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WO2013106039A1 - Réactions de déshydrogénation du n-butène en butadiène - Google Patents

Réactions de déshydrogénation du n-butène en butadiène Download PDF

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Publication number
WO2013106039A1
WO2013106039A1 PCT/US2012/032670 US2012032670W WO2013106039A1 WO 2013106039 A1 WO2013106039 A1 WO 2013106039A1 US 2012032670 W US2012032670 W US 2012032670W WO 2013106039 A1 WO2013106039 A1 WO 2013106039A1
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WO
WIPO (PCT)
Prior art keywords
dehydrogenation
catalyst
butadiene
reaction
reactor
Prior art date
Application number
PCT/US2012/032670
Other languages
English (en)
Inventor
Olga Khabashesku
James R. Butler
Darek Wachowicz
Original Assignee
Fina Technology, Inc.
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
Priority claimed from US13/094,877 external-priority patent/US20110245568A1/en
Application filed by Fina Technology, Inc. filed Critical Fina Technology, Inc.
Publication of WO2013106039A1 publication Critical patent/WO2013106039A1/fr

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Classifications

    • 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
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • 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
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • 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

Definitions

  • the present invention generally relates to the dehydrogenation of hydrocarbons.
  • Butadiene also known as 1,3-butadiene, is a common monomer in the production of synthetic rubber. Butadiene is a raw material for many high-volume industrial applications including tire manufacturing.
  • Butadiene is most commonly produced as a by-product in the steam cracking processes used to produce ethylene and other olefins.
  • the crude C4 stream isolated from the steam cracking is fed to butadiene extraction units, where butadiene is separated from the other C4s by extractive distillation.
  • the amount of crude C4s produced in steam cracking is dependent on the composition of the feed to the cracking unit. Heavier feeds, such as naphtha, yield higher amounts of C4s and butadiene than do lighter feeds. Crackers using light feeds typically produce low quantities of C4s and do not have butadiene extraction units.
  • Ethylene production from lighter feeds such as C2, C3 and C4s, yield significantly less amounts of butadiene.
  • emerging technologies for producing ethylene and propylene such as Methanol-To- Olefins (MTO), metathesis and olefins catalytic cracking generally do not co-produce butadiene. Production of on-purpose butadiene may become necessary.
  • MTO Methanol-To- Olefins
  • metathesis and olefins catalytic cracking generally do not co-produce butadiene. Production of on-purpose butadiene may become necessary.
  • the present invention in its many embodiments is a method for the dehydrogenation of n-butene over a dehydrogenation catalyst, at a pressure of 1,000 mbar or less, under reaction conditions to produce 1,3-butadiene at a yield level of at least 40 mol%.
  • the yield optionally can be at least 45 moI%.
  • steam can be supplied in a steam to hydrocarbon molar ratio of at least 10:1, optionally between 10:1 and 30:1.
  • the dehydrogenation reaction can be operated in a reactor at a LHSV of from 0.1 hr -1 to 1.0 hr -1 .
  • the dehydrogenation reaction can be operated in a reactor at a pressure of 350 mbar or less, optionally 300 mbar or less.
  • the dehydrogenation reaction can be operated in a reactor at a temperature of at least 500°C, optionally at least 600°C.
  • the temperature can be increased in order to keep the 1,3-butadiene molar yield at least 40 mol%, optionally at least 45 mol%.
  • the dehydrogenation catalyst can be a catalyst that is used for the dehydrogenation of ethylbenzene to styrene.
  • the dehydrogenation catalyst can have an average effective pore diameter of at least 500 nanometers.
  • the dehydrogenation catalyst can have ferric oxide and potassium as components.
  • the dehydrogenation catalyst is a commercial catalyst.
  • the dehydrogenation reaction produces less than 1 mol% of undesirable acetylenic side products.
  • the dehydrogenation reaction can operate in excess of 30 days, optionally 45 days, before the catalyst becomes a deactivated catalyst.
  • Figure 1 shows the molar yield of butadiene and reactor inlet temperature over catalyst age for the dehydrogenation reaction of the example.
  • Figure 2 shows the 1-butene conversion and reactor inlet temperature over catalyst age for the dehydrogenation reaction of the example.
  • the present invention involves the production of diolefins by dehydrogenating an olefin containing feed.
  • the present invention is for production of butadiene by dehydrogenating an n-butene containing feed.
  • the feed is subjected to catalytic dehydrogenation under vacuum conditions that enable the dehydrogenation of the n-butene to form a product having a 1,3-butadiene content equivalent to a yield of at least 40 mol%.
  • Equation 1 shows the reactions that take place to convert 1-butene into 1,3- butadiene.
  • the first stage of 1-butene dehydrogenation is isomerisation, in which 1- butene changes into 2-butene isomers. Conversion of 1-butene into 2-butene is thermodynamically favorable because of the stabilizing effect of two alkyl groups on either side of the olefin ⁇ -bond.
  • the second stage is dehydrogenation, in which 1,3- butadiene is formed along with hydrogen gas. Dehydrogenation is highly endothermic, and high temperatures around 600°C can be economical for the conversion of n-butene to 1,3-butadiene.
  • Suitable reaction temperature for the invention can range from 300°C to 800°C, or from 500°C to 650°C.
  • Steam can be added to the dehydrogenation reactor to aid the reaction. Because dehydrogenation involves an increase in the number of moles of gas produced, the reaction can be favored by the addition of steam to reduce partial pressure. Steam can also reduce coke deposition, by reacting with carbon to form carbon monoxide and hydrogen gas. Reducing coke formation can prolong catalyst life and reduce the need for frequent regeneration.
  • steam and the n-butene containing hydrocarbon feedstock can be supplied in a steam to hydrocarbon molar ratio of between 1:1 to 30:1, optionally between 10:1 to 25:1; optionally between 20:1 to 25:1.
  • the steam can be mixed with the hydrocarbon either prior to introduction to the reactor, or the steam and hydrocarbon can be supplied separately to the reactor through separate lines.
  • the steam is condensed and forms a liquid portion, this liquid water along with any liquid hydrocarbons that may have been present in the feed or produced in the reaction, such as aromatics, for example benzene, toluene or xylene, can be drained from the reactor or a subsequent separation stage, in any suitable method.
  • the reacted hydrocarbon can be removed as either a liquid or a vapor, depending on the reactor conditions.
  • substantially all of the produced butadiene and unreacted hydrocarbon containing feed are vaporized and are removed in a vapor phase by any suitable method, such as a vacuum compressor, which can maintain the reactor pressure at the desired vacuum conditions.
  • reactors in parallel or series, wherein the catalyst is located and one or more reaction zones exist.
  • a subsequent separation stage that enables the liquid from the reactor to be recovered and the vapor product to be removed.
  • a heat exchanger may also be utilized to cool the reaction effluent prior to the separation stage.
  • the operating pressure of a separation stage may be essentially the same as the outlet pressure of the reactor, other than the pressure drop that may occur across the heat exchanger. In alternate embodiments the operating pressure of a separation stage may be different than the reactor.
  • a dehydrogenation reactor can be modified to enable the removal of a vapor stream from the reactor and reduce the reactor pressure to vacuum conditions of 1000 mbar or less, optionally 500 mbar or less, optionally 350 mbar or less.
  • Methods and processes of dehydrogenation disclosed in U.S. Patent Application 11/811,084 filed June 8, 2007 by Merrill, incorporated by reference herein, may be suitable for embodiments of the present invention.
  • the dehydrogenation catalyst can be any dehydrogenation catalyst having a large enough pore size in order to avoid excessive diffusion limitations leading to restriction of the conversion of n-butene to butadiene, such as for a non-limiting example, those with an average effective pore diameter of at least 300 nanometers, at least 400 nanometers, or at least 500 nanometers.
  • the dehydrogenation catalyst may be of any suitable type, such as a catalyst containing iron as a major component with a lesser amount of potassium.
  • the dehydrogenation catalyst is a ferric oxide, potassium carbonate based dehydrogenation catalyst having a relatively large average pore diameter, such as a pore diameter of at least 500 nanometers.
  • Suitable catalyst compositions may comprise ferric oxide in amounts ranging from 40 to 80 wt%, potassium oxide or potassium carbonate in an amount of about 5 to 30 wt% and may also include lesser amounts of cerium, and other suitable catalyst promoters, such as from 0.1 wt% to 5 wt%.
  • Catalysts disclosed in U.S. Patent Application 11/811,084 filed June 8, 2007 by Merrill, incorporated by reference herein, may be utilized in the present invention.
  • the catalyst may be formed by milling the iron and potassium components with, for example, a plastic hydraulic cement binder followed by extruding the material to form catalyst particles of about from 2.5 mm to 5.0 mm in diameter having an average effective pore diameter of at least 500 nanometers. More specifically the dehydrogenation catalyst may have an average effective pore diameter of at least 500 nanometers and may have an average effective pore diameter of between 500 nanometers and 2,000 nanometers, optionally between 500 nanometers and 1,500 nanometers, optionally between 500 nanometers and 1,000 nanometers.
  • the catalyst can be a dehydrogenation catalyst used in the production of styrene from ethylbenzene. Such a catalyst may also be used for other dehydrogenation reactions, including the dehydrogenation of C5 alkenes and isoamylene.
  • the dehydrogenation catalyst can be a commercial dehydrogenation catalyst, for example Hypercat sold by CRI Catalyst, which is a non-chromium-containing iron oxide catalyst used for the dehydrogenation of ethylbenzene to styrene.
  • the dehydrogenation catalyst can also be, by non-limiting example: Styromax Plus from Sud-Chemie or Hypercat GV from Criterion.
  • the LHSV can be any flow rate wherein the subject reaction can be achieved; such as for example embodiments of the invention can range from 0.1 hr -1 to 10.0 hr -1 , or from 0.1 hr -1 to 5.0 hr -1 , or from 0.1 hr -1 to 1.0 hr -1 .
  • Suitable reactor pressure for the invention can be less than 1000 mbar, optionally can range from 100 mbar to 1000 mbar, or from 200 mbar to 900 mbar, or optionally from 200 mbar to S00 mbar. In an embodiment the reactor pressure is operated at less than 350 mbar. Reduced pressures can also prolong catalyst life.
  • the product butadiene may be used in the production of synthetic rubbers, such as copolymers containing polystyrene, for example.
  • a 1-butene containing hydrocarbon stream was converted to butadiene over a commercial catalyst, Hypercat, from CRI catalyst.
  • the reactor was a dehydrogenation reactor that had been used previously for the dehydrogenation of isoamylene to isoprene.
  • Around 500 mL of Hypercat was loaded in the reactor at low temperature. After a . pressure check, the reactor was brought to 300°C with a nitrogen flow. Steam flow was started at 531 g/hr of H 2 O and the temperature was raised to 500°C. Nitrogen flow was stopped and isoamylene was started at 105 g/hr. The temperature was increased overnight to 600°C, and the pressure was decreased to 300 mbar.
  • the temperature was adjusted to achieve 40 % isoprene yield in the effluent. When yield of isoprene reached 45 mol%, the feed was then switched from isoamylene to n-butene. Samples were collected daily, using a chilling bath at -78°C, and the off-gas flow rate was measured utilizing a wet test meter installed in the fume hood. LHSV was 0.31 hr -1 , and the steam to hydrocarbon ratio was from 20: 1 to 24: 1. The temperature was adjusted until a steady production of butadiene above 40 mol% conversion was achieved.
  • Figure 1 shows the molar yield of butadiene and reactor inlet temperature over catalyst age. Over the 50 days, 1,3-butadiene molar yield varied from just under 30 mol% to over 45 mol% at temperatures ranging from around 590°C to 610 °C. The yield of butadiene was between 42 mol% and 47 mol% at 602°C to 610°C inlet reactor temperature, at 290 mbar pressure, at LHSV of 0.31 hr -1 and a 22:1 steam to hydrocarbon molar ratio.
  • Figure 2 shows the 1-butene conversion and reactor inlet temperature over catalyst age. Over the 50 days, butene conversion varied from just under 40 mole % to near 55 mole % at temperatures ranging from around 590°C to 610°C.
  • Table 1 shows reaction products composition for day 50 on stream. As can be seen in the table, direct dehydrogenation of 1-butene according to the present invention did not lead to significant production of undesirable side products, such as acetylenic compounds. The acetylenic side products were less than 0.1 mol% of the product stream.
  • Table 1 Products composition for 1-butene dehydrogenation.
  • Table 2 shows experimental results of dehydrogenation of 1-butene when the steam-to-hydrocarbon ratio (SHR) was varied from 20: 1 to 24: 1.
  • SHR steam-to-hydrocarbon ratio
  • conversion refers to the mol percent of the n-butene content in the feed is converted into product during the dehydrogenation process and is contained in the product stream.
  • yield refers to the moles of butadiene present in the product stream relative to the moles of n-butene converted during the reaction
  • EB dehydrogenation catalyst refers to a catalyst based on iron oxide that has the capability to catalyze the dehydrogenation reaction of ethylbenzene to styrene.
  • the EB dehydrogenation catalyst is not limited to a commercially available catalyst or one that is commercially used for the dehydrogenation of ethylbenzene to styrene.
  • the term EB dehydrogenation catalyst would include those catalysts that are in commercial use for the dehydrogenation reaction of ethylbenzene to styrene and catalysts that are commercially available for the dehydrogenation reaction of ethylbenzene to styrene.
  • catalyst life refers to the length of time in which a catalyst is active before the catalyst has lost enough catalyst activity to no longer be efficient in a specified process. Such efficiency is determined by individual process parameters.
  • regeneration refers to a process for renewing catalyst activity and/or making a catalyst reusable after its activity has reached an unacceptable/inefficient level. Examples of such regeneration may include passing steam over a catalyst bed or burning off carbon residue, for example.
  • butene refers to n-butenes or 1-butene, cis-2-butene, trans-2- butene.
  • butadiene refers to 1,3-butadiene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de déshydrogénation du n‑butène pour former du butadiène sur un catalyseur de déshydrogénation, un rendement en butadiène étant d'au moins 40 % en moles. Des modes de réalisation de l'invention consistent à faire fonctionner le réacteur de déshydrogénation à une pression inférieure ou égale à 1 000 mbar.
PCT/US2012/032670 2011-04-27 2012-04-09 Réactions de déshydrogénation du n-butène en butadiène WO2013106039A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/094,877 US20110245568A1 (en) 2008-07-22 2011-04-27 Dehydrogenation Reactions of N-Butene to Butadiene
US13/094,877 2011-04-27

Publications (1)

Publication Number Publication Date
WO2013106039A1 true WO2013106039A1 (fr) 2013-07-18

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016075065A1 (fr) 2014-11-14 2016-05-19 Basf Se Procédé de production de 1,3-butadiène par déshydrogénation de n-butènes grâce à la préparation d'un flux de matières contenant du butane et du 2-butène
US10358399B2 (en) 2014-11-03 2019-07-23 Basf Se Process for preparing 1,3-butadiene from n-butenes by oxidative dehydrogenation

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925498A (en) * 1970-05-27 1975-12-09 Petro Tex Chem Corp Oxidative dehydrogenation process
US4595788A (en) * 1983-11-25 1986-06-17 Nippon Zeon Co. Ltd. Process for producing butadiene
US5756207A (en) * 1986-03-24 1998-05-26 Ensci Inc. Transition metal oxide coated substrates
US6166280A (en) * 1996-03-08 2000-12-26 Montecatini Technologies S.R.L. Catalyst for the dehydrogenation of ethylbenzene to styrene
US20070167661A1 (en) * 2003-12-30 2007-07-19 Basf Aktiengesellschaft Method for the production of butadiene
US20070179330A1 (en) * 2003-12-30 2007-08-02 Basf Aktiengesellschaft Method for the production of butadiene
US20080119680A1 (en) * 2004-12-21 2008-05-22 Basf Aktiengesellschaft Method for Producing Butadiene from N-Butane
US20100099936A1 (en) * 2008-10-17 2010-04-22 Chae-Ho Shin Complex oxide catalyst of bi/mo/fe for the oxidative dehydrogenation of 1-butene to 1,3-butadiene and process thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925498A (en) * 1970-05-27 1975-12-09 Petro Tex Chem Corp Oxidative dehydrogenation process
US4595788A (en) * 1983-11-25 1986-06-17 Nippon Zeon Co. Ltd. Process for producing butadiene
US5756207A (en) * 1986-03-24 1998-05-26 Ensci Inc. Transition metal oxide coated substrates
US6166280A (en) * 1996-03-08 2000-12-26 Montecatini Technologies S.R.L. Catalyst for the dehydrogenation of ethylbenzene to styrene
US20070167661A1 (en) * 2003-12-30 2007-07-19 Basf Aktiengesellschaft Method for the production of butadiene
US20070179330A1 (en) * 2003-12-30 2007-08-02 Basf Aktiengesellschaft Method for the production of butadiene
US20080119680A1 (en) * 2004-12-21 2008-05-22 Basf Aktiengesellschaft Method for Producing Butadiene from N-Butane
US20100099936A1 (en) * 2008-10-17 2010-04-22 Chae-Ho Shin Complex oxide catalyst of bi/mo/fe for the oxidative dehydrogenation of 1-butene to 1,3-butadiene and process thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIU ET AL.: "Oxidative dehydrogenation of 1-butene to butadiene over carbon nanotube catalysts", CARBON, vol. 46, 2008, pages 547, 549 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10358399B2 (en) 2014-11-03 2019-07-23 Basf Se Process for preparing 1,3-butadiene from n-butenes by oxidative dehydrogenation
WO2016075065A1 (fr) 2014-11-14 2016-05-19 Basf Se Procédé de production de 1,3-butadiène par déshydrogénation de n-butènes grâce à la préparation d'un flux de matières contenant du butane et du 2-butène
US10384990B2 (en) 2014-11-14 2019-08-20 Basf Se Method for producing 1,3-butadiene by dehydrogenating n-butenes, a material flow containing butanes and 2-butenes being provided

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