EP0616633A4 - Fixed-bed/moving-bed two stage catalytic reforming. - Google Patents
Fixed-bed/moving-bed two stage catalytic reforming.Info
- Publication number
- EP0616633A4 EP0616633A4 EP93900921A EP93900921A EP0616633A4 EP 0616633 A4 EP0616633 A4 EP 0616633A4 EP 93900921 A EP93900921 A EP 93900921A EP 93900921 A EP93900921 A EP 93900921A EP 0616633 A4 EP0616633 A4 EP 0616633A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- reforming
- stage
- stream
- catalyst
- bed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000001833 catalytic reforming Methods 0.000 title description 5
- 238000002407 reforming Methods 0.000 claims abstract description 129
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 26
- 230000008929 regeneration Effects 0.000 claims abstract description 23
- 238000011069 regeneration method Methods 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000376 reactant Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 238000000895 extractive distillation Methods 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims 3
- 239000007789 gas Substances 0.000 abstract description 19
- 239000007788 liquid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000006057 reforming reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- -1 chloride Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- ILVUABTVETXVMV-UHFFFAOYSA-N hydron;bromide;iodide Chemical compound Br.I ILVUABTVETXVMV-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention relates to a two stage process for catalytically reforming a gasoline boiling range hydrocarbonaceous feedstock.
- the reforming is conducted in two stages wherein the first stage is operated in a fixed bed mode, and the second stage is operated in a moving-bed continual catalyst regeneration mode.
- a gaseous stream comprised of hydrogen and predominantly C 4 " hydrocarbon gases are separated between stages and at least a portion of it is recycled.
- Catalytic reforming is a well established refinery process for improving the octane quality of naphthas or straight run gasolines. Reforming can be defined as the total effect of the molecular changes, or hydrocarbon reactions, produced by dehydrogenation of cyclohexanes, dehydroisomerization of alkylcyclopentanes, and dehydrocyclization of paraffins and olefins to yield aro atics; isomerization of substituted aro atics; and hydrocracking of paraffins which produces gas, and inevitably coke, the latter being deposited on the catalyst.
- a multifunctional catalyst which contains a metal hydrogenation-dehydrogenation (hydrogen transfer) component, or components, usually platinum, substantially atomically dispersed on the surface of a porous, inorganic oxide support, such as alumina.
- the support which usually contains a halide, particularly chloride, provides the acid functionality needed for isomerization, cyclization, and hydrocracking reactions.
- Reforming reactions are both endothermic and exothermic, the former being predominant, particularly in the early stages of reforming with the latter being predominant in the latter stages.
- a reforming unit comprised of a plural ty of serially connected reactors with provision for heating the reaction stream as it passes from one reactor to another.
- Fixed-bed reactors are usually employed in semi- regenerative and cyclic reforming, and moving-bed reactors in continuous reforming.
- the entire reforming process unit is operated by gradually and progressively increasing the temperature to compensate for deactivation of the catalyst caused by coke deposition, until finally the entire unit is shut-down for regeneration and reactivation of the catalyst.
- cyclic reforming the reactors are individually isolated, or in effect swung out of line, by various piping arrangements. The catalyst is regenerated by removing coke deposits, and then reactivated while the other reactors of the series remain on stream. The "swing reactor” temporarily replaces a reactor which is removed from the series for regeneration and reactivation of the catalyst, which is then put back in the series.
- the reactors are moving-bed reactors, as opposed to fixed-bed reactors, with continuous addition and withdrawal of catalyst. The catalyst descends the reactor in an annular bed and is passed to a regeneration zone where it is regenerated, the sent back to the reforming zone. This cycle is continuously repeated.
- U.S. Patent No. 3,992,465 teaches a two stage reforming ' process wherein the first stage is comprised of at least one fixed-bed reforming zone and the second stage is comprised of a moving-bed reforming zone.
- the teaching of U.S. Patent No. 3,992,465 is primarily to subject the reformate, after second stage reforming to a series of fractionations and an extractive distillation of the C 6 -C 7 cut to obtain an aromatic-rich stream.
- the catalyst may be either onofunctional or bifunctional.
- the Group VIII noble metal for catalysts in all stages is platinum and the catalyst of the first stage is comprised of platinum and tin on substantially spherical alumina support particles.
- an aromatics-rich stream is separated and collected between stages and the remaining aromatics-1ean stage is sent to second stage reforming.
- the sole figure hereof depicts a simplified flow diagram of a preferred reforming process of the present invention.
- the reforming process unit is comprised of a first stage which includes a lead reforming zone, which is represented by a lead fixed-bed reactor, and a first downstream fixed-bed reforming zone, which is represented by another fixed-bed reactor, which first stage is operated in semi- regenerative mode, but which may also be designed to operate in a cyclic mode.
- There is also a second stage which contains two serially connected moving-bed reforming zones in fluid communication with a regeneration zone, which reforming zones are represented by annular radial flow reactors wherein the catalyst continuously descends through the reactors and is transported to the regeneration zone, then back to the reactors, etc.
- Feedstocks also sometimes referred to herein as reactant streams, which are suitable for reforming in accordance with the instant invention are any hydrocarbonaceous feedstocks boiling in the gasoline range.
- feedstocks include the light hydrocarbon oils boiling from about 70° F to about 500° F, preferably from about 180° F to about 400° F, for example straight run naphthas, synthetically produced naphthas such as coal and oil-shale derived naphthas, thermally or catalytically cracked naphthas, hydrocracked naphthas, or blends or fractions thereof.
- a gasoline boiling range hydrocarbon reactant stream which is preferably first hydrotreated by any conventional hydrotreating method to remove undesirable components such as sulfur and nitrogen, is passed to a first reforming stage represented by heater or preheat furnaces, F, and F 2 , and reactors R, and R 2 .
- a reforming stage as used herein, is any one or more of a particular type of reforming zone, in this figure reactors, and its associated equipment (e.g., preheat furnaces etc.). That is, each reforming stage will contain one or more of the same type of reactor, for example, fixed-bed or moving-bed, but not both.
- the reactant stream is fed into heater, or preheat furnace, F lt via line 10 where it is heated to an effective reforming temperature. That is, to a temperature high enough to initiate and maintain dehydrogenation reactions, but not so high as to cause excessive hydrocracking.
- the heated reactant stream is then fed, via line 12, into reforming zone R x which contains a catalyst suitable for reforming.
- a catalyst typically contains at least one Group VIII noble metal, preferably platinum, with or without a promoter metal, on a refractory support, preferably alumina. Reforming zone R lf as well as all the other reforming zones in this first stage, are operated at reforming conditions.
- Typical reforming operating conditions for the reactors of this first fixed-bed stage include temperatures from about 800° to about 1200° F; pressures from about 100 psig to about 500 psig, preferably from about 150 psig to about 300 psig; a weight hourly space velocity (WHSV) of about 0.5 to about 20, preferably from about 0.75 to about 5 and a hydrogen to oil ratio of about 1 to 10 moles of hydrogen per mole of C 5 * feed, preferably 1.5 to 5 moles of hydrogen per mole of C 5 * feed.
- WHSV weight hourly space velocity
- the effluent stream from reforming zone R. is fed to preheat furnace F 2 via line 14, then to reforming zone R 2 via line 16. Because reforming reactions are typically endothermic, the reactant stream must be reheated to reforming temperatures between reforming zones.
- the effluent stream from this first stage is sent to cooling zone K, via line 18 where it is cooled to condense a liquid phase to a temperature within the operating range of the recycle gas separation zone, which is represented in the Figure hereof by a separation drum S x .
- the temperature will generally range from about 60° to about 300°F, preferably from about 80 to 125°F.
- the cooled effluent stream is then fed to separation zone Si via line 20 where a gaseous stream and a heavier liquid stream are produced.
- the preferred separation would result in a hydrogen-rich predominantly C 4 ⁇ gaseous stream and a predominantly C 5 + liquid stream. It is understood that these streams are not pure streams.
- the separation zone will not provide complete separation between the C 4 " components and the C 5 + liquids.
- the gaseous stream will contain minor amounts of C 5 + components and the liquid stream will contain minor amounts of C 4 ⁇ components and hydrogen.
- a portion of the gaseous stream which can be characterized as being a hydrogen-rich C 4 ⁇ gaseous stream, is recycled, via line 22, to line 10 by first passing it through compressor C j to increase its pressure to feedstock pressure.
- the unit is pressured-up with hydrogen from an independent source until enough hydrogen can be generated in the first stage for recycle. It is preferred that the first stage be operated in semi-regenerative mode, although a cyclic mode can also be used.
- the remaining hydrogen-rich predominantly C 4 ⁇ gaseous stream from separation zone S L is passed to the second reforming stage via pressure control valve 26 where pressure is reduced to the level required for second stage operation.
- the amount of pressure reduction will depend on the operating pressure of the second stage separation zone S 2 and the pressure drop in furnaces F 3 and F 4 , reactors R 3 and R 4 , and the connecting piping.
- the reduced pressure gas from line 25 is mixed with the C 5 + liquid which passes from separation zone Si through a level control valve (not shown) and the mixture is then passed via line 24 to furnace F 3 .
- the heated stream from furnace F 3 is passed to reforming zone R 3 via line 28, which is operated in a moving-bed continual catalyst regeneration mode.
- Reforming conditions for the moving-bed reforming zones will include temperatures from about 800° to 1200°F, preferably from about 800° to 1000° F; pressures from about 30 to 300, preferably from about 50 to 150 psig; a weight hourly space velocity from about 0.5 to 20, preferably from about 0.75 to 6.
- Hydrogen-rich gas should be provided to maintain the hydrogen to oil ratio between the range of about 0.5 to 5, preferably from about 0.75 to 3.
- all of the hydrogen gas is supplied by the hydrogen-rich predominantly C 4 " gaseous stream which passes through pressure control valve 26.
- Instances may exist in which the gas flowing from the first stage is insufficient to supply the needed hydrogen to oil ratio. This could occur if the feedstock to the first stage was highly paraffinic or had a boiling range which included predominantly hydrocarbons in the 6 to 8 carbon number range. In these instances, hydrogen would need to be supplied from external sources such as a second reforming unit or a hydrogen plant. An additional, but less preferred source of hydrogen would be from compressing and recycling stream 56. This option would require additional compressor or a larger capacity compressor C 2 .
- Such reforming zones, or reactors are well known in the art and are typical of those taught in U.S. Patent Nos. 3,652,231; 3,856,662; 4,167,473; and 3,992,465 which are all incorporated herein by reference.
- the general principle of operation of such reforming zones is that the catalyst is contained in a annular bed formed by spaced cylindrical screens within the reactor.
- the reactant stream is processed through the catalyst bed, typically in an out-to-in radial flow, that is, it enters the reactor at the top and flows radially from the reactor wall through the annular bed of catalyst 30 which is descending through the reactor, and passes into the cylindrical space 32 created by said annular bed.
- reforming zone R 4 It exits the bottom of the reforming zone and is passed, via line 34, to furnace F 4 , then to reforming zone R 4 via line 35.
- the reactant stream passes out-to-in radially through the catalyst bed and into the cylindrical space 44 defined by said annular bed of catalyst.
- the effluent stream from reforming zone R 4 is passed via line 46 to cooling zone K 2 where the temperature of the stream is dropped to about 60° to 200°F, preferably from about 80° to 125°F. It is then passed into separation zone S 2 via line 52 where it is separated into a light hydrogen-rich C 4 ⁇ gaseous stream and a C 5 + liquid stream.
- the C 5 + stream is collected for blending in the gasoline pool via line 54, and the light hydrogen-rich C 4 ⁇ gaseous stream is sent through compressor C 2 via line 56 and used as a product gas.
- Fresh and/or regenerated catalyst is charged to reforming zone R 3 by way of line 33 and distributed in the annular moving-bed 30 by means of catalyst transfer conduits 36, the catalyst being processed downwardly as an annular dense-phase moving bed.
- the reforming catalyst charged to reforming zones R 3 and R 4 is comprised of at least one Group VIII noble metal, preferably platinum; and one or more promoter metals, preferably tin, on spherical particles of a refractory support, preferably alumina.
- the spherical particles have an average diameter of about 1 to 3 mm, preferably about 1.5 to 2 mm, the bulk density of this solid being from about 0.5 to 0.9 and more particularly from about 0.5 to 0.8.
- the annular moving bed of catalyst exits from the bottom section of reforming zone R 3 and is passed via line 38 to reforming zone R 4 where it is distributed into the annular moving catalyst bed 42 by transfer from conduits 40.
- the catalyst of reforming zone R 4 descends through the zone where it exits and is passed to catalyst regeneration zone CR via line 48 and transfer conduit 50 where the catalyst is subjected to one or more steps common to the practice of reforming catalyst regeneration.
- the catalyst regeneration zone CR represents all of the steps required to remove at least a portion of the carbon from the catalyst and return it to the state needed for the reforming reactions occurring in reforming zone R 3 .
- the specific steps included in CR will vary with the selected catalyst.
- the only required step is one where accumulated carbon is burned-off at temperatures from about 600° to 1200°F and in the presence of an oxygen-containing gas, preferably air.
- Additional steps which may also be contained in the catalyst regeneration equipment represented by CR include, but are not limited to, adding a halide to the catalyst, purging carbon oxides, redispersing metals, and adding sulfur or other compounds to lower the rate of cracking when the catalyst first enters the reforming zone.
- the regenerated catalyst is then charged to reforming zone R 3 via line 33 and the cycle of continuous catalyst regeneration is continued until the entire reforming unit (both stages) is shut down, such as for catalyst regeneration of first stage (fixed-bed) reforming, which if operated in a semi-regenerative mode would need to be regenerated from time to time by shutting off the feed and raising the reactors to regeneration temperatures in the presence of an oxygen- containing gas.
- the catalyst in the moving- bed reforming and regeneration zones may not be constantly moving, but may only move intermittently through the system. This may be caused by the opening an closing of various valves in the system.
- the word “continuous” is not to be taken literally and the word “continual” is sometimes used interchangeably with “continuous”.
- the moving-bed zones of the second stage may be arranged in series, side-by-side, each of them containing a reforming catalyst bed slowly flowing downwardly, as mentioned above, either continuously or, more generally, periodically, said bed forming an uninterrupted column of catalyst particles.
- the moving bed zones may also be vertically stacked in a single reactor, one above the other, so as to ensure the downward flow of catalyst by gravity from the upper zone to the next below.
- the reactor then consists of reaction zones of relatively large sections through which the reactant stream, which is in a gaseous state, flows from the periphery of the interior of the reactor (although a reactor may be designed to have the reactant stream flow from the center to the periphery) to the center (or from the center to the periphery) interconnected by catalyst zones of relatively small sections, the reactant stream issuing from one catalyst zone of large section divided into a first portion (preferably from 1 to 10%) passing through a reaction zone of small section for feeding the subsequent reaction zone of large section and a second portion (preferably from 99 to 90%) sent to a thermal exchange zone and admixed again to the first portion of the reactant stream at the inlet of the subsequent catalyst zone of large section.
- the fluid of the lift used for conveying the catalyst may be any convenient gas, for example nitrogen or still for example hydrogen and more particularly purified hydrogen or recycle hydrogen.
- Catalysts suitable for use in any of the reactors of any of the stages include both monofunctional and bifunctional, monometallic and multimetallic noble metal containing reforming catalysts.
- the acid function which is important for isomerization reactions, is thought to be associated with a material of the porous, adsorptive, refractory oxide type which serves as the support, or carrier, for the metal component, usually a Group VIII noble metal, preferably Pt, to which is generally attributed the hydrogenation-dehydrogenation function.
- the preferred support for both stages of reforming is an alumina material, more preferably gamma alumina.
- the support material for the second stage reforming must be in the form of particles which are substantially spherical in shape, as previously described.
- One or more promoter metals selected from metals of Groups IIIA, IVA, IB, VIB, and VIIB of - li ⁇ the Periodic Table of the Elements may also be present.
- the promoter metal can be present in the form of an oxide, sulfide, or in the elemental state in an amount from about 0.01 to about 5 wt.%, preferably from about 0.1 to about 3 wt.%, and more preferably from about 0.2 to about 3 wt.%, calculated on an elemental basis, and based on total weight of the catalyst composition.
- the catalyst compositions have a relatively high surface area, for example, about 100 to 250 m 2 /g.
- the Periodic Table of which all the Groups herein refer to can be found on the last page of Advanced Inorganic Chemistry, 2nd Edition, 1966, Interscience publishers, by Cotton and Wilkinson.
- the acid function of the catalyst is typically provided by a halide component which may be fluoride, chloride, iodide bromide, or mixtures thereof. Of these, fluoride, and particularly chloride, are preferred. Generally, the amount of halide is such that the final catalyst composition will contain from about 0.1 to about 3.5 wt.%, preferably from about 0.5 to about 1.5 wt.% of halogen calculated on an elemental basis.
- the Group III noble metal the most preferred which is platinum
- the catalyst comprises from about 0.1 to about 2 wt.% platinum group component, especially about 0.1 to 2 wt.% platinum.
- Other preferred platinum group metals include palladium, iridium, rhodium, osmium, ruthenium and mixtures thereof.
- the first stage reactors are operated at conventional reforming temperatures and pressures in semiregenerative or cyclic mode while the reactors of the second stage are moving bed reactors operated substantially at lower pressures.
- Such pressures in the second stage may be from as low as about 30 psig to about 100 psig.
- the downstream reactors can be operated in once-through gas mode because there is an adequate amount of hydrogen generated, that when combined with the hydrogen-rich gas stream from the first stage, is an adequate amount of hydrogen to sustain the reforming reactions taking place.
- the second stage reactors when operated in a once-through hydrogen-rich gas mode, permit a smaller product-gas compressor (C 2 in the Figure) to be substituted for a larger capacity recycle gas compressor. Pressure drop in the second stage is also reduced by virtue of once-through gas operation.
- the second stage reactors can be operated in a mode wherein the hydrogen-rich gas is recycled.
- an aromatics separation unit where aromatic materials are separated in one or more steps to produce an aromatics-rich stream, an aromatics-lean stream, and optionally a stream containing predominantly C 5 and lighter hydrocarbons which comprise a portion of the aromatics-lean stream.
- This optional stream might be required to effect an economical separation of the remaining C 6 + product and can be removed as product or may be mixed back with the aromatics-rich stream for processing in the second stage.
- aromatics-rich and aromatics-lean as used herein refer to the level of aromatics in the liquid fraction reaction stream after aromatic separation relative to the level of aromatics prior to separation. That is, after a reaction stream is subjected to an aromatics separation, two fractions result.
- Aromatics separation can be accomplished by any suitable method.
- Non-limiting methods suitable for use herein for aromatics separation include: extraction, extractive distillation, distillation, flashing, adsorption, and by permeation through a semipermeable membrane, or by any other appropriate aromatics or paraffins removal process.
- Preferred are extractive distillation, distillation, and flashing.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/805,334 US5211838A (en) | 1991-12-09 | 1991-12-09 | Fixed-bed/moving-bed two stage catalytic reforming with interstage aromatics removal |
US07/805,360 US5354451A (en) | 1991-12-09 | 1991-12-09 | Fixed-bed/moving-bed two stage catalytic reforming |
US805334 | 1991-12-09 | ||
PCT/US1992/010538 WO1993012203A1 (en) | 1991-12-09 | 1992-12-08 | Fixed-bed/moving-bed two stage catalytic reforming |
US805360 | 2001-03-12 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0616633A1 EP0616633A1 (en) | 1994-09-28 |
EP0616633A4 true EP0616633A4 (en) | 1995-01-04 |
EP0616633B1 EP0616633B1 (en) | 2000-01-26 |
Family
ID=27122775
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93900921A Expired - Lifetime EP0616633B1 (en) | 1991-12-09 | 1992-12-08 | Fixed-bed/moving-bed two stage catalytic reforming |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0616633B1 (en) |
DE (1) | DE69230621T2 (en) |
WO (1) | WO1993012203A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1039818C (en) * | 1995-10-06 | 1998-09-16 | 中国石油化工总公司石油化工科学研究院 | Multiple-metal reforming catalyst |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1469681A (en) * | 1974-08-06 | 1977-04-06 | Uop Inc | Multiple-stage process for the catalytic reforming of a hydro carbon feed stream |
FR2600668A1 (en) * | 1986-06-25 | 1987-12-31 | Inst Francais Du Petrole | Process for catalytic reforming through at least two catalyst beds |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2213335B1 (en) * | 1973-01-10 | 1976-04-23 | Inst Francais Du Petrole | |
CA1088958A (en) * | 1975-12-22 | 1980-11-04 | James P. Gallagher | Catalytic reforming method for production of benzene and toluene |
US4206035A (en) * | 1978-08-15 | 1980-06-03 | Phillips Petroleum Company | Process for producing high octane hydrocarbons |
US4992158A (en) * | 1989-01-03 | 1991-02-12 | Exxon Research & Engineering Company | Catalytic reforming process using noble metal alkaline zeolites |
US4985132A (en) * | 1989-02-06 | 1991-01-15 | Uop | Multizone catalytic reforming process |
-
1992
- 1992-12-08 WO PCT/US1992/010538 patent/WO1993012203A1/en active IP Right Grant
- 1992-12-08 DE DE69230621T patent/DE69230621T2/en not_active Expired - Fee Related
- 1992-12-08 EP EP93900921A patent/EP0616633B1/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1469681A (en) * | 1974-08-06 | 1977-04-06 | Uop Inc | Multiple-stage process for the catalytic reforming of a hydro carbon feed stream |
FR2600668A1 (en) * | 1986-06-25 | 1987-12-31 | Inst Francais Du Petrole | Process for catalytic reforming through at least two catalyst beds |
Non-Patent Citations (1)
Title |
---|
See also references of WO9312203A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1993012203A1 (en) | 1993-06-24 |
DE69230621D1 (en) | 2000-03-02 |
EP0616633A1 (en) | 1994-09-28 |
DE69230621T2 (en) | 2000-08-10 |
EP0616633B1 (en) | 2000-01-26 |
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