WO2013096624A1 - Homologation de méthanol - Google Patents

Homologation de méthanol Download PDF

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Publication number
WO2013096624A1
WO2013096624A1 PCT/US2012/070951 US2012070951W WO2013096624A1 WO 2013096624 A1 WO2013096624 A1 WO 2013096624A1 US 2012070951 W US2012070951 W US 2012070951W WO 2013096624 A1 WO2013096624 A1 WO 2013096624A1
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WO
WIPO (PCT)
Prior art keywords
meoh
kpa
homologation
methanol
parr reactor
Prior art date
Application number
PCT/US2012/070951
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English (en)
Inventor
John Kramer
Sara Klamo
Original Assignee
Dow Global Technologies Llc
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 Dow Global Technologies Llc filed Critical Dow Global Technologies Llc
Publication of WO2013096624A1 publication Critical patent/WO2013096624A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/08—Ethanol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols

Definitions

  • This disclosure relates to methanol homologation.
  • Methanol homologation products and/or ethanol equivalents are used in the production of plastics, fuels, disinfectants, reagents, solvents, and others.
  • methanol (MeOH) homologation products include, but are not limited to,
  • MeOH homologation products are formed by the reaction of MeOH with syngas resulting in reductive MeOH carbonylation and/or MeOH carbonylation production such as acetaldehyde, DME, ethanol, methyl acetate, and ethyl acetate.
  • ethanol equivalents are the subset of MeOH homologation products which arise from the reductive carbonylation of MeOH.
  • examples of ethanol equivalents include, but are not limited to, acetaldehyde, DME, ethanol, diethyl ether, methylethylether, ethyl iodide, ethyl acetate, and combinations thereof.
  • ethyl acetate is included as an ethanol equivalent because it contains ethanol, a product formed from reductive MeOH carbonylation.
  • a promoter (sometimes referred to as a co-catalyst) is used in addition to a transition metal catalyst.
  • the role of the promoter is to activate MeOH to make it more reactive with the transition metal catalyst.
  • Previous processes to obtain MeOH homologation products employed an iodide promoter component of the composition used in excess relative to the transition metal catalyst (e.g., 4 to 40 equivalents or greater). Iodide promoters are corrosive.
  • the disclosed method does not employ an iodide promoter as a component of the
  • the disclosed method has a higher selectivity than previous processes of methanol homologation.
  • the method provides an increase in homologation % (the moles of MeOH homologation products divided by the moles of MeOH reactants) as compared to the previous processes, and an increase in Ethanol Equivalents % (the moles of Ethanol Equivalents formed via MeOH homologation divided by the moles of MeOH reactant) as compared to the previous processes. Therefore, the Selectivity % (the Ethanol Equivalents % divided by the Homologation %) is increased as compared to previous processes.
  • This disclosure provides a method of MeOH homologation.
  • the method includes contacting a discrete rhodium catalyst that includes iodine and optionally a promoter that does not include iodine with MeOH at a temperature in a range of from 100 degrees Celsius (°C) to 170 °C and at a pressure in a range of from 3548 kilo Pascals (kPa) to 10444 kPa to produce a methanol homologation product, where an initial methanol (MeOH) : iodide ( ⁇ ion) molar ratio is in a range of from 200 : 1 to 5000 : 1.
  • the rhodium catalyst is a discrete rhodium catalyst.
  • a "discrete" catalyst is not formed in-situ, but is formed independently prior to being used in a reaction.
  • a discrete catalyst can be isolated, characterized, and carefully metered into a reaction to better understand the catalyst reactivity.
  • the discrete rhodium catalyst is formed from a rhodium compound, such as, rhodium metal, rhodium salts and oxides, organo rhodium compounds, and/or coordination compounds of rhodium.
  • the discrete rhodium catalyst is formed from at least one of the rhodium compounds and a 1,3- bis(diphenylphosphino)propane (dppp) ligand.
  • Dppp ligands include but are not limited to, 1 ,3-bis(diphenylphosphino)propane, 1,3-bis(diphenylphosphino)-(2,2- dimethyl)propane, 1 ,3-bis(diphenylphosphino)-(l -methyI)propane, 1,3-bis(di(para-tolyl) phosphino)propane, 1,3-bis(di(para-phenyl-phenyl) phosphino)propane, 1,3-bis(di(para- benzyl-phenyl) phosphino)propane, 1,3-bis(di(para-alkyl-phenyl) phosphino)propane where alky
  • alkoxy is an alkylether having a C1 to C20 carbyl group
  • siloxy is a silylether group substituted with any combination of C2 to C20 carbyl groups or unsubstituted or substituted phenyl groups, 1,3-bis(di(para- chlorophenyl)phosphino)propane, 1,3-bis(di(ortho-tolyl) phosphino)propane, 1,3- bis(di(ortho-phenyI-phenyl) phosphino)propane, 1,3-bis(di(ortho-benzyl-phenyl) phosphino)propane, 1,3-bis(di(ortho-alkyl-phenyl) phosphino)propane where alkyl is C2 to C20 hydrocarbyl, 1,3-bis(di(ortho-silyl-phenyl) phosphino)propane where silyl is a silyl group substituted with any combination of C2
  • the discrete rhodium catalyst may include 1 ,3- bis(diphenylphosphino)propane-rhodium(acyl)di-iodide ((dppp)Rh(acyl)(I 2 )).
  • the acyl group may include, but is not limited to, methanoyl, ethanoyl, propanoyl, benzoyl, propenoyl, and combinations thereof.
  • the discrete rhodium catalyst may be employed in a range of 0.01 mol% to 10.00 mol% of the amount of MeOH employed in the process.
  • the method conditions may optionally include a promoter that does not include iodine.
  • promoters that do not include iodine include phosphines, thiophenols, tosylates, transition metals, Lewis acids, combinations thereof, or other promoters that do not include iodine.
  • the method conditions may include a solvent such as toluene, diethylcarbitol, diglyme, diphenylelher, N-methylpyrrolidone.
  • the solvent may be in a range of from 0 % to 50 % by volume of initial MeOH charge.
  • the method conditions include contacting the discrete rhodium catalyst that includes iodine with MeOH at a temperature in a range of from 100 °C to 170 °C.
  • the method conditions may include the use of a co-catalyst such as ruthenium (III) chloride hydrate (RuCl 3 (H 2 O) n ). RuCl 3 (H 2 O) n can be used in a homologation system as a catalyst to reduce ethanol equivalents to ethanol.
  • the increased temperature range of the method conditions allow the method to use less co-catalyst as compared to previous processes.
  • the method may include an initial MeOH : Iodide ( I- ion) molar ratio
  • the method conditions include contacting the discrete rhodium catalyst that includes iodine with MeOH at a pressure in a range of from 3548 kPa to 10444 kPa.
  • the discrete rhodium catalyst may be contacted with MeOH where a partial pressure of H 2 is in a range of from 1480 kPa to 9065 kPa.
  • the method may include contacting the discrete rhodium catalyst that includes iodine with MeOH, at pressure of syngas in a range of from 3548 kPa to 9065 kPa.
  • the syngas may include, for example, a H 2 and carbon monoxide (CO) molar ratio in a range of 1 : 5 to 5 : 1, H 2 : CO.
  • the method may include a reaction time in a range of from 5 minutes to 5 hours. Reaction times for various applications may differ, for example, due to particular process parameters.
  • the method may include a continuous process, a batch process, and combinations thereof.
  • the method includes conducting the MeOH homologation in a batch process reactor.
  • the reactor may have a head volume above a liquid level in the reaction vessel in a range of 40% to 60% of the volume of the reaction vessel.
  • the reactor head volume allows for sufficient partial pressures of hydrogen gas (H 2 ), syngas, and combinations thereof.
  • Tables 7 and 8 show that the dpppRh(acyl)I 2 catalyst can be reactivated for MeOH homologation following a hydrogenation cycle without loss of selectivity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des modes de réalisation qui comprennent l'homologation de méthanol en présence d'un catalyseur à base de rhodium. Le catalyseur à base de rhodium peut comprendre du rhodium diphosphène di-iodure.
PCT/US2012/070951 2011-12-23 2012-12-20 Homologation de méthanol WO2013096624A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161579790P 2011-12-23 2011-12-23
US61/579,790 2011-12-23

Publications (1)

Publication Number Publication Date
WO2013096624A1 true WO2013096624A1 (fr) 2013-06-27

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Family Applications (1)

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PCT/US2012/070951 WO2013096624A1 (fr) 2011-12-23 2012-12-20 Homologation de méthanol

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WO (1) WO2013096624A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101182340A (zh) * 2007-12-20 2008-05-21 中国科学院化学研究所 一种甲醇羰基化生产醋酸的方法及其专用催化剂与制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101182340A (zh) * 2007-12-20 2008-05-21 中国科学院化学研究所 一种甲醇羰基化生产醋酸的方法及其专用催化剂与制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200860, Derwent World Patents Index; AN 2008-K09035, XP002696455 *
MOLOY K G ET AL: "Rhodium-catalyzed reductive carbonylation of methanol", ORGANOMETALLICS, ACS, WASHINGTON, DC, US, vol. 8, no. 12, 1 January 1989 (1989-01-01), pages 2883 - 2892, XP002694166, ISSN: 0276-7333 *

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