WO2020214181A1 - Systems and processes for maintaining ethylbenzene dehydrogenation catalyst activity - Google Patents
Systems and processes for maintaining ethylbenzene dehydrogenation catalyst activity Download PDFInfo
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- WO2020214181A1 WO2020214181A1 PCT/US2019/028159 US2019028159W WO2020214181A1 WO 2020214181 A1 WO2020214181 A1 WO 2020214181A1 US 2019028159 W US2019028159 W US 2019028159W WO 2020214181 A1 WO2020214181 A1 WO 2020214181A1
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- liquid
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- ethylbenzene
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 43
- 230000000694 effects Effects 0.000 title claims description 18
- 239000007788 liquid Substances 0.000 claims abstract description 110
- 238000002347 injection Methods 0.000 claims abstract description 91
- 239000007924 injection Substances 0.000 claims abstract description 91
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 43
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 42
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 17
- 239000006193 liquid solution Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 51
- 239000011591 potassium Substances 0.000 claims description 44
- 229910052700 potassium Inorganic materials 0.000 claims description 44
- 239000003513 alkali Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 8
- 230000003716 rejuvenation Effects 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000002826 coolant Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 50
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 37
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 11
- -1 alkenyl aromatic hydrocarbons Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 150000004996 alkyl benzenes Chemical class 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000003112 potassium compounds Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/321—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts 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
- B01J23/78—Catalysts 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00893—Feeding means for the reactants
- B01J2208/00902—Nozzle-type feeding elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
- B01J2219/00351—Means for dispensing and evacuation of reagents
- B01J2219/0036—Nozzles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts 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
- B01J23/84—Catalysts 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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- Embodiments disclosed herein relate generally to the dehydrogenation of alkyl aromatics to form alkenyl aromatics, such as the dehydrogenation of ethylbenzene to form styrene. More specifically, embodiments herein relate to the processes and systems for maintaining catalyst activity within the dehydrogenation reactor.
- US6936743 teaches that the life of a potassium or chromium stabilized dehydrogenation catalyst can be extended by injecting 0.1 to 10 ppm of a“catalyst life extender.”
- a life extender noted is potassium acetate.
- US5739071 teaches that the life of an iron-based / alkali metal stabilized catalyst can be extended by continuous injection of alkali metal or alkali metal compound, such as injection of about 0.01 to 100 ppm of the alkali metal or the alkali metal compound.
- alkali metal or alkali metal compound such as injection of about 0.01 to 100 ppm of the alkali metal or the alkali metal compound.
- Compounds noted include potassium hydroxide, potassium carbonate, and potassium oxide. Metals are also noted, including potassium or sodium metal.
- inert nitrogen can be used to carry the vaporized alkali metal or alkali metal compound into the reactor feed stream.
- temperature of the vaporization device needed to be between 200°C and 480 °C for the injection of a 10% potassium acetate solution.
- the potassium or potassium compound may evaporate in the process pipe before they reach the catalyst bed and thoroughly mix with the feed stream so that the potassium is well dispersed throughout the catalyst bed. While prior practice focused on vaporizing the material prior to injecting it into the reactor feed, embodiments herein use a different approach, and purposely do not vaporize the potassium, potassium compound, or potassium solution prior to the injection.
- inventions disclosed herein relate to processes for dehydrogenating ethylbenzene.
- the processes may include mixing a steam stream and an ethylbenzene stream to form an ethylbenzene / steam feed mixture.
- the ethylbenzene / steam feed mixture may then be fed to a dehydrogenation reactor containing an alkali metal promoted catalyst to convert a portion of the ethylbenzene to styrene.
- a liquid selected from an alkali metal liquid, an alkali metal compound liquid, or a liquid solution comprising an alkali metal, may be injected into a feed stream comprising at least one of the steam stream, the ethylbenzene stream, or the ethylbenzene / steam feed mixture. Following injection, the liquid vaporizes and disperses into the feed stream upstream of the dehydrogenation reactor.
- the liquid (the alkali metal, the alkali metal compound liquid, or the liquid solution comprising an alkali metal) may be maintained in a liquid state from a point upstream of injection to an injection nozzle.
- the liquid is dispersed through the injection nozzle, in liquid form, to form droplets of liquid dispersed in the feed stream, after which point the liquid evaporates and/or dissolves into the vaporous feed stream.
- inventions disclosed herein relate to systems for maintaining catalyst activity in an ethylbenzene dehydrogenation reactor.
- the systems may include a liquid alkali feed stream, where the feed stream is heated or insulated, as needed, to maintain in a liquid state a liquid alkali feed selected from at least one of an alkali metal, an alkali metal compound liquid, and a liquid solution comprising an alkali metal.
- the system may also include an injection nozzle for injecting the liquid alkali feed, as a liquid, into a process feed stream selected from a steam stream, an ethylbenzene feed stream, and an ethylbenzene / steam feed stream to form an alkali-containing feed.
- the system also includes a dehydrogenation reactor containing an alkali metal promoted catalyst and having an inlet for receiving the alkali-containing feed or a mixture comprising the alkali-containing feed.
- the alkali feed stream may be steam traced, insulated, or coolant traced upstream of the injection nozzle.
- the steam tracing, insulation, etc. may be continued up to the injection nozzle, or as close as may be practicable.
- the system may further include a water feed stream fluidly connected to the injection nozzle.
- a control system may be provided, in some embodiments, to alternate feed of the liquid alkali feed and the water feed stream to the injection nozzle.
- inventions disclosed herein relate to processes for maintaining catalytic activity in a reactor.
- the processes may include injecting a liquid comprising a catalyst rejuvenating compound into a vaporous feed stream comprising an inert and/or a reactant upstream of an inlet of a reactor.
- the liquid may be vaporized and dispersed into the vaporous feed stream within a flow pipe upstream of the reactor to form a vaporous mixture comprising the catalyst rejuvenating compound and at least one of an inert or a reactant.
- a catalyst contained within the reactor may be contacted with the vaporous catalyst rejuvenating compound to enhance an activity of the catalysts within the reactor, while the catalyst in the reactor is concurrently performing its intended reaction.
- Figure 1 is a simplified process flow diagram of a system for the dehydrogenation of ethylbenzene to form styrene according to embodiments herein.
- Figure 2 is a simplified process flow diagram of a system for injecting a compound into a dehydrogenation process according to embodiments herein.
- Figure 3 presents graphical result of simulations injecting compounds into a flow stream of a dehydrogenation process according to embodiments herein.
- Embodiments disclosed herein relate generally to the dehydrogenation of alkyl aromatics, such as alkylbenzenes, to form alkenyl aromatics, such as for the dehydrogenation of ethylbenzene to make styrene. More specifically, embodiments herein relate to the processes and systems for maintaining catalyst activity within the dehydrogenation reactor. Even more specifically, embodiments herein relate to the injection of catalyst rejuvenating compounds into a reaction system. For example, embodiments herein may be directed toward the injection of potassium or potassium compounds to maintain catalyst activity within the dehydrogenation reactor.
- Embodiments herein are described below in relation to dehydrogenation of ethylbenzene to form styrene.
- the processes disclosed herein may be applicable to processes for the dehydrogenation of other alkylaromatic hydrocarbons to form alkenyl aromatic hydrocarbons, such as for the dehydrogenation of cumene to form alpha methyl styrene, ethyl toluene to form vinyl toluene, and many numerous other alkenyl aromatic compounds.
- FIG. 1 a simplified flow diagram of a typical configuration for the dehydrogenation reaction area of a styrene plant is illustrated.
- Styrene monomer is manufactured by dehydrogenating the ethylbenzene (EB) feed, which is an endothermic reaction.
- EB ethylbenzene
- a vaporized azeotropic mixture of ethylbenzene and water is fed via flow line 24 to the reaction zone, which may include two to four dehydrogenation reactors 26, 28.
- the effluent from each reactor 26 may be reheated using steam before entering the next reactor 26 or final reactor 28.
- the steam used for reheating the reactor effluents is commonly referred to as Main Steam (MS), which is provided from a steam superheater 30 via flow line 32 and coil 38 and eventually enters at the inlet 34 of the first reactor 26 along with the vaporized EB/water mixture, which may also be preheated against the effluent from final reactor 28 in exchanger 36.
- MS Main Steam
- Figure 1 is an exemplary dehydrogenation system, and other processes and systems for dehydrogenating ethylbenzene may also benefit from embodiments herein.
- the catalyst contained in reactors 26, 28 may lose activity due to migration of catalytic or co-catalytic components. It is desirable to inject compounds to help maintain or retain activity of the catalyst, thereby extending the catalyst life and the overall run time of the reaction system before necessary shutdown and catalyst replacement.
- a potassium stabilized dehydrogenation catalyst may benefit from the introduction of potassium or a potassium compound into the reactor.
- Embodiments herein may provide the potassium in a useful form, with minimal or no buildup of potassium or potassium salts in the injection system or the associated piping.
- Processes and systems disclosed herein may thus be used to inject molten potassium metal or a solution of potassium salt or potassium hydroxide directly into a vaporized reactor feed stream via one or more injection systems 50.
- the liquid metal or solution may be introduced to ethylbenzene (EB) feed 24/25, the main steam line 40, or the main EB/steam feed 42 that is going into the reactor 26 via one or more injection systems 50.
- EB ethylbenzene
- molten, liquid potassium may be injected into the EB/steam stream.
- a steam traced vessel may be used to store the potassium metal, and steam traced or insulated piping may maintain the metal in a liquid form and allow it to flow into the process unit.
- the liquid potassium may be metered directly into the pipe containing the EB/steam feed to the dehydrogenation reactor, such as stream 42 as illustrated in Figure 1, for example.
- the feed to the dehydrogenation reactor is at a temperature in the range of 500°C to about 650°C.
- the process temperature of the EB/steam is hot enough to keep the potassium melted, but not hot enough to boil the potassium.
- the potassium metal may be sprayed or atomized with nitrogen, or another appropriate inert gas, through a nozzle into the EB/steam feed mixture, for example. As the potassium metal will not be boiled or vaporized in the piping leading to the nozzle, it will not leave behind any fouling deposits that can plug the line.
- the expected feed rate of potassium into the system may be, for example, 50 to 1000 g/h, depending upon the size of the reactor and catalyst content, and thus the feed rate may be controlled with commonly available components.
- a solution of a potassium salt or potassium hydroxide may be injected into the EB/steam stream upstream of the reactor 26.
- Potassium salts dissolved in water may start to boil or could mostly vaporize in the pipe leading to the injection nozzle, resulting in deposits of precipitated potassium salt or potassium hydroxide in the pipe, plugging the system.
- the boiling point of a 50 wt% solution of KOH in water is about 145°C, which is much cooler than the 500°C to 650°C temperature of the feed to the reactor.
- a potassium solution is injected into the reactor feed via an insulated pipe, maintaining the potassium solution at a low enough temperature such that the solution will not boil and the nozzle will not foul.
- FIG. 2 A simplified flow diagram of a system 50 for injecting a potassium solution, without boiling the solution, is illustrated in Figure 2.
- the main EB/steam feed 8 is traversing through pipe 7 toward reactor inlet 6.
- a potassium solution 1 is fed through an injection nozzle assembly, which may include a feed pipe 4, nozzle 5, and shell 2, and insulation 3.
- the insulation layer 3 surrounds and maintains a temperature of the potassium solution within feed pipe 4 at a temperature below its boiling point all the way up to nozzle 5, where the liquid solution is atomized into the EB / steam feed 8. Because the potassium solution is maintained as a liquid within pipe 4 all the way to nozzle 5, nozzle fouling may be minimized or eliminated.
- the type of insulation and the thickness of the insulation layer needed to prevent boiling of the potassium solution will depend on the potassium salt or compound used, as well as the expected flow rate of the solution travelling through the pipe to the injection nozzle. Higher boiling solutions and higher flow rates of the solutions will require less insulation.
- the flow rate of the solution may be used to target injection of the potassium into the reactor feed at a concentration between 0.01 and 10 ppm by weight.
- the solution feed line may be insulated.
- the solution feed line may be cooled via heat exchange with water or other cool or cold heat exchange mediums, such as via heat exchange tracing, for example, where the heat exchange tracing may include annular piping or coils wrapped around the solution feed pipe.
- the annular piping or coils may encompass the solution feed line at least proximate the EB, steam, or EB/steam injection location, such as at least within a few feet, to negate any heat exchange with the significantly hotter EB, steam, or EB/steam piping and feed.
- the system as illustrated in Figure 2 may be used to continuously or intermittently inject a potassium solution into the feed stream.
- a pipe 4 including a jacket 2 may also be used, where a heat exchange medium 3 is circulated through the pipes to maintain the potassium solution as a liquid up to the injection nozzle 5.
- a jacket 2 being used to provide a heating medium 3 in the annular region, such as steam tracing, to maintain potassium metal as molten up to injection nozzle 5.
- Intermittent injection may include a continuous water flush, thereby maintaining movement of a solution or fluid through pipe 4.
- the spray angle of the nozzle can be configured to provide good distribution, as well as to atomize the injected metal or solution with an appropriate particle size to mix and vaporize without accumulating on the wall of the EB/steam feed pipe.
- multiple injection nozzles may be located around the circumference of the pipe, spraying toward the center of the feed line; this could be a good way of distributing the potassium in cases where the feed pipe diameter is very large (several inches).
- the spray nozzles should be oriented so that the salt solution or molten metal is kept away from the wall of the pipe, as much as practical, in order to minimize deposits and corrosion.
- potassium salt or potassium hydroxide it has been found advantageous to use fairly dilute solutions of potassium salt or potassium hydroxide. For example, 0.02 to 0.5 wt% solutions may be used. While seeming counter-intuitive, as the boiling point of the solution may be lower than for a concentrated solution, it has been found that having a lower solution viscosity will help the solution spray into smaller droplets and disperse / vaporize more readily. Having a low solution concentration also means that pure or essentially pure water may be continuously fed through the injector to keep it clear and clean.
- the potassium salt or potassium hydroxide could also be introduced intermittently, in some embodiments, to maintain catalyst activity. If the solution is fairly dilute, this would hardly impact process conditions. Further, a dilute solution may require a higher flow rate to introduce the same amount of potassium, and thus the insulation requirements to maintain the potassium solution below its boiling point may be decreased.
- embodiments herein are directed toward a process for dehydrogenating an alkylbenzene, such as ethylbenzene, while maintaining catalyst activity.
- the process may include mixing a steam stream and an ethylbenzene stream to form an alkylbenzene / steam feed mixture.
- the alkylbenzene / steam feed mixture may then be fed to a dehydrogenation reactor, containing an alkali metal promoted catalyst, to dehydrogenate a portion of the alkylbenzene, such as the dehydrogenation of ethylbenzene to form styrene.
- processes according to embodiments herein include injecting a liquid, selected from an alkali metal liquid, an alkali metal compound liquid, or a liquid solution comprising an alkali metal, into a feed stream comprising at least one of a steam stream, an alkylbenzene feed stream, or an alkylbenzene / steam feed mixture.
- the liquid is injected into the feed stream as a liquid, and the liquid vaporizes and disperses into the feed stream upstream of the dehydrogenation reactor.
- the alkali metal promoted catalyst comprises a potassium promoted catalyst.
- the alkali metal promoted catalyst may include an iron-based dehydrogenation catalyst in some embodiments. Numerous examples of suitable iron-based catalysts are described in US5739071, such as various catalysts including Fe203 promoted with potassium, for example. Other catalyst systems may also benefit from the injection methods disclosed herein, such as the injection of vanadium or vanadium compounds into a maleic anhydride reactor, for example.
- the alkali metal is injected as a liquid solution.
- the liquid solution may be, for example, a very dilute solution of an alkali metal compound or alkali metal salt in water.
- a liquid solution containing an alkali metal may be an aqueous solution including 0.01 to 1.0 wt%, such as 0.02 to 0.5 wt% alkali metal in water.
- Injection systems herein may be configured to maintain the liquid (i.e., the alkali metal, the alkali metal compound liquid, or the liquid solution comprising an alkali metal) in a liquid state from a point upstream of injection to the injection nozzle.
- the injection system may then be used to disperse the liquid through the injection nozzle and to form droplets of liquid dispersed in the feed stream, at which point the liquid injected may dissolve or evaporate into the vaporous feed stream.
- the injection nozzle may be configured to disperse droplets of the liquid, where the droplets may have an initial particle size of 100 microns or less, 75 microns or less, or 50 microns or less.
- the particle size of the droplets may decrease as the liquid is dispersed and dissolves into the vapor or otherwise evaporates. Accordingly,“initial” particle size relates to the size of the droplet particles as they are ejected from the injection nozzle.
- the injection nozzle may be disposed centrally within the feed stream (such as proximate a longitudinal axis of the feed stream pipe).
- the liquid may be dispersed through two or more injection nozzles located circumferentially around the feed stream, where the nozzles are configured to spray co-current with the feed (such as EB, steam, or EB/steam) and toward a center of the feed stream.
- Co-current injection allows the liquids to be pulled downstream with the significantly larger steam / hydrocarbon mixture being fed to the reactor. Further, the co-current injection may be configured to avoid direct spray of the liquid onto the piping walls, thus minimizes accumulation of liquid droplets on the transfer piping.
- Maintenance or restoration of catalyst activity may require continuous injection of an alkali metal or alkali metal compound in some embodiments.
- the maintenance or restoration of catalyst activity may require only intermittent injection of the alkali metal or alkali metal compound.
- processes herein may include alternating injection of the liquid and injection of a pure water stream through the injection nozzle.
- the process may include intermittently stopping injection of the liquid and instead injecting pure water through the injection nozzle.
- the injection of water may be performed in a similar manner, where the water is maintained as a liquid up to the injection nozzle distributing the water.
- the intermittent presence of a pure water liquid stream may help maintain the walls of the piping and the injection nozzle clean, removing any accumulation of alkali metal or alkali metal compound that may have occurred due to normal operation or upsets.
- the process of injecting the liquid may include atomizing the liquid with an inert gas.
- an inert gas For example, nitrogen, carbon dioxide, steam, argon, or other gases considered inert to the reaction system of interest may be used.
- the inert gas may be admixed with the liquid immediately upstream or within the distribution nozzle, enhancing the dispersion of the liquid into the steam / hydrocarbon transfer pipe at a desired initial particle size.
- the droplets may evaporate and disperse as a vapor into the feed stream.
- Full vaporization of the liquid upstream of the reactor entrance is desirable, so as to distribute the alkali metal or alkali metal compound throughout the catalyst beds, and avoiding settling of liquid on only the catalyst particles proximate the inlet.
- the evaporating of the liquid may be accomplished within a distance of about 5 meters, 10 meters, or 15 meters, depending upon the atomization and initial particle size, stream temperatures, initial liquid droplet particle size, and other factors readily recognizable to one skilled in the art.
- the injection nozzle assembly and associated components may be located an appropriate distance upstream of the reactor inlet, such as at least 5 meters upstream of the reactor inlet, at least 10 meters upstream of the reactor inlet, or at least 15 meters upstream of the reactor inlet, in various embodiments.
- the injection nozzle is located in a main ethylbenzene / steam feed stream at a distance between about 5 meters and 10 meters upstream of the dehydrogenation reactor inlet.
- the liquid may be injected into a main steam line 40, for example, it is preferred to have the liquid vaporize and disperse into the stream well in advance of any mixing, bends, or other portions of the piping system. Introducing the liquid too short of a distance in advance of such portions of the piping system may result in direct impingement of the atomized liquids, resulting in unwanted accumulation, restricted flow, and/or plugging of the piping components.
- the injection nozzle assembly and associated components may be located in a straight run of pipe an appropriate distance upstream of a bend, tee, or other piping components, such as at least 5 meters upstream of the piping components, at least 10 meters upstream of the piping components, or at least 15 meters upstream of the piping components, in various embodiments.
- Embodiments herein are also directed toward a system for maintaining catalyst activity in a reactor.
- the system may include a liquid feed stream, such as a liquid alkali feed stream.
- the liquid alkali feed stream may be configured to maintain, in a liquid state, a liquid alkali feed selected from at least one of an alkali metal, an alkali metal compound liquid, and a liquid solution comprising an alkali metal.
- the system may also include an injection nozzle for injecting the liquid alkali feed, as a liquid, into a process feed stream selected from a steam stream, an alkyl aromatic (ethylbenzene) feed stream, and an alkyl aromatic (ethylbenzene) / steam feed stream, to form an alkali-containing feed upstream of a reactor.
- Systems herein may also include a dehydrogenation reactor containing an alkali metal promoted catalyst and having an inlet for receiving the alkali-containing feed or a mixture comprising the alkali-containing feed.
- Systems according to embodiments herein may include an alkali feed stream that is steam traced, insulated, or coolant traced so as to maintain the alkali feed as a liquid upstream of the injection nozzle.
- the injection nozzle may be disposed proximate an axial center of the process feed stream.
- two or more injection nozzles may be disposed circumferentially about the process feed stream.
- Systems herein may also include a water feed stream fluidly connected to the injection nozzle.
- Control systems and associated valving may also be used to intermittently inject a liquid water feed stream in lieu of the alkali feed stream.
- the control system may be configured to alternate feed of the liquid alkali feed and the water feed stream to the injection nozzle.
- embodiments herein may provide for maintenance of catalyst activity by the injection of a liquid agent into a vaporous feed stream.
- Embodiments herein advantageously deliver the liquid agent, as a liquid, to the vaporous feed stream, thereby minimizing accumulation of salts or metals within and around the injection system and the associated piping.
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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CN201980095639.3A CN113710632A (en) | 2019-04-18 | 2019-04-18 | System and method for maintaining activity of ethylbenzene dehydrogenation catalyst |
KR1020217037574A KR20210143339A (en) | 2019-04-18 | 2019-04-18 | Systems and Methods for Maintaining Ethylbenzene Dehydrogenation Catalyst Activity |
PCT/US2019/028159 WO2020214181A1 (en) | 2019-04-18 | 2019-04-18 | Systems and processes for maintaining ethylbenzene dehydrogenation catalyst activity |
BR112021020674-4A BR112021020674B1 (en) | 2019-04-18 | SYSTEMS AND PROCESSES FOR MAINTAINING THE ACTIVITY OF THE ETHYLBENZENE DEHYDROGENATION CATALYST | |
JP2021561914A JP7416824B2 (en) | 2019-04-18 | 2019-04-18 | System and process for maintaining ethylbenzene dehydrogenation catalyst activity |
EP19925131.5A EP3956278A4 (en) | 2019-04-18 | 2019-04-18 | Systems and processes for maintaining ethylbenzene dehydrogenation catalyst activity |
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PCT/US2019/028159 WO2020214181A1 (en) | 2019-04-18 | 2019-04-18 | Systems and processes for maintaining ethylbenzene dehydrogenation catalyst activity |
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JP (1) | JP7416824B2 (en) |
KR (1) | KR20210143339A (en) |
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CN101992129A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Potassium supplementing method of styrene catalyst prepared via ethyl benzene dehydrogenation |
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US5461179A (en) * | 1993-07-07 | 1995-10-24 | Raytheon Engineers & Constructors, Inc. | Regeneration and stabilization of dehydrogenation catalysts |
EP2000450A1 (en) * | 2007-06-05 | 2008-12-10 | Total Petrochemicals France | Regeneration and stabilization of dehydrogenation catalyst |
US10961169B2 (en) * | 2019-04-18 | 2021-03-30 | Lummus Technology Llc | Systems and processes for maintaining ethylbenzene dehydration catalyst activity |
-
2019
- 2019-04-18 WO PCT/US2019/028159 patent/WO2020214181A1/en active Application Filing
- 2019-04-18 JP JP2021561914A patent/JP7416824B2/en active Active
- 2019-04-18 EP EP19925131.5A patent/EP3956278A4/en active Pending
- 2019-04-18 KR KR1020217037574A patent/KR20210143339A/en not_active Application Discontinuation
- 2019-04-18 CN CN201980095639.3A patent/CN113710632A/en active Pending
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CN113710632A (en) | 2021-11-26 |
JP7416824B2 (en) | 2024-01-17 |
JP2022529471A (en) | 2022-06-22 |
EP3956278A1 (en) | 2022-02-23 |
EP3956278A4 (en) | 2022-12-14 |
KR20210143339A (en) | 2021-11-26 |
BR112021020674A2 (en) | 2021-12-07 |
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