WO2009148773A1 - Catalytic reforming process to produce high octane gasoline - Google Patents
Catalytic reforming process to produce high octane gasoline Download PDFInfo
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- WO2009148773A1 WO2009148773A1 PCT/US2009/043586 US2009043586W WO2009148773A1 WO 2009148773 A1 WO2009148773 A1 WO 2009148773A1 US 2009043586 W US2009043586 W US 2009043586W WO 2009148773 A1 WO2009148773 A1 WO 2009148773A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
- C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
Definitions
- the present invention relates to a multistage reforming process using a medium pore molecular sieve catalyst to produce a high octane naphtha at high liquid yield and hydrogen production.
- Catalytic reforming is one of the basic petroleum refining processes for upgrading light hydrocarbon feedstocks, frequently referred to as naphtha feedstocks.
- Products from catalytic reforming can include high octane gasoline useful as automobile fuel, aromatics (for example benzene, toluene, xylenes and ethylbenzene), and/or hydrogen.
- Reactions typically involved in catalytic reforming include dehydrocylization, isomerization and dehydrogenation of naphtha range hydrocarbons, with dehydrocyclization and dehydrogenation of linear and slightly branched alkanes and dehydrogenation of cycloparaffins leading to the production of aromatics.
- Dealkylation and hydrocracking are generally undesirable due to the low value of the resulting light hydrocarbon products.
- Catalysts commonly used in commercial reforming reactions often include a Group VIII metal, such as platinum or palladium, or a Group VIII metal plus a second catalytic metal, which acts as a promoter.
- metals useful as promoters include rhenium, tin, tungsten, germanium, cobalt, nickel, rhodium, ruthenium, iridium or combinations thereof.
- the catalytic metal or metals may be dispersed on a support such as alumina, silica, or silica-alumina Typically, a halogen such as chlorine is incorporated on the support to add acid functionality.
- other reforming catalysts include aluminosilicate zeolite catalysts.
- U.S. Pat. Nos. 3,761,389, 3,756,942 and 3,760,024 teach aromatization of a hydrocarbon fraction with a ZSM-5 type zeolite catalyst.
- U.S. Pat. No.4,927,525 discloses catalytic reforming processes with beta zeolite catalysts containing a noble metal and an alkali metal.
- Other reforming catalysts include other molecular sieves such as borosilicates and silicoaluminophosphates, layered crystalline clay-type phyllosilicates, and amorphous clays.
- 3,950,241 discloses a process for upgrading naphtha by separating it into low- and high-boiling fractions, reforming the low-boiling fraction, combining the high-boiling naphtha with the reformate, and contacting the combined fractions with a ZSM-5-type catalyst-
- U.S. Pat. No. 4,181,599 discloses a process for reforming naphtha comprising separating the naphtha into heavy and light fractions and reforming and isomerizing the naphtha fractions.
- 4,190,519 teaches a process for upgrading a naphtha-boiling-range hydrocarbon which comprises separating the naphtha feedstock into a light naphtha fraction containing C6 paraffins and lower- boiling hydrocarbons and a heavy naphtha fraction containing higher-boiling hydrocarbons, reforming the heavy naphtha traction and passing at least a portion of the reformate together with the light naphtha fraction over a zeolite catalyst to produce an aromatics-enriched effluent.
- Different catalysts may be employed in different process steps during the reforming of naphtha feedstocks as described in U.S. Pat. Nos. 4,627,909, U.S. 4,443,326, U.S.
- the present invention relates to processes for catalytically reforming a naphtha fuel feed to produce a product reformate in a multistage reforming operation.
- the process comprises contacting a naphtha boiling range hydrocarbon feedstock in a penultimate stage of a multi-stage reforming process at a first reforming pressure to produce a penultimate effluent; separating at least a portion of the penultimate effluent into at least an intermediate reformate and a heavy reformate, wherein the intermediate reformate has a mid-boiling point that is lower than that of the heavy reformate; and contacting the intermediate reformate in a final stage of the multi-stage reforming process at a second reforming pressure with a catalyst comprising at least one medium pore molecular sieve to produce a final effluent comprising a final reformate, wherein the first reforming pressure is greater than the second reforming pressure.
- the catalyst within the penultimate stage comprises a
- the catalyst within the final stage comprises a Group VIII metal.
- a reforming process comprises contacting a naphtha boiling range hydrocarbon feedstock in a penultimate stage of a multi-stage reforming process at a first reforming pressure to produce a penultimate effluent; separating at least a portion of the penultimate effluent into at least a light reformate, an intermediate reformate and a heavy reformate, wherein the light reformate has a mid-boiling point that is lower than that of the intermediate reformate, and wherein the intermediate reformate has a mid-boiling point that is lower than that of the heavy reformate; and contacting the intermediate reformate in a final stage of the multi-stage reforming process at a second reforming pressure with a catalyst comprising at least one medium pore molecular sieve to produce a final effluent comprising a final reformate, wherein the first reforming pressure is greater than the second reforming pressure.
- Fig. 1 is a schematic diagram of one embodiment of the invention.
- Fig. 2 is a schematic diagram of a second embodiment of the invention.
- a naphtha boiling range hydrocarbon feedstock is processed in a multi-stage reforming process, which process involves at least a penultimate stage for reforming the naphtha feedstock to a penultimate stage naphtha product which has an octane number higher than that of the naphtha feed and a final stage for further reforming a portion of an effluent product from the penultimate stage, producing a final naphtha having an octane number higher than that of the penultimate stage naphtha product.
- the reforming process is operated at conditions and with catalysts selected for conducting dehydrocyclization, isomerization and dehydrogenation reactions for converting low octane normal paraffins and cycloparaffms into high octane materials. In this way, a product having increased octane and/or containing an increased amount of aromatics is produced.
- the multi-stage reforming process is operated at conditions and with one more catalysts for producing a net positive quantity of hydrogen.
- the multi-stage reforming process comprises passing a refinery stream through at least two reforming stages in series.
- each reforming stage is characterized by one or more reforming reactor vessels, each containing a catalyst and maintained at reforming reaction conditions.
- the product from each stage before the final stage is passed, in whole or in part, to the succeeding stage in the multi-stage process.
- the temperature of the product from each stage which is passed to a succeeding stage may be increased or decreased to meet the particular needs of the process.
- the pressure of the product which is passed to a succeeding stage before the final stage may be increased or decreased, with the proviso that the pressure in the penultimate stage is higher than the pressure in the final stage.
- boiling point temperatures are based on ASTM D-
- the mid-boiling point is defined as the 50% by volume boiling temperature, based on an ASTM D-2887 simulated distillation.
- carbon number values i.e. Cs, Ce, Cg, C 9 and the like
- Cs, Ce, Cg, C 9 and the like may be determined by standard gas chromatography methods.
- feed rate to a catalytic reaction zone is reported as the volume of feed per volume of catalyst per hour.
- the feed rate as disclosed herein, referred to as liquid hourly space velocity (LHSV) is reported in reciprocal hours (i.e. hr ' ).
- a C 4 - stream comprises a high proportion of hydrocarbons with 4 or fewer carbon atoms per molecule.
- a Cs+ stream comprises a high proportion of hydrocarbons with 5 or more carbon atoms per molecule.
- hydrocarbon streams in refinery processes are generally separated by boiling range using a distillation process.
- the C4- stream would be expected to contain a small quantity OfC 5 , Ce and even C7 molecules.
- a typical distillation would be designed and operated such that at least about 70% by volume of a Gj- stream would contain molecules having 4 carbon atoms or fewer per molecule.
- Cs+, Cg-Ce, C 9 + and other hydrocarbon fractions identified by carbon number ranges would be interpreted likewise.
- silicon to alumina ratio refers to the molar ratio of silicon oxide (S1O 2 ) to aluminum oxide (AI 2 O 3 ).
- molecular sieve refers to a crystalline material containing pores, cavities, or interstitial spaces of a uniform size in which molecules small enough to pass through the pores, cavities, or interstitial spaces are adsorbed while larger molecules are not.
- molecular sieves include zeolites and non-zeolitic molecular sieves such as zeolite analogs including, but not limited to, SAPOs (silicoaluminophosphates), MeAPOs (metalloaluminophosphates), AIPO 4 , and ELAPOs (nonmetal substituted aluminophosphate families).
- the present invention is based on the discovery that selective reforming of paraffins, especially C ⁇ -C ⁇ paraffins, in a separate or additional reforming stage provides improved performance of the overall reforming process.
- a penultimate reforming stage using a conventional reforming catalyst is operated at relatively low severity, since it is not required to reach the high octane levels normally desired for a naphtha fuel or fuel blend stock. Under these conditions the catalyst catalyzes the more facile reactions, such as cyclohexane and alkycyclohexane dehydrogenation, while keeping hydrocracking to a minimum.
- a conventional catalyst used to dehydrocyclize paraffins under more severe conditions produces higher quantities of light gases, on account of the catalyst being somewhat unselective for dehydrocyclization.
- an intermediate reformate from a penultimate reforming stage is passed to a final reforming stage containing a medium pore molecular sieve catalyst.
- the performance characteristics of the medium pore molecular sieve catalyst permits operating a final stage in the multi-stage reforming process at a reduced pressure, which increases the selectivity of Ce-Cg paraffin dehydrocyclization while maintaining low catalyst fouling rates.
- the C9+ fraction from the penultimate stage has higher octane than the the high octane C 9 + fraction from the penultimate stage will undergo some cracking and/or dealkylation reactions in the final stage, which lowers the liquid yield and consumes hydrogen. Consequently, the performance characteristics of the catalyst of the final stage provide complementary benefits, resulting in an overall process which produces a high octane product at an improved liquid yield and hydrogen production.
- the naphtha boiling range feedstock entering the penultimate stage of the multi-stage process is a naphtha fraction boiling within the range from about of 50° to about 55O 0 F and preferably from 70° to 45O 0 F.
- the reformer feed is a Cs+ feed.
- the reformer feed can include, for example, straight run naphthas, paraffinic raffmates from aromatic extraction or adsorption, and Ce-Cio paraffin-rich feeds, bioderived naphtha, naphtha from hydrocarbon synthesis processes, including Fischer Tropsch and methanol synthesis processes, as well as naphtha products from other refinery processes, such as hydrocracking or conventional reforming.
- the reformer feed may comprise at least a portion of the product generated in a preceding stage.
- the reforming catalyst used in the penultimate reforming stage may be any catalyst known to have catalytic reforming activity.
- the penultimate stage catalyst comprises a Group VIII metal disposed on an oxide support.
- Example Group VIII metals include platinum and palladium.
- the catalyst may further comprise a promoter, such as rhenium, tin, germanium, cobalt, nickel, iridium, tungsten, rhodium, ruthenium, or combinations thereof.
- the promoter metal is rhenium or tin.
- These metals are disposed on a support, such as alumina, silica/alumina, or silica. In some such embodiments, the support is alumina.
- the support may also include natural or man-made zeolites.
- the catalyst may also include between 0.1 and 3 weight percent chloride, preferably between 0.5 and 1.5 weight percent chloride.
- the catalyst if it includes a promoter metal, suitably includes sufficient promoter metal to provide a promoter to platinum ratio between 0.5:1 and 10:1 or between 1 :1 and 6:1.
- the precise conditions, compounds, and procedures for catalyst manufacture are known to those persons skilled in the art.
- Some examples of conventional catalysts are shown in U.S. Patents Nos. 3,631,216; 3,415,737; and 4,511,746, which are hereby incorporated by reference in their entireties.
- the catalysts in both the penultimate stage and the final stage may be employed in the form of pills, pellets, granules, broken fragments, or various special shapes, disposed as a fixed bed within a reaction zone, and the charging stock may be passed therethrough in the liquid, vapor, or mixed phase, and in either upward, downward or radial flow.
- they can be used in moving beds or in fluidized-solid processes, in which the charging stock is passed upward through a turbulent bed of finely divided catalyst.
- a fixed bed system or a dense-phase moving bed system are preferred due to the lower catalyst attrition losses and other operational advantages.
- the feed is preheated (by any suitable heating means) to the desired reaction temperature and then passed into a reaction zone containing a fixed bed of the catalyst.
- This reaction zone may be one or more separate reactors with suitable means to maintain the desired temperature at the reactor entrance. The temperature must be maintained because reforming reactions are typically endothermic in nature.
- the penultimate stage is maintained at relatively mild reaction conditions, so as to inhibit the cracking of the stream being upgraded, and to increase the useful lifetime of the catalyst in the penultimate stage.
- the naphtha boiling range feedstock to be upgraded in the penultimate stage contacts the penultimate stage catalyst at reaction conditions, which conditions include a temperature in the range from about 800 0 F to about 1100 0 F, a pressure in the range from greater than 70 psig to about 400 psig, and a feed rate in the range of from about 0.5 hr -1 to about 5 hr ⁇ LHSV.
- the pressure in the penultimate stage is in the range from about 200 psig to about 400 psig.
- the effluent from the penultimate stage is an upgraded product, in that the RON has been increased during reaction in the penultimate stage.
- the penultimate stage effluent comprises hydrocarbons and hydrogen generated during reaction in the penultimate stage and at least some of the hydrogen, if any, which is added to the feed upstream of the penultimate stage.
- the effluent hydrocarbons may be characterized as a mixture of C 4 - hydrocarbons and C 5 + hydrocarbons, the distinction relating to the molecular weight of the hydrocarbons in each group.
- the C 5 + hydrocarbons in the effluent have a combined RON of at least 85.
- penultimate effluent comprises C 5 + hydrocarbons which are separated into at least an intermediate reformate and a heavy reformate.
- the effluent further comprises hydrogen and C 4 - hydrocarbons.
- a hydrogen-rich stream may separate from the effluent in a preliminary separation step, using, for example, a high pressure separator or other flash zone.
- C4- hydrocarbons in the effluent may also be separated in a preliminary separation, either along with the hydrogen or in a subsequent flash zone.
- the intermediate reformate is characterized as having a lower mid-boiling point than that of the heavy reformate. In some embodiments, the intermediate reformate boils in the range from about 7O 0 F to about 28O 0 F.
- the intermediate reformate comprises at least 70 vol% C 5 -Cs hydrocarbons. In some embodiments, the intermediate reformate boils in the range from about 100 0 F to about 280 0 F. In some such embodiments, the intermediate reformate comprises at least 70 vol% C 6 -Cs hydrocarbons. In some embodiments, the intermediate reformate boils in the range from about 100 0 F to about 23O 0 F. In some such embodiments, the intermediate reformate comprises at least 70 vol% Ce-C 7 hydrocarbons. Recovery of an intermediate reformate fraction may be accompanied by the further recovery of a largely Cs light reformate fraction. The light reformate is characterized as having a lower mid-boiling point than that of the intermediate reformate.
- the light reformate fraction boils in the range from about 70 0 F to about 14O 0 F. In some such embodiments, the light reformate fraction comprises at least 70 vol% Cs hydrocarbons.
- the heavy reformate that is produced during separation of the upgraded product boils in the range of about 220 0 F and higher. In some such embodiments, the heavy reformate comprises at least 70 vol% C 9 + hydrocarbons.
- the RON of the intermediate reformate is indicative of the mild reforming conditions in the penultimate stage.
- the intermediate reformate typically has an RON of greater than 65.
- the intermediate reformate has an RON within the range of about 65 to less than 100.
- the intermediate reformate has an RON within the range of 65 to less than 95.
- the final stage reforming catalyst comprises at least one medium pore molecular sieve.
- the molecular sieve is a porous inorganic oxide characterized by a crystalline structure which provides pores of a specified geometry, depending on the particular structure of each molecular sieve.
- the phrase "medium pore” as used herein means having a crystallographic free diameter in the range of from about 3.9 to about 7.1 Angstrom when the porous inorganic oxide is in the calcined form.
- the crystallographic free diameters of the channels of molecular sieves are published in the "Atlas of Zeolite Framework Types", Fifth Revised Edition, 2001, by Ch. Baerlocher, W. M. Meier, and D. H.
- Non-limiting examples of medium pore molecular sieves include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48 MCM-22, SSZ-20, SSZ-25, SSZ-32, SSZ-35, SSZ-37, SSZ-44, SSZ-45, SSZ-47, SSZ-57, SSZ-58, SSZ-74, SUZ-4, EU-I, NU-85, NU-87, NU-88, IM-5, TNU-9, ESR-10, TNU-10 and combinations thereof.
- the medium pore molecular sieve useful in the present process is a high silica ZSM-5 zeolite with a molar ratio of S1O 2 /M 2 O 3 of at least 40: 1 , preferably at least 200: 1 and more preferably at least 500:1, where M is selected from Al, B, or Ga.
- the high silica ZSM-5 molecular sieve which is useful as a component of the catalyst in the present process has a molar silica to alumina molar ratio of at least 40:1, or at least 200:1, or at least 500:1.
- An example high silica molecular sieve has a silica to alumina molar ratio of at least 1000:1.
- the molecular sieve is characterized as having a crystallite size less than 10 ⁇ m, or less man 5 ⁇ m or less than 1 ⁇ m.
- Methods for determining crystallite size using, for example Scanning Electron Microscopy, are well known.
- the high silica ZSM-5 is characterized as having at least 80% crystallinity, or at least 90% crystallinity, or at least 95% crystallinity.
- Methods for determining crystallinity, using, for example, X-ray Diffraction are well known. Strong acidity is undesirable in the catalyst because it promotes cracking, resulting in lower selectivity to Cs+ liquid product.
- the molecular sieve preferably contains an alkali metal and/or an alkaline earth metal.
- the alkali or alkaline earth metals are preferably incorporated into the catalyst during or after synthesis of the molecular sieve.
- at least 90% of the acid sites are neutralized by introduction of the metals, more preferably at least 95%, most preferably at least 99%,
- the medium pore molecular sieve has less than 5,000 ppm alkali.
- Such medium pore silicate molecular sieves are disclosed, for example, in U.S. Patent No. 4,061,724 and in U.S. Patent No. 5,182,012.
- SSZ-20 is disclosed in U.S. Pat. No. 4,483,835, and SSZ-23 is disclosed in U.S. Pat. No. 4,859,442, both of which are incorporated herein by reference.
- ZSM-5 is more particularly described in U.S. Pat. No. 3,702,886 and
- ZSM-12 is more particularly described in U.S. Pat. No. 3,832,449, the entire contents of which are incorporated herein by reference.
- ZSM-23 is more particularly described in U.S. Pat. No. 4,076,842, the entire contents of which are incorporated herein by reference.
- ZSM-35 is more particularly described in U.S. Pat. No. 4,016,245, the entire contents of which are incorporated herein by reference.
- ZSM-38 is more particularly described in U.S. Pat. No. 4,046,859, the entire contents of which are incorporated herein by reference.
- ZSM-48 is more particularly described in U.S. Pat. No. 4,397,827 the entire contents of which are incorporated herein by reference.
- the crystalline molecular sieve may be in the form of a borosilicate, where boron replaces at least a portion of the aluminum of the more typical aluminosilicate form of the molecular sieve.
- Borosilicate molecular sieves are described in U.S. Pat. Nos. 4,268,420; 4,269,813; 4,327,236 to Klotz, the disclosures of which patents are incorporated herein, particularly those disclosures related to borosilicate preparation.
- SAPOs Silicoaluminophosphates
- SAPOs comprise a molecular framework of corner-sharing [SiO 4 ] tetrahedra, [AlO 4 ] tetrahedra and [PO 4 ] tetrahedra linked by oxygen atoms.
- P/Al and Si/Al By varying the ratio of P/Al and Si/Al the acidity of the SAPO can be modified to minimize unwanted hydrocracking and maximize advantageous isomerization reactions.
- Preferred molar ratios of P/Al are from about 0.75 to 1.3 and preferred molar ratios of Si/Al are from about 0.08 to 0.5.
- Examples of a silcoaluminophosphate useful to the present invention include SAPO- 11, SAPO-31, and SAPO-41, which are also disclosed in detail in U.S. Pat. No. 5,135,638.
- the catalysts used in the final reforming stage according to the present invention contain one or more Group VIII metals, e.g., nickel, ruthenium, rhodium, palladium, iridium or platinum.
- the preferred Group VIII metals are iridium, palladium, and particularly platinum. They are more selective with regard to dehydrocyclization and are also more stable under the dehydrocyclization reaction conditions than other Group VIII metals.
- the preferred percentage of the Group VIII metals, such as platinum, in the catalyst is between 0.1 wt.% and 5 wt.%, more preferably from 0.3 wt.% to 2.5 wt.%.
- the catalyst may further comprise a promoter, such as rhenium, tin, germanium, cobalt, nickel, indium, tungsten, rhodium, ruthenium, or combinations thereof.
- the crystalline zeolite is preferably bound with a matrix.
- the matrix is not catalytically active for hydrocarbon cracking.
- Satisfactory matrices include inorganic oxides, including alumina, silica, naturally occurring and conventionally processed clays, such as bentonite, kaolin, sepiolite, attapulgite and halloysite. Such materials have few, if any, acid sites and therefore have little or no cracking activity.
- reaction conditions in the final reforming stage are specified to effectively utilize the particular performance advantages of the catalyst used in the stage.
- the reaction pressure of the final reforming stage is less than the pressure in the penultimate stage.
- Operating the final reforming stage at a lower pressure is made possible, at least in part, by the high catalytic stability of the medium pore molecular sieve catalyst of the present invention, which permits the catalyst to operate at lower pressures without significant fouling and premature activity failure. This, in turn, permits the operation of the penultimate stage at relatively mild conditions, providing long catalyst life and high vieids of hvdrneen and desired hi eh octane nroducts.
- the naphtha feed to the final stage is the intermediate reformate which is separated from the effluent of the penultimate stage.
- the intermediate reformate contacts the catalyst in the final stage at reforming reaction conditions, which reaction conditions include a temperature in the range from about 800 0 F to about HOO 0 F, a pressure in the range from about 50 psig to about 250 psig and a feed rate in the range of from about 0.5 hr -1 to about 5 hr -1 LHSV.
- the pressure in the reforming stage is less than 100 psig. Hydrogen may be added as an additional feed to the final reforming stage, but it is not required.
- hydrogen added with the feed is recovered from the process for separating the final stage effluent and is recycled to the final stage.
- the final stage is operated at conditions to maintain a molar H 2 /hydrocarbon ratio in the range of 1 : 1 to 10:1.
- a molar H 2 /hydrocarbon ratio in the range of 1 :1 to 4:1 is exemplary.
- final effluent from the final reforming stage may contain light (i.e. C4- products and/or hydrogen) products which may be removed from the reformate in a final separation step prior to further processing for blending or use as a fuel.
- a hydrogen- rich stream may be separated from the effluent prior to the separation step, using, for example, a high pressure separator or other flash zone.
- C4- hydrocarbons in the effluent may also be separated in a preliminary flash zone, either along with the hydrogen or in a subsequent flash zone.
- the reformate which is produced in the final reforming stage has an increased RON relative to that of the intermediate reformate which is the feed to the final reforming stage.
- the RON of the final reformate is at least 90 or at least 95, or at least 98.
- the final reformate boils in the range from about 7O 0 F to about 280 0 F.
- the final reformate comprises at least 70 vol% C 5 -C 8 hydrocarbons.
- the final reformate boils in the range from about 100 0 F to about 280 0 F.
- the final reformate comprises at least 70 vol% Ce- Cg hydrocarbons.
- the final reformate boils in the range from about 100 0 F to about 230 0 F.
- the final reformate comprises at least 70 vol% C 6 -C 7 hydrocarbons.
- a final light stream may also be recovered from the final effluent.
- the final light stream boils in the range of about 70° to about 14O 0 F.
- the reformate is useful as a fuel or as a blend stock for a fuel.
- at least a portion of the reformate from the final reforming stage is blended with at least a portion of the heavy reformate, which is recovered from the penultimate reforming stage; the blend may be used as a fuel or as a blend stock for a fuel.
- a naphtha boiling range fraction 5 which boils within the range of 5O 0 F to 550 0 F passes into the reaction stage 10 at a feed rate in the range of about 0.5 hr -1 to about 5 hr *1 LHSV.
- Reaction conditions in the reforming stage 10 include a temperature in the range from about 800 0 F to about 1100 0 F and a total pressure in the range of greater than 70 psig to about 400 psig.
- the effluent 11 from the penultimate stage is an upgraded product, ⁇ i that the RON has been increased during reaction in the penultimate stage 10,
- the penultimate stage effluent 11 comprises hydrocarbons and hydrogen generated during reaction in the penultimate stage and at least some of the hydrogen (if any) added to the feed upstream of the penultimate stage.
- the effluent is separated in separation zone 20 into a hydrogen-rich stream 21, a C 4 - stream 22, an intermediate reformate 25 and a heavy reformate 26.
- this separation occurs in a single separation zone.
- this separation is done in sequential zones, with the hydrogen, and optionally the C 4 - stream, separated in one or more preliminary separation zones prior to the separation of the intermediate reformate 25 and the heavy reformate 26.
- the intermediate reformate 25 comprises a substantial amount of the Cs-Cg hydrocarbons contained in the effluent, with smaller quantities of C 4 and C 9 hydrocarbons. At least a portion of intermediate reformate 25 is passed to final reforming stage 30. Heavy reformate 26 contains a substantial amount of the C9+ hydrocarbons contained in the effluent 11, and has an RON of greater than 98, preferably greater than 100.
- Intermediate reformate 25 is passed to final reforming stage 30 for contact with a catalyst comprising platinum and at least one medium pore molecular sieve, at reaction conditions which include a temperature in the range from about 80O 0 F to about 1100 0 F and a pressure in the range from about 50 psig to about 250 psig.
- Effluent 31 from the final reforming stage is separated in separation zone 40, yielding at least a hydrogen-rich stream 41, a C4- stream 42, and a final reformate stream 45.
- the final reformate stream boils in the C5+ boiling range. As described above, this separation may take place in one, or multiple, separation zones, depending on the specific requirements of a particular process.
- the final reformate stream 45 may be further combined with the heavy reformate 26 before further processing or use as a fuel or fuel blend stock.
- Hydrogen-rich stream 41 is combined with hydrogen-rich stream 21 before using in other refinery processes, and C + - stream 42 is combined with C 4 - stream 22.
- a naphtha boiling range fraction 5 which boils within the range of 50F° to 550 0 F passes into the reaction stage 10 at a feed rate in the range of about 0.5 hr -1 to about 5 hr -1 LHSV.
- Reaction conditions in the reforming stage 10 include a temperature in the range from about 800 0 F to about 1100 0 F and a total pressure in the range of greater than 70 psig to about 400 psig.
- the effluent 11 from the penultimate stage is an upgraded product, in that the RON has been increased during reaction in the penultimate stage 10.
- the penultimate stage effluent 11 comprises hydrocarbons and hydrogen generated during reaction in the penultimate stage and at least some of the hydrogen (if any) added to the feed upstream of the penultimate stage.
- the effluent is separated in separation zone 20 into a hydrogen-rich stream 21, a C4- stream 22, a light reformate 23, an intermediate reformate 24 and a heavy reformate 26.
- this separation occurs in a single separation zone.
- this separation is done in sequential zones, with the hydrogen, and optionally the C 4 - stream, separated in one or more preliminary separation zones prior to the separation of the light reformate 23, the intermediate reformate 24 and the heavy reformate 26.
- the light reformate 23 comcrises a substantial amount of the C « hydrocarbons contained in the effluent, with smaller quantities of C ⁇ and C 6 hydrocarbons.
- the intermediate stream comprises a substantial portion of the Ce - Ce hydrocarbons contained in the effluent; the heavy reformate 26 contains a substantial amount of the Cg+ hydrocarbons contained in the effluent 11.
- Intermediate reformate 24 is passed to final reforming stage 30 at a feed rate in the range of from about 0.5 hr -1 to about 5 hr -1 LHSV, for contact with a catalyst comprising platinum and at least one medium pore molecular sieve, at reaction conditions which include a temperature in the range from about 800 0 F to about 1100 0 F and a pressure in the range from about 50 psig to about 250 psig.
- Effluent 31 from the final reforming stage is separated in separation zone 40, yielding at least a hydrogen-rich stream 41, a C4- stream 42, a final Cs stream 43 and a final reformate stream 44.
- the final reformate stream boils in the C 6 + boiling range. As described above, this separation may take place in one, or multiple, separation zones, depending on the specific requirements of a particular process. As shown in the embodiment illustrated in Fig.
- the final reformate stream 44 is further combined with the heavy reformate 26 before further processing or use as a fuel or fuel blend stock
- hydrogen-rich stream 41 is combined with hydrogen-rich stream 21 before using in other refinery processes
- C4- stream 42 is combined with C 4 - stream 22
- final C 5 stream 43 is combined with C 5 stream 23.
- the Cj+ liquid product from Example 1 was distilled into an intermediate reformate and a heavy reformate.
- the intermediate reformate was found to represent 80 vol.% of the Cs+ liquid product from Example 1.
- the intermediate reformate having an API of 55.7, an RON of 85 and an ASTM D-2887 simulated distillation as shown in Table 3, was used as feed to a final reforming stage in Example 3 and Comparative Example 1.
- the heavy reformate was found to represent 20 vol.% of the C5+ liquid product from Example 1.
- the heavy reformate had an API of 28.9 and an RON of 105, and is further described in Table 5.
- Example 2 The intermediate reformate produced in Example 2 was used as feed to the final reforming stage which used a ZSM-5 zeolite based catalyst composited with 35% alumina binder material.
- the ZSM-5 had a SiO2/A12O3 molar ratio of -2000 and was ion exchanged to the ammonium form before incorporating in a 65% zeolite/35% alumina extrudate.
- the extrudate was impregnated with 0.8% Pt, 0.3% Na, and 0.3% Mg by an incipient wetness procedure to make the final catalyst.
- Table 4 Comparison of the results from Example 3 and Comparative Example 1
- Example 2 The intermediate reformate produced in Example 2 was contacted with a commercial platinum/rhenium on alumina based catalyst described in Example 1 in a final reforming stage.
- the reaction conditions and experimental results are listed in Table 4 and compared with the results from Example 3 which uses a ZSM-5 zeolite based catalyst.
- Example 3 and Comparative Example 1 show the benefit of ZSM-5 zeolite based catalysts when compared with commercial platinum on alumina catalysts in terms of C 5 + yield and hydrogen production at similar C 5 + RON.
- Example 2 A product which was produced in the final stage reforming of the intermediate reformate in Example 3 was blended with the heavy reformate (Example 2) which was not subjected to the final stage reforming.
- the total RON of Cs+, total C5+ yield and total H2 production of the blended final product are given in Table 5 based on using the total Cs+ penultimate effluent as feed (which is distilled into intermediate reformate and heavy reformate in Example 2).
- the results are compared to those obtained from Comparative Example 2 where the total C 5 + product was produced from the total Cs+ penultimate effluent as feed, without distillation into an intermediate and heavy reformate.
- Example 2 The total C$+ product produced in Example 1 , without distillation into an intermediate and heavy reformate, was contacted with a ZSM-5 zeolite based catalyst described in Example 3 in a final reforming stage at 93O 0 F, 80 psig, 2:1 molar ratio of hydrogen to hydrocarbon and 1.5 hr -1 LHSV feed rate.
- the C 5 + liquid yield was 89.9 wt,% and RON of the Cj+ liquid product from the final reforming stage was 97.4.
- the hydrogen production was 190 standard cubic feet per barrel feed.
- Example 5 the results from Example 4, where the final product was is a blend from (i) the product produced in the final stage reforming of the intermediate reformate in Example 3 and (ii) the heavy reformate (Example 2) which was not subjected to the final stage reforming, are compared to those obtained from Comparative Example 2, where the total Cj-f product was produced from the total C 5 + penultimate effluent as feed, without distillation into an intermediate and heavy reformate.
- Example 3 RON of C 5 +, C 5 + yield and H ⁇ production of the product are given based on the intermediate reformate as feed.
- Example 4 Total RON of C 5 +, total C 5 + yield and total H 2 production are given based on the total C 5 + penultimate effluent as feed (which is distilled into intermediate reformate and heavy reformate in Example 2).
- the final product of Example 4 consists of a blend of (i) the product from the final stage reforming of the intermediate reformate and (ii) the heavy reformate which is not subjected to the final stage reforming.
- Example 4 and Comparative Example 2 show the benefit of the intermediate reformate as feed to the final reforming stage when compared with using the full boiling range C 5 + feed, with the ZSM-5 zeolite based catalyst, in terms of C 5 + yield, hydrogen production and C 5 + RON.
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
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Priority Applications (5)
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CN2009801278859A CN102099444A (en) | 2008-06-05 | 2009-05-12 | Catalytic reforming process to produce high octane gasoline |
CA2726912A CA2726912A1 (en) | 2008-06-05 | 2009-05-12 | Catalytic reforming process to produce high octane gasoline |
AU2009255498A AU2009255498A1 (en) | 2008-06-05 | 2009-05-12 | Catalytic reforming process to produce high octane gasoline |
EP09758936A EP2310475A1 (en) | 2008-06-05 | 2009-05-12 | Catalytic reforming process to produce high octane gasoline |
JP2011512505A JP2011522927A (en) | 2008-06-05 | 2009-05-12 | Catalytic reforming process for high-octane gasoline production |
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US12/134,131 | 2008-06-05 | ||
US12/134,131 US20090301933A1 (en) | 2008-06-05 | 2008-06-05 | Catalytic reforming process to produce high octane gasoline |
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US (1) | US20090301933A1 (en) |
EP (1) | EP2310475A1 (en) |
JP (1) | JP2011522927A (en) |
CN (1) | CN102099444A (en) |
AU (1) | AU2009255498A1 (en) |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109569714A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of F- T synthesis naphtha reforming catalyst and preparation method thereof |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US8658021B2 (en) | 2008-06-05 | 2014-02-25 | Chevron U.S.A. Inc. | Multi-stage reforming process to produce high octane gasoline |
US8366909B2 (en) * | 2009-02-26 | 2013-02-05 | Chevron U.S.A. Inc. | Reforming process at low pressure |
US8222473B1 (en) * | 2011-12-22 | 2012-07-17 | Chevron U.S.A. Inc. | Isomerization of light paraffins |
US9266091B2 (en) * | 2012-03-29 | 2016-02-23 | Uop Llc | Reforming catalysts with tuned acidity for maximum aromatics yield |
US8926735B1 (en) * | 2014-01-30 | 2015-01-06 | Chevron U.S.A. Inc. | Separation of gases using zeolite SSZ-45 |
US20160145507A1 (en) * | 2014-11-20 | 2016-05-26 | Chevron U.S.A. Inc. | Two-stage reforming process configured for increased feed rate to manufacture reformate and benzene |
US20160145506A1 (en) * | 2014-11-20 | 2016-05-26 | Chevron U.S.A. Inc. | Two-stage reforming process configured for increased feed rate to manufacture reformate |
CN107971016B (en) * | 2016-10-21 | 2019-10-25 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof containing phosphorous IMF structure molecular screen |
RU2748456C1 (en) * | 2020-07-13 | 2021-05-25 | Общество с ограниченной ответственностью "ЭНЕРДЖИ ЭНД ИНЖИНИРИНГ" | Method for processing hydrocarbon raw materials |
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- 2009-05-12 AU AU2009255498A patent/AU2009255498A1/en not_active Abandoned
- 2009-05-12 CN CN2009801278859A patent/CN102099444A/en active Pending
- 2009-05-12 EP EP09758936A patent/EP2310475A1/en not_active Withdrawn
- 2009-05-12 JP JP2011512505A patent/JP2011522927A/en active Pending
- 2009-05-12 CA CA2726912A patent/CA2726912A1/en not_active Abandoned
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US3729409A (en) * | 1970-12-24 | 1973-04-24 | Mobil Oil Corp | Hydrocarbon conversion |
US3770614A (en) * | 1971-01-15 | 1973-11-06 | Mobil Oil Corp | Split feed reforming and n-paraffin elimination from low boiling reformate |
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CN109569714A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of F- T synthesis naphtha reforming catalyst and preparation method thereof |
CN109569714B (en) * | 2017-09-28 | 2021-11-16 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis naphtha conversion catalyst and preparation method thereof |
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CA2726912A1 (en) | 2009-12-10 |
EP2310475A1 (en) | 2011-04-20 |
JP2011522927A (en) | 2011-08-04 |
AU2009255498A1 (en) | 2009-12-10 |
US20090301933A1 (en) | 2009-12-10 |
CN102099444A (en) | 2011-06-15 |
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