JP2008517761A - Isomerization catalyst and process - Google Patents

Abstract

  Catalysts and processes are disclosed for selectively improving paraffinic feedstocks to obtain isoparaffin-rich products for blending with gasoline. The catalyst comprises a Group IVB (IUPAC 4) metal tungsten oxide or hydroxide support, at least one lanthanide element, a yttrium component or mixture thereof, preferably a first component that is ytterbium or holmium, and preferably Is composed of at least one platinum group metal component which is platinum.

Description

  The present invention relates to improved catalyst composites for hydrocarbon conversion, and processes for hydrocarbon conversion, particularly useful for selective improvement of paraffinic feedstocks by isomerization.

  The extensive removal of lead anti-knock agents from gasoline and the increasing demand for high quality fuels for high performance internal combustion engines has made the oil refining industry a new and improved for greater “octane number” or anti-knock properties in gasoline pools. Have to introduce a new method. The oil refining industry has become a variety of options for improving gasoline pools, including more stringent catalytic reforming, higher FCC (fluid catalytic cracking) gasoline octane, light naphtha isomerization, and the use of oxygenates I have relied on. Such major options such as increased reform stringency and higher FCC gasoline octane result in higher gasoline pool aromatic content at the expense of low octane heavy paraffin.

  The oil refining industry is also working on the supply of reformate gasoline to address the tightening standards for automobile exhaust emissions. Reformed gasoline differs from conventional products in that it has a lower vapor pressure, a lower final boiling point, a higher content of oxygenates, and a lower content of olefins, benzene and aromatics. . The benzene content is generally limited to 1% or less, and is regulated to 0.8% in US reformed gasoline. The aromatic content of gasoline can be reduced, especially when the distillation end point (usually characterized as 90% of the distillation temperature) is lowered because the high-boiling part of gasoline that is normally removed is an aromatic concentrate. Is expensive. Aromatics are a major source of gasoline octane improvement in recent lead reduction programs, so strict restrictions on benzene / aromatics content and high boiling point pose process problems for the oil refining industry become. These issues include the isomerization of light naphtha to increase its octane number, the isomerization of butane as the alkylation feedstock, and the feed for the alkylation and production of oxygenates using FCC and dehydrogenation. It has been addressed through techniques such as the production of additional light olefins as feedstock. This challenge is often addressed by raising the cut point between light and heavy naphtha and increasing the relative amount of naphtha to the isomerization unit.

Also, instead of reforming, increase the content of aromatic compounds by utilizing isomerization of long-chain hydrocarbons such as C ₇ and C ₈ hydrocarbons to branched hydrocarbons with higher octane number It is also possible to improve the octane number. However, many isomerization catalysts are associated with great difficulty when applied to long chain hydrocarbons. A major challenge is the generation of by-products such as hydrocarbon crackers. This cracking material reduces the content of long chain paraffins available for isomerization and reduces its final yield.

Several catalysts for isomerization are known and a group of tungsten zirconia catalysts have been used. For example, U.S. Pat. Nos. 5,510,309 B1, 5,780,382 B1, 5,854,170, and 6,124,232 B1 describe group VIB (IUPAC 6) metal oxy, such as zirconia modified with tungstic acid. Teaches the preparation of acidic solids with anion modified Group IVB (IUPAC 4) metal oxides. US Pat. No. 6,184,430 B1 teaches a process for cracking this feedstock by contacting the feedstock with a metal promoted anion-modified metal oxide catalyst. Wherein the metal oxide is one or more of ZrO ₂ , HfO ₂ , TiO ₂ and SnO ₂ , the modifier is one or both of SO ₄ and WO ₃ , and the metal Is one or more of Pt, Ni, Pd, Rh, Ir, Ru, Mn, and Fe.

  In other examples, a noble metal such as platinum was added to the above-described tungsten zirconia catalyst. See U.S. Pat. Nos. 5,719,097, 6,080,904 B1, and 6,118,036 B1. Catalysts having oxides or metal oxides of Group IVB (IUPAC 4) metals modified with Group VIB (IUPAC 6) metal and Group IB (IUPAC 11) metal anions or oxy anions are disclosed in US Pat. No. 5,902,767. Is disclosed. In US Pat. Nos. 5,648,589 and 5,422,327, a catalyst having a zirconia support impregnated with a Group VIII (IUPAC 8, 9, and 10) metal and silica and tungsten oxide, and isomerization using the catalyst are described. A method is disclosed. Also, in US Pat. No. 5,780,703 B1, in a method for forming a diesel fuel blend component, a Group IVB (IUPAC 4) metal oxide modified with an oxy anion of a Group VIB (IUPAC 6) metal and iron or An acidic solid catalyst having manganese is used.

  U.S. Pat. No. 5,310,868 and U.S. Pat. No. 5,214,017 describe (1) a support containing an oxide or hydroxide of IUPAC 4 (Ti, Zr, Hf), (2) IUPAC 6 (Cr, Mo, W); IUPAC 7 (Mn, Tc, Re), or IUPAC 8, 9, and 10 (Group VIII) metal oxides or hydroxides, (3) IUPAC 11 (Cu, Ag, Au), IUPAC 12 ( Zn, Cd, Hg), IUPAC 3 (Sc, Y), IUPAC 13 (B, Al, Ga, In, Tl), IUPAC 14 (Ge, Sn, Pb), IUPAC 5 (V, Nb, Ta), or Disclosed is a catalyst composition comprising a sulfated and calcined mixture of an IUPAC 6 (Cr, Mo, W) oxide or hydroxide and (4) a lanthanide series metal.

Summary of the Invention

The inventor has developed catalysts for the isomerization of hydrocarbons, in particular C ₇ and C ₈ hydrocarbons, which are found to be significantly better than known catalysts. .

  The present invention is an improved catalyst for hydrocarbon conversion reactions and a process for hydrocarbon conversion reactions. The present invention also provides an improved technique for improving naphtha to gasoline, more specifically, an improved catalyst and process for the isomerization of full boiling range naphtha to obtain high octane gasoline components. provide. The present invention is based on the discovery that a catalyst comprising a lanthanide series and a platinum group component provides superior capacity and stability in the isomerization of full boiling range naphtha and increases its isoparaffin content.

  The present invention is a catalyst comprising a tungsten support of a Group IVB (IUPAC 4) metal oxide, preferably a zirconium oxide or hydroxide, a first component and a second component. The at least first component is a lanthanide series element and / or an yttrium component, and at least the second component is a platinum group metal component. The first component preferably consists of a single lanthanide series element or yttrium, and the second component preferably consists of a single platinum group metal. Preferably, the first component is ytterbium, holmium, yttrium, cerium, europium, or a mixture thereof, and the second component is platinum. The catalyst optionally includes an inorganic oxide binder, preferably alumina. In one method of preparing the catalyst of the present invention, a Group IVB (IUPAC 4) metal oxide or hydroxide is tungsten and the first component is at least one lanthanide element, yttrium or any mixture thereof and The catalyst is prepared by incorporating the two component platinum group metal and preferably combining the catalyst with a refractory inorganic oxide.

  The catalyst of the present invention can also be used for hydrocarbon conversion, such as in the isomerization of isomerizable hydrocarbons. The hydrocarbon is preferably isomerized and composed of full boiling range naphtha that increases its isoparaffin content and octane number as a gasoline mixed stock.

  These and other embodiments will be apparent from the detailed description of the invention.

  The catalyst support material according to the present invention is composed of an oxide or hydroxide of a Group IVB (IUPAC 4) metal (see Cotton and Wilkinson, Advanced Inorganic Chemistry, John Wiley & Sons (Fifth Edition, 1988)), It also contains zirconium, titanium and hafnium. Preferably, the metal is selected from zirconium and titanium, with zirconium being particularly preferred. Preferred zirconium oxides or hydroxides are converted to crystalline form through calcination. The tungstate is complexed onto the support material and is not considered to limit the invention so much, but forms a mixture of Bransted acid and Lewis acid sites. At least one component of the lanthanide series element, yttrium, or a mixture thereof is incorporated into the composite by any suitable means. The platinum group metal component is added to the catalyst composite by any means known in the art to produce the catalyst according to the invention, for example, by impregnation. Optionally, the catalyst is combined with a refractory inorganic oxide. The support, tungstate, metal component and optional binder may be combined in any order effective for the preparation of a catalyst useful for hydrocarbon conversion, specifically hydrocarbon isomerization. .

The production of the catalyst support according to the invention can be based on a hydroxide of a group IVB (IUPAC 4) metal as feedstock. For example, suitable zirconium hydroxide is available from MEI of Flemington, New Jersey. Alternatively, hydroxides can be prepared by hydrolyzing metal oxyanion compounds such as, for example, ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (OH) NO ₃ , ZrOSO ₄ , TiOCl ₂ . Note that commercially available ZrO (OH) ₂ contains a significant amount, ie, 1% by weight of HF. Zirconium alkoxides such as zirconyl acetate and zirconium propoxide may be used. Hydrolysis can be performed using a hydrolyzing agent such as ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium sulfate, (NH ₄ ) ₂ HPO ₄ and other such compounds well known in the art. Is possible. Similarly, the metal oxy-anion component can be prepared from materials available, for example, by treating ZrOCO ₃ with nitric acid. The purchased or hydrolyzed hydroxide is preferably dried at a temperature of 100 to 300 ° C. in order to vaporize the volatile compounds.

The tungsten support is prepared by treatment with a suitable tungsten agent to form a solid strong acid. Liquid acids that are stronger than sulfuric acid are called "superacids". Numerous liquid superacids are known in the literature, for example, substituted protonic acids such as trifluoromethyl substituted H ₂ SO ₄ , triflic acid, and protonic acids activated by Lewis acids (HF plus BF ₃ ). Determining the acid strength of a liquid superacid is relatively simple, but the exact acid strength of a solid strong acid is less characteristic of the surface state of a solid compared to fully solvated molecules found in liquids. Since it is not clear, it is difficult to measure accurately directly. Therefore, there is no generally applicable correlation between a liquid superacid and a solid strong acid, and just because a liquid superacid has been found to catalyze a reaction, There is no corresponding solid strong acid selectable. Accordingly, as used herein, a “solid strong acid” is assumed to have a higher acid strength than a sulfonic acid resin such as Amberlyst-15®. Furthermore, because there is disagreement in the literature as to whether some of these solid acids are “superacids”, only the term solid strong acid as defined above is used herein. Another way of defining a solid strong acid is a solid consisting of interacting protonic acid and Lewis acid sites. Accordingly, the solid strong acid may be a combination of a brainsted (proton) acid and a Lewis acid component. In other cases, the Bransted acid and Lewis acid components are not easily distinguished or do not exist as separate species, but still meet the above criteria.

  Tungstate ions are incorporated into the catalyst composite, for example, by treatment with ammonium metatungstate with a tungsten concentration of typically 0.1-20 wt.%, Preferably 1-15 wt. Compounds such as metatungstic acid, sodium tungstate, ammonium tungstate, and ammonium paratungstate that can form tungstate ions during firing can be used as alternative raw materials. Preferably, ammonium tungstate is used to supply tungstate ions to form a solid strong acid catalyst. The tungstate content of the finished catalyst is usually in the range of 0.5-25% by weight, preferably 1-25% by weight, on an element basis. The tungsten composite is dried and then preferably calcined at a temperature of 450-1000 ° C., especially if the platinum group metal is to be incorporated, especially after tungsten.

  The first component composed of one or more of the lanthanide series elements, yttrium and mixtures thereof is another important component of the catalyst according to the present invention. Lanthanide series elements include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. Preferred lanthanide series elements include ytterbium, cerium, holmium, europium, and mixtures thereof. Ytterbium and holmium are the most preferred first components of the catalyst according to the invention, and it is particularly preferred that the first component consists essentially of ytterbium or holmium components. The first component may be a chemistry with elemental metals or as compounds such as oxides, hydroxides, halides, oxyhalides, carbonates or nitrates, or with one or more other inclusions of the catalyst. As a binder, it can usually be present in any available form of catalyst composite as a catalyst. The first component is preferably an oxide, an alloy with platinum, a sulfate, or in the zirconium lattice. The material is generally fired at a temperature between 600-900 ° C. and takes the form of an oxide. Although it is not intended to limit the invention as such, substantially all of the first is on top of basic conditions such as oxide, oxyhalide or halide form, or mixtures thereof. It is believed that the best results are obtained when the first component is present in a composite that is in the form of a component of which is present in an oxidized state, and is preferably used in the preparation of the present catalyst composite. The oxidation and reduction steps described are specifically designed to achieve this goal. The first component can be incorporated into the catalyst in any amount effective as a catalyst, preferably 0.01 to 10 wt% of the first component on an elemental basis in the catalyst. The best results are usually achieved with 1-5% by weight of the first component, calculated on an element basis.

  The first component may be co-precipitated, co-extruded with a porous carrier material, or a porous carrier material into tungstate either before, after, or at the same time, but not necessarily with equivalent results. Incorporated into the catalyst composite by any suitable method known in the art, such as by impregnation. In order to simplify the operation, it is preferred to incorporate the first component into the tungstate simultaneously. Most preferably, the platinum group metal component is incorporated last. For lanthanide series elements, yttrium or mixtures thereof and platinum group metals, the additional order between the two does not have a significant effect.

  One method of depositing the first component includes impregnating the support with a solution (preferably water soluble) of the decomposable compound of the first component. Decomposable means that when heated, the compound releases a byproduct and is converted to an element or oxide. Examples of decomposable compounds are complexes or compounds such as nitrates, halides, sulfates, acetates, organic alkyls, hydroxides and similar compounds. Conditions for decomposition include temperatures in the range of 200 ° C to 400 ° C. The first component does not necessarily give comparable results, but can be impregnated on the support either before, after, or simultaneously with the platinum group metal component. When using sequential techniques, the composite can be dried or impregnated and calcined between impregnations.

  The second component, the platinum group metal, is an important component of the catalyst. The second component is composed of at least one of platinum, palladium, ruthenium, rhodium, iridium or osmium, preferably platinum, and particularly preferably the platinum group metal is substantially composed of platinum. The platinum group metal component can be a compound such as an oxide, sulfide, halide, oxyhalide, etc. chemically bonded to one or more other components of the composite, or as a metal, in the final catalyst composite. Can exist inside. An amount of platinum group metal component in the range of 0.01 to 2% by weight on the element basis is effective, and an amount of platinum group metal component in the range of 0.1 to 1% by weight on the element basis is preferred. The best results are obtained when substantially all of the platinum group metal is present in the elemental state.

  The second component, the platinum group metal component, is deposited on the composite using the same method as for the first component described above. Examples of decomposable compounds of platinum group metals include chloroplatinic acid, ammonium chloroplatinate, bromide platinate, dinitrodiaminoplatinum, sodium tetranitroplatinate, rhodium trichloride, rhodium chloride, carbonyl chloride, Rhodium, sodium hexanitrorhodium salt, palladium chloride, palladium chloride, palladium nitrate, palladium hydroxide diammine, palladium tetraammine chloride, hexachloroiridium (IV) acid, hexachloroiridium (III) acid, ammonium hexachloroiridium (III), aqua Examples thereof include ammonium hexachloroiridium (IV), ruthenium tetrachloride, hexachlororuthenium salt, hexaammineruthenium chloride, osmium trichloride, and ammonium chloride / osmium. The second component, which is a platinum group component, does not necessarily give comparable results, but is deposited on the support either before, after, or simultaneously with the tungstate and / or the first component. The platinum group component is preferably deposited on the support either after or simultaneously with the tungstate and / or the first component.

  In addition to the first and second components, the catalyst optionally further comprises a third component, iron, cobalt, nickel, rhenium or mixtures thereof. Iron is preferred, and iron can be present in an amount ranging from 0.1 to 5% by weight on an element basis. The third component, such as iron, functions to reduce the amount of the first component, such as ytterbium, required for optimal preparation. The third component is deposited on the composite using the same method as for the first and second components described above. When the third component is iron, suitable compounds include iron nitrate, iron halide, iron sulfate and any other soluble iron compound.

The catalyst composite described above can be used as a powder or formed into any desired shape such as tablets, cakes, extrusions, powders, granules, spheroids, etc. And they can be used in any particular size. The composite is formed into a specific shape by means well known in the art. In making various shapes, it is desirable to mix the composite with a binder. However, it must be emphasized that the catalyst can be made without a binder and used without problems. If a binder is used, it usually constitutes 0.1-50% by weight of the finished catalyst, preferably 5-20% by weight. Refractory inorganic oxides are suitable binders. Examples of binders are silica, alumina, silica-alumina, magnesia, zirconium and mixtures thereof. A preferred binder is alumina, with eta-alumina and / or gamma-alumina being preferred. Typically, the composite and optional binder are mixed with a peptizer such as HCl, HNO ₃ , KOH, etc. to form a homogeneous mixture, which is well known in the art. It is formed into a desired shape by molding means. These forming means include extrusion, spray drying, oil dripping, marumarizing, conical screw mixing and the like. Examples of the extrusion molding means include a screw extruder and an extrusion press. The shaping means, if used, determines how much moisture is added to the mixture. Thus, if extrusion is used, the mixture should be in the form of a soft mass, and if spray drying or oil dripping is used, sufficient water must be present to form a slurry. These pieces are fired at a temperature of 260-650 ° C. for 0.5-2 hours.

  The catalyst composite according to the invention, either synthesized or after calcination, can be used as a catalyst in a hydrocarbon conversion process. Calcination is required, for example, to form zirconium oxide from zirconium hydroxide. Hydrocarbon conversion processes are well known in the art and include cracking, hydrocracking, alkylation of both aromatics and isoparaffins, isomerization, polymerization, reforming, dewaxing, hydrogenation, dehydrogenation, trans There are alkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenitrification, hydrodesulfurization, methane production, ring opening and syngas shift processes. Specific reaction conditions and feed types that can be used in these processes are described in US Pat. Nos. 4,310,440 and 4,440,871, incorporated by reference. A preferred hydrocarbon conversion process is paraffin isomerization.

  In the paraffin isomerization process, a typical naphtha feedstock that boils within the boiling range of gasoline contains paraffins, naphthenes and aromatics and may be composed of small amounts of olefins. Feedstocks that can be used include straight run naphtha, natural gasoline, synthetic naphtha, hot gasoline, catalytic cracked gasoline, partially reformed naphtha, or raffinate from extraction of aromatic compounds. The feedstock is basically included by the full-range naphtha range or within the boiling range of 0-230 ° C.

The main components of the preferred feedstock are alkanes and cycloalkanes having 4 to 10 carbon atoms per molecule, in particular 7 to 8 carbon atoms per molecule. Smaller amounts of aromatic and olefinic hydrocarbons may be present. Typically, the concentration of C ₇ and heavier components is a value greater than 10 wt% of the feedstock. Although there is no particular restriction on the total content of the cyclic hydrocarbon feed, the feed generally contains between 2 and 40% by weight of cyclic material composed of naphthene and aromatic compounds. The aromatic compound contained in the naphtha feedstock is generally less than alkanes and cycloalkanes, but constitutes 0-20% by weight, more generally 0-10% by weight of the total. Benzene usually constitutes the main aromatic component of the preferred feedstock, optionally with a smaller amount of toluene and higher boiling aromatics within the boiling range mentioned above.

  Contact within the isomerization zone can be carried out using the catalyst in a fixed bed system, moving bed system, fluidized bed system, or batch operation. A fixed bed system is preferred. The reactants can be contacted with the bed of catalyst particles either up, down, or radially. When the reactants are in contact with the catalyst particles, they are in a liquid phase, a gas-liquid mixed phase or a gas phase, and excellent results can be obtained by applying the present invention mainly to liquid phase operations. The isomerization zone may be in one reactor or in two or more separate reactors with appropriate means in between to ensure that the desired isomerization temperature is maintained at the entrance of each zone. A series of two or more reactors is preferred, and through improved temperature control of the individual reactors allows improved isomerization for partial replacement of the catalyst without stopping the process.

The isomerization conditions in the isomerization zone include reactor temperature, which is usually in the range of 25-300 ° C. Lower reactor temperatures are generally preferred to encourage equilibrium mixtures with maximum concentrations of high octane, highly branched isoalkanes, and to minimize decomposition of the feed to lighter hydrocarbons. A temperature in the range of 100-250 ° C is preferred in the process of the present invention. The reactor operating pressure is usually in the range of 100 kPa to 10 MPa, preferably 0.3 to 4 MPa in absolute units. The liquid hourly space velocity is in the range of 0.2 to 25 hr ⁻¹ , preferably 0.5 to 10 hr ⁻¹ .

  Hydrogen is mixed with the paraffinic feedstock or fed as is to the isomerization zone with the paraffinic feedstock at a molar ratio of hydrogen to carbohydrate feedstock of 0.01-20, preferably 0.05-5. Hydrogen may be supplied entirely from outside the process or may be replenished by hydrogen that is recycled to the feed after separation from the reactor effluent. Light hydrocarbons and small amounts of inert materials such as nitrogen and argon can be present in the hydrogen. Moisture should preferably be removed from hydrogen supplied from outside the process by an adsorption system as is well known in the art. In one preferred embodiment, the hydrogen to hydrocarbon molar ratio of the reactor effluent is equal or less than 0.05, generally eliminating the need to recycle hydrogen from the reactor effluent to the feed. To do.

  Upon contact with the catalyst, at least a portion of the paraffinic feed is converted to the desired higher octane isoparaffin product. The catalyst according to the invention offers the advantages of high activity and improved stability.

  The isomerization zone generally also has a separation section, preferably consisting of one or more fractionation columns that have associated appendages and separate lighter components from a product rich in isoparaffins. Is done. As an option, the rectification column can separate the isoparaffin concentrate from the cyclic material concentrate, the latter being recycled to the ring cutting zone.

  Preferably, some or all of the isoparaffin-rich product and / or isoparaffin concentrate is, but is not limited to, one or more of butane; butene; pentane; naphtha; Isomers; alkylates; polymers; aromatic extracts; heavy aromatic compounds; gasoline from catalytic cracking, hydrocracking, thermal cracking, thermal reforming, steam pyrolysis and coking; methanol, ethanol, From purification processes such as propanol, isopropanol, tert-butyl alcohol, sec-butyl alcohol, methyl tertiary butyl ether, ethyl tertiary butyl ether, methyl tertiary amyl ether, and oxygenated compounds such as higher alcohols and ethers Along with other gasoline components, it is mixed into the finished gasoline with a small amount of additives. Improves gasoline stability and homogeneity, avoids corrosion and weathering problems, maintains a clean engine, and improves driving operability.

  The following examples are intended to illustrate some specific embodiments according to the present invention. However, these examples should not be construed as limiting the scope of the invention as set forth in the claims. As will be appreciated by those of ordinary skill in the art, there are many possible other variations within the scope of the present invention.

  To prepare the catalyst samples of Table 1, zirconium hydroxide was first prepared by precipitating zirconium nitrate with ammonium hydroxide at 65 ° C. The zirconium hydroxide was dried at 120 ° C. and ground to 40-60 mesh. A number of discrete parts of zirconium hydroxide were prepared. Solutions of either ammonium metatungstate or metal salts (component 1) were prepared and added to the zirconium hydroxide portion. The material was vigorously stirred for a short time and dried with air at 80-100 ° C. with rotation. The impregnated sample was then dried in air at 150 ° C. for 2 hours in a muffle oven. A solution of metal salt (component 2, where component 2 is not identical to component 1) was prepared and added to the dried material. The sample was vigorously stirred for a short time and dried with rotation. The sample was then fired at 600-850 ° C. for 5 hours. A final impregnation solution of chloroplatinic acid was prepared and added to the solid. The sample was vigorously stirred as before and dried while rotating. Finally, the sample was calcined in air at 525 ° C. for 2 hours. In Table 1 below, modifier levels of 2.5% and 5%; tungstate levels of 5%, 10% and 15%; and 650 ° C, 700 ° C, 750 ° C , 800 ° C., and 850 ° C., with the exception of Gd prepared at 650 ° C., 700 ° C., and 750 ° C. only.

For example, the first row of Table 1 contains the WO ₄ 2.5 mass% of Ce and 5% by weight, contains the catalyst was calcined at 650 ° C., of 5% by weight of Ce and 5% by weight of WO ₄ Catalyst containing calcination at 650 ° C., 2.5% by weight of Ce and 10% by weight of WO ₄ and catalyst calcined at 650 ° C., containing 5% by weight of Ce and 10% by weight of WO ₄ Catalyst containing calcination at 650 ° C., 2.5% by weight of Ce and 15% by weight of WO ₄ and catalyst calcined at 650 ° C., containing 5% by weight of Ce and 15% by weight of WO ₄ Catalyst containing calcination at 650 ° C., 2.5% by weight of Ce and 5% by weight of WO ₄ and catalyst calcined at 700 ° C., containing 5% by weight of Ce and 5% by weight of WO ₄ Catalyst baked at 700 ° C., containing 2.5% by weight of Ce and 10% by weight of WO ₄ , catalyst baked at 700 ° C., containing 5% by weight of Ce and 10% by weight of WO ₄ Catalyst calcined at 700 ℃, 2.5% by mass Includes WO ₄ of Ce and 15 wt%, the catalyst was calcined at 700 ° C., it includes a WO ₄ of 5 wt% of Ce and 15 wt%, the catalyst was calcined at 700 ° C., of 2.5 mass% A catalyst containing Ce and 5% by weight WO ₄ and calcined at 750 ° C., a catalyst containing 5% by weight Ce and 5% by weight WO ₄ and calcined at 750 ° C., 2.5% by weight Catalyst containing Ce and 10% by weight WO ₄ and calcined at 750 ° C. Catalyst containing 5% by weight Ce and 10% by weight WO ₄ and calcined at 750 ° C., 2.5% by weight A catalyst containing Ce and 15% by weight WO ₄ and calcined at 750 ° C., a catalyst containing 5% by weight Ce and 15% by weight WO ₄ and calcined at 750 ° C., 2.5% by weight A catalyst containing Ce and 5% by weight WO ₄ and calcined at 800 ° C., a catalyst containing 5% by weight Ce and 5% by weight WO ₄ and calcined at 800 ° C., 2.5% by weight Contains Ce and 10 wt% WO ₄ Catalyst containing 5% by weight of Ce and 10% by weight of WO ₄ , calcined at 800 ° C, catalyst containing 2.5% by weight of Ce and 15% by weight of WO ₄ Catalyst containing 5% by weight of Ce and 15% by weight of WO ₄ calcined at 800 ° C. Catalyst containing 2.5% by weight of Ce and 5% by weight of WO ₄ calcined at 800 ° C. , Baked at 850 ° C., containing 5% by weight of Ce and 5% by weight of WO ₄ ; baked at 850 ° C., containing 2.5% by weight of Ce and 10% by weight of WO ₄ , the catalyst was calcined at 850 ° C., includes a WO ₄ of 5 wt% of Ce and 10 wt%, contains catalyst was calcined at 850 ° C., 2.5 mass% of Ce and 15 wt% of WO ₄ , A catalyst calcined at 850 ° C., containing 5% by weight of Ce and 15% by weight of WO ₄ and showing a catalyst calcined at 850 ° C., indicating that a total of 30 different catalysts were produced. And all these catalysts Also contains 0.5% by weight of platinum. Accordingly, Table 1 shows that a total of 228 different catalysts were made.

The catalyst of Example 1 was prepared as described in Example 1. A reference catalyst was also prepared as described in Example 1. However, the step of adding a modifier was omitted. Approximately 95 mg of each sample was subjected to a multi-unit reactor assay. The catalyst was pretreated in air at 450 ° C. for 6 hours and reduced at 200 ° C. in H ₂ for 1 hour. Next, 8 mol% n-heptane in hydrogen was passed over the sample at 120 ° C., 150 ° C. and 180 ° C., about 1 atm, and 0.3, 0.6 and 1.2 hr ⁻¹ WHSV (heptane only base). The product was analyzed using an on-line gas chromatograph.

For validation of the data, selected results of experiments conducted at 180 ° C. and 1.2 hr ⁻¹ WHSV with a catalyst consisting of 15 wt% W, 0.5 wt% Pt are shown in FIGS. Shown in The identity of the modifier (or first component), the amount of modifier, and the firing temperature are identified along the x-axis of the plots of FIGS. The data marked as “none” for the modifier corresponds to a reference catalyst that does not contain the modifier. FIG. 1 shows a plot of the conversion of heptane obtained with each catalyst. All catalysts show activity, with ytterbium, yttrium and holmium showing the highest conversion. However, it is surprising that many catalysts exhibit the highest conversion when calcined at 800 ° C. In many cases, the conversion tends to decrease as the firing temperature increases. However, many catalysts of the present invention show higher conversions when calcined at 800 ° C than at 750 ° C or 850 ° C. Therefore, a preferable firing temperature is 800 ° C.

FIG. 2 shows the selectivity of the catalyst for C ₇ isomerization. This plot shows that although some degradation occurs, the selectivity for C ₇ isomerization remains high. FIG. 3 shows the selectivity of the catalyst for C ₇ isomerization to produce the two desired dimethyl branched isomers, 2,2-dimethylpentane and 2,4-dimethylpentane. The data also shows that ytterbium and yttrium have shown excellent results and are therefore preferred modifiers. FIG. 4 shows the catalyst yield for C ₇ isomerization to produce the two desired dimethyl branched isomers, 2,2-dimethylpentane and 2,4-dimethylpentane.

The data described above shows that ytterbium as a regulator is particularly preferred. Thus, FIGS. 5-8 show further selected results of experiments in which ytterbium is the modifier. In each of FIGS. 5-8, the amount of tungsten on the catalyst, the amount of modifier on the catalyst, the calcination temperature of the catalyst, and the hourly weight space velocity of operation are shown on the x-axis. In FIG. 5, the y-axis indicates the conversion rate of the n-heptane feedstock. This plot shows that the conversion increases as the amount of tungsten increases, but the conversion decreases as the weight space velocity per hour increases. However, while the other variables remain constant, increasing the amount of modifier by 2.5% to 5% by weight does not significantly affect the conversion. FIG. 6 shows that the selectivity for C ₇ isomerization increases with increasing space velocity. However, FIG. 7 shows that the opposite event occurs when considering selectivity for the two desired dimethyl branched isomers, 2,2-dimethylpentane and 2,4-dimethylpentane. FIG. 8 shows the yields of the two desired dimethyl branched isomers, 2,2-dimethylpentane and 2,4-dimethylpentane. Overall, the results of FIG. 8 show that the yield for a particular dimethylpentane isomer decreases (1) with increasing space velocity; (2) is highest at a calcination temperature of 800 ° C .; and (3 ) It shows that it becomes higher when the level of the modifier is low.

FIG. 2 is a plot of n-heptane conversion obtained with a selected catalyst prepared in Example 1. FIG. 2 is a plot of selectivity of the catalyst of FIG. 1 against n-heptane isomerization. FIG. 2 is a plot of selectivity of the catalyst of FIG. 1 for isomerization of n-heptane to 2,2-dimethylpentane and 2,4-dimethylpentane. FIG. 2 is a plot of the yield of the catalyst of FIG. 1 for the isomerization of n-heptane to 2,2-dimethylpentane and 2,4-dimethylpentane. FIG. 2 is a plot of the conversion of n-heptane obtained with a selected catalyst prepared in Example 1 where ytterbium is the modifier. FIG. 6 is a plot of selectivity of the catalyst of FIG. 5 against n-heptane isomerization. FIG. 6 is a plot of the selectivity of the catalyst of FIG. 5 for the isomerization of n-heptane to 2,2-dimethylpentane and 2,4-dimethylpentane. FIG. 6 is a plot of the yield of the catalyst of FIG. 5 for the isomerization of n-heptane to 2,2-dimethylpentane and 2,4-dimethylpentane.

Claims (10)

  A support composed of tungsten oxide or hydroxide of at least one element of group IVB (IUPAC 4) of the periodic table and deposited on said support; at least one lanthanide series element, yttrium, and their A catalyst comprising a first component selected from the group consisting of a mixture, and a second component composed of at least one platinum group metal component or a mixture thereof.   On an elemental basis, the first component comprises 0.01 to 10% by weight of the catalyst, the second component comprises 0.01 to 2% by weight of the catalyst, and the catalyst comprises 0.5 to 25% by weight of tungsten. The catalyst according to claim 1, wherein:   The group IVB (IUPAC 4) element is comprised of zirconium and the first component is selected from the group consisting of ytterbium, yttrium, cerium, holmium, europium, and combinations thereof. 2. The catalyst according to 2.   The catalyst according to claim 1, 2 or 3, further comprising 0.1 to 50% by weight of a refractory inorganic oxide binder.   And further comprising a third component selected from the group consisting of iron, cobalt, nickel, rhenium, and mixtures thereof, wherein the third component is present in an amount of 0.1 to 5% by mass. The catalyst according to any one of claims 1 to 4.   6. The first component according to claim 1, wherein the first component is selected from the group consisting of ytterbium, yttrium, cerium, holmium, europium, or a mixture thereof, and the second component is platinum. The catalyst according to 1.   A process for converting hydrocarbons by contacting a feedstock with the solid acid catalyst of any one of claims 1 to 6 to produce a conversion product, wherein the hydrocarbon conversion process comprises cracking, Hydrocracking, aromatic alkylation, isoparaffin alkylation, isomerization, polymerization, reforming, dewaxing, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreatment, hydrogen A process characterized in that it is selected from the group consisting of denitrification, hydrodesulfurization, methanation, ring opening and syngas shift. In a process for isomerizing paraffinic feedstock and obtaining a product with increased isoparaffin content, a temperature of 25 to 300 ° C., a pressure of 100 kPa to 10 MPa and a liquid per hour of 0.2 to 15 hr ⁻¹ Contacting the paraffinic feedstock with the solid acid catalyst according to any one of claims 1-7 in an isomerization zone maintained at isomerization conditions composed of space velocity, and enriched with isoparaffins; A process comprising the step of recovering the contained product. The isomerization conditions, 100 ° C. to 250 DEG ° C. temperature, 300 pressure KPa～4MPa, and consists of 1 hour per liquid hourly space velocity of 0.5 to 15 hr ^-1, also C ₅ present in the isomerization zone ⁺ 9. Process according to claim 7 or 8, characterized in that an amount of 0.01 to 20 moles of free hydrogen per mole of hydrocarbon is present in the zone.   10. A process according to claim 7, 8 or 9, further comprising the step of using at least a part of the isoparaffin-rich product for mixing the gasoline product.

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