WO2021151813A1 - Procédé de déshydrogénation d'une charge d'alimentation hydrocarbonée dans un réacteur à lit fixe - Google Patents

Procédé de déshydrogénation d'une charge d'alimentation hydrocarbonée dans un réacteur à lit fixe Download PDF

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Publication number
WO2021151813A1
WO2021151813A1 PCT/EP2021/051561 EP2021051561W WO2021151813A1 WO 2021151813 A1 WO2021151813 A1 WO 2021151813A1 EP 2021051561 W EP2021051561 W EP 2021051561W WO 2021151813 A1 WO2021151813 A1 WO 2021151813A1
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WO
WIPO (PCT)
Prior art keywords
containing gas
oxygen containing
process according
fixed bed
catalyst
Prior art date
Application number
PCT/EP2021/051561
Other languages
English (en)
Inventor
Joachim Harteg JACOBSEN
David Norman MCCARTHY
Lived Yegres LEMUS-OLSEN
Michael Dennis KNUDSEN
Original Assignee
Haldor Topsøe A/S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haldor Topsøe A/S filed Critical Haldor Topsøe A/S
Publication of WO2021151813A1 publication Critical patent/WO2021151813A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • 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
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12—Silica and alumina
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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

  • the present invention relates to a process for dehydrogena- tion of a hydrocarbon feed stock in presence of a dehydro genation catalyst arranged in a fixed bed manner. More par ticularly, the invention focuses on regeneration and heat ing of the spent catalyst after a dehydrogenation cycle.
  • the important Houdry process also known as Catofin process, is characterized by the heat of reaction being supplied by pre-heating of the catalyst bed.
  • the typ ical Catofin process is carried out in 3 to 8 fixed bed ad iabatic reactors, using a chromium oxide/alumina catalyst containing about 20 wt% chromium oxide.
  • the catalyst is typically supplemented with an inert material having a high heat capacity, and possibly with a material which will se lectively combust or react with the hydrogen formed, the so-called heat generating material (HGM).
  • HGM heat generating material
  • the Catofin process is a well-established process and still the one of the dominant industrial process for alkane dehy drogenation. Since the reaction heat is supplied by the catalyst bed, a sequential operation is used. First the catalyst bed is used for dehydrogenation, during which the catalyst bed cools due to the endothermic reaction and some coke is formed on the catalyst. After dehydrogenation, the gas is purged away, and then the catalyst is regenerated from the coke and heated using a mix of fuel gas and air, and after reheating the Cr(VI) oxide is then reduced with hydrogen. Finally, the catalyst bed is purged with steam before the next dehydrogenation step. The fact that Cr catalysts present an environmental issue, new formulations are being tested, with the combination of Pt/Ga being promising.
  • Prolonged reaction times, high temperatures (up to 650°C) and high O2 partial pressures during a regeneration step have proven beneficial for the performance of platinum-gal lium based catalysts for propane dehydrogenation in the subsequent propane dehydrogenation cycle.
  • a comparison of these catalysts with chromium catalysts has shown that the Pt/Ga catalyst outperforms the Cr catalyst in the first cycle, but that Cr has a better steady-state performance during later cycles. The drop for the Pt/Ga catalyst from the first cycle to later cycles is due to an insufficient regeneration.
  • the purpose of this invention is to modify the catalyst re- generation step of known Catofin / Houdry type process.
  • the catalyst is usually exposed to wa ter/steam present in an oxygen containing regeneration gas.
  • the water stems from ambient air used in the regeneration step, as well as from the fuel burning in order to heat said air.
  • catalyst regeneration with air having a limited humidity or with dry air improves the per- formance and stability of platinum-gallium based dehydro genation catalysts.
  • the invention provides a process for dehydrogenation of a hydrocarbon feed stock in at least one fixed bed reac- tor, the fixed bed reactor containing a platinum and gal lium comprising dehydrogenation catalyst, the process being a cyclic process with alternating steps comprising a step of dehydrogenating the hydrocarbon feed stock and a step of regenerating the platinum and gallium comprising dehydro genation catalyst by heating and regenerating in an oxygen containing gas stream, wherein the oxygen containing gas contains water in an amount of less than 3% by volume.
  • the water content in the oxygen containing gas is less than
  • the water content in the oxygen containing gas is less than 1% by volume; the water content in the oxygen containing gas is less than 0.5% by volume; the water content in the oxygen containing gas is less than 0.1% by volume; the water content in the oxygen containing gas is less than
  • the oxygen containing gas is prepared by drying ambient air; the oxygen containing gas is heated without blending a gas containing hydrogen or hydrocarbons into the gas; the oxygen containing gas is heated by electrical heating; the oxygen containing gas is heated by electric resistance heating; heat is generated in at least one fixed bed reactor by electrical heating; heat is generated in at least one fixed bed reactor by in duction heating; the oxygen containing gas is dried by refrigerated drying; the oxygen containing gas is dried by adsorption (des sicant) type dryers, optionally operated in parallel. the oxygen gas is dried by means of absorbents, optionally operated in parallel.
  • Fig 1. shows iso-butane dehydrogenation at start of cycle (1 min) at 610°C.
  • Black circles represent the test with 3 vol.% 3 ⁇ 40 present during regeneration.
  • Diamond points rep resent the test performed in dry air conditions.
  • FIG. 1 shows iso-butane dehydrogenation at 610°C at end of cycle (11 min). Black circles represent the test with 3 vol.% 3 ⁇ 40 present during regeneration. Diamond points rep resent the test performed in dry air conditions.
  • the invention is disclosed further by the Examples which follow. Example 1:
  • Example 2 4.0 g of a 5 wt% Ga solution, 0.20 g of a 0.5 wt% Pt solu tion and 0.10 g KNO3 are dissolved with 11 ml water. This solution is used to impregnate 20 g of the selected S1O2- AI2O3 support. The sample is rolled for 1 hour to ensure complete pore volume impregnation, dried at 100°C overnight and then calcined at 700°C for 2 h with a 4 h heating ramp.
  • Example 2 Example 2:
  • the tests were performed for 180 cycles, alternating be tween 10 min regenerations in 4 Nl/h air, and 13 min dehy- drogenation with 1.5 Nl/h isobutane and 1.5 Nl/h N2.
  • Two GC measurements are recorded during dehydrogenation, at the beginning of the cycle and close to the end of cycle.
  • the tests were initiated by first heating the catalyst from room temperature to 610°C in a flow of dry air for 2 hrs and a flow of air containing 3 vol.% water.

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

Abstract

La présente invention concerne un procédé de déshydrogénation d'une charge d'alimentation hydrocarbonée dans au moins un réacteur à lit fixe, le réacteur à lit fixe contenant un catalyseur de déshydrogénation comprenant du platine et du gallium, le procédé étant un procédé cyclique présentant des étapes alternées comprenant une étape de déshydrogénation de la charge d'alimentation hydrocarbonée et une étape de régénération du catalyseur de déshydrogénation comprenant du platine et du gallium dans un courant gazeux contenant de l'oxygène, le gaz contenant de l'oxygène contenant de l'eau en une proportion inférieure à 3 % en volume.
PCT/EP2021/051561 2020-01-30 2021-01-25 Procédé de déshydrogénation d'une charge d'alimentation hydrocarbonée dans un réacteur à lit fixe WO2021151813A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA202000114 2020-01-30
DKPA202000114 2020-01-30

Publications (1)

Publication Number Publication Date
WO2021151813A1 true WO2021151813A1 (fr) 2021-08-05

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Country Status (1)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0553520A1 (fr) * 1991-01-09 1993-08-04 Uop Méthode pour la revalorisation d'un catalyseur non-acide utilisé pour la deshydrogénation d'hydrocarbures légers à haute sévérité
US20140200385A1 (en) * 2011-07-13 2014-07-17 Dow Global Technologies Llc Reactivating propane dehydrogenation catalyst
US20170120222A1 (en) * 2015-11-03 2017-05-04 Sk Innovation Co., Ltd. Transition metal-noble metal complex oxide catalyst for dehydrogenation prepared by one-pot synthesis and use thereof
CN109320392A (zh) * 2018-11-15 2019-02-12 西南化工研究设计院有限公司 一种丙烷脱氢制丙烯固定流化床反应及再生工艺
US20190046968A1 (en) * 2016-03-01 2019-02-14 Dow Global Technologies Llc Catalyst regeneration
WO2019223918A1 (fr) * 2018-05-22 2019-11-28 Haldor Topsøe A/S Promoteur de silice pour catalyseurs de déshydrogénation de propane à base de platine et de gallium

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0553520A1 (fr) * 1991-01-09 1993-08-04 Uop Méthode pour la revalorisation d'un catalyseur non-acide utilisé pour la deshydrogénation d'hydrocarbures légers à haute sévérité
US20140200385A1 (en) * 2011-07-13 2014-07-17 Dow Global Technologies Llc Reactivating propane dehydrogenation catalyst
US20170120222A1 (en) * 2015-11-03 2017-05-04 Sk Innovation Co., Ltd. Transition metal-noble metal complex oxide catalyst for dehydrogenation prepared by one-pot synthesis and use thereof
US20190046968A1 (en) * 2016-03-01 2019-02-14 Dow Global Technologies Llc Catalyst regeneration
WO2019223918A1 (fr) * 2018-05-22 2019-11-28 Haldor Topsøe A/S Promoteur de silice pour catalyseurs de déshydrogénation de propane à base de platine et de gallium
CN109320392A (zh) * 2018-11-15 2019-02-12 西南化工研究设计院有限公司 一种丙烷脱氢制丙烯固定流化床反应及再生工艺

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