WO2011068964A1 - Increasing octane number of light naphtha using a germanium-zeolite catalyst - Google Patents
Increasing octane number of light naphtha using a germanium-zeolite catalyst Download PDFInfo
- Publication number
- WO2011068964A1 WO2011068964A1 PCT/US2010/058723 US2010058723W WO2011068964A1 WO 2011068964 A1 WO2011068964 A1 WO 2011068964A1 US 2010058723 W US2010058723 W US 2010058723W WO 2011068964 A1 WO2011068964 A1 WO 2011068964A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- zeolite
- range
- germanium
- acidic
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/13—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation with simultaneous isomerisation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/065—Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/047—Germanosilicates; Aluminogermanosilicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
- C07C5/41—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
Definitions
- This invention relates to a process for the increasing the octane number of a naphtha hydrocarbon feed having a predominantly paraffin content with a base- exchanged zeolite with germanium in the crystalline framework and with a noble metal deposited on the zeolite, for example Pt/CsGeZSM-5.
- Naphtha is a mixture mainly of straight-chained, branched and cyclic aliphatic hydrocarbons, light naphtha having from five to nine carbon atoms per molecule and heavy naphtha having from seven to nine carbons per molecule.
- light naphtha contains naphthenes.; such as cyclohexane and methylcyclopentane, and linear and branched paraffins, such as hexane and pentane.
- Light naphtha typically contains 60% to 99 % by weight of paraffins and cyclop araffms.
- Light naphtha can be characterized as a petroleum distillate having a molecular weight range of 70-150 g/mol, a specific gravity range of 0.6-0,9 g/cm 3 , a boiling point range of 50-320°F and a vapor pressure of 5 to 500 mm Hg (torr) at room temperature.
- Light naphtha may be obtained from crude oil, natural gas condensate or other hydrocarbons streams by a variety of processes, e.g., distillation.
- the octane number of a liquid hydrocarbon is the measure of the ignition quality when burnt in a standard ⁇ spark-ignition internal combustion) engine.
- the octane number represents a mixture of isooctane and n-heptane having the same antiknock properties as the fuel, i.e., a hydrocarbon having an octane number of 92 has the same- knock as a mixture of 92% isooctane and 8% n-heptane.
- the octane number is often determined by means of a standardized test, such as ASTM 2699 or ASTM 2700. Generally, the octane number is increased by decreasing the linear paraffin content of the hydrocarbon.
- U.S. Patent no. 7,414,007 discloses a catalyst and process for isomerization of a paraffmic feedstock to obtain a higher octane hydrocarbon.
- the catalyst is a support of an oxide or hydroxide of a Group IVB metal (zirconium, titanium or hafnium) which has been tungstated by treatment with a tungsten compound to form a strong acid and on which is deposited a phosphorus compound and a platinum compound.
- the catalyst is used in the isomerization process to convert linear paraffins to isoparaffins.
- U.S. Patent no. 7,037,422 discloses a process for producing a high RON (research method octane number, ASTM C2699) naphtha by contacting a hydrocarbon feed stream of a mixture of isomers of C 5 and C 6 paraffins with a CFI zeolite, such as CIT-5, in an adsorption zone whereby the branched isomers of the C 5 and C(, paraffins are preferentially adsorbed compared to the straight chain isomers and recovering a naphtha product form the adsorption zone.
- RON search method octane number, ASTM C2699
- the CFI zeolite can also be a hydroisomerization catalyst to selectively isomerize n-C 5 and n-C 6 to branched isomers.
- the CFI zeolite may contain, a metal such as platinum, palladium, iridium or a mixture or platinum and palladium, active for hydroisomerization.
- U.S . Patent no. 7,029,572 discloses a similar process using an ATC zeolite, such as SSZ-55.
- U.S. Patent no. 6,083 ,379 discloses a process for desulfurizing and enhancing octane number by aromatizing hydrocarbons.
- the catalyst is a zeolite, such as ZSM- 5, with an activity promoter, such as a metal or metal oxide of Groups IA, ILA., IIIA, IV A, VA, VIA, IIB, IIIB, IVB, VB, VIB or VIII.
- U.S. Patent no. 6,245,219 discloses a process for reforming a naphtha-containing hydrocarbon feedstream containing at least about 25 wt% of C5 to C9 aliphatic and cycloaliphatic hydrocarbons with a catalyst of a ZSM-5 and a dehydrogenation metal, such as gallium, zinc, indium, iron, tin or boron, said catalyst being modified with a Group ILA. alkaline earth metal, such as barium, or an organosilicon compound sufficient to neutralize 50%-90% of the surface acidic sites.
- a catalyst of a ZSM-5 and a dehydrogenation metal such as gallium, zinc, indium, iron, tin or boron
- alkaline earth metal such as barium, or an organosilicon compound sufficient to neutralize 50%-90% of the surface acidic sites.
- the aromatization of the n-paraffins to aromatics results in a higher octane rating of the resulting product.
- U.S. Patent no, 6,177.374 discloses a catalyst of oxides of silicon, zinc and aluminum used for the production of high octane aromatics, such as benzene, toluene, xylenes, from natural gas condensate (NGC) and light naphtha.
- NGC natural gas condensate
- the catalyst is represented as M 2 / n O, x AI2O3, y Si0 2 , z ZnO, where M is a proton and/or a metallic cation, n is the valency of the cation and x, y and z is the number of moles of AI2O3, SiO 2 and ZnO and y/x (SiO 2 /ZnO molar ratio) is a number ranging from 5 to 1000.
- U.S. Patent no. 5,510,016 discloses a .process for catalytically desulfurizing cracked fractions in gasoline with a hydrotreating step which reduces octane number followed by treatment with self-bound or binder-free zeolite to restore lost octane.
- Light naphtha generally does not contribute higher octane values without reforming
- Catalytic reforming can increase octane number by converting a portion of paraffins and . cycloparaffins to aromatics but a platinum type reforming catalyst is generally not sulfur tolerant.
- Desulfurization with hydrotreating lowers the octane number of the feed which is restored by converting low octane number paraffins to higher octane number products, e.g., selective cracking of heavy paraffins to lighter paraffins, cracking of low octane paraffins, generation of olefins, ring opening to yield high octane components and dehydrocyclization and aromatization of paraffins to alkylbenzenes. It would be advantageous to have a sulfur-tolerant catalyst for increasing the octane number of a naphtha hydrocarbon feed having a predominantly paraffin content.
- the octane number of a naphtha hydrocarbon feed with a predominantly paraffin content is increased by contacting the hydrocarbon feed with a catalyst which comprises a non-acidic germanium zeolite on which a noble metal, such as platinum, has been deposited.
- the zeolite is non-acidic.
- Examples of the zeolite structure are MTW, FER, MEL, TON, MRE, MWW, MFL BE A, MOR, LTL or MTT.
- fire zeolite has a MF1 structure.
- ZSM-5" is used in this Specification to mean a zeolite having a MFI structure.
- the zeolite has silicon, germanium and, optionally, aluminum in the crystalline framework of the zeolite structure.
- One example of the catalyst is an aluminosiiicate zeolite having germanium in the framework which has been base-exchanged such that it is nonacidic and on which platinum has been deposited, e.g., Pt/CsGeZSM-5. This catalyst is sulfur tolerant up to a level of 1000 ppm in the hydrocarbon feed.
- the process for increasing octane number of a hydrocarbon feed comprising: a) contacting at conditions for concurrently isomerizing n-paraffms to isoparaffms. further isomerizing isoparaffins to more highly branched isoparaffms, cracking n-paraffms to smaller n-isoparaffins, dehydrogenatmg both n- and iso- paraffins and dehydrocyclizing n-paraffms to aromatics a hydrocarbon feed comprising naphtha having C 6 -C 8 alkanes, with a catalyst comprising a non-acidic medium pore or large pore zeolite comprising silicon, germanium and. optionally, aluminum on which a noble metal has been deposited; and b) recovering a hydrocarbon product.
- the naphtha feed may have a C e -C 8 content of at least 30%, at least 40% or at least 50%.
- Zeolite is a crystalline hydrated aluminosilicate that may also contain elements other than aluminum and silicon in the crystalline framework.
- the term "zeolite" includes not only aluminosilicates but substances in which the aluminum is replaced by other trivalent elements, and substances in which silicon is replaced by other tetravalent elements.
- zeolites are structures of T0 4 tetrahedra, which form a three dimensional network by sharing oxygen atoms where T represents tetravalent elements, such as silicon, and trivalent elements, such as aluminum.
- Zeolites are known catalysts for isomerization, toluene disproportionation, transalkylation, hydro genation and alkane oligomerization and aromatization. Some zeolite catalysts, especially those containing a Group VIII deposited metal, are susceptible to sulfur poisoning.
- a catalyst of a germanium zeolite (Ge-zeolite) on which a noble metal has been deposited is base- exchanged with an alkali metal or alkaline earth metal to reduce acidity.
- the base-exchange may occur before or after the noble metal is deposited.
- the catalyst is used to increase the octane number of natural gas condensate, light naphtha or raffinate from aromatics extraction and other refinery or chemical processes, prodded such condensate, naphtha or raffinate has a predominant paraffin content.
- the silicon to aluminum atomic ratio (Si:Al 2 ) of the zeolite is 40- ⁇ .
- Si:Al 2 atomic ratio in the range from 40 to 500.
- SLAL atomic ratio in the range from 50 to 150.
- the zeolite of the present invention is a medium pore zeolite or large pore zeolite.
- medium pore in this Specification should be taken to mean average pore size is in the range from about 5 to about 7 angstroms.
- large pore in this Specification should be taken to mean average pore size is in the range from about 7 to about 10 angstroms. It is possible that these ranges could overlap and a. particular zeolite might be considered either a medium pore zeolite or a large pore zeolite.
- Zeolites having an average pore size of less than about 5 angstroms would not be considered either a medium pore zeolite or a large pore zeolite, A small pore zeolite would not allow molecular diffusion of the molecules of the desired aromatic products, e.g., benzene, ethyl benzene, toluene and xylenes, in its pores and channels.
- Some zeolites have two distinct channels of different sizes, e.g., MOR has a 12-ring channel that is 7.0 x6.5 angstroms as well as an 8-ring channel than is ⁇ 5 angstroms.
- Multichannel zeolites which have at least one channel which is within the ranges above for a medium pore zeolite or a large pore zeolite are considered within the scope of zeolites useful for the present invention.
- the germanium content of the zeolite is in the range from 1.0% to 10.0% by weight.
- One example of germanium content of the zeolite is from 3.5% to 6.0% by weight.
- the noble metal is deposited on the zeolite by any known method of depositing a metal on a zeolite. Typical methods of depositing a metal on zeolite are ion exchange and impregnation. Deposition of the noble metal results in the noble metal being present not only on the surface of the zeolite but also in the pores and channels of the zeolite. In one example of the present invention, the noble metal is present in the catalyst in the range from 0.05% to 3% by weight. In another example of the present invention, the noble metal is from 0.2% to 2% by weight. In another example, the noble metal is from 0.2 to 1.5% by weight. Examples of the noble metal are platinum, palladium, iridium, rhodium, ruthenium and combinations thereof.
- the zeolite of the present invention is non-acidic.
- One meaning of the term "non-acidic' ' ' in this Specification should be taken to mean a zeolite which has been base-exchanged with an alkali metal or alkaline earth metal, such as cesium, potassium, sodium, rubidium, barium, calcium, magnesium, lithium and mixtures thereof, to reduce acidity.
- Base-exchange may take place during synthesis of the zeolite with an alkali metal or alkaline earth metal being added as a component of the reaction mixture or may take place with a crystalline zeolite before, after or simultaneous with deposition of the noble metal.
- the zeolite is base-exchanged to the extent that most or all of the cations associated with aluminum are alkali metal or alkaline earth metal.
- An example of a monovalent baseialuminum molar ratio in the zeolite after base exchange is at least about 0.9.
- cesium is the aikaii metal and is present in a molar ratio to aluminum in the range from about 1 to about 2.
- Another meaning of "non-acidic" within the present invention is an aluminum-free zeolite.
- An aluminum-free zeolite need not be base-exchanged to be nonacidic.
- the aluminum-free zeolite may contain another tetravalent or trivalent element, such as titanium, iron, gallium, boron, germanium or tin.
- "Aluminum -free” has a meaning of having aluminum content of no more than 0.4 wt%. Within the meaning and for the purposes of the present invention, a zeolite may be "non- acidic" by exchange with a base or by having a low aluminum content.
- the zeolite may contain promoters or modifiers as are known in the art. These promoters or modifiers are present in a catalytically effective amount, e.g., about 0.1 weight percent to about 1.0 weight percent. Examples of promoters or modifiers are rhenium, iridium, palladium and tin.
- the catalyst may be supported on or bound with a material, such as a metal oxide; a mixed metal oxide, e.g., oxides of magnesium, aluminum, titanium, zirconium, thorium, silicon or mixtures thereof; a clay, e.g., kaolin or montmorillonite; carbon, e.g., carbon black, graphite, activated carbon, polymers or charcoal; a metal carbide or nitride, e.g., molybdenum carbide, silicon carbide or tungsten nitride; zeolites; a metal oxide hydroxide, e.g., boehmite, to change the physical properties of the catalyst.
- a material such as a metal oxide; a mixed metal oxide, e.g., oxides of magnesium, aluminum, titanium, zirconium, thorium, silicon or mixtures thereof; a clay, e.g., kaolin or montmorillonite; carbon, e.g., carbon black,
- the hydrocarbon feed may contain sulfur up to 1000 ppm. In one embodiment of the invention, the hydrocarbon feed contains sulfur from about 1 ppm to about 500 ppm. In another embodiment of the invention, the hydrocarbon feed contains sulfur from about 10 ppm to about 100 ppm.
- One particular example of a hydrocarbon conversion process using a zeolite catalyst is dehydrocyclization of alkanes to aromatics, e.g.. C 6 ⁇ alkanes to aromatics, primarily benzene, toluene and xylenes, as disclosed, in U.S. Patent Application Publication no. 2008/0255398 published October 16. 2008, hereby incorporated by reference.
- the dehydrocyclization process promotes cyclization and dehydrogenates cyclics to their respective aromatics.
- U.S. Patent no. 6,784.333 discloses a catalyst of an aluminum -silicon germanium zeolite on which platinum has been deposited.
- the catalyst can be used in aromatization of alkanes, specifically, aromatization of lower alkanes, such as propane.
- the catalyst may be a MFl zeolite in which germanium is incorporated into the crystalline framework, i.e., Pt/Ge-ZSM-5.
- the catalyst may be sulfided before or during the aromatization process.
- the present invention increases octane number by several reaction mechanisms which convert hydrocarbons having a relatively lower octane number to hydrocarbons having a relatively higher octane number.
- Nonstoichiometric examples of these reaction mechanisms are shown below.
- One example is isomerizing n-paraffms to isoparaffins, e.g.,
- Another example is further isomerizing isoparaffins to more highly branched isoparaffins, e.g.,
- Another example is dehydrogenating both n- and iso- paraffins, e.g.,
- the catalyst of the present, invention is capable of concurrently functioning as an isomerization, cracking, dehydrogenation and dehydrocyclization catalyst.
- the octane numbers for the above hydrocarbons are numerical averages of the research octane number (RON) and the motor octane number (MON) from ASTM Special Technical Publication #225. "Knocking Characteristics of Pure Hydrocarbons", i.e., (RON + MON)/2.
- the process feed may contain hydrocarbons other than C 6 -C 8 alkanes and nonhydrocarbons, i.e., compounds which are not hydrocarbons. It may contain lower alkanes, such as pentane. and higher alkanes, such as nonane and decane.
- the process feed may contain isoparaffins, olefins, napthenes and even aromatics. Those components of the feed which are not C 6 -C 8 alkanes may be hydrocarbons which catalytically react or hydrocarbons or nonhydrocarbons which are catalytically nonreactive or inert, such as diluents.
- the process feed is naphtha having at least 30% C 6 -C 8 alkanes.
- the process feed is naphtha having at least 40% C 6 -C 8 alkanes.
- the process feed is naphtha having at least 50% C 6 -C 8 alkanes.
- the aromatization process may be carried out at a liquid hourly space velocity in the range between 0.1 and 100 h -1 , at a temperature in the range between 200 and 600°C and at a pressure in the range between 1 and 315 psia.
- the catalyst used in the examples was prepared according to the following procedure:
- Solution #1 was made by diluting 15.84 g of 50 wt % NaOH solution with 131.25 g of deionized (DI) water and subsequently dissolving 7.1 1 g of germanium dioxide.
- Solution #2 was made by diluting 3.84 g sodium aluminate solution (23.6 wt % alumina and 19.4 wt % sodium oxide) with 153,9 g DI water.
- Solution #1 was added to 150 g Ludox AS-40 (40 wt % silica in a colloidal state) and vigorously stirred for 10 minutes to obtain a homogeneous mixture. Solution #2 was stirred into this mixture.
- GeZSM-5 prepared as described above, was washed with aqueous CsNO 3 (0.5M) then filtered. The filtrate was then rewashed 3 more times with 0.5M CsNO 3 and rinsed with distilled water on the final filtering. The zeolite powder was then calcined for 3 hours at 280°C in air. 1% Pt was added by incipient wetness impregnation, carried out by adding drop-wise a solution of Pt(NH 2 )4(NO 3 ) 2 dissolved in. deionized water to the Cs-exchanged GeZSM-5. The material was dried for 1 hour in a 1 10°C drying oven then calcined at 280°C for 3 hours.
- the catalyst powder was pressed and sized to 20-40 mesh. 2.16 cm 3 of the sized catalyst was mixed with 5.84 cm 3 of inert silicon carbide chips and was pretreated at 460°C for 1 hour in flowing hydrogen.
- a synthetically-blended light naphtha was made by calculating a composition based on a PIONA analysis disclosed for a light naphtha in U.S. Patent no. 6,884,531, weighing out each component individually to obtain the desired mole fraction and mixing the components to make the feed mixture, which was vaporized into a stream of flowing hydrogen at a temperature of approximately 150°C. This gas mixture was passed through the reactor, which was maintained at the specified conditions in the tables below. The reaction products were analyzed by gas chromatography. Results are shown in the Table 1 below. The octane number increased from 51 for the naphtha feed to 95 for the reformate.
- the octane number was estimated by using the pure component values for the research octane number (RON) and the motor octane number (MON) from ASTM Special Teclmical Publication #225, "Knocking Characteristics of Pure Hydrocarbons". A numerical average [(RON + MON)/2] of each component was weighted by volume to estimate the octane number of the feed and of the reform ate.
- Concentrations of low octane components have been decreased from 87.4% to 26.2%.
- the concentrations of high octane components has increased (2,2 and 2,3-dimethylbutane: 5.3% to 6.0%, benzene: 1 .4% to 38.5%, n-butane, isobutene and isopentane: 0.0% to 2.5%, cyclic and branched olefins, such as 2- methylpentane related olefins, 3 -methylpentane related olefins, methylcyclopentenes and isobutene: . 0.0% to 16.0%).
- Fuel standards may limit the amount of olefins that are present in gasoline and may require that some or all of the olefins are hydrogenated to the corresponding paraffins.
- Table 2 shows the calculated composition and octane number of the product stream if all of the olefins were hydrogenated. The octane number would be inci'eased from 51 for the naphtha feed to 89 for the reformate.
- benzene may be extracted from reformate.
- Table 3 shows the calculated composition and octane number of the reformate if all of the benzene were removed. The octane number would be increased from 51 for the naphtha to 78 for the reformate.
- the increase in octane number is not due only to the increase in aromatic content from aromatizing n-paraffms. but also from isomerizing n-paraffrns to isoparaffins. further isomerizing isoparaffins to more highly branched isoparaffins, cracking n- paraffins to smaller n -isoparaffins and dehydrogenating both n- and iso- paraffins. Concentrations of low octane components, such as n-hexane, 2-metylpentane and 3-methylpentane.
- the catalyst of the present invention may be in a series process with a conventional acidic reforming catalyst, such as a Group VIII metal on an oxide support, e.g., platinum deposited on alumina or silica to reform a hydrocarbon feed having a linear Ce-Cs alkane content of at least 25%.
- a conventional acidic reforming catalyst may contain a promoter, such as rhenium, tin, cobalt, nickel, iridium, rhodium, ruthenium and combinations thereof.
- the acidic reforming catalyst would be platinum and either rhenium or iridium deposited on alumina. Either catalyst may be the first catalyst in the series process.
- an acidic reforming catalyst comprising platinum deposited on alumina or silica is the first catalyst and a non-acidic medium pore or large pore zeolite comprising silicon, germanium and, optionally, aluminum on which a noble metal has been deposited comprising Pt/CsGeZSM-5 is the second catalyst.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10835119.8A EP2507195A4 (en) | 2009-12-04 | 2010-12-02 | Increasing octane number of light naphtha using a germanium-zeolite catalyst |
IN3131DEN2012 IN2012DN03131A (en) | 2009-12-04 | 2010-12-02 | |
JP2012541234A JP2013512317A (en) | 2009-12-04 | 2010-12-02 | Increasing octane number of light naphtha using germanium-zeolite catalyst |
CN2010800544104A CN102639472A (en) | 2009-12-04 | 2010-12-02 | Increasing octane number of light naphtha using a germanium-zeolite catalyst |
KR1020127014437A KR20120088829A (en) | 2009-12-04 | 2010-12-02 | Increasing octane number of light naphtha using a germanium-zeolite catalyst |
SG2012040028A SG181153A1 (en) | 2009-12-04 | 2010-12-02 | Increasing octane number of light naphtha using a germanium-zeolite catalyst |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/592,883 | 2009-12-04 | ||
US12/592,883 US20110132804A1 (en) | 2009-12-04 | 2009-12-04 | Increasing octane number of light naphtha using a germanium-zeolite catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011068964A1 true WO2011068964A1 (en) | 2011-06-09 |
Family
ID=44080965
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2010/058723 WO2011068964A1 (en) | 2009-12-04 | 2010-12-02 | Increasing octane number of light naphtha using a germanium-zeolite catalyst |
Country Status (8)
Country | Link |
---|---|
US (1) | US20110132804A1 (en) |
EP (1) | EP2507195A4 (en) |
JP (1) | JP2013512317A (en) |
KR (1) | KR20120088829A (en) |
CN (1) | CN102639472A (en) |
IN (1) | IN2012DN03131A (en) |
SG (1) | SG181153A1 (en) |
WO (1) | WO2011068964A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013165471A1 (en) * | 2012-05-02 | 2013-11-07 | Saudi Basic Industries Corporation | Catalyst for light naphtha aromatization |
US9782758B2 (en) | 2013-04-23 | 2017-10-10 | Saudi Basic Industries Corporation | Method of preparing hydrocarbon aromatization catalyst, the catalyst, and the use of the catalyst |
WO2023114690A1 (en) * | 2021-12-14 | 2023-06-22 | Uop Llc | Process for naphtha aromatization using a multi-stage fluidized system |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8772192B2 (en) | 2012-06-29 | 2014-07-08 | Saudi Basic Industries Corporation | Germanium silicalite catalyst and method of preparation and use |
US9180441B2 (en) | 2012-09-20 | 2015-11-10 | Saudi Basic Industries Corporation | Method of forming zeolite shaped body with silica binder |
KR101451902B1 (en) * | 2012-11-26 | 2014-10-22 | 한국과학기술원 | Zeolite with MRE structure and their analogue materials possessing mesopore, and synthesis method thereof |
EP3071326B1 (en) * | 2013-11-22 | 2022-08-24 | Saudi Basic Industries Corporation | Catalyst with improved activity/selectivity for light naphtha aromatization |
US9446389B2 (en) | 2013-12-13 | 2016-09-20 | Saudi Basic Industries Corporation | Hydrocarbon aromatization catalyst composition and method of formation |
CN106660896A (en) * | 2014-06-26 | 2017-05-10 | Sabic环球技术有限责任公司 | Process for producing purified aromatic hydrocarbons from mixed hydrocarbon feedstream |
EP3160925B1 (en) | 2014-06-26 | 2018-08-15 | SABIC Global Technologies B.V. | Process for producing alkylated aromatic hydrocarbons from a mixed hydrocarbon feedstream |
CA3005448A1 (en) * | 2015-11-16 | 2017-05-26 | Exxonmobil Upstream Research Company | Adsorbent materials and methods of adsorbing carbon dioxide |
CN107955644B (en) * | 2016-10-18 | 2020-07-14 | 中国石油化工股份有限公司 | Efficient aromatization method of non-aromatic light hydrocarbon |
EP3318619A1 (en) * | 2016-11-03 | 2018-05-09 | Wolfdieter Klein Consulting GmbH Oel- und Gastechnologie | Method for the production of fuels from gas condensates |
CN106582793A (en) * | 2016-12-07 | 2017-04-26 | 张吉照 | Naphtha isomerization and desulfuration double-effect catalyst and preparation method thereof |
CN109382115B (en) * | 2017-08-02 | 2021-08-10 | 中国石油化工股份有限公司 | Sulfur-tolerant pre-shift catalyst and preparation method thereof |
CA3073502A1 (en) * | 2017-08-23 | 2019-02-28 | Phillips 66 Company | Processes for selective naphtha reforming |
ES2782052B2 (en) | 2017-12-15 | 2021-02-08 | Invista Textiles Uk Ltd | PROCESSES TO PREPARE HYDROCARBON COMPOSITIONS |
US10787618B2 (en) | 2018-01-23 | 2020-09-29 | Saudi Arabian Oil Company | Modified USY-zeolite catalyst for reforming hydrocarbons |
DE112019004296T5 (en) * | 2018-08-30 | 2021-07-22 | Sabic Global Technologies B.V. | FLAVORING CATALYST WITH IMPROVED ISOMERIZATION, MANUFACTURING PROCESS AND USE OF IT |
US11305264B2 (en) * | 2019-09-12 | 2022-04-19 | Saudi Arabian Oil Company | Manufacturing hydrocracking catalyst |
US11365358B2 (en) * | 2020-05-21 | 2022-06-21 | Saudi Arabian Oil Company | Conversion of light naphtha to enhanced value products in an integrated two-zone reactor process |
US11332678B2 (en) | 2020-07-23 | 2022-05-17 | Saudi Arabian Oil Company | Processing of paraffinic naphtha with modified USY zeolite dehydrogenation catalyst |
US11274068B2 (en) | 2020-07-23 | 2022-03-15 | Saudi Arabian Oil Company | Process for interconversion of olefins with modified beta zeolite |
US11420192B2 (en) | 2020-07-28 | 2022-08-23 | Saudi Arabian Oil Company | Hydrocracking catalysts containing rare earth containing post-modified USY zeolite, method for preparing hydrocracking catalysts, and methods for hydrocracking hydrocarbon oil with hydrocracking catalysts |
US11154845B1 (en) | 2020-07-28 | 2021-10-26 | Saudi Arabian Oil Company | Hydrocracking catalysts containing USY and beta zeolites for hydrocarbon oil and method for hydrocracking hydrocarbon oil with hydrocracking catalysts |
US11142703B1 (en) | 2020-08-05 | 2021-10-12 | Saudi Arabian Oil Company | Fluid catalytic cracking with catalyst system containing modified beta zeolite additive |
US11673845B2 (en) | 2020-09-03 | 2023-06-13 | Saudi Arabian Oil Company | Aromatization of light hydrocarbons using metal-modified zeolite catalysts |
US11465950B2 (en) | 2020-09-03 | 2022-10-11 | Saudi Arabian Oil Company | Aromatization of light hydrocarbons using metal-doped zeolite catalysts with enhanced mesoporosity |
US20220389334A1 (en) * | 2021-06-04 | 2022-12-08 | Saudi Arabian Oil Company | Conversion of light naphtha to enhanced value products in an integrated reactor process |
US11618858B1 (en) | 2021-12-06 | 2023-04-04 | Saudi Arabian Oil Company | Hydrodearylation catalysts for aromatic bottoms oil, method for producing hydrodearylation catalysts, and method for hydrodearylating aromatic bottoms oil with hydrodearylation catalysts |
US11548842B1 (en) | 2022-06-01 | 2023-01-10 | Saudi Arabian Oil Company | Conversion of light naphtha to enhanced value aromatics in an integrated reactor process |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4645586A (en) * | 1983-06-03 | 1987-02-24 | Chevron Research Company | Reforming process |
US20060205990A1 (en) * | 2005-03-11 | 2006-09-14 | Rice Lynn H | Isomerization process |
US20080255398A1 (en) * | 2007-04-12 | 2008-10-16 | Saudi Basic Industries Corporation | Aromatization of alkanes using a germanium-zeolite catalyst |
US20080293990A1 (en) * | 2007-05-24 | 2008-11-27 | Saudi Basic Industries Corporation | Catalyst for Conversion of Hydrocarbons, Process of Making and Process of Using Thereof - Ge Zeolites |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL238183A (en) * | 1962-08-03 | |||
US6740228B1 (en) * | 1989-10-30 | 2004-05-25 | Exxonmobil Chemical Patents Inc. | Process for reforming petroleum hydrocarbon stocks |
US5114565A (en) * | 1990-01-26 | 1992-05-19 | Chevron Research And Technology Company | Reforming naphtha with boron-containing large-pore zeolites |
US5510016A (en) * | 1991-08-15 | 1996-04-23 | Mobil Oil Corporation | Gasoline upgrading process |
US6177374B1 (en) * | 1997-01-17 | 2001-01-23 | Council Of Scientific & Industrial Research | Catalyst comprising oxides of silicon, zinc and aluminium used for the preparation of LPG and high octane aromatics and a process for preparing the same |
US6245219B1 (en) * | 1997-04-18 | 2001-06-12 | Exxonmobil Chemical Patents Inc. | Naphtha aromatization process |
US6083379A (en) * | 1998-07-14 | 2000-07-04 | Phillips Petroleum Company | Process for desulfurizing and aromatizing hydrocarbons |
US6884531B2 (en) * | 2001-05-21 | 2005-04-26 | Saudi Arabian Oil Company | Liquid hydrocarbon based fuels for fuel cell on-board reformers |
US6784333B2 (en) * | 2002-08-06 | 2004-08-31 | Saudi Basic Industries Corporation | Catalyst for aromatization of alkanes, process of making and using thereof |
US7414007B2 (en) * | 2002-09-13 | 2008-08-19 | Uop Llc | Isomerization catalyst and process |
US7029572B2 (en) * | 2003-02-25 | 2006-04-18 | Chevron U.S.A. Inc | Process for producing high RON gasoline using ATS zeolite |
US7037422B2 (en) * | 2003-02-25 | 2006-05-02 | Chevron U.S.A. Inc | Process for producing high RON gasoline using CFI Zeolite |
WO2005047915A1 (en) * | 2003-11-12 | 2005-05-26 | Koninklijke Philips Electronics N.V. | Mri system with rf receiver coils fixed to the housing |
US9221723B2 (en) * | 2007-05-24 | 2015-12-29 | Saudi Basic Industries Corporation | Catalyst for conversion of hydrocarbons, process of making and process of using thereof—incorporation-1 |
-
2009
- 2009-12-04 US US12/592,883 patent/US20110132804A1/en not_active Abandoned
-
2010
- 2010-12-02 WO PCT/US2010/058723 patent/WO2011068964A1/en active Application Filing
- 2010-12-02 IN IN3131DEN2012 patent/IN2012DN03131A/en unknown
- 2010-12-02 SG SG2012040028A patent/SG181153A1/en unknown
- 2010-12-02 JP JP2012541234A patent/JP2013512317A/en active Pending
- 2010-12-02 CN CN2010800544104A patent/CN102639472A/en active Pending
- 2010-12-02 EP EP10835119.8A patent/EP2507195A4/en not_active Withdrawn
- 2010-12-02 KR KR1020127014437A patent/KR20120088829A/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4645586A (en) * | 1983-06-03 | 1987-02-24 | Chevron Research Company | Reforming process |
US20060205990A1 (en) * | 2005-03-11 | 2006-09-14 | Rice Lynn H | Isomerization process |
US20080255398A1 (en) * | 2007-04-12 | 2008-10-16 | Saudi Basic Industries Corporation | Aromatization of alkanes using a germanium-zeolite catalyst |
US20080293990A1 (en) * | 2007-05-24 | 2008-11-27 | Saudi Basic Industries Corporation | Catalyst for Conversion of Hydrocarbons, Process of Making and Process of Using Thereof - Ge Zeolites |
Non-Patent Citations (1)
Title |
---|
See also references of EP2507195A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013165471A1 (en) * | 2012-05-02 | 2013-11-07 | Saudi Basic Industries Corporation | Catalyst for light naphtha aromatization |
US9242233B2 (en) | 2012-05-02 | 2016-01-26 | Saudi Basic Industries Corporation | Catalyst for light naphtha aromatization |
US9782758B2 (en) | 2013-04-23 | 2017-10-10 | Saudi Basic Industries Corporation | Method of preparing hydrocarbon aromatization catalyst, the catalyst, and the use of the catalyst |
WO2023114690A1 (en) * | 2021-12-14 | 2023-06-22 | Uop Llc | Process for naphtha aromatization using a multi-stage fluidized system |
Also Published As
Publication number | Publication date |
---|---|
KR20120088829A (en) | 2012-08-08 |
JP2013512317A (en) | 2013-04-11 |
IN2012DN03131A (en) | 2015-09-18 |
US20110132804A1 (en) | 2011-06-09 |
EP2507195A1 (en) | 2012-10-10 |
SG181153A1 (en) | 2012-07-30 |
EP2507195A4 (en) | 2014-11-26 |
CN102639472A (en) | 2012-08-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20110132804A1 (en) | Increasing octane number of light naphtha using a germanium-zeolite catalyst | |
Du et al. | The chemistry of selective ring-opening catalysts | |
US7902413B2 (en) | Aromatization of alkanes using a germanium-zeolite catalyst | |
EP0393099B1 (en) | A dehydrogenation catalystsynthesis and its use | |
PL98293B1 (en) | METHOD OF MAKING A XYLENE MIXTURE | |
US20080035529A1 (en) | Process And Catalysts For The Opening Of Naphthene Rings | |
JPH0113755B2 (en) | ||
CN1902145A (en) | Process for alkane aromatization using platinum-zeolite catalyst | |
US5013423A (en) | Reforming and dehydrocyclization | |
JP2007533807A5 (en) | ||
US4935566A (en) | Dehydrocyclization and reforming process | |
CN106391098B (en) | A kind of catalyst for reforming naphtha and preparation method thereof | |
WO2015128317A1 (en) | Process for producing btx from a c5-c12 hydrocarbon mixture | |
US4867864A (en) | Dehydrogenation, dehydrocyclization and reforming catalyst | |
US4882040A (en) | Reforming process | |
WO2010080360A2 (en) | Process and catalysts for reforming fischer tropsch naphthas to aromatics | |
US8366909B2 (en) | Reforming process at low pressure | |
WO2012066012A1 (en) | Isomerisation catalyst preparation process | |
US5011805A (en) | Dehydrogenation, dehydrocyclization and reforming catalyst | |
US11318452B2 (en) | Single step process for the simultaneous production of aromatics, naphthenics and isoparaffins using transition metal functionalized zeolite based catalyst | |
WO2013095762A1 (en) | Isomerization of light paraffins | |
US4929792A (en) | Dehydrogenation, dehydrocyclization and reforming catalyst | |
US12018221B2 (en) | Synthetic fuels, and methods and apparatus for production thereof | |
JPH09188633A (en) | Production of hydrocarbon containing methylcyclopentane | |
RU2322478C2 (en) | Method for decreasing benzene content in gasoline fractions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080054410.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10835119 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 3131/DELNP/2012 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012541234 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20127014437 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010835119 Country of ref document: EP |