US20060183953A1 - Method and apparatus for addition of aqueous solutions to high temperature processes - Google Patents

Method and apparatus for addition of aqueous solutions to high temperature processes Download PDF

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US20060183953A1
US20060183953A1 US11/058,849 US5884905A US2006183953A1 US 20060183953 A1 US20060183953 A1 US 20060183953A1 US 5884905 A US5884905 A US 5884905A US 2006183953 A1 US2006183953 A1 US 2006183953A1
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conduit
feedstream
catalytic dehydrogenation
aromatic hydrocarbon
life extender
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US11/058,849
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Marcus Ledoux
Jim Butler
Jim Merrill
Clint Persick
Ashley Rabalais
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Fina Technology Inc
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Fina Technology Inc
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Priority to US11/058,849 priority Critical patent/US20060183953A1/en
Assigned to FINA TECHNOLOGY, INC. reassignment FINA TECHNOLOGY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEDOUX, MARCUS, PERSICK, CLINT, RABALAIS, ASHLEY, BUTLER, JIM, MERRILL, JIM
Priority to EA200701723A priority patent/EA200701723A1/en
Priority to CA002591950A priority patent/CA2591950A1/en
Priority to KR1020077018634A priority patent/KR20070103030A/en
Priority to PCT/US2006/003243 priority patent/WO2006088632A2/en
Priority to MX2007009854A priority patent/MX2007009854A/en
Priority to EP06734060A priority patent/EP1848677A2/en
Priority to CNA2006800047980A priority patent/CN101124183A/en
Priority to BRPI0607322-0A priority patent/BRPI0607322A2/en
Priority to TW095104245A priority patent/TW200640831A/en
Publication of US20060183953A1 publication Critical patent/US20060183953A1/en
Priority to US12/238,552 priority patent/US7569738B2/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64Addition to a carbon atom of a six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321Catalytic processes
    • C07C5/324Catalytic processes with metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006Controlling or regulating processes
    • B01J19/002Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333Catalytic processes
    • C07C5/3335Catalytic processes with metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00654Controlling the process by measures relating to the particulate material
    • B01J2208/00707Fouling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002Chemical plants
    • B01J2219/00027Process aspects
    • B01J2219/0004Processes in series
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04Alkali metals
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74Iron group metals
    • C07C2523/745Iron
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • Embodiments of the present invention generally relate to aqueous salt addition to high temperature processes.
  • Catalytic dehydrogenation processes generally include the conversion of a paraffin alkylaromatic to the corresponding olefin in the presence of a dehydrogenation catalyst. During such dehydrogenation processes, it is desirable to maintain both high levels of conversion and high levels of selectivity. Unfortunately, dehydrogenation catalysts tend to lose activity when exposed to reaction environments, thereby reducing the level of conversion and/or the level of selectivity. Such losses may result in an undesirable loss of process efficiency. Various methods for catalyst regeneration exist, but such methods generally involve stopping the reaction process and in some cases, removing the catalyst for external regeneration, resulting in increased costs, such as costs related to heat loss and lost production.
  • One regeneration method includes the addition of a catalyst life extender to the dehydrogenation process. Such processes may avoid/delay the need for catalyst removal from the reaction vessel for regeneration and/or disposal. Unfortunately, such processes generally have required costly implementation systems to avoid system problems, such as fouling and plugging of the process lines.
  • Embodiments of the invention generally include a catalytic dehydrogenation system.
  • the catalytic dehydrogenation system generally includes at least one reaction vessel loaded with a dehydrogenation catalyst adapted to convert an alkyl aromatic hydrocarbon to a vinyl aromatic hydrocarbon, the reaction vessel including a vessel inlet and a vessel outlet and a first conduit operably connected to the vessel inlet and adapted to provide a feedstream thereto, the feedstream comprising the alkyl aromatic hydrocarbon.
  • a supply system including a second conduit adapted to provide an aqueous catalyst life extender to the feedstream at a linear velocity sufficient to minimize fouling within the first conduit.
  • Another embodiment includes providing a reaction vessel loaded with a dehydrogenation catalyst with a feedstream.
  • the feedstream is provided via a conduit in operable communication with the reaction vessel, the feedstream including an alkyl aromatic hydrocarbon and the dehydrogenation catalyst adapted to convert the alkyl aromatic hydrocarbon to a vinyl aromatic hydrocarbon.
  • Such an embodiment also includes contacting the feedstream with an aqueous catalyst life extender, wherein the aqueous catalyst life extender enters the conduit at a linear velocity sufficient to prevent vaporization of the catalyst life extender in the conduit prior to contact with the feedstream.
  • Yet another embodiment includes at least one reaction vessel loaded with a dehydrogenation catalyst, the reaction vessel including a vessel inlet and a vessel outlet adapted to pass a feedstream therethrough to contact the dehydrogenation catalyst and form a product, a first conduit operably connected to the vessel inlet and adapted to provide the feedstream thereto and a supply system, the supply system including a second conduit adapted to provide an aqueous catalyst life extender to the feedstream at a linear velocity sufficient to minimize fouling within the first conduit.
  • FIG. 1 illustrates a catalytic dehydrogenation system
  • FIG. 2 illustrates a multistage catalytic dehydrogenation system.
  • FIG. 3 illustrates an embodiment of a supply system.
  • FIG. 4 illustrates an alternative embodiment of a supply system.
  • conversion means the percentage of paraffins or alkylaromatic hydrocarbon transformed.
  • selectivity means percentage of alkylaromatic hydrocarbon transformed to the desired product.
  • the term “activity” refers to the weight of product produced per weight of the catalyst used in the dehydrogenation process per hour of reaction at a standard set of conditions (e.g., grams product/gram catalyst/hr).
  • loaded refers to introduction of a catalyst within a reaction vessel.
  • alkali metal includes but is not limited to, potassium, sodium, lithium and other members of the group IA and IIA metals of the periodic table, such as rubidium and cesium.
  • the alkali metal is generally potassium, but depends upon the alkali metal present in the dehydrogenation catalyst.
  • regeneration means a process for renewing catalyst activity and/or making the catalyst reusable after it's activity has reached an unacceptable level. Examples of such regeneration may include passing steam over the catalyst bed or burning off carbon residue.
  • FIG. 1 illustrates a catalytic dehydrogenation system 100 including at least one reaction vessel 102 loaded with a dehydrogenation catalyst (not shown).
  • An alkyl aromatic hydrocarbon (AAH) feedstream 104 enters the reaction vessel 102 and contacts the dehydrogenation catalyst to form a vinyl aromatic hydrocarbon (VAH) exit stream 108 .
  • AAH alkyl aromatic hydrocarbon
  • the process is described here in terms of an alkyl aromatic hydrocarbon feedstream and a vinyl aromatic hydrocarbon exit stream, it is within embodiments of the invention described herein that the feedstream may be and/or include other compounds that may be contacted with a dehydrogenation catalyst to form a product, such as propane (converted to propylene) or butylene (converted to butadiene.) It is further contemplated that the embodiments described herein, such as the supply system described further below, may be used for high temperature processes not utilizing dehydrogenation catalysts, but in need of aqueous injection into the feedstream.
  • One example of a catalytic dehydrogenation process includes dehydrogenating alkyl aromatic hydrocarbons over a solid catalyst component in the presence of steam (not shown) to form the VAH.
  • the steam contacts the AAH feedstream 104 prior to the AAH feedstream 104 entering the reaction vessel 102 , but may be added to the system 100 in any manner known to one skilled in the art.
  • the AAH feedstream 104 may have a steam to AAH weight of from about 0.01 to about 15:1, or from about 0.3:1 to about 10:1, or from about 0.6:1 to about 3:1, or from about 0.8:1 to about 2:1, for example.
  • One specific embodiment includes the conversion of ethylbenzene to styrene, where the VAH exit stream 108 may include styrene, toluene, benzene, and/or unreacted ethylbenzene, for example.
  • the process includes the conversion of ethyltoluene to vinyltoluene, cumene to alpha-methylstyrene and/or normal butylenes to butadiene, for example.
  • high temperature refers to process operation temperatures, such as reaction vessel and/or process line temperatures (e.g., the temperature of the feedstream at the vessel inlet) of from about 150° C. to about 1000° C., or from about 300° C. to about 800° C., or from about 500° C. to about 700° C., or from about 550° C. to about 650° C., for example.
  • catalysts can be used in the catalytic dehydrogenation system 100 .
  • a representative discussion of some of those catalysts is included below, but is in no way limiting the catalysts that can be used in the embodiments described herein.
  • the dehydrogenation catalysts discussed herein generally include an iron compound and at least one alkali metal compound.
  • the dehydrogenation catalyst may include from about 40 weight percent to about 90 weight percent iron, or from about 70 wt. % to about 90 wt. % iron, or from about 80 wt. % to about 90 wt. % iron.
  • the iron compound can be iron oxide, or another iron compound known to one skilled in the art.
  • the dehydrogenation catalyst may include from about 5 weight percent to about 60 weight percent alkali metal compound, or from about 8 wt. % to about 30 wt. % alkali metal compound, for example.
  • the alkali metal compound may be potassium oxide, potassium hydroxide, potassium acetate, potassium carbonate or another alkali metal compound known to one skilled in the art, for example.
  • the dehydrogenation catalysts may further include additional catalysis promoters (e.g., up to about 20 wt. % measured as their oxides, or from about 1 wt. % to about 4 wt. %), such as nonoxidation catalytic compounds of Groups IA, IB, IIA, IIB, IIIA, VB, VIB, VIIB and VIII and rare earth metals, such as zinc oxide, magnesium oxide, chromium or copper salts, potassium oxide, potassium carbonate, oxides of chromium, manganese, aluminum, vanadium, magnesium, thorium and/or molybdenum, for example.
  • additional catalysis promoters e.g., up to about 20 wt. % measured as their oxides, or from about 1 wt. % to about 4 wt.
  • additional catalysis promoters e.g., up to about 20 wt. % measured as their oxides, or from about 1 wt. % to about 4
  • dehydrogenation catalysts are well known in the art and some of those that are available commercially include: the S6-20, S6-21 and S6-30 series from BASF Corporation; the C-105, C-015, C-025, C-035, and the FLEXICAT series from CRI Catalyst Company, L.P.; and the G-64, G-84 and STYROMAX series from Sud Chemie, Inc. Dehydrogenation catalysts are further described in U.S. Pat. No. 5,503,163 (Chu); U.S. Pat. No. 5,689,023 (Hamilton, Jr.) and U.S. Pat. No. 6,184,174 (Rubini, et al.), which are incorporated by reference herein.
  • the dehydrogenation catalyst may be loaded into any reaction vessel 102 known to one skilled in the art for the conversion of an AAH to a VAH.
  • the reaction vessel 102 may be a fixed bed vessel, a fluidized bed vessel and/or a tubular reactor.
  • FIG. 2 illustrates three reactors/stages, any number or combination of reactors may be utilized.
  • the exit stream ( 204 , 206 ) of one reaction vessel ( 102 A, 102 B) becomes the feedstream ( 204 , 206 ) to another reaction vessel ( 102 B, 102 C). Therefore, when the dehydrogenation process is a multistage process, the term “feedstream” as used herein, may be the exit stream from a previous reactor, a “fresh” feedstream and/or a recycled stream, for example.
  • the feedstream (e.g., 204 , 206 ) may include steam, partially reacted alkyl aromatic hydrocarbon, unreacted alkyl aromatic hydrocarbon and/or vinyl aromatic hydrocarbon, for example.
  • additional process equipment such as reheaters (not shown) may be included to maintain and/or restore process stream temperatures within a desired range, such as within a high temperature range at a reaction vessel inlet.
  • catalysts tend to lose activity when exposed to reaction environments, thereby reducing the level of conversion and/or the level of selectivity. Such losses may result in an undesirable loss of process efficiency.
  • One method for overcoming the loss of catalyst activity includes raising the temperature of the feedstream and/or the reaction vessel. Such temperature increases raise the rate of reaction in order to offset the continuing loss of catalyst activity.
  • the embodiments described herein contemplate such temperature increases in combination with other processes for catalyst regeneration. Unfortunately, above a certain temperature, the mechanical temperature limit of the process equipment or the dehydrogenation catalyst may be reached, thereby increasing the potential degradation of the catalyst physical structure and/or the integrity of the process equipment.
  • one regeneration method that is described further below includes the addition of a catalyst life extender (CLE) 106 to the dehydrogenation process 100 .
  • the CLE 106 may be added to the system 100 at various points, including the reaction vessel 102 , the catalyst bed (not shown) and/or process stream 104 , for example. Such processes may avoid/delay the need for catalyst removal from the reaction vessel 102 for regeneration and/or disposal.
  • the catalyst life extender 106 may be selected from non-halogen sources of alkali metal ions and may include a combination thereof.
  • the amount of catalyst life extender 106 added to the process depends at least in part on the reaction conditions, equipment, feedstream composition and/or the catalyst life extender 106 being used, for example.
  • the catalyst life extender 106 is a compound containing potassium, is neither excessively deliquescent nor dangerously reactive and has a melting point or vapor point such that it can be used at dehydrogenation process temperatures without blocking process lines or fouling process equipment.
  • the catalyst life extender 106 may be a potassium salt of a carboxylic acid, such as potassium acetate.
  • catalyst life extenders in aqueous form
  • aqueous addition of the carboxylic acids described above resulted in markedly decreased fouling and in some instances, no fouling for extended periods of time.
  • Previous attempts at aqueous potassium hydroxide addition resulted in plugging/fouling after only a short period of time, such as days, versus weeks or months.
  • the catalyst life extender 106 is generally substantially free of any catalysts poisons. For example, it has been reported that halogen ions, such as chloride, may poison dehydrogenation catalysts. Therefore, the catalyst life extender 106 includes little or no halogen substituents.
  • the catalyst life extender 106 may be supplied to the system 100 at a rate equivalent to a continuous addition of from about 0.01 to about 100 parts per million by weight of catalyst life extender relative to the weight of the total alkyl aromatic hydrocarbon in the feedstream 104 , or from about 0.10 to about 10 parts per million, for example.
  • the catalyst life extenders 106 can be introduced into the dehydrogenation process by more that one method, it is also within the scope of the present invention to introduce the catalyst life extenders 106 to the dehydrogenation process at more than one rate.
  • the catalyst life extenders 106 can be introduced continuously or periodically, such as when catalyst activity levels fall below a predetermined level.
  • the catalyst life extenders may be added at a relatively low level with additional catalyst life extender being added to the process when catalyst activity levels fall below a predetermined level.
  • the system may include monitoring means (not shown) to monitor temperatures and chemical compositions to determine when conversion drops below a predetermined level.
  • aqueous addition methods have been unsuccessful, at least in part because the feedstream 104 is usually passing at a very high velocity, such as 20 ft/s, or from about 10 ft/s to about 30 ft/s, or from about 15 ft/s to about 25 ft/s, or at a velocity of about 15 ft/s or more, for example, through a large diameter conduit, such as 54 inches to 60 inches.
  • a very high velocity such as 20 ft/s, or from about 10 ft/s to about 30 ft/s, or from about 15 ft/s to about 25 ft/s, or at a velocity of about 15 ft/s or more, for example, through a large diameter conduit, such as 54 inches to 60 inches.
  • the embodiments described herein are capable of adding catalyst life extenders to high temperature process streams while exhibiting minimal fouling/plugging of the either the reactors or process lines.
  • FIG. 3 illustrates a supply system 300 .
  • the supply system 300 is adapted to provide an aqueous catalyst life extender 106 to a first conduit 302 in which the feedstream ( 104 a , 104 b ) is passing there through.
  • the supply system 300 generally includes a second conduit 304 adapted to provide the catalyst life extender 106 to the first conduit 302 .
  • the second conduit 304 is formed of a material compatible with high temperature processes, such as stainless steel, for example.
  • the second conduit 304 may extend into the first conduit 302 .
  • the second conduit 304 may be fitted through an aperture in the first conduit 302 .
  • the second conduit 304 (shown in FIG. 3 ) is substantially flush with the first conduit 302 .
  • the second conduit 304 is operably connected to the first conduit 302 so as to reduce shearing of the second conduit 304 .
  • the catalyst life extender 106 is added to the first conduit 302 at a velocity sufficient to minimize fouling, which is also herein also referred to herein as a “sufficient linear velocity.”
  • a velocity sufficient to minimize fouling refers to a velocity such that any fouling experienced in the process lines and/or equipment does not have an unacceptable detrimental effect on the feedstream 104 flowing therethrough.
  • the second conduit 304 has a small diameter.
  • the “small diameter” is selected to provide either the sufficient linear velocity or may be selected to be used in combination with other embodiments to provide the sufficient linear velocity.
  • the second conduit 304 may have a diameter of about 0.1 inches, or less than about 0.25 inches, for example.
  • a CLE gas 306 (e.g., a gas that is nonreactive with the catalyst life extender 106 or the feedstream 104 ) is supplied to the catalyst life extender 106 to increase the linear velocity of such.
  • the CLE gas 306 may be non-oxygen containing and may include fuel gas or nitrogen.
  • the CLE gas 306 may be premixed with or supplied to the second conduit 304 from a separate source.
  • the catalyst life extender 106 is generally an aqueous solution including from about 1 wt. % to about 50 wt. % catalyst life extender
  • the specific composition of the CLE 106 is determined by specific process parameters, such as the gas being used and the sufficient linear velocity. For example, a CLE water content of greater than about 50 wt. % may reduce the temperature of the gas 306 , thereby reducing the actual linear velocity of the CLE 106 .
  • FIG. 4 illustrates another embodiment wherein a supply system 400 includes a third conduit 402 formed around the perimeter of the second conduit 304 .
  • the second conduit may extend into the first conduit 302 (not shown), may be flush with an entrance into the first conduit 302 or may not extend to the entrance (not shown).
  • Such placement may be used to overcome shearing of the second conduit 304 due to the high velocity of the feedstream 104 passing through the first conduit 302 .
  • the second conduit 304 may include a nozzle (not shown) to further aid the mixing of the CLE 106 with the feedstream 104 .
  • a nozzle is adapted to minimize shearing and/or displacement due to the feedstream velocity.
  • the junction of the second conduit 304 and the third conduit 402 is sealed.
  • the term “fluid” refers to liquid or gas.
  • the end of the third conduit 402 opposite the junction is open to the first conduit 302 and any fluid passing through the third conduit may also flow into the first conduit.
  • this embodiment enables the on-line replacement of portions of the supply system should they experience an unacceptable amount of plugging.
  • the tubing can be removed and replaced with an unfouled conduit without or minimizing costly shutdown time.
  • the fouled conduit may be disposed of or cleaned for future use.
  • the supply system 400 may further include a gas supply 404 to cool the CLE 106 .
  • Such cooling gas 406 is generally adapted to prevent and/or minimize flashing of the CLE 106 upon contact with the feedstream 104 .
  • the cooling gas 406 may be the same gas as the CLE gas 306 or a different gas, but again is not reactive with the feedstream 104 .
  • the embodiments described herein may be used for aqueous salt addition into any high temperature conversion process, including the formation of gasoline fraction hydrocarbons from syntheses gas, dealkylation of alkylaromatics (e.g., toluene to benzene) and syntheses of ammonia from nitrogen and hydrogen.
  • the aqueous salt is added to a process stream having such high temperature.
  • a steam and ethylbenzene feedstream was contacted with a potassium promoted iron oxide dehydrogenation catalyst in a reaction to form styrene.
  • the feedstream (10:1 molar ratio of steam:ethylbenzene) was fed to the reaction via a first conduit (54 inch diameter) at a temperature of about 1200° F. (649° C.) and a velocity of about 20 ft/s.
  • aqueous potassium acetate was injected into the first conduit to contact and mix with the feed stream. The potassium acetate was at ambient temperature prior to injection.
  • a steam and ethylbenzene feedstream was contacted with a potassium promoted iron oxide dehydrogenation catalyst in a reaction to form styrene.
  • the feedstream (10:1 molar ratio of steam:ethylbenzene) was fed to the reaction via a first conduit (54 inch diameter) at a temperature of about 1200° F. (649° C.) and a velocity of about 20 ft/s.
  • aqueous potassium acetate was injected into the first conduit to contact and mix with the feed stream. The potassium acetate was at ambient temperature prior to injection

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

Methods and systems for extending the life of a dehydrogenation catalyst are described herein. For example, one embodiment includes providing a reaction vessel loaded with a dehydrogenation catalyst with a feedstream via a conduit in operable communication with the reaction vessel. The feedstream may include an alkyl aromatic hydrocarbon and the dehydrogenation catalyst may be adapted to convert the alkyl aromatic hydrocarbon to a vinyl aromatic hydrocarbon. The feedstream may be contacted with an aqueous catalyst life extender, wherein the aqueous catalyst life extender enters the conduit at a linear velocity sufficient to prevent vaporization of the catalyst life extender in the conduit prior to contact with the feedstream.

Description

    FIELD
  • Embodiments of the present invention generally relate to aqueous salt addition to high temperature processes.
  • BACKGROUND
  • Catalytic dehydrogenation processes generally include the conversion of a paraffin alkylaromatic to the corresponding olefin in the presence of a dehydrogenation catalyst. During such dehydrogenation processes, it is desirable to maintain both high levels of conversion and high levels of selectivity. Unfortunately, dehydrogenation catalysts tend to lose activity when exposed to reaction environments, thereby reducing the level of conversion and/or the level of selectivity. Such losses may result in an undesirable loss of process efficiency. Various methods for catalyst regeneration exist, but such methods generally involve stopping the reaction process and in some cases, removing the catalyst for external regeneration, resulting in increased costs, such as costs related to heat loss and lost production.
  • One regeneration method includes the addition of a catalyst life extender to the dehydrogenation process. Such processes may avoid/delay the need for catalyst removal from the reaction vessel for regeneration and/or disposal. Unfortunately, such processes generally have required costly implementation systems to avoid system problems, such as fouling and plugging of the process lines.
  • Therefore, it is desirable to overcome catalyst degradation, while at the same time ensuring that such methods of overcoming the degradation do not result in costly implementation systems, fouling and/or plugging.
  • SUMMARY
  • Embodiments of the invention generally include a catalytic dehydrogenation system. In one embodiment, the catalytic dehydrogenation system generally includes at least one reaction vessel loaded with a dehydrogenation catalyst adapted to convert an alkyl aromatic hydrocarbon to a vinyl aromatic hydrocarbon, the reaction vessel including a vessel inlet and a vessel outlet and a first conduit operably connected to the vessel inlet and adapted to provide a feedstream thereto, the feedstream comprising the alkyl aromatic hydrocarbon. Such an embodiment further includes a supply system including a second conduit adapted to provide an aqueous catalyst life extender to the feedstream at a linear velocity sufficient to minimize fouling within the first conduit.
  • Another embodiment includes providing a reaction vessel loaded with a dehydrogenation catalyst with a feedstream. The feedstream is provided via a conduit in operable communication with the reaction vessel, the feedstream including an alkyl aromatic hydrocarbon and the dehydrogenation catalyst adapted to convert the alkyl aromatic hydrocarbon to a vinyl aromatic hydrocarbon. Such an embodiment also includes contacting the feedstream with an aqueous catalyst life extender, wherein the aqueous catalyst life extender enters the conduit at a linear velocity sufficient to prevent vaporization of the catalyst life extender in the conduit prior to contact with the feedstream.
  • Yet another embodiment includes at least one reaction vessel loaded with a dehydrogenation catalyst, the reaction vessel including a vessel inlet and a vessel outlet adapted to pass a feedstream therethrough to contact the dehydrogenation catalyst and form a product, a first conduit operably connected to the vessel inlet and adapted to provide the feedstream thereto and a supply system, the supply system including a second conduit adapted to provide an aqueous catalyst life extender to the feedstream at a linear velocity sufficient to minimize fouling within the first conduit.
  • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 illustrates a catalytic dehydrogenation system.
  • FIG. 2 illustrates a multistage catalytic dehydrogenation system.
  • FIG. 3 illustrates an embodiment of a supply system.
  • FIG. 4 illustrates an alternative embodiment of a supply system.
  • DETAILED DESCRIPTION
  • Introduction and Definitions
  • A detailed description will now be provided. Each of the appended claims defines a separate invention, which for infringement purposes is recognized as including equivalents to the various elements or limitations specified in the claims. Depending on the context, all references below to the “invention” may in some cases refer to certain specific embodiments only. In other cases it will be recognized that references to the “invention” will refer to subject matter recited in one or more, but not necessarily all, of the claims. Each of the inventions will now be described in greater detail below, including specific embodiments, versions and examples, but the inventions are not limited to these embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the inventions, when the information in this patent is combined with available information and technology. Various terms as used herein are shown below. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in printed publications and issued patents at the time of filing.
  • As used herein, the term “conversion” means the percentage of paraffins or alkylaromatic hydrocarbon transformed.
  • The term “selectivity” means percentage of alkylaromatic hydrocarbon transformed to the desired product.
  • The term “activity” refers to the weight of product produced per weight of the catalyst used in the dehydrogenation process per hour of reaction at a standard set of conditions (e.g., grams product/gram catalyst/hr).
  • The term ” loaded” refers to introduction of a catalyst within a reaction vessel.
  • As used herein, the term “alkali metal” includes but is not limited to, potassium, sodium, lithium and other members of the group IA and IIA metals of the periodic table, such as rubidium and cesium. In the conversion of ethylbenzene to styrene, the alkali metal is generally potassium, but depends upon the alkali metal present in the dehydrogenation catalyst.
  • As used herein, the term “regeneration” means a process for renewing catalyst activity and/or making the catalyst reusable after it's activity has reached an unacceptable level. Examples of such regeneration may include passing steam over the catalyst bed or burning off carbon residue.
  • Process
  • FIG. 1 illustrates a catalytic dehydrogenation system 100 including at least one reaction vessel 102 loaded with a dehydrogenation catalyst (not shown). An alkyl aromatic hydrocarbon (AAH) feedstream 104 enters the reaction vessel 102 and contacts the dehydrogenation catalyst to form a vinyl aromatic hydrocarbon (VAH) exit stream 108. Although the process is described here in terms of an alkyl aromatic hydrocarbon feedstream and a vinyl aromatic hydrocarbon exit stream, it is within embodiments of the invention described herein that the feedstream may be and/or include other compounds that may be contacted with a dehydrogenation catalyst to form a product, such as propane (converted to propylene) or butylene (converted to butadiene.) It is further contemplated that the embodiments described herein, such as the supply system described further below, may be used for high temperature processes not utilizing dehydrogenation catalysts, but in need of aqueous injection into the feedstream.
  • One example of a catalytic dehydrogenation process includes dehydrogenating alkyl aromatic hydrocarbons over a solid catalyst component in the presence of steam (not shown) to form the VAH. Generally, the steam contacts the AAH feedstream 104 prior to the AAH feedstream 104 entering the reaction vessel 102, but may be added to the system 100 in any manner known to one skilled in the art. Although the amount of steam contacting the AAH is determined by individual process parameters, the AAH feedstream 104 may have a steam to AAH weight of from about 0.01 to about 15:1, or from about 0.3:1 to about 10:1, or from about 0.6:1 to about 3:1, or from about 0.8:1 to about 2:1, for example.
  • One specific embodiment includes the conversion of ethylbenzene to styrene, where the VAH exit stream 108 may include styrene, toluene, benzene, and/or unreacted ethylbenzene, for example. In other embodiments, the process includes the conversion of ethyltoluene to vinyltoluene, cumene to alpha-methylstyrene and/or normal butylenes to butadiene, for example.
  • The dehydrogenation processes discussed herein are high temperature processes. As used herein, the term “high temperature” refers to process operation temperatures, such as reaction vessel and/or process line temperatures (e.g., the temperature of the feedstream at the vessel inlet) of from about 150° C. to about 1000° C., or from about 300° C. to about 800° C., or from about 500° C. to about 700° C., or from about 550° C. to about 650° C., for example.
  • A variety of catalysts can be used in the catalytic dehydrogenation system 100. A representative discussion of some of those catalysts (e.g., dehydrogenation catalysts) is included below, but is in no way limiting the catalysts that can be used in the embodiments described herein.
  • The dehydrogenation catalysts discussed herein generally include an iron compound and at least one alkali metal compound. For example, the dehydrogenation catalyst may include from about 40 weight percent to about 90 weight percent iron, or from about 70 wt. % to about 90 wt. % iron, or from about 80 wt. % to about 90 wt. % iron. The iron compound can be iron oxide, or another iron compound known to one skilled in the art.
  • Further, the dehydrogenation catalyst may include from about 5 weight percent to about 60 weight percent alkali metal compound, or from about 8 wt. % to about 30 wt. % alkali metal compound, for example. The alkali metal compound may be potassium oxide, potassium hydroxide, potassium acetate, potassium carbonate or another alkali metal compound known to one skilled in the art, for example.
  • Additionally, the dehydrogenation catalysts may further include additional catalysis promoters (e.g., up to about 20 wt. % measured as their oxides, or from about 1 wt. % to about 4 wt. %), such as nonoxidation catalytic compounds of Groups IA, IB, IIA, IIB, IIIA, VB, VIB, VIIB and VIII and rare earth metals, such as zinc oxide, magnesium oxide, chromium or copper salts, potassium oxide, potassium carbonate, oxides of chromium, manganese, aluminum, vanadium, magnesium, thorium and/or molybdenum, for example.
  • Such dehydrogenation catalysts are well known in the art and some of those that are available commercially include: the S6-20, S6-21 and S6-30 series from BASF Corporation; the C-105, C-015, C-025, C-035, and the FLEXICAT series from CRI Catalyst Company, L.P.; and the G-64, G-84 and STYROMAX series from Sud Chemie, Inc. Dehydrogenation catalysts are further described in U.S. Pat. No. 5,503,163 (Chu); U.S. Pat. No. 5,689,023 (Hamilton, Jr.) and U.S. Pat. No. 6,184,174 (Rubini, et al.), which are incorporated by reference herein.
  • The dehydrogenation catalyst may be loaded into any reaction vessel 102 known to one skilled in the art for the conversion of an AAH to a VAH. For example, the reaction vessel 102 may be a fixed bed vessel, a fluidized bed vessel and/or a tubular reactor.
  • Although a single stage process is shown in FIG. 1, multistage processes are often utilized to form vinyl aromatic hydrocarbons and an example of such (three stages 200) is shown in FIG. 2. Although FIG. 2 illustrates three reactors/stages, any number or combination of reactors may be utilized. In a multistage process, such as process 200, the exit stream (204, 206) of one reaction vessel (102A, 102B) becomes the feedstream (204, 206) to another reaction vessel (102B, 102C). Therefore, when the dehydrogenation process is a multistage process, the term “feedstream” as used herein, may be the exit stream from a previous reactor, a “fresh” feedstream and/or a recycled stream, for example. In such embodiments, the feedstream (e.g., 204, 206) may include steam, partially reacted alkyl aromatic hydrocarbon, unreacted alkyl aromatic hydrocarbon and/or vinyl aromatic hydrocarbon, for example. Further, it is known in the art that additional process equipment, such as reheaters (not shown) may be included to maintain and/or restore process stream temperatures within a desired range, such as within a high temperature range at a reaction vessel inlet.
  • One process for preparing vinyl aromatic hydrocarbons is the “Dow Process”, which supplies superheated steam (720° C.) to a vertically mounted fixed bed catalytic reactor. The steam is generally injected into the reactor in the presence of a vaporized feedstream. See, The Chemical Engineers Resource Page at www.cheresources.com/polystymonzz.shtml.
  • Catalyst Life Extender
  • During such dehydrogenation processes, it is desirable to maintain both high levels of conversion and high levels of selectivity. Unfortunately, catalysts tend to lose activity when exposed to reaction environments, thereby reducing the level of conversion and/or the level of selectivity. Such losses may result in an undesirable loss of process efficiency. Various methods for catalyst regeneration exist, but such methods generally involve stopping the reaction process and in some cases, removing the catalyst for external regeneration, resulting in increased costs, such as costs related to heat loss and lost production.
  • One method for overcoming the loss of catalyst activity includes raising the temperature of the feedstream and/or the reaction vessel. Such temperature increases raise the rate of reaction in order to offset the continuing loss of catalyst activity. The embodiments described herein contemplate such temperature increases in combination with other processes for catalyst regeneration. Unfortunately, above a certain temperature, the mechanical temperature limit of the process equipment or the dehydrogenation catalyst may be reached, thereby increasing the potential degradation of the catalyst physical structure and/or the integrity of the process equipment.
  • Returning to FIG. 1, one regeneration method that is described further below includes the addition of a catalyst life extender (CLE) 106 to the dehydrogenation process 100. The CLE 106 may be added to the system 100 at various points, including the reaction vessel 102, the catalyst bed (not shown) and/or process stream 104, for example. Such processes may avoid/delay the need for catalyst removal from the reaction vessel 102 for regeneration and/or disposal.
  • The catalyst life extender 106 may be selected from non-halogen sources of alkali metal ions and may include a combination thereof. The amount of catalyst life extender 106 added to the process depends at least in part on the reaction conditions, equipment, feedstream composition and/or the catalyst life extender 106 being used, for example.
  • Unfortunately, such an addition method may result in costly addition methods, such as the vaporization of molten potassium in order to eliminate and/or reduce fouling. For example, in the initial phases of industry implementation, aqueous potassium hydroxide (KOH) addition was attempted. It was determined that KOH addition, with the KOH being at ambient temperature, resulted in severe reactor fouling and plugging of the injection hardware and/or process line. Therefore, such catalyst life extenders are generally preheated to a temperature similar to that of the feedstream prior to addition.
  • However, in one embodiment, the catalyst life extender 106 is a compound containing potassium, is neither excessively deliquescent nor dangerously reactive and has a melting point or vapor point such that it can be used at dehydrogenation process temperatures without blocking process lines or fouling process equipment. For example, the catalyst life extender 106 may be a potassium salt of a carboxylic acid, such as potassium acetate.
  • Unexpectedly, it has been found that such catalyst life extenders (in aqueous form) are capable of being injected into high temperature process lines without the expected plugging/fouling. Rather, aqueous addition of the carboxylic acids described above resulted in markedly decreased fouling and in some instances, no fouling for extended periods of time. Previous attempts at aqueous potassium hydroxide addition resulted in plugging/fouling after only a short period of time, such as days, versus weeks or months.
  • Further, the catalyst life extender 106 is generally substantially free of any catalysts poisons. For example, it has been reported that halogen ions, such as chloride, may poison dehydrogenation catalysts. Therefore, the catalyst life extender 106 includes little or no halogen substituents.
  • The catalyst life extender 106 may be supplied to the system 100 at a rate equivalent to a continuous addition of from about 0.01 to about 100 parts per million by weight of catalyst life extender relative to the weight of the total alkyl aromatic hydrocarbon in the feedstream 104, or from about 0.10 to about 10 parts per million, for example.
  • Just as the catalysts life extenders can be introduced into the dehydrogenation process by more that one method, it is also within the scope of the present invention to introduce the catalyst life extenders 106 to the dehydrogenation process at more than one rate. For example, the catalyst life extenders 106 can be introduced continuously or periodically, such as when catalyst activity levels fall below a predetermined level. In still another embodiment, the catalyst life extenders may be added at a relatively low level with additional catalyst life extender being added to the process when catalyst activity levels fall below a predetermined level. Accordingly, the system may include monitoring means (not shown) to monitor temperatures and chemical compositions to determine when conversion drops below a predetermined level.
  • Prior to the embodiments described herein, aqueous addition methods have been unsuccessful, at least in part because the feedstream 104 is usually passing at a very high velocity, such as 20 ft/s, or from about 10 ft/s to about 30 ft/s, or from about 15 ft/s to about 25 ft/s, or at a velocity of about 15 ft/s or more, for example, through a large diameter conduit, such as 54 inches to 60 inches.
  • Supply System
  • Surprisingly, the embodiments described herein are capable of adding catalyst life extenders to high temperature process streams while exhibiting minimal fouling/plugging of the either the reactors or process lines.
  • FIG. 3 illustrates a supply system 300. The supply system 300 is adapted to provide an aqueous catalyst life extender 106 to a first conduit 302 in which the feedstream (104 a, 104 b) is passing there through.
  • The supply system 300 generally includes a second conduit 304 adapted to provide the catalyst life extender 106 to the first conduit 302. The second conduit 304 is formed of a material compatible with high temperature processes, such as stainless steel, for example. The second conduit 304, may extend into the first conduit 302. For example, the second conduit 304 may be fitted through an aperture in the first conduit 302. In another embodiment, the second conduit 304 (shown in FIG. 3) is substantially flush with the first conduit 302. Further, the second conduit 304 is operably connected to the first conduit 302 so as to reduce shearing of the second conduit 304.
  • The catalyst life extender 106 is added to the first conduit 302 at a velocity sufficient to minimize fouling, which is also herein also referred to herein as a “sufficient linear velocity.” As used herein, the term “velocity sufficient to minimize fouling” refers to a velocity such that any fouling experienced in the process lines and/or equipment does not have an unacceptable detrimental effect on the feedstream 104 flowing therethrough.
  • Various embodiments are described below that may be used alone or in combination with one another to provide the catalyst life extender 106 to the feedstream 104 at a sufficient linear velocity.
  • In one embodiment, the second conduit 304 has a small diameter. The “small diameter” is selected to provide either the sufficient linear velocity or may be selected to be used in combination with other embodiments to provide the sufficient linear velocity. For example, when the first conduit 302 has a diameter of from about 50 inches to about 65 inches, the second conduit 304 may have a diameter of about 0.1 inches, or less than about 0.25 inches, for example.
  • In another embodiment, a CLE gas 306 (e.g., a gas that is nonreactive with the catalyst life extender 106 or the feedstream 104) is supplied to the catalyst life extender 106 to increase the linear velocity of such. For example, the CLE gas 306 may be non-oxygen containing and may include fuel gas or nitrogen. As shown in FIG. 3, the CLE gas 306 may be premixed with or supplied to the second conduit 304 from a separate source. While the catalyst life extender 106 is generally an aqueous solution including from about 1 wt. % to about 50 wt. % catalyst life extender, the specific composition of the CLE 106 is determined by specific process parameters, such as the gas being used and the sufficient linear velocity. For example, a CLE water content of greater than about 50 wt. % may reduce the temperature of the gas 306, thereby reducing the actual linear velocity of the CLE 106.
  • FIG. 4 illustrates another embodiment wherein a supply system 400 includes a third conduit 402 formed around the perimeter of the second conduit 304. In such an embodiment, the second conduit may extend into the first conduit 302 (not shown), may be flush with an entrance into the first conduit 302 or may not extend to the entrance (not shown). Such placement may be used to overcome shearing of the second conduit 304 due to the high velocity of the feedstream 104 passing through the first conduit 302.
  • In one embodiment, the second conduit 304 may include a nozzle (not shown) to further aid the mixing of the CLE 106 with the feedstream 104. Such nozzle is adapted to minimize shearing and/or displacement due to the feedstream velocity.
  • In such an embodiment, the junction of the second conduit 304 and the third conduit 402 is sealed. As used herein, the term “fluid” refers to liquid or gas. The end of the third conduit 402 opposite the junction is open to the first conduit 302 and any fluid passing through the third conduit may also flow into the first conduit.
  • Further, this embodiment enables the on-line replacement of portions of the supply system should they experience an unacceptable amount of plugging. In such a situation, the tubing can be removed and replaced with an unfouled conduit without or minimizing costly shutdown time. The fouled conduit may be disposed of or cleaned for future use.
  • The supply system 400 may further include a gas supply 404 to cool the CLE 106. Such cooling gas 406 is generally adapted to prevent and/or minimize flashing of the CLE 106 upon contact with the feedstream 104. The cooling gas 406 may be the same gas as the CLE gas 306 or a different gas, but again is not reactive with the feedstream 104.
  • Although described herein in terms of catalytic dehydrogenation processes, the embodiments described herein may be used for aqueous salt addition into any high temperature conversion process, including the formation of gasoline fraction hydrocarbons from syntheses gas, dealkylation of alkylaromatics (e.g., toluene to benzene) and syntheses of ammonia from nitrogen and hydrogen. Generally, when referring to high temperature processes, the aqueous salt is added to a process stream having such high temperature.
  • EXAMPLES Example 1
  • Via a system such as that illustrated in FIG. 4, wherein the diameter of the second conduit was 1 inch, a steam and ethylbenzene feedstream was contacted with a potassium promoted iron oxide dehydrogenation catalyst in a reaction to form styrene. The feedstream (10:1 molar ratio of steam:ethylbenzene) was fed to the reaction via a first conduit (54 inch diameter) at a temperature of about 1200° F. (649° C.) and a velocity of about 20 ft/s. Prior to the reactor inlet, aqueous potassium acetate was injected into the first conduit to contact and mix with the feed stream. The potassium acetate was at ambient temperature prior to injection.
  • After 2 months, a gamma scan was done of the first conduit, which revealed deposits near the junction of the first and second conduits.
  • Example 2
  • Via a system such as that illustrated in FIG. 4, wherein the diameter of the second conduit was ¼ inch, a steam and ethylbenzene feedstream was contacted with a potassium promoted iron oxide dehydrogenation catalyst in a reaction to form styrene. The feedstream (10:1 molar ratio of steam:ethylbenzene) was fed to the reaction via a first conduit (54 inch diameter) at a temperature of about 1200° F. (649° C.) and a velocity of about 20 ft/s. Prior to the reactor inlet, aqueous potassium acetate was injected into the first conduit to contact and mix with the feed stream. The potassium acetate was at ambient temperature prior to injection
  • Two months after startup of the above process, a gamma scan of the conduit and the reactor observed essentially no deposits therein.

Claims (33)

1. A catalytic dehydrogenation system comprising:
at least one reaction vessel loaded with a dehydrogenation catalyst adapted to convert an alkyl aromatic hydrocarbon to a vinyl aromatic hydrocarbon, the reaction vessel comprising a vessel inlet and a vessel outlet;
a first conduit operably connected to the vessel inlet and adapted to provide a feedstream thereto, the feedstream comprising the alkyl aromatic hydrocarbon; and
a supply system comprising a second conduit adapted to provide an aqueous catalyst life extender to the feedstream at a linear velocity sufficient to minimize fouling within the first conduit.
2. The catalytic dehydrogenation system of claim 1, wherein the alkyl aromatic hydrocarbon comprises ethylbenzene and the vinyl aromatic hydrocarbon comprises styrene.
3. The catalytic dehydrogenation system of claim 1, wherein the dehydrogenation catalyst comprises an iron compound and an alkali metal compound.
4. The catalytic dehydrogenation system of claim 3, wherein the alkali metal compound comprises potassium.
5. The catalytic dehydrogenation system of claim 1, wherein the catalytic dehydrogenation system is a multistage process.
6. The catalytic dehydrogenation system of claim 1, wherein the aqueous catalyst life extender comprises non-halogen sources of alkali metals.
7. The catalytic dehydrogenation system of claim 6, wherein the aqueous catalyst life extender comprises potassium hydroxide.
8. The catalytic dehydrogenation system of claim 6, wherein the aqueous catalyst life extender comprises a potassium salt of a carboxylic acid.
9. The catalytic dehydrogenation system of claim 1, wherein the feedstream is passing through the first conduit at a high velocity.
10. The catalytic dehydrogenation system of claim 1, wherein the second conduit comprises a diameter of about 0.25 inches or less.
11. The catalytic dehydrogenation system of claim 1 further comprising a nozzle operably connected to the second conduit and adapted to provide the aqueous catalyst life extender to the first conduit.
12. The catalytic dehydrogenation system of claim 1 further comprising a third conduit adapted to provide a gas to an exterior portion of the second conduit.
13. A method comprising:
providing a reaction vessel loaded with a dehydrogenation catalyst with a feedstream via a conduit in operable communication with the reaction vessel, the feedstream comprising an alkyl aromatic hydrocarbon and the dehydrogenation catalyst adapted to convert the alkyl aromatic hydrocarbon to a vinyl aromatic hydrocarbon; and
contacting the feedstream with an aqueous catalyst life extender, wherein the aqueous catalyst life extender enters the conduit at a linear velocity sufficient to prevent vaporization of the catalyst life extender in the conduit prior to contact with the feedstream.
14. The method of claim 13, wherein the alkyl aromatic hydrocarbon comprises ethylbenzene and the vinyl aromatic hydrocarbon comprises styrene.
15. The method of claim 13, wherein the dehydrogenation catalyst comprises an iron compound and an alkali metal compound.
16. The method of claim 15, wherein the alkali metal compound comprises potassium.
17. The method of claim 13, wherein the aqueous catalyst life extender comprises non-halogen sources of alkali metals.
18. The method of claim 17, wherein the aqueous catalyst life extender comprises potassium hydroxide.
19. The method of claim 17, wherein the aqueous catalyst life extender comprises a potassium salt of a carboxylic acid.
20. The method of claim 13, wherein the feedstream is passing through the conduit at a high velocity.
21. The method of claim 13 further comprising supplying a gas to the aqueous catalyst life extender.
22. The method of claim 21, wherein the gas comprises a non oxygen containing gas.
23. The method of claim 13, wherein the feedstream comprises a high first temperature.
24. The method of claim 23 further comprising increasing a temperature of the feedstream to a second temperature that is greater than the first temperature.
25. A catalytic dehydrogenation system comprising:
at least one reaction vessel loaded with a dehydrogenation catalyst, the reaction vessel comprising a vessel inlet and a vessel outlet adapted to pass a feedstream therethrough to contact the dehydrogenation catalyst and form a product;
a first conduit operably connected to the vessel inlet and adapted to provide the feedstream thereto; and
a supply system comprising a second conduit adapted to provide an aqueous catalyst life extender to the feedstream at a linear velocity sufficient to minimize fouling within the first conduit.
26. The catalytic dehydrogenation system of claim 25, wherein, the feedstream comprises propane and the product comprises propylene.
27. The catalytic dehydrogenation system of claim 25, wherein the feedstream comprises butylene and the product comprises butadiene.
28. The catalytic dehydrogenation system of claim 25, wherein the feedstream comprises an alkyl aromatic hydrocarbon and the product comprises a vinyl aromatic hydrocarbon.
29. The catalytic dehydrogenation system of claim 28, wherein the dehydrogenation catalyst comprises an iron compound and an alkali metal compound.
30. The catalytic dehydrogenation system of claim 25, wherein the catalytic dehydrogenation system is a multistage process.
31. The catalytic dehydrogenation system of claim 25, wherein the feedstream is passing through the first conduit at a high velocity.
32. The catalytic dehydrogenation system of claim 25, wherein the second conduit comprises a diameter of about 0.25 inches or less.
33. The catalytic dehydrogenation system of claim 25 further comprising a third conduit adapted to provide a gas to an exterior portion of the second conduit.
US11/058,849 2005-02-15 2005-02-15 Method and apparatus for addition of aqueous solutions to high temperature processes Abandoned US20060183953A1 (en)

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