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    • 专利摘要:
    A catalytic reforming process using a platinum-containing halogenated zeolite catalyst in a metal-coated reactor system in which halogen acid is removed from the catalyst prior to catalyst filling and reforming is disclosed. This process provides a reforming reactor system having a metal coating; Providing a platinum-containing halogenated zeolite catalyst prepared by a method comprising the step of removing volatile halogen acids; Catalytically reforming hydrocarbons to aromatics, characterized in that the metals from the metal coated reactor system do not remove catalytic activity. The coating metal is in particular tin and the zeolite catalyst is especially Pt L-zeolite catalyst. The present invention also relates to a method for reducing catalyst contamination due to metals used in reactor system coatings. The method includes pretreatment of the halogenation catalyst with hydrogen to remove volatile halogen acids. The resulting catalyst is then charged to a metalcoated reactor system and the hydrocarbons are converted.
    公开号:KR20000070055A
    申请号:KR1019997006275
    申请日:1997-11-19
    公开日:2000-11-25
    发明作者:찰스알. 윌슨；데니스엘. 홀터만
    申请人:체브론 케미칼 컴퍼니 엘엘씨；
    IPC主号:
    专利说明:

    REFORMING PROCESS WITH CATALYST PRETREATMENT}
    Platinum L-zeolite catalysts for low-sulfur reforming processes were invented in the early 1980s. After about 10 years, the low sulfur reforming process was commercialized in the early 1990s. Progress towards commercialization required numerous discoveries. Two key findings are the importance of extremely low sulfur content in the feed and the effect of this extremely low sulfur content on reactor metallurgy, namely the need to avoid coking, carburizing and metal contamination. The preferred method for preventing coking, carburizing and metal contamination is to utilize a metal protective layer, in particular a layer comprising tin.
    While commercialization of the ultra-low sulfur reforming process was pursued, a second generation sulfur sensitive platinum L-zeolite catalyst was developed. This new catalyst is a halide reaction. The catalyst allows processing under more stringent conditions, withstands a wide range of hydrocarbon feeds, and has high activity and long life.
    Recent attempts to utilize second generation catalysts for ultra low sulfur reforming processes have led to unexpected and undesirable reductions in catalyst activity. After research and experiments it was found that the catalyst was partially eroded by a protective layer metal such as tin that was used to prevent carburization and metal contamination of the reactor system surface. Probably some of the tin migrates and precipitates on the catalyst. In contrast, when the conventional platinum-L catalyst is used for the ultra low sulfur reforming process in a tin-coated reactor system, no catalyst activator due to tin migration or tin migration is observed. The cause of this problem is low levels of volatile hydrogen halides released from the catalyst itself under certain conditions. These halides can react with reactive tin to remove catalytic activity.
    Therefore, it is an object of the present invention to reduce catalysis due to metals derived from metal coated reactor systems. It is another object of the present invention to reduce catalyst contamination resulting from catalyst activator from a newly metal coated reactor system. This new process will improve catalyst activity and lifetime and thus improve the reproducibility of the catalytic process.
    The use of metal coatings and metal protective layers, in particular tin protective layers, in hydrocarbon conversion processes is known. These layers provide improved resistance to coking, carburization and metal contamination, especially under very low sulfur conditions. For example, in WO 92/1856, Heyse et al. Cover a steel reactor system for use in platinum L-zeolite reforming processes with a metal coating comprising tin (see US Pat. Nos. 5,405,525, 5,413,700). Metal-coated reactor systems are known to prevent carburizing, coking and metal contamination in dehydrogenation and dehydroalkylation processes performed under low sulfur conditions (US Pat. No. 5,406,014, WO 94/15896). Example 3 of US Pat. No. 5,406,014 shows the interaction of tin coupons with hydrocarbons, methyl chloride and hydrogen at 1000 ° F and 1200 ° F. The coupon is stable at 1000 ppm of methyl chloride at 1000 ° F., which shows that the tin coating is stable to halogen at reforming temperatures.
    The use of catalysts treated with halogen-containing compounds for catalytic reforming is also known (see US Pat. No. 5,091,351, Murakawa). Murakawa prepared a Pt L-zeolite catalyst and subsequently treated with a halogen containing compound. The resulting catalyst has a long lifetime and is useful for producing high yields of aromatic hydrocarbons such as benzene, toluene and xylene from C 6 -C 8 aliphatic hydrocarbons. Other patents that disclose halide L-zeolite catalysts are described in US Pat. Nos. 4,681,865, 4,761,512, 5,073,652 to Katsuno; U.S. Patents 5,196,631, 5,260,238 (Murakawa); And EP 498,182 (A).
    None of these patents and patent applications address issues with metalcoated reactor systems. These patents do not specifically teach the necessity or preference of metal removal from the reactor system but prior to catalyst filling or hydrocarbon treatment.
    Indeed, the art offers the advantage of combining tin, one of the preferred coatings, with a reforming catalyst, in particular a Pt L-zeolite catalyst. U.S. Patent 5,279,998 (Mulaskey) teaches that the improvement in activity and fouling rate is related to the treatment of tin particles (tin dust) having an average particle size of 1 to 5 microns outside of the Pt L-zeolite catalyst. For example, Table 1 of the Mulaskey patent shows improved catalyst performance when metal tin dust is combined with a Pt L-zeolite catalyst treated with fluoride according to the process of US 4,681,865.
    In light of the above teachings we have surprisingly found that the catalytic activity is reduced upon reforming in a newly tincoated reactor system using a halide Pt L-zeolite catalyst (see Examples below).
    Tin coated steel is useful for a variety of purposes. For example, a surface coating composition known as a stop-off or resist is temporarily applied to the steel tool surface to block the surface during case hardening. For example, stop-off in US Pat. No. 5,110,854 (Ratliff) is an aqueous alkyd resin containing tin and titanium dioxide.
    We have found that there are problems associated with the use of metal coated reactor systems, especially freshly coated systems in the presence of certain catalysts, and have found the cause and solution of these problems. One object of the present invention is therefore to reduce catalyst contamination from a newly metal coated reactor system. Another object is to enable catalyst contamination to be prevented, for example, when replacing a conventional catalyst with a halide catalyst.
    Summary of the Invention
    In one embodiment, the invention is a catalytic reforming process using a halogenated Pt L-zeolite catalyst wherein volatile halogenated acids are removed from the catalyst prior to the catalyst filling and reforming process, the process comprising the following steps: (a) metal Providing a reforming reactor system having a coating; (b) providing a halogenated Pt L-zeolite catalyst prepared by a process comprising removing the volatile halogenated acid; (c) filling said catalyst into a reactor system; (d) catalytically reforming the hydrocarbon with an aromatic. All volatile halide acids are removed so that metals from the metal coated reactor system do not remove catalytic activity during the reforming process.
    In a preferred embodiment volatile halogen acid is removed by contacting the catalyst with a reducing gas at elevated temperature. This reducing gas comprises hydrogen, in particular a hydrogen / nitrogen mixture. In particular, volatile acids are removed by a reduction step after preparation of the catalyst. Reduction is carried out under conditions in which volatile halogen acids are fixed by caustic scrubbing or contact with a disposable or renewable solid adsorbent. The reduction step is established under conditions where the catalytic metal dispersion is not significantly reduced.
    Preferred metal coatings are made of tin-, germanium-, antimony and aluminum-containing compositions. In particular, the coating metal is a tin-containing composition comprising elemental tin, tin compound or tin alloy.
    In a preferred embodiment the process of the present invention removes volatile halogen acids (including HCl or HF) from halogenated Pt L-zeolite catalysts by contacting the catalysts with a hydrogen containing gas and treating the treated halogenation catalysts with a metal coated reactor system. Filling and reforming the hydrocarbon with an aromatic.
    In another embodiment the invention is a method of reducing catalyst contamination due to metals used in reactor system coatings. The method includes contacting the halogenation catalyst with a hydrogen containing gas at a temperature of about 300 ° F. or more for a time sufficient to remove volatile halogen acid. At least a portion of the volatile halogen acids are fixed by contact with the scrubbing solution or by adsorption on a solid phase. The metal coated reactor system is then charged with catalyst and the hydrocarbons are converted; The metal of the metal coated reactor system does not significantly deactivate the catalyst. This method is applied to freshly metal coated reactor systems, especially those with tin coated surfaces. The newly metalcoated reactor system is a system that has not been used for hydrocarbon treatment after coating or after coating and curing. Naturally, the conditions of the hydrocarbon contacting step should be chosen to prevent or minimize aggregation and sintering of the catalytic metal (eg Pt).
    Among other factors, the present invention is based on the observation that the halide Pt L-zeolite catalyst is partially deactivated during the catalytic reforming process initiation, especially when the process is initiated in a freshly tin coated reactor. This was not observed in conventional Pt L-zeolite catalysts (unhalideed catalysts) where no catalytic activator due to tin coating was observed.
    Tin coated reactor systems, especially those with newly formed tin intermetallic compounds, can lose tin from the tin coated surface during the start of the reforming process using halogenated Pt L-zeolite catalysts. These catalysts generate halogen acids, including HCl, if not pretreated. The interaction of tin with volatile halogen acids reduces the catalytic activity. Thus, the newly tin coated reactor system produces tin that can move unexpectedly upon contact with halogen acid (HCl or HF), which interacts with the platinum catalyst to deactivate the catalyst. Based on these findings, a simple and inexpensive procedure was developed to quickly and effectively remove volatile halogen acids from the catalyst prior to the reforming process. The treated catalyst is charged to a metal coated reactor system and there is little deactivation due to tin coating when the hydrocarbon treatment begins.
    The present invention is a hydrocarbon reforming process characterized in that the catalyst is pretreated to prevent catalyst activator removal during the reforming process in a metal coated reactor system. The invention is applicable to low sulfur catalytic reforming processes in tin coated reactor systems using halogenated catalysts, in particular halogenated Pt L-zeolites. The present invention is also a method of reducing catalyst contamination due to metals used in reactor system coatings.
    1 shows HCl evolution from halogenated reforming catalyst as a function of temperature and hydrogen is added at 500 ° F. in 79 hours.
    2 shows an experimental configuration for the screening test described in Example 3. FIG.
    The present invention is a process for reforming hydrocarbons in metal coated reactor systems. This process includes the following steps: a) providing a reforming reactor system with a metal coating; b) providing a halogenated Pt L-zeolite catalyst prepared by a process comprising the step of removing volatile halogen acids; c) filling said catalyst with said reactor system and catalytically reforming the hydrocarbon with aromatics. All volatile halogen acids are removed to prevent the metals from the metalcoated reactor system from removing catalytic activity. Volatile halogenic acid removal conditions should be selected to minimize catalytic metal damage, such as Pt dispersion reduction.
    In another embodiment, the present invention is a method of reducing catalyst contamination due to metals that have been used in coating reactor systems. In one embodiment, the present invention is a method for reducing contamination of Pt L-zeolite reforming catalyst by tin from a fresh tin coated reactor system having intermetallic tin compounds on the surface to be contacted with hydrocarbons. This method involves the pretreatment of the halogenation catalyst with hydrogen to remove volatile halogen acids. The resulting catalyst is then charged to a metal coated reactor system and the hydrocarbon is converted.
    "Reactor system" includes the hot zone of a chemical conversion unit, in particular a hydrocarbon conversion unit. The unit comprises one or more conversion reactors and reactors including a plurality of reactor tubes for heating the feed. A "reactor system" includes a unit containing a reactor tube where the conversion takes place in a tube of the furnace (ie inside the furnace). A "hot zone" is a zone where the feed is above the reaction or process temperature or where hydrocarbon conversion occurs.
    A "metal coated reactor system" includes a reactor system in which a metal containing cladding, plating, paint or other coating is applied to at least a portion of the surface to be contacted with hydrocarbons above the process temperature. In particular, more than half of the surface area, even more than three quarters, even more, are all in contact with the hydrocarbon above the process temperature. A "metal coated reactor system" also includes a reactor system having a protective layer, such as an intermetallic layer formed from cladding, plating, paint or coating. Depending on the metal, the reactor system with the coating can be cured by heating, in particular in a reducing environment, to produce an intermetallic layer. The metal coated reactor system comprises a base structural material (carbon steel, chromium steel or stainless steel) with one or more adhesive metal layers attached thereto. Examples of metal layers include elemental chromium, aluminum treated surfaces and iron-tin intermetallic compounds such as FeSn 2 . Freshly coated reactor systems, such as freshly tinned systems, are those systems that have not been used to treat hydrocarbons after coating or after coating and curing.
    "Metal containing coating" or "coating" includes cladding, plating, paint and other coatings including elemental metals, metal oxides, organometallic compounds, metal alloys, mixtures thereof. Metals or metal compounds are the key components of the coating. Flowable paints that can be sprayed or brushed are the preferred coatings.
    Although described for tin-interlayers or tin coatings, germanium-, bis-, and antimony-intermetallic layers, especially newly prepared layers, also include reactive metals and our findings apply to these metals as well. Tin coating or tin interlayer only shows a preferred example.
    Volatile Halogenate Removal
    A "volatile halogen acid" is a halogen acid including HCl, HF, HBr, HI and mixtures thereof. It also includes gases generated in halogenated catalysts, such as halogenated Pt L-zeolite catalysts when heated in the presence of hydrogen, in particular in the presence of platinum. Volatile halogen acids may include NH 3 . Volatile halogen acids are gases and acids which can be removed from the catalyst under process conditions, i.
    Volatile halogen acids are removed by a process including a reduction step after preparation of the catalyst. In particular the reduction is carried out under conditions in which the volatile halogen acid is fixed by caustic scrubbing or by trapping on the disposable adsorbent. The removal of volatile halogen acids prevents the attack of the acid on the coating of the metal-coated hydrocarbon conversion reactor to prevent catalysis.
    Volatile halogen acids can be removed from the halogenation catalyst after the drying / calcination step of catalyst preparation in various ways. During calcination (heat treatment with oxygen), the platinum complex decomposes. The halogen content of the catalyst is then reduced by reduction. This reduction reaction can be carried out at temperatures below calcination, in particular at temperatures above 500 ° F.
    The reduction reaction can be carried out in various facilities such as vacuum equipment, moving belt heat treatment machine, rotary kiln with controlled atmosphere, fixed bed heat treatment machine. Care must be taken not to contaminate the halogenation catalyst with sulfur by corrosion or byproducts produced by the reaction of metals or catalysts in the process equipment with halogenic acid gases during reduction.
    In a preferred embodiment the volatile halogen acid is removed by contacting the catalyst with a reducing gas at elevated temperature. Preferred reducing gases are CO; Hydrogen; Hydrogen / nitrogen mixtures are preferred reducing gases, including mixtures of hydrogen and inert gases or mixtures of hydrogen and CO. The reducing gas is used once or recycled. In this way, gas scrubbers, dryers, and adsorbent systems that remove impurities and clean the gas before use or reuse are minimized, thereby reducing gas costs.
    When hydrogen is used, the concentration varies from dilute hydrogen to pure hydrogen. The preferred concentration depends on the type of plant used, the time required to remove volatile halogen acids, and the safety. The ratio of hydrogen to nitrogen is not critical when a mixture of hydrogen and nitrogen is used but is 1: 100 to 1: 1, in particular 1:40 to 1: 2, even more 1:20 to 1: 5. In the case of catalysts that are very susceptible to sulfur, the reducing gas should be sulfurless, ie less than 50 ppb sulfur, even less than 5 ppb sulfur. In a preferred embodiment, hydrogen sulfate and nitrogen-free (10% H 2 / N 2 mixture) are used to remove volatile halogen acids. The water content of the reducing gas is preferably less than 100 ppm.
    Useful reducing conditions include temperatures of at least 300 ° F., in particular from 300 to 1200 ° F., further from 500 to 1000 ° F .; Gas flow rates of 100 to 10,000 GHSV, in particular 500 to 5000 GHSV. The pressure is not critical but is vacuum to 350 psi, in particular atmospheric to 200 psi. In general, the pressure depends on the facility used. For example, 50 to 150 psi for separate pressurizable vessels, atmospheric pressure for moving belt processors, and subatmospheric pressures for vacuum vessels.
    Reduction conditions are selected to prevent catalyst damage, in particular metal (Pt) sintering and agglomeration. Aggregation of platinum results in loss of catalytic activity and lifetime. Therefore, conditions should be selected to minimize the loss of Pt dispersion, high gas flow rates, and catalyst heating rates of 10 ° F./hour or more. The water concentration in the process gas should be less than 1% by weight, in particular less than 0.1% by weight, even less than 100 ppm. The platinum dispersion of the catalyst after halogen acid removal should be the same or better than the platinum dispersion before halogen acid removal. Metal dispersions can be monitored by hydrogen chemisorption or CO chemisorption or other methods.
    One way of removing volatile halogen acids is to use steps similar to those used during reforming catalyst initiation. Initiation conditions are known in the art. For example, the initiation may be accomplished by drying the catalyst at N 2 and heating the catalyst in hydrogen by heating to 500 ° F. at room temperature for 80 hours (eg, 500 ° F. to 932 ° F. in a 10% H 2 / N 2 mixture over 40 hours) Heating at a rate of 10 ° F./hour and maintaining the catalyst at 932 ° F. for 24 hours). The gas flow rate per hour is chosen to quickly remove volatile halogen acids. That is, GHSV can be maintained at about 1300 hours −1 during the drying and reducing periods. The catalyst is then cooled to room temperature. In a preferred embodiment the catalyst is kept free of oxygen and water until stored and used under nitrogen. However, this is not important if the catalyst is oxidizing or adsorbing water since the catalyst may be dried and re-reduced during the start of the reforming process.
    The concentrations of NH 3 and H 2 O during the reduction should be below the level which would damage the halogenated L-zeolite catalyst or reduce the platinum dispersion. Reduction temperature limitations, high flow rates and catalyst predrying all ensure good metal dispersion.
    Since the reduction process can be carried out in a variety of facilities, such as vacuum equipment, moving belt heat treatment machine, air-controlled rotary kiln, fixed bed heat treatment machine, there are various ways of introducing a reducing gas and heating the halogenation catalyst. For example, a hot flowable gas stream comprising refined flue gas or indirectly ignited gas may be used. Heat treatment may be performed on hydrogen flowing in a separate reactor vessel, such as a hydrotreating reactor, if a facility is available that can operate at elevated pressures. As long as a reducing (especially hydrogen-containing) atmosphere is used and volatile halogen acids are removed, the details of the reduction step are not important. Important for this removal is: (a) removing volatile halogen acids on the halogenation catalyst; (b) maintain maximum dispersibility of the catalyst metal; (c) does not contaminate the catalyst; (d) Treat the catalyst in a safe manner, avoiding explosions, fires, etc.
    Halogen acids released from halogenation catalysts during normal catalyst initiation can attack the protective coating of metal coated systems. Volatile HCl is rapidly generated from the catalyst early in the reforming run. Chlorides impregnated with the Pt L-zeolite reforming catalyst at 0.7 wt% levels quickly generate volatile chloric acid during the reforming process. After 200 to 300 hours the rate of chlorine loss is greatly reduced. About half of the chlorine initially added after the initial stage remains on the catalyst. Loss of chlorine during the initial stage can lead to large metal losses from protective coatings on the reactor and tubes.
    In the case of catalysts prepared using ammonium salts, about 50% of the added chloride and about 10% of the added fluoride are easily removed by the method described above. This is therefore a useful goal for halide removal. In addition, residual nitrogen in the form of ammonia can be released during the halogen acid removal step, in particular when the halogenation catalyst is prepared by impregnation using NH 4 Cl and NH 4 F as the halide source.
    It is preferred to capture or fix volatile halogen acids. These gases are toxic and dangerous. For example, effluent HCl and HF can be fixed using solid or liquid substances (absorbents or adsorbents) that capture halogen acids. Suitable liquid adsorbents are water, caustic soda (NaOH) or other basic scrubbing solutions or disposable solid adsorbents. The location of the adsorbent is not critical but it is advisable to fix the volatile halogen acid as soon as possible so that the volatile halogen acid does not cause corrosion. The amount of fixative is not critical and may be sufficient to fix the released halogen acid.
    Plating, cladding, paint and other coating
    Metallic coatings are generally applied to reactor systems for process improvement. The reactor system of the present invention has a metal protective layer applied for coking, carburization and metal dust reduction.
    The invention does not apply to all coated metals. Many metal containing platings, claddings, paints and coatings do not generate reactive metals under conversion / process conditions. However, the simple test described in the Examples easily identifies the metals and coatings that require the metal removal process of the present invention.
    The metal used in the coating depends on the conditions of the hydrocarbon conversion process, such as temperature and reactants. Coating metals that melt at temperatures below the process conditions to form complexes between the substrate material and the metal are preferred. They can more easily provide a complete substrate cover. Such metals are selected from tin, antimony, germanium, arsenic, bismuth, aluminum, gallium, indium, copper or mixtures thereof and intermetallic compounds and alloys thereof. Preferred metal-containing coatings are selected from tin, antimony, germanium, arsenic, bismuth, aluminum or mixtures thereof, metal compounds and alloys. Particular preference is given to tin-, antimony- and germanium-containing coatings. These metals form a continuous and adhesive protective layer. Tin coating is particularly preferred because it is easy to apply to steel, cheap and environmentally friendly. The most preferred metals interact or react with the base material of the reactor system to produce a continuous and adhesive metal protective layer at temperatures below hydrocarbon conversion conditions.
    The coating should be thick enough to completely cover the base metal and leave the resulting protective layer intact after removal of the removable metal to protect the steel even for years of operation. At the same time, a thin layer is preferred. Thin layers are easily produced, cost less than thick layers, and are less prone to breakage under thermal stress. Thus, the optimum thickness of the protective layer depends on the intended use conditions and the coating metal. Tin paints, for example, can be applied in thicknesses of 1 to 6 millimeters, in particular 2 to 4 millimeters. Generally, the thickness after curing is 0.1 to 50 millimetres, in particular 0.5 to 10 millimetres, even more about 1 millimetre. It is also preferable that the coating and the resulting intermetallic layer initially be firmly bonded to the steel, which is possible by curing at elevated temperatures. For example, the applied tin paint can be cured at 1100 ° F. hydrogen for 24 hours.
    Metal-containing coatings are applicable in a variety of ways known in the art. Coating methods include electroplating, chemical vapor deposition and sputtering. Preferred application methods are painting and plating. In particular the coating is applied as a paint. Such paint may be sprayed, brushed, or pigged on the reactor system surface.
    Tin is the preferred coating metal and other metals such as germanium are similar to those for tin. Preferred paints include metal components selected from: hydrogen decomposable metal compounds such as organometallic compounds; Finely divided metals; Metal oxide that can be reduced at a tube temperature. In a preferred embodiment a curing step is used to create an intermetallic protective layer that is bonded to steel through an intermediate bonding layer, such as a carbide rich bonding layer (US Pat. No. 5,406,014, Heyse).
    Preferred coating and paint compositions are disclosed in US patent application 803,063 (Heyse), corresponding to WO 92/15653. Particularly preferred tin paints comprise four components: (i) a hydrolyzable tin compound, (ii) a solvent system such as isopropanol, (i) finely divided tin metal and (i) tin oxide. As hydrolyzable tin compounds organometallic compounds such as tin octanoate or neodecanoate are particularly useful. Component (i) Tin oxide is a porous tin-containing compound capable of absorbing organometallic tin compounds. This paint contains especially finely divided solids for minimizing precipitation. Finely divided tin metal is used to allow the tin to react with the surface to be coated at the lowest possible temperature. Tin particles are preferably as small as 1 to 5 microns. When tin paint is applied to an appropriate thickness, heating under reducing conditions results in tin migration, covering small areas that are not painted (eg welds). The base metal is thus completely coated.
    Some coating compositions need to be cured by heat treatment to produce a continuous adhesive protective layer. Curing conditions depend on the metal coating as well as the hydrocarbon conversion process to which the present invention is applied. For example, the gas flow rate and contact time depend on the process configuration, coating metal, coating composition components and curing temperature. Curing conditions are selected to result in a continuous protective layer adhering to the steel substrate. Curing conditions can be easily determined. For example, in a simple test apparatus, the coated coupon is heated in the presence of hydrogen and the formation of a continuous protective layer can be measured using petroleum analysis. After the curing step, it is desirable to contact the metal-coated reactor system with the getter, especially when an interlayer is formed during heat treatment. Tin paint cures at 900 to 100 ° F and germanium and antimony paints at 1000 to 1400 ° F. Curing takes place over several hours, with the temperature increasing over time when the paint comprises a reducible oxide or an oxygen containing organometallic compound. Reduction / curing is carried out in particular in the absence of hydrocarbons using hydrogen containing gas.
    In the case of tin paint curing, the system including the painted area is compressed using a flow order and then a hydrogenated stream is added. The reactor inlet temperature is raised to 800 ° F at a rate of 50-100 ° F / hour. The temperature is then raised to 950-975 ° F at 50 ° F / hour and held for 48 hours.
    In a preferred embodiment the metalcoated reactor system comprises an intermetallic layer. This layer comprises two or more metals present as intermetallic compounds in stoichiometric proportions (covering a base structural material such as steel substrate). Intermetallic compounds are known in the art and are more structural than molecular mixtures or alloys. In addition, they have properties (eg color) and chemical properties inherent to intermetallic acids.
    For example, the intermetallic tin compound layer includes tin and at least one other metal, which are present as compounds having elements in stoichiometric proportions that differ in a narrow range. Examples of such intermetallic tin compounds are Fe 3 Sn, FeSn 2 , Ni 3 Sn 2 , Ni 3 Sn, Ni 3 Sn 4 . Other examples include intermetallic tin compounds, such as (Fe, Ni) x Sn y , where Fe and Ni are freely replaced and combined to exist in a stoichiometric ratio with tin.
    There will be some metal that has not reacted with the base structural material in the newly metallized reactor system, including the surface interlayer. These unreacted coating metals, at least in part, cause the catalyst to decay upon exposure to volatile halogen acids.
    Metal-coated reactor systems are particularly useful in processes operating under low sulfur conditions as the coating prevents coking, carburization and metal dust. The hydrocarbon conversion process is carried out under "low sulfur" conditions. In such low sulfur systems the feed comprises less than 50 ppm, in particular less than 20 ppm, even less than 10 ppm sulfur. In another embodiment the invention is carried out under “extremely low sulfur” conditions. Sulfur here has a sulfur content of less than 100 ppb, in particular less than 50 ppb, even less than 20 ppb, with a sulfur content of less than 10 ppb and even less than 5 ppb being particularly preferred.
    Base structural material
    There are a variety of base structural materials to which the process of the invention may be applied. In particular, a wide range of steels and alloys are used in reactor systems. In general, steel is chosen because it meets the minimum strength and elasticity requirements for hydrocarbon conversion processes. These conditions depend on conditions such as process temperature and pressure. The steel is chosen so that there is no risk of further corrosion.
    Useful steels include carbon steel; Low alloy steels such as 1.25, 2.25, 5, 7, 9 chromium steels, which may include molybdenum; 300 series stainless steels including type 304, 316, 347 stainless steels; Heat resistant steels including HK-40, HP-50 and manuite; There are treated steels, such as aluminum or chrome treated brown steel.
    Catalytic Reforming Process
    The present invention is applicable to catalytic reforming or dehydrogenation cyclization as disclosed in US Pat. No. 4,456,527 (Buss) and WO 92/1856 (Heyse).
    In a preferred embodiment of the present invention medium to large pore size zeolite catalysts containing alkali or alkaline earth metals and filled with one or more Group 8 metals are used. These catalysts are used to modify or dehydrocycle cyclize paraffinic naphtha feeds containing C 6 or C 8 hydrocarbons to aromatics such as C 6 to C 8 UDEX raffinate. The present invention is particularly useful for very low sulfur reforming reactions using medium to large pore size halogen containing zeolite catalysts such as halide platinum on non-acidic L-zeolite catalysts.
    A "medium pore size" zeolite is a zeolite having an effective pore size of 5 to 6.5 mm 3 when the zeolite is H-type. This zeolite allows side chain hydrocarbons in the zeolite feed to distinguish small side chain alkanes from n-alkanes, for example compared to larger side chain alkanes having quaternary carbon atoms. Useful mesoporous zeolites are ZSM-5 of US 3,702,886, 3,770,614; ZSM-11 of US 3,709,979; ZSM-12 from US 3,832,449; ZSM-21 of US 4,061,724; US 4,061,724 silicalite. Preferred zeolites are salicalite, ZSM-5, ZSM-11. Pt catalysts on zeolites are disclosed in US 4,347,394 (Detz).
    "Large pore size zeolite" is a zeolite having effective pores of 6 to 15 microns. Large pore size zeolites useful in the present invention are L-zeolites, zeolites X, zeolites Y and faujasite. Zeolite Y is disclosed in US 3,130,007 and Zeolite X in US 2,882,244. Zeolites having an effective pore size of 7 to 9 microns are preferred. The present invention uses a medium or large pore size zeolite containing alkali or alkaline earth metal and filled with one or more Group 8 metals.
    The zeolite catalyst used in the present invention has at least one Group 8 metal such as Ni, Ru, Rh, Pd, Ir or Pt. Preferred Group 8 metals are Ir, in particular Pt. The weight percentage of Pt in the catalyst is 0.1-5%. Group 8 metals are introduced into the zeolites by exchange, impregnation or synthesis in aqueous solutions of the appropriate salts. When introducing two Group 8 metals into the zeolite, the process is carried out simultaneously or sequentially.
    Particularly preferred catalysts in the present invention are Group 8 metals on large pore size zeolites, such as Pt containing L zeolite catalysts, in particular Pt on non-acidic L zeolites. The halide Pt L-zeolite catalyst is most preferred. L-zeolites, declared by the molar ratio of oxide, can be represented by the following formula: (0.9-1.3) M 2 / n O: Al 2 O 3 (5.2-6.9) SiO 2 : y H 2 O.
    Where M is a cation, n is the valence of M, and y is an integer from 0 to 9. Zeolite L, its X-ray diffraction pattern, properties, and methods of preparation are detailed in US Pat. No. 3,216,789: The actual chemical formula can be changed without changing the crystal structure. Pt catalysts on L zeolites are disclosed in US 4,634,518 (Buss, Hughes), US 5,196,631 (Murakawa), US 4,593,133 (Wortel), and US 4,648,960 (Poeppelir). In particular, the catalyst is free of acids.
    In one embodiment, the present invention is a catalytic reforming process using a platinum-containing halogenated zeolite catalyst. Volatile halogen acids are removed from the catalyst prior to filling the catalyst in a metal coated reactor system. The catalyst is then charged and the hydrocarbon is reformed. This method involves the following steps:
    a) providing a metal coated reforming reactor system;
    b) providing a platinum-containing halogenated zeolite catalyst pretreated with hydrogen to remove volatile halogen acids including HCl;
    c) filling the reactor system with the treated halogenated zeolite catalyst;
    d) reforming the hydrocarbon with an aromatic compound.
    Metal-coated donor reforming reactor systems have, in particular, tin-coated surfaces. In particular, the pretreatment process removes volatile HF. HCl is then fixed by contact with the scrubbing solution or by adsorption on a solid phase.
    In a preferred embodiment the catalytic reforming process comprises the following steps using a Pt L-zeolite catalyst:
    a) coating the reforming reactor system with tin-containing paint and contacting the painted reactor system with hydrogen-containing gas at 800-1150 ° F. to produce tin coating;
    b) providing a halogenated Pt L-zeolite catalyst prepared by a process comprising impregnating the catalyst with NH 4 Cl and NH 4 F and treating the halogenation catalyst with hydrogen to remove volatile halogen acids;
    c) filling the reactor system with a treated halogenated Pt L-zeolite catalyst;
    d) reforming the hydrocarbon with an aromatic compound under very low sulfur reforming conditions of less than 10 ppb sulfur.
    In particular all volatile halogen acids are removed in step (b).
    Thus, a preferred embodiment of the present invention uses Pt L-zeolite catalysts treated with halogen containing compounds called halogenation catalysts. US 5,091,351 (Murakawa) discloses the preparation of Pt L catalysts and the treatment with halogen containing compounds. Other patents that disclose halogenated L-zeolite catalysts include EP 498,182A (coprecipitation using NH 4 Cl and NH 4 F); US 4,681,865, 4,761,512, 5,073,652 (Katsuno); US 5,196,631, 5,260,238 (Murakawa). These catalysts include spent catalysts recovered by addition of halogen containing compounds (see US 5,260,238). Halogenated catalysts disclosed in these patents are treated with halogen containing compounds, in particular chlorine containing or fluorine containing compounds. In particular, the catalyst is treated with chlorine and fluorine containing chemicals or one or more compounds containing chlorine and fluorine. These halogenated catalysts have a long catalyst life and activity. They are particularly useful for preparing aromatic hydrocarbons such as benzene, toluene and xylene from C 6 -C 8 aliphatic hydrocarbons.
    These catalysts generate small amounts of HCl or HF when heated to elevated temperatures (in process conditions) or when contacted with hydrogen at temperatures above 300-400 ° F. The halogenated gas generated in this way reacts with the reactive metal present in the metal-coated reactor system. Treatment with halogen containing compounds differs from those involved with white muscle filling by impregnation or ion exchange of platinum and halogen containing compounds. This treatment differs from that associated with wash liquors used during impregnation or ion exchange of conventional catalysts to which small amounts of halides can be added.
    In very low sulfur reforming with a non-acidic Pt L-zeolite catalyst, the feed to the catalyst is effectively sulfur-free, ie less than 50 ppb, in particular less than 10 ppb, even more than 5 ppb sulfur content.
    Preferred reforming conditions include temperatures of 700 to 1050 ° F, in particular 800 to 1025 ° F; A pressure of 0 to 400 psig, in particular 15 to 150 psig; Recycle hydrogen rate such that the molar ratio of hydrogen to hydrocarbon of the feed to the reforming reaction zone is 0.1 to 20, in particular 0.5 to 10; Liquid space velocity per hour for a hydrocarbon feed on a reforming catalyst of 0.1 to 10, in particular 0.5 to 5.
    It is often necessary to heat the tube to a higher temperature in order to achieve a suitable reformer temperature. This temperature is between 800 and 1250 ° F, in particular between 850 and 1200 ° F and even more, between 900 and 1150 ° F.
    Example 1 Preparation of Halogenated Pt L-zeolite Catalysts (Comparative)
    Halogenated Pt L-zeolite catalysts are prepared in a similar manner to Example 4 of EP 498,182 A1. 20 parts by weight of silica binder is added to 100 parts by weight of the L-type zeolite with stirring, kneading and molding. Air-calcination of the resulting molded mixture at 500 ° C. (932 ° F.) for 2 hours yields a silica binder-containing shaped L-zeolite. An impregnation liquid containing 0.097 g of NH 4 F, 0.075 g NH 4 Cl, 0.171 g of platinum tetraamine chloride, and 4.8 g of ion-exchanged water is prepared. This liquid is slowly added to 10 g of the molded L-type zeolite with stirring. The resulting zeolite is dried overnight at room temperature and treated at 300 ° C. (572 ° F.) for 3 hours in air. The calcination temperature and time should not be exceeded to limit platinum agglomeration. The calcined catalyst comprises about 0.7 wt% F and 0.7 wt% Cl. Similar catalysts are prepared at slightly higher halogen content.
    This halogenated Pt L-zeolite is filled in a fresh tin coated pilot plant. The catalyst is then subjected to initiation treatment. Initiation treatment dried the catalyst at N 2 from room temperature to 500 ° F. for 79 hours; Then heat the catalyst in a 10% H 2 / N 2 mixture from 500 ° F. to 932 ° F. at a rate of 10 ° F./hour over 43 hours; Maintaining the catalyst at 932 ° F for 24 hours. The hourly space gas velocity (GHSV) is maintained at 1300 hours −1 during the drying and reducing periods. The entire reactor is then cooled to room temperature.
    It was observed that the catalyst generates HCl and HF when heated over 500 ° F and introduced hydrogen during the course of the experiment. 1 shows HCl generation as a function of temperature. HF loss was also observed. Gastec tubes were used to measure HCl concentration. Hydrogen is added after 79 hours. Halide levels on the catalyst were measured; 50% of the initially added chloride (ammonium chloride) and 15% of the first added fluoride (NH 4 F) are released.
    This catalyst was used in the catalytic reforming process (Example 3). Catalyst deactivation was observed compared to equivalent catalysts in reactors without tin coating. This deactivation is due to the migration of tin to the catalyst. The halogen acid generated during the initiation reaction reacts with the surface of the tin coated crucible to produce mobile tin that removes the catalytic activity.
    Example 2 Preparation of Pt L-zeolite Catalysts by Pre-Calcination (Comparative)
    Pt L-zeolite catalyst is prepared in two steps. The pre-calcination step prior to platinum filling lowers the level of volatile halogen acids. In the first step, the L-zeolite catalyst base is impregnated with 0.9% by weight fluorine and 0.55% by weight chlorine as the ammonium salt. The resulting halogenated base is calcined in 950 ° F. air for 2 hours. The calcined catalyst base is impregnated with Pt as in Example 1 and calcined at 570 ° F. for 1 hour. The final halide content on the catalyst is measured. No loss of chlorine or fluorine ions was observed compared to similar catalysts prepared without calcination prior to Pt filling. Clearly, calcination is not effective for removing volatile halogen acids.
    Example 3 Modified Screening Test
    The effect of tin coating on the catalytic performance was evaluated in pilot plant tests. Run 1 (144-181) was performed in an uncoated type 316 stainless steel reactor. 130 cc of catalyst prepared according to Example 1 is packed up to 60 cc of another catalyst bed. The installation shown in Figure 2-1 is used. This catalyst acts as an HCl / HF source. Initiation treatment of the catalyst is performed. Start drying the catalyst for 79 hours at N2 from room temperature to 500 ° F; Heating the catalyst for 43 hours at a rate of 10 ° F./hour in a 10% H 2 / N 2 mixture of 500 to 932 ° F., followed by holding the catalyst at 932 ° F. for 24 hours. GHSV is maintained at 1300 hours −1 during drying and reduction. The entire reactor is then cooled to room temperature.
    The upper catalyst layer is removed under nitrogen. The catalytic performance test is done using only the bottom catalyst. Test conditions are 100 psig, 1.6 LHSV, 3.0 H 2 / hydrocarbon and 46.5 wt% aromatic hydrocarbon target yield. The feed is a C 6 -C 8 UDEX raffinate from the aromatic extraction unit.
    Implementation 2 (144-182) is set as shown in Figs. 2-2. Here a newly tin coated Type 347 stainless steel coupon and a fresh tin coated reactor are used. Because of the process configuration, the ratio of tin-coated surface area to total catalyst volume is 20 times that of a commercial scale facility. An 80 cc catalyst prepared according to Example 1 is packed upstream of the tin coated coupon. Another 80 cc of catalyst is charged downstream of the coupon. The starting procedure of Embodiment 1 is performed. After cooling, the upper catalyst layer and the coupon are removed under nitrogen. Catalyst performance tests are performed using only the bottom catalyst as in Example 1. The bottom catalyst layer after the performance test was analyzed to contain about 1000 ppm tin.
    The onset (SOR) temperature after 1200 hours on the stream was determined for runs 1 and 2 by extrapolating the temperature required to achieve the aromatic target yield to time = 0. The SOR temperature shows that the catalyst of Example 2 is 10 ° F. less active than the catalyst of Example 1. It is believed that the reactive tin reacts with the halide containing HCl released from the first catalyst layer to produce movable tin. This movable tin removes the activity of the catalyst in the second catalyst bed.
    Example 4-Preparation of Pt L-zeolite Catalysts Useful in the Present Invention
    The effect of volatile halogen acid removal prior to catalyst filling is assessed with a pilot plant test. The catalyst was prepared using the procedure of Example 1 and dried in nitrogen at 1300 GHSV. It is then placed in an uncoated pilot plant and heated from room temperature to 500 ° F. at this flow rate. Hydrogen is then introduced, the nitrogen rate is reduced and the total flow rate remains constant. The hydrogen flow rate is maintained at 10% of the total flow rate. The catalyst is activated by treatment with hydrogen in a nitrogen stream (H 2 / N 2 = 1/9) while heating at a rate of 10 ° F./hour from 500 ° F. to 932 ° F. over 40 hours. The catalyst is then held at 932 ° F. for 24 hours in the absence of feed. HCl generation is monitored using Gastec tubes. About 50% of the chlorine ions added to the catalyst are released after this procedure.
    The catalyst is then cooled from nitrogen to room temperature and filled into a fresh tincoated reactor system. No catalyst deactivation was observed by tin after catalyst initiation. The catalytic activity is the same as that of the reforming process in the uncoated pilot plant.
    Example 5 Removal of Volatile Halogens from Recovered Catalysts
    The spent catalyst prepared similarly to Example 1 is deactivated by prolonged use in an extremely low sulfur reforming process. The resulting catalyst lost most of the initially added chlorine and fluorine ions. The catalyst is oxidized to 2% oxygen in nitrogen at atmospheric pressure and heated at 300, 400 and 500 ° C. for one hour. It is then cooled to room temperature and the halide content is measured.
    2 g of this catalyst are recovered by impregnation with a mixed solution of 0.284 g of 3.6 wt% aqueous NH 4 Cl solution, 0.0195 g of solid NH 4 F and 0.8 g of deionized water. The impregnated catalyst is dried overnight at room temperature and calcined at 120 ° C. and 400 ° C. for 3 hours, respectively. This restores the catalyst to an initial chlorine and fluorine ion content of about 1%. Volatile halogen acid is released when the procedure of Example 4 is performed. Treated catalysts are used for catalytic reforming in tin-coated reforming reactors. Catalytic activation by tin in the reactor coating is not observed.
    Example 6 Preparation of Catalysts Useful in the Present Invention
    Example 6a—The catalyst is prepared by pretreating the halogenated Pt L-zeolite catalyst with hydrogen to remove the halogen acid. Pretreatment is carried out in reactor vessels that are not metal coated. Similar to Example 1, a dried and calcined catalyst is prepared. It is then heated under N 2 at a pressure of 70 psig and a GHSV of 1300 h −1 . The temperature is raised to 500 ° F over 6 hours and held at 500 ° F for 5 hours. Introduce a 9: 1 N 2 / H 2 mixture and heat the reactor to 932 ° F. at a rate of 10 ° F./hour and hold at 932 ° F. for 24 hours. The catalyst is cooled in nitrogen and stored. Volatile halogen acids are adsorbed by contact with a solid halogen adsorbent bed. By this procedure volatile halogen acids can be removed from the catalyst prior to filling the catalyst in the tin-coated reactors and prior to the start of the process. The removal of volatile halogen acids prevents catalytic contamination since they do not interact with the tin coating of the reactor.
    Example 6b—The catalyst is prepared by pretreating the halogenated Pt L-zeolite catalyst with hydrogen to remove the halogen acid. The pretreatment is carried out in a mobile bed apparatus in which the atmosphere is controlled. The dried and calcined catalyst prepared similarly to Example 1 in the first zone is heated from room temperature to 500 ° F. using nitrogen which is indirectly burned through the catalyst bed. The residence time is about 2 hours. The second zone is maintained at 500 ° F. for 1 hour and the atmosphere is converted to a preheated H 2 / N 2 mixture (2% by volume H 2 ). In the third zone, the temperature is raised to 800 ° F for 1 hour. In the fourth and final zone, the catalyst is quenched to room temperature under dry nitrogen and discharged to a nitrogen drum for storage.
    Example 7-Large Scale Testing
    This example presents a large scale test.
    Small scale catalytic reformers can be operated at very low sulfur reforming conditions using a C 6 -C 8 UDEX raffinate feed and a Pt L-zeolite catalyst. The sulfur content of the feed in contact with the catalyst is less than 5 ppb sulfur. This reactor system includes a sulfur converter / sulfur absorber, four reforming reactors, associated reactors and tubes. This reactor is made of 1 1/4 Cr, 1/2 Mo steel. The tube is made of 304 stainless steel.
    Prior to catalyst filling, the reactor, reaction tubes and ancillary pipes are treated with reducible tin paint. Several coupons are placed in the reactor system. Paint is applied to all reactor system surfaces in contact with the hydrocarbon feed above the coupon and reforming temperature. The paint contains 1 part by weight 20% Tin Ten-Cem (Mooney Chemical Inc., Cleveland, Ohio), 2 parts by weight tin oxide powder, 2 parts by weight tin metal powder (1-5 microns) and isopropyl alcohol (for fluidity) It consists of. Tin Ten-Cem contains 20% tin as octanoate in octanoic acid. After the paint was applied to a thickness of 3 millimeters, the coated reactor system was heated in a flowing hydrogen / nitrogen (1/9) mixture for 24 hours and then held at 1050 ° F. for 48 hours. Then cooled to room temperature. This procedure results in a tin coated surface. Tin is used to coat unpainted small areas (eg welds). The reactor and tubes are inspected to remove easily removable tin clumps. Microscopic examination of the coupon shows the presence of shiny tin balls.
    In another embodiment a reduced halogenated Pt L-zeolite catalyst (Examples 6a, 6b) is charged to a tin-coated reactor and the initiation procedure of Example 1 is used. The raffinate feed is modified to aromatic at temperatures between 800 and 1000 ° F. The reduction in activity measured by SOR was not observed in this catalyst as expected after halogenation catalysts in untinned reactor systems after 300 hours on the stream. The pretreatment procedures of Examples 6a and 6b were effective.
    权利要求:
    Claims (19)
    [1" claim-type="Currently amended] a) providing a reforming reactor system with a metal coating;
    b) providing a halogenated Pt L-zeolite catalyst prepared by a method comprising removing volatile halogen acid;
    c) filling said reactor system with said catalyst;
    d) A catalytic reforming process using a halogenated Pt L-zeolite catalyst in a metal-coated reactor system in which volatile halogen acids are removed from the catalyst prior to catalyst filling and reforming comprising catalytically reforming the hydrocarbon with an aromatic compound.
    [2" claim-type="Currently amended] The process of claim 1, wherein in step (b) the volatile halogen acid is fixed.
    [3" claim-type="Currently amended] 2. The process of claim 1, wherein in step (b) the volatile halogen acid is fixed by contact with the scrubbing solution or by adsorption on a solid phase.
    [4" claim-type="Currently amended] The method of claim 1 wherein the volatile halogen acid is removed from the platinum impregnated catalyst by reduction.
    [5" claim-type="Currently amended] The process of claim 1, wherein in step (b) the volatile halogen acid is removed by contacting the halogenation catalyst with hydrogen gas at a temperature of 500 to 1000 ° F.
    [6" claim-type="Currently amended] The method of claim 1 wherein the volatile halogen acid comprises HCl.
    [7" claim-type="Currently amended] The method of claim 1 wherein the metal coating comprises a metal selected from tin-, germanium-, antimony- and aluminum-containing compositions.
    [8" claim-type="Currently amended] The method of claim 1 wherein the metal coating comprises a tin, tin compound or tin alloy.
    [9" claim-type="Currently amended] The method of claim 1 wherein the metal coating is newly applied to at least a portion of the reactor system.
    [10" claim-type="Currently amended] a) providing a metal-coated reforming reactor system;
    b) providing a platinum-containing halogenated zeolite catalyst pretreated with hydrogen to remove HCl;
    c) charge the treated halogenated zeolite catalyst to the reactor;
    d) catalytic reforming using a halogenated zeolite catalyst in a metal-coated reactor system comprising reforming a hydrocarbon with an aromatic compound.
    [11" claim-type="Currently amended] The method of claim 10 wherein the metal is tin.
    [12" claim-type="Currently amended] The method of claim 10, wherein the HCl is fixed by contact with a scrubbing solution or by adsorption on a solid phase.
    [13" claim-type="Currently amended] a) coating the reforming reactor system with tin-containing paint and contacting the reactor system painted at 800-1150 ° F. with a hydrogen-containing gas to produce tin coating;
    b) providing a halogenated Pt L-zeolite catalyst prepared by a process comprising impregnating the catalyst with NH 4 Cl and NH 4 F and treating the halogenation catalyst with hydrogen to remove volatile halogen acids;
    c) charge the treated halogenated Pt L-zeolite catalyst to the reactor system;
    d) Catalytic reforming process using a halogenated Pt L-zeolite catalyst comprising reforming a hydrocarbon with an aromatic compound under sulfur-containing ultra low sulfur reforming conditions of less than 10 ppb.
    [14" claim-type="Currently amended] The method of claim 13 wherein all volatile halogen acids are removed.
    [15" claim-type="Currently amended] The method of claim 13, wherein the volatile halogen phase is fixed by contact with the scrubbing solution or by adsorption on a solid phase.
    [16" claim-type="Currently amended] Contacting the halogenation catalyst with a hydrogen containing gas at a temperature of at least 300 ° F. for a time sufficient to remove volatile halogen acid; A method for reducing catalyst contamination due to metals used in a reactor system comprising filling the catalyst in a metal-coated reactor system and converting hydrocarbons, wherein the metal of the metal-coated reactor system does not remove catalytic activity. How to.
    [17" claim-type="Currently amended] The method of claim 16 wherein the metal comprises tin.
    [18" claim-type="Currently amended] 17. The method of claim 16, wherein the method is applied to a newly metalcoated reactor system.
    [19" claim-type="Currently amended] 17. The method of claim 16, wherein said halogen acid is fixed by contact with a scrubbing solution or by adsorption of a solid phase.
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    同族专利:
    公开号 | 公开日
    CA2277289A1|1998-07-16|
    JP2001508481A|2001-06-26|
    WO1998030657A1|1998-07-16|
    MY117119A|2004-05-31|
    AU5361398A|1998-08-03|
    DE69715457D1|2002-10-17|
    EP0951523B1|2002-09-11|
    JP3974188B2|2007-09-12|
    CA2277289C|2007-06-05|
    EP0951523A1|1999-10-27|
    DE69715457T2|2003-01-09|
    ID22817A|1999-12-09|
    US5914028A|1999-06-22|
    KR100496698B1|2005-06-23|
    ES2184143T3|2003-04-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-01-10|Priority to US8/781,433
    1997-01-10|Priority to US08/781,433
    1997-01-10|Priority to US08/781,433
    1997-11-19|Application filed by 체브론 케미칼 컴퍼니 엘엘씨
    1997-11-19|Priority to PCT/US1997/021486
    2000-11-25|Publication of KR20000070055A
    2005-06-23|Application granted
    2005-06-23|Publication of KR100496698B1
    优先权:
    申请号 | 申请日 | 专利标题
    US8/781,433|1997-01-10|
    US08/781,433|1997-01-10|
    US08/781,433|US5914028A|1997-01-10|1997-01-10|Reforming process with catalyst pretreatment|
    PCT/US1997/021486|WO1998030657A1|1997-01-10|1997-11-19|Reforming process with catalyst pretreatment|
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