on any of the plated screens, except locally on the copper-plated screen where the plating had blistered and peeled. Thin coke coatings were observed on unplated samples of 304 stainless steel run simultaneously with the plated screens.
  • Samples were tested of a 304 stainless steel screen; each sample being electroplated with one of tin and chromium. These samples were tested along with a sample of 446 stainless steel in a carburization test at 1100°F (593°C). The samples were exposed or five weeks. Each week the samples were cooled to room temperature for observation and photographic documentation. They were then re-heated to 1100°F (593°C). The tin plated screen was free of coke; the chromium-plated screen was also free of coke, except locally where the chrome plate had peeled; and the piece of 446 stainless steel was uniformly coated with coke.
  • steel wool was used to study methane formation in a micro pilot plant.
  • a 1 ⁇ 4 inch (6.35 mm) stainless steel tube was packed with 0.14 grams of steel wool and placed into a furnace at 1175°F (635°C). Hexane and hydrogen were passed over the iron and the exit stream was analyzed for feed and products.
  • the steel wool was pretreated in hydrogen for twenty hours before introduction of the hexane. Then hexane was introduced into the reactor at a rate of 25 microliters/min. with a hydrogen rate of about 25 cc/min.
  • Example 5 Additional tests were conducted using tetrabutyl tin pre-coated steel wool.
  • three injections of 0.1 cc of tetrabutyl tin dissolved in 2 cc of hexane were injected into a 1 ⁇ 4 inch (6.35 mm) stainless steel tube containing 0.15 grams of steel wool.
  • the solution was carried over the steel wool in a hydrogen stream of 900°F (482°C).
  • the hydrocarbon feed was then introduced at 1175°F at a hydrocarbon rate of 25 microliters/min with a hydrogen rate of about 25 cc/min.
  • the exit gas was analyzed for methane and remained below 1% for 24 hours.
  • the reactor was then shut down, and the reactor tube was split open and examined. Very little carburization had occurred on the steel wool.
  • organo-tin compounds can prevent carburization of steel wool under reforming conditions.
  • Example 2 Another run like the control run of Example 1 was conducted to investigate the effect of carburization conditions on vapor tin coated stainless steel wires in a gold plated reactor tube. The only other difference from the control run was that a higher hydrogen rate of 100 ml/min was used.
  • portions of steel in the reactor system can be coated with niobium, zirconium, silica ceramics, tungsten, or chromium (chromizing), although these techniques could be excessively difficult to do or use, or prohibitively expensive.
  • the use of heat exchangers to heat hydrocarbons to reaction temperature could be minimized.
  • the heat could be provided by super-heated hydrogen.
  • the exposure of heating surfaces to hydrocarbons can be reduced by using larger tube diameters and higher tube velocities.

Claims (36)

  1. Procédé pour le reformage catalytique d'une charge d'hydrocarbures pour produire des composés aromatiques pendant une longue période de fonctionnement sans colmatage du système de réacteur par le coke, en utilisant un catalyseur de reformage sensible au soufre, auquel ont été incorporés un ou plusieurs métaux du Groupe III, comprenant les étapes consistant :
    (i) à prendre une charge contenant des hydrocarbures, à basse teneur en soufre, préparée en réduisant la teneur en soufre de la charge d'hydrocarbures à moins 50 ppb de soufre pour parvenir à des valeurs acceptables de stabilité et d'activité du catalyseur de reformage ;
    (ii) à utiliser un système de réacteur de reformage présentant une résistance améliorée à la carburation et à la formation de poussière métallique lors du reformage en utilisant une charge contenant moins de 50 ppb de soufre, ledit système comprenant au moins un four pour le chauffage de ladite charge aux températures de reformage catalytique, ledit four comprenant, en contact avec ladite charge, une pluralité de tubes de four présentant une résistance à la carburation et à la formation de poussière métallique au moins aussi grande que celle de l'acier inoxydable (347) lorsqu'elle est déterminée en gain de carbone, en pourcentage en poids, comparativement à cet acier inoxydable (347) par exposition à un gaz de carburation à une température comprise dans l'intervalle de 1100 à 1200°F (593 à 649°C) ; et
    (iii) à faire passer ladite charge contenant des hydrocarbures, à basse teneur en soufre, à travers ledit système de réacteur pour la mise en contact de la charge avec ledit catalyseur de reformage afin de produire des composés aromatiques.
  2. Procédé suivant la revendication 1, dans lequel :
    (a) les tubes du four sont constitués d'acier inoxydable (347) ou d'un acier présentant une résistance à la carburation et la formation de poussière métallique au moins aussi grande que celle de l'acier inoxydable (347) ; ou
    (b) les tubes du four ont été traités par un procédé comprenant un placage, un gainage, une peinture ou un revêtement des surfaces des tubes du four pour la mise en contact avec la charge afin d'obtenir une résistance améliorée à la carburation et à la formation de poussière métallique ; ou
    (c) les tubes du four, et facultativement en outre les revêtements du four, sont constitués d'une matière céramique.
  3. Procédé suivant la revendication 1 ou 2, dans lequel le catalyseur de reformage est un catalyseur consistant en une zéolite à larges pores.
  4. Procédé suivant la revendication 3, dans lequel le catalyseur est un catalyseur consistant en zéolite L au platine.
  5. Procédé suivant la revendication 1, 2, 3 ou 4, dans lequel les tubes du four sont constitués d'acier et dans lequel un placage, un gainage, une peinture ou un revêtement a été appliqué aux portions de surface en acier qui doivent être mises en contact avec la charge chauffée.
  6. Procédé suivant la revendication 1, 2, 3 ou 4, dans lequel les portions de surface des tubes du four sont constituées d'un acier présentant une résistance à la carburation au moins aussi grande que celle de l'acier inoxydable (347).
  7. Procédé suivant la revendication 6, dans lequel un placage, un gainage, une peinture ou un revêtement a été appliqué aux portions en acier qui doivent être mises en contact avec la charge chauffée.
  8. Procédé pour le reformage d'une charge d'hydrocarbures suivant l'une quelconque des revendications précédentes, dans lequel les hydrocarbures sont mis en contact avec le catalyseur dans des conditions de faible teneur en eau.
  9. Procédé pour le reformage d'une charge d'hydrocarbures suivant l'une quelconque des revendications précédentes, comprenant le reformage dans un système de réacteur, dont au moins une portion présente une résistance à la carburation supérieure à celle des aciers aluminés, dans des conditions de basses teneurs en soufre et basses teneurs en eau.
  10. Procédé pour le reformage d'une charge d'hydrocarbures suivant l'une quelconque des revendications précédentes, dans lequel au moins une portion du système de réacteur en contact avec la charge est constituée d'un alliage ne contenant pratiquement pas de nickel.
  11. Procédé pour le reformage d'une charge d'hydrocarbures suivant l'une quelconque des revendications précédentes, dans lequel au moins une portion d'une paroi de réacteur du système de réacteur en contact avec la charge présente une résistance à la carburation au moins aussi grande que celle de l'acier inoxydable (347).
  12. Procédé pour le reformage d'une charge d'hydrocarbures suivant l'une quelconque des revendications précédentes, dans lequel au moins une portion du système de réacteur en contact avec la charge est constituée d'une matière choisie dans le groupe consistant en cuivre, étain, arsenic, antimoine, laiton, plomb, bismuth, chrome, ainsi que leurs composés intermétalliques et leurs alliages.
  13. Procédé pour le reformage d'une charge d'hydrocarbures suivant la revendication 12, dans lequel au moins une portion du système de réaction en contact avec les hydrocarbures est constituée d'un alliage Cu-Sn ou d'un alliage Cu-Sb.
  14. Procédé pour le reformage d'une charge d'hydrocarbures suivant la revendication 12 ou 13, dans lequel la matière est une matière choisie entre l'étain ainsi que ses composés intermétalliques ou alliages.
  15. Procédé pour le reformage d'une charge d'hydrocarbures suivant la revendication 12, 13 ou 14, dans lequel la matière est efficace pour maintenir sa résistance à la carburation après oxydation.
  16. Procédé pour le reformage d'une charge d'hydrocarbures suivant l'une quelconque des revendications précédentes, comprenant la mise en contact de la charge avec le catalyseur de reformage dans des conditions de basse teneur en soufre tout en ajoutant au moins un agent anti-carburation et anti-cokéfaction dépourvu de soufre afin de conférer au système de réacteur une résistance à la carburation supérieure à celle de l'acier inoxydable (347).
  17. Procédé pour le reformage d'une charge d'hydrocarbures suivant la revendication 16, comprenant l'addition d'un agent anti-carburation et anti-cokéfaction choisi dans le groupe consistant en composés organiques d'étain, composés organiques d'antimoine, composés organiques de bismuth, composés organiques d'arsenic et composés organiques de plomb.
  18. Procédé pour le reformage d'une charge d'hydrocarbures suivant la revendication 17, dans lequel un agent anti-carburation et anti-cokéfaction consistant en un composé organique d'étain ne contenant pas de soufre est ajouté.
  19. Procédé pour le reformage d'une charge d'hydrocarbures suivant la revendication 1, 2, 3, 4, 5 ou 7, dans lequel au moins une portion du système de réacteur est constituée d'un acier riche en chrome portant un revêtement métallique contenant de l'étain, de l'antimoine, du bismuth ou de l'arsenic.
  20. Procédé pour le reformage d'une charge d'hydrocarbures suivant la revendication 19, dans lequel au moins une portion du système de réacteur est constituée d'un acier riche en chrome portant un revêtement métallique comprenant de l'étain.
  21. Procédé pour le reformage d'une charge d'hydrocarbures suivant la revendication 1, 2, 3, 4, 5 ou 7, dans lequel au moins une portion des surfaces en acier dans le système de réacteur a été initialement revêtue avec de l'aluminium ou de l'étain, puis a été munie d'un revêtement mince d'oxyde de chrome.
  22. Procédé pour le reformage d'une charge d'hydrocarbures suivant la revendication 1, 2, 3, 4, 5 ou 7, dans lequel au moins une portion des surfaces en acier dans le système de réacteur a été initialement revêtue avec un revêtement comprenant de l'aluminium, puis a été soumise à un procédé de post-traitement comprenant l'application d'un revêtement métallique comprenant l'étain.
  23. Procédé pour le reformage d'une charge d'hydrocarbures suivant la revendication 1, 2, 3, 4, 5 ou 7, dans lequel au moins une portion du système de réacteur est préchauffée avec un courant d'hydrogène gazeux chauffé à une température d'environ 399 à 621°C (750 à 1150°F), puis ladite portion préchauffée du système de réacteur est exposée à un courant gazeux de refroidissement à une température d'environ 204 à 427°C (400 à 800°F) qui comprend de l'hydrogène et un composé organométallique renfermant de l'étain.
  24. Procédé suivant la revendication 1, 2, 3, 4, 5 ou 7, dans lequel une portion des surfaces métalliques dans le système de réacteur a été revêtue avec un film d'aluminium, d'alumine, de chrome ou d'oxyde de chrome, ou bien est constituée d'une matière aluminée ou chromisée.
  25. Procédé suivant la revendication 1, 2, 3 ou 4, dans lequel le système de réacteur est constitué au moins partiellement d'une matière céramique.
  26. Procédé suivant la revendication 1, 2, 3, 4, 5 ou 7, dans lequel au moins une portion des surfaces métalliques dans le système de réacteur est revêtue avec un film mince de silice ou de silicium.
  27. Procédé suivant l'une quelconque des revendications précédentes, dans lequel, au cours du reformage dans des conditions consistant en une teneur inférieure à 50 ppb de soufre, les températures des portions du système de réacteur constituées d'acier doux n'excèdent pas 510°C (950°F) et les températures des portions du système de réacteur constituées d'aciers inoxydables n'excèdent pas 552°C (1025°F).
  28. Procédé suivant l'une quelconque des revendications 1 à 9, dans lequel une peinture réactive décomposable contenant de l'étain est appliquée à au moins une portion en acier du système de réacteur de reformage, peinture qui se transforme par réduction en étain réactif qui forme un stannure de fer avec ladite portion du système de réacteur de reformage à laquelle elle est appliquée par chauffage dans des conditions de réduction.
  29. Procédé suivant la revendication 28, dans lequel la peinture comprend (i) un composé d'étain décomposable par l'hydrogène, (ii) un système de solvant, (iii) de l'étain métallique finement divisé, et (iv) un oxyde d'étain.
  30. Procédé suivant la revendication 29, dans lequel le composé d'étain décomposable par l'hydrogène consiste en octanoate d'étain.
  31. Procédé suivant la revendication 29 ou 30, dans lequel l'étain métallique finement divisé a un diamètre de particules de 1 à 5 micromètres.
  32. Procédé suivant la revendication 29, 30 ou 31, dans lequel le système de solvant contient au moins un membre du groupe consistant en alcool isopropylique, hexane et pentane.
  33. Procédé suivant la revendication 32, dans lequel le système de solvant contient de l'alcool isopropylique.
  34. Procédé suivant la revendication 29, 30, 31, 32 ou 33, dans lequel n'est présente aucune matière non réactive qui empêche l'étain réactif de réagir avec la portion du système de réacteur de reformage à laquelle la peinture doit être appliquée.
  35. Procédé suivant la revendication 5 ou 7, dans lequel la peinture est une peinture comprenant :
    (i) un ou plusieurs composés contenant de l'étain, et
    (ii) un ou plusieurs composés de fer, dans lequel le rapport Fe/Sn va jusqu'à 1:3 en poids.
  36. Procédé suivant la revendication 35, dans lequel le composé de fer consiste en Fe2O3.
EP92908806A 1991-03-08 1992-03-06 Procedes de reformage en presence de faibles quantites de soufre Expired - Lifetime EP0576571B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP97110024A EP0798363B1 (fr) 1991-03-08 1992-03-06 Procédés de réformage en présence de faibles quantités de soufre
EP98100396A EP0845521B1 (fr) 1991-03-08 1992-03-06 Procédé de reformage à basse teneur en soufre

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
US666696 1984-10-31
US66669691A 1991-03-08 1991-03-08
US80321591A 1991-12-06 1991-12-06
US80282191A 1991-12-06 1991-12-06
US80306391A 1991-12-06 1991-12-06
US803063 1991-12-06
US803215 1991-12-06
US802821 1991-12-06
PCT/US1992/001856 WO1992015653A1 (fr) 1991-03-08 1992-03-06 Procedes de reformage en presence de faibles quantites de soufre

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP97110024A Division EP0798363B1 (fr) 1991-03-08 1992-03-06 Procédés de réformage en présence de faibles quantités de soufre
EP97110024.3 Division-Into 1997-06-19

Publications (3)

Publication Number Publication Date
EP0576571A1 EP0576571A1 (fr) 1994-01-05
EP0576571A4 EP0576571A4 (fr) 1994-03-23
EP0576571B1 true EP0576571B1 (fr) 1997-10-08

Family

ID=27505330

Family Applications (3)

Application Number Title Priority Date Filing Date
EP98100396A Expired - Lifetime EP0845521B1 (fr) 1991-03-08 1992-03-06 Procédé de reformage à basse teneur en soufre
EP92908806A Expired - Lifetime EP0576571B1 (fr) 1991-03-08 1992-03-06 Procedes de reformage en presence de faibles quantites de soufre
EP97110024A Expired - Lifetime EP0798363B1 (fr) 1991-03-08 1992-03-06 Procédés de réformage en présence de faibles quantités de soufre

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP98100396A Expired - Lifetime EP0845521B1 (fr) 1991-03-08 1992-03-06 Procédé de reformage à basse teneur en soufre

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP97110024A Expired - Lifetime EP0798363B1 (fr) 1991-03-08 1992-03-06 Procédés de réformage en présence de faibles quantités de soufre

Country Status (16)

Country Link
EP (3) EP0845521B1 (fr)
JP (1) JP3836499B2 (fr)
KR (1) KR100230727B1 (fr)
CN (1) CN1039720C (fr)
AT (1) ATE159040T1 (fr)
AU (1) AU665534B2 (fr)
BR (1) BR9205738A (fr)
DE (3) DE69222633T2 (fr)
ES (3) ES2201223T3 (fr)
HU (1) HUT75107A (fr)
MY (1) MY109992A (fr)
NO (1) NO933165D0 (fr)
OA (1) OA09910A (fr)
SA (1) SA92130085B1 (fr)
SG (2) SG96561A1 (fr)
WO (1) WO1992015653A1 (fr)

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US5516421A (en) * 1994-08-17 1996-05-14 Brown; Warren E. Sulfur removal
US5565087A (en) * 1995-03-23 1996-10-15 Phillips Petroleum Company Method for providing a tube having coke formation and carbon monoxide inhibiting properties when used for the thermal cracking of hydrocarbons
AU7006596A (en) * 1995-06-07 1997-01-09 Chevron Chemical Company Using hydrocarbon streams to prepare a metallic protective l ayer
AU6846096A (en) * 1995-08-18 1997-03-12 Chevron Chemical Company Llc Diffusion barriers for preventing high temperature hydrogen attack
US6497809B1 (en) * 1995-10-25 2002-12-24 Phillips Petroleum Company Method for prolonging the effectiveness of a pyrolytic cracking tube treated for the inhibition of coke formation during cracking
AU2114297A (en) * 1996-02-02 1997-08-22 Chevron Chemical Company Llc Hydrocarbon processing in equipment having increased halide stress-corrosion cracking resistance
CN1043782C (zh) * 1996-03-21 1999-06-23 中国石油化工总公司 提高低品质汽油辛烷值的催化转化方法
US5914028A (en) * 1997-01-10 1999-06-22 Chevron Chemical Company Reforming process with catalyst pretreatment
US5879538A (en) * 1997-12-22 1999-03-09 Chevron Chemical Company Zeolite L catalyst in conventional furnace
US6258330B1 (en) * 1998-11-10 2001-07-10 International Fuel Cells, Llc Inhibition of carbon deposition on fuel gas steam reformer walls
US6120926A (en) * 1998-11-10 2000-09-19 International Fuel Cells, Llc Inhibition of carbon deposition on fuel gas steam reformer walls
AU6784601A (en) 2000-06-28 2002-01-08 Sanyo Electric Co., Ltd. Fuel reforming reactor and method for manufacture thereof
CN1394981A (zh) * 2001-07-09 2003-02-05 李兰根 气氛热处理助剂及其用法
RU2470065C2 (ru) * 2007-10-31 2012-12-20 Чайна Петролеум & Кемикал Корпорейшн Способ пассивации для установки непрерывного риформинга (варианты)
DE202009005950U1 (de) 2009-04-27 2009-08-20 Holland-Letz, Peter Gewebe zur Körperabdeckung zur Applikation von Arzneimitteln
US20120277511A1 (en) * 2011-04-29 2012-11-01 Uop Llc High Temperature Platformer
US20120277500A1 (en) * 2011-04-29 2012-11-01 Uop Llc High Temperature Platforming Process
CN102898265B (zh) * 2011-07-29 2014-08-06 中国石油化工股份有限公司 一种烯烃的生产方法
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Also Published As

Publication number Publication date
DE69222633D1 (de) 1997-11-13
DE69232891D1 (de) 2003-02-13
DE69222633T2 (de) 1998-04-23
EP0798363A3 (fr) 1998-03-11
JP3836499B2 (ja) 2006-10-25
EP0798363A2 (fr) 1997-10-01
HUT75107A (en) 1997-04-28
BR9205738A (pt) 1994-08-23
EP0845521A1 (fr) 1998-06-03
EP0845521B1 (fr) 2003-01-08
CN1067258A (zh) 1992-12-23
SG72690A1 (en) 2000-05-23
ES2108112T3 (es) 1997-12-16
CN1039720C (zh) 1998-09-09
NO933165D0 (no) 1993-09-06
DE69233084T2 (de) 2004-01-29
AU1580192A (en) 1992-10-06
EP0576571A4 (fr) 1994-03-23
EP0798363B1 (fr) 2003-05-28
MY109992A (en) 1997-10-31
SA92130085B1 (ar) 2006-04-22
AU665534B2 (en) 1996-01-11
HU9302543D0 (en) 1993-12-28
DE69233084D1 (de) 2003-07-03
SG96561A1 (en) 2003-06-16
JPH06507191A (ja) 1994-08-11
KR100230727B1 (ko) 1999-11-15
ES2190551T3 (es) 2003-08-01
ES2201223T3 (es) 2004-03-16
WO1992015653A1 (fr) 1992-09-17
DE69232891T2 (de) 2003-11-06
OA09910A (en) 1994-09-15
EP0576571A1 (fr) 1994-01-05
ATE159040T1 (de) 1997-10-15

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