EP2462100A1 - Procédé pour l'hydrogénation - Google Patents

Procédé pour l'hydrogénation

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Publication number
EP2462100A1
EP2462100A1 EP10740231A EP10740231A EP2462100A1 EP 2462100 A1 EP2462100 A1 EP 2462100A1 EP 10740231 A EP10740231 A EP 10740231A EP 10740231 A EP10740231 A EP 10740231A EP 2462100 A1 EP2462100 A1 EP 2462100A1
Authority
EP
European Patent Office
Prior art keywords
carbon atom
catalyst
process according
reactant
proton
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP10740231A
Other languages
German (de)
English (en)
Inventor
Rene Johan Haan
Jean-Paul Lange
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to EP10740231A priority Critical patent/EP2462100A1/fr
Publication of EP2462100A1 publication Critical patent/EP2462100A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups

Definitions

  • This invention relates to processes for the
  • Non-cyclic saturated esters are known to be useful as fuel components.
  • Ethyl pentanoate is known as a gasoline component, for example, and pentyl pentanoate is a diesel component.
  • Non-cyclic saturated esters of this type may be formed by hydrogenation of a reactant such as a lactone or a carboxylic acid or ester having a gamma- carbonyl group. Such reactants are available from
  • biomass in particular from cellulose feedstock material, rendering their use in the preparation of ester fuel components commercially attractive.
  • the catalyst used in the process of WO-2006/067171 is a strongly acidic heterogenous catalyst comprising a hydrogenating metal on a typically zeolite base.
  • non-acidic, zeolite-free catalysts comprising a hydrogenating metal on silica, included by way of
  • VTL Gamma valerolactone
  • GVL is more easily formed under catalytic hydrogenating conditions than non-cyclic hydrogenated compounds such as pentanoic (valeric) acid or
  • GB-1240580 describes the hydrogenolysis of esters and lactones, such as the hydrogenolysis of gamma- valerolactone to valeric acid.
  • the hydrogenolysis of an ester or lactone to a carboxylic acid is said to be carried out in the presence of a hydrogenolysis catalyst.
  • the hydrogenolysis catalyst is described to comprise a dual functional catalyst system or material made up of a hydrogenation component and a solid acid-acting
  • the described two-component catalyst may be used as a loose physical mixture of particles of
  • hydrogenation component and particles of acid solid or both components may be incorporated in the same
  • GB-1240580 mentions a wide range of possible solid acid-acting components. In passing acid solids of lesser acid activity, such as silica-alumina, are
  • GB-1240580 further teaches that the greater the acid activity of the acid solid, the better conversions and selectivities.
  • GB-1240580 mentions vapor phase operation to be possible, it is indicated that generally the ester or lactone and also the product acid are in the liquid phase. GB-1240580 does not disclose a process using an acid solid of lesser acid activity, such as silica- alumina, in the vapor phase.
  • catalysts for use in hydrogenation processes to give non- cyclic saturated carboxylic acids or esters useful as fuel components are provided.
  • the present invention provides a process for the hydrogenation of a reactant selected from:
  • the catalyst is a weakly acidic heterogeneous catalyst comprising a hydrogenating metal .
  • weakly acidic heterogenous catalysts comprising a hydrogenating metal are slower to deactivate over prolonged use than strongly acidic catalysts and also show good selectivity for the desired non-cyclic hydrogenated compounds.
  • a weakly acidic heterogenous catalyst such as an amorphous silica-alumina
  • the reactant may be a lactone, a carboxylic acid having a gamma-carbonyl group and a proton at a carbon atom adjacent to the carbonyl group or an ester of such a carboxylic acid.
  • the reactant is a lactone
  • this is a 5- or 6- membered lactone that is substituted at the ring-closing carbon atom and has a proton at a carbon atom adjacent to the ring-closing of general molecular formula
  • R 1 , R 2 , R 3 , R 4 , and R 5 each are, independently, an proton or an organic group that is connected with a carbon atom to the carbon atom
  • R 6 is an organic group that is connected with a carbon atom to the ring-closing carbon atom.
  • R 3 or R 4 is a proton or any of R 5 and R 6 is an organic group that is connected with a proton-bearing carbon atom to the ring-closing carbon atom.
  • each of R 3 and R4 at each carbon atom may differ from each other.
  • R is an alkyl group.
  • R 1 to R 5 each are a hydrogen atom.
  • suitable lactones are delta hexanolactone and gamma valerolactone .
  • the lactone is a 5-membered lactone.
  • a carboxylic acid having a gamma carbonyl group and a proton (i.e. a hydrogen atom) at a carbon atom adjacent to the carbon atom of the carbonyl group or an ester thereof is suitably a compound with the general molecular formula
  • R ⁇ OC-CR ⁇ -CR ⁇ -CO-R 6 (2) wherein R 1 , R 2 , R 3 , R 4 and R 6 are as defined hereinabove and R 7 is a proton in the case of a carboxylic acid as reactant and an organic group that is connected with a carbon atom to the oxygen atom in case of an ester as reactant.
  • R 3 or R 4 is a proton. If the carbon atom of R6 that is connected to the gamma carbon atom has a proton, R 3 or R 4 does not need to be a proton.
  • the reactant is a compound that is obtainable from biomass, in particular from cellulosic or lignocellulosic material.
  • examples of such compounds are gamma valerolactone, levulinic acid or an ester of levulinic acid (R" is a methyl group, R-*-, R ⁇ , R3 and R ⁇ each are a H atom) , a dimer of levulinic acid or a mono- or di-ester of such dimer.
  • levulinic acid with a gamma carbonyl group are 4- methyl-6-oxononanedioic acid, 3-acetyl-4- methylheptanedioic acid, or their lactones, i.e. 5- (2- methyl-5- oxotetrahydrofuran-2-yl) -4-oxopentanoic acid or 3- (2- methyl-5-oxotetrahydrofuran-2-yl ) -4-oxopentanoic acid.
  • the catalyst for use in the process of the present invention is a weakly acidic heterogenous catalyst comprising a hydrogenating metal. It will be appreciated that the catalyst may suitably be any weakly acidic catalytic material which is resistant to the process conditions used.
  • the acidity of a bifunctional catalyst may be evaluated through the heptane isomerisation test
  • catalyst acidity is defined as the temperature that is required to achieve 40% yield in isoheptane under the conditions given below. The weaker the acidity, the higher the temperature needed for the reaction.
  • a weakly acidic catalyst is a catalyst which exhibits a temperature requirement of 310- 400 0 C in the heptane isomerisation test procedure.
  • Catalysts with strong acidity exhibit a temperature requirement of less than 300 0 C whereas non-acidic
  • catalysts exhibit a temperature requirement of greater than 400°C.
  • a weakly acidic heterogenous catalyst comprising a hydrogenating metal is herein understood an acidic heterogeneous catalyst comprising a hydrogenating metal, which catalyst requires a temperature of 310 to 400 0 C to achieve 40% yield in isoheptane in a heptanes isomerisaton test.
  • the yield in isoheptane can suitably be quantified by means of gas chromatography.
  • yield can be indifferently defined in terms of mole, weight or volume (when operating in gasphase as applies here) .
  • the yields are suitably expressed in mol% .
  • the weakly acidic catalysts according to the present invention not only afford both acceptable activity and selectivity but they are also slower to deactivate over long periods of use.
  • the process of the invention can advantageously be operated during a period of at least 139 hours, preferably of at least 206 hours and most preferably of at least 334 hours. This is
  • Zeolite-based strongly acidic catalysts need to be regenerated by an H 2 -strip process involving heating for several hours at 400 0 C under a hydrogen stream at reaction pressure without GVL feed and air-decoking for several hours at 45O 0 C under oxygen-lean air followed by reduction at 300 0 C.
  • heterogenous catalyst comprises a hydrogenation metal supported on a catalyst support.
  • the catalyst support is suitably a weakly acidic material.
  • the catalyst support is a weakly acidic mixed oxide such as amorphous silica-alumina
  • ASA ASA
  • Nb- Nb-
  • Ti- and Zr-phosphates and Ti-niobate or a weakly acidic simple oxide such as Niobia.
  • the catalyst support comprises amorphous silica-alumina (ASA) .
  • ASA amorphous silica-alumina
  • the weakly acidic material may suitably be bound with a binder, for example silica, alumina, acidic clays, titania or zirconia.
  • weakly acidic zeolite bases may be any weakly acidic zeolite bases.
  • heterogenous catalyst comprises a zeolite free catalyst.
  • the hydrogenating metal of the catalyst suitably comprises a metal of any one of groups 7 to 11 of the Periodic Table of Elements such as Ni, Rh, Pd, Pt, Re, Ru or a combination of two or more thereof.
  • the hydrogenating metal comprises
  • the hydrogenating metal comprises both Pt and Pd.
  • the concentration of the hydrogenating metal based on the total weight of the catalyst will typically be in the range of from 0.05 to 5 wt%, suitably from 0.1 to 2 wt%.
  • the catalyst comprises hydrogenating metal supported on the weakly acidic material.
  • a temperature in the range of 150-350 0 C, particularly 200-300 0 C, more particularly 250-300°C. It will be appreciated that the temperature may be varied depending on the metals present in the catalyst and the support used.
  • the process of the invention may be performed at any suitable pressure provided that it is low enough to avoid condensation of the heaviest feed component at the temperature chosen. This is understood to mean that the process of the invention is carried out under gasphase conditions .
  • the reactant is suitably contacted with the catalyst at a pressure of 1-150 bar. In one embodiment, the process is conducted at a pressure of 5-50 bar.
  • an ester will be formed, for example, where the feedstock is itself an ester or if an alcohol is added to the feedstock; alternatively, where the product is a carboxylic acid, this can be esterified subsequently to give an ester.
  • the ester products can be of use as fuel
  • esters include those formed by reacting gamma valerolactone, levulinic acid, or its esters or by reacting dimers of levulinic acid, such as 4-methyl- 6- oxononanedioic acid, 3-acetyl-4-methylheptanedioic acid, their esters, or their lactones.
  • esters of pentanoic acid gamma valerolactone, levulinic acid or its esters as reactant
  • di-esters of 4- methylnonanedioic acid (4-methyl-6-oxononanedioic acid, its lactone, or its (di) ester as reactant) or di-esters of 3-ethyl-4-methylheptanedioic (3-acetyl-4- ethylheptanedioic acid, its lactone, or its (di) ester as reactant)
  • the ethyl esters are particularly preferred as fuel components.
  • any feature disclosed herein may be replaced by an alternative feature serving the same or a similar purpose.
  • a known amount (0.35 g) of catalyst was loaded in a reactor and reduced for 1.5 h at 440 0 C under H 2 flow of gas hourly space velocity (GHSV) 6200 L/kg/h at 30 bar.
  • the catalyst was subsequently contacted with a flow of n- heptane in H 2 (4 vol%) at GHSV of 4000 L/kg/h and 30 bar and cooled down to 200 0 C over 20 hours while the yield of isoheptane was quantified by means of gas chromatography.
  • H-ZSM-5, H-ZSM-12 and H-Beta are commercially available zeolites.
  • Silica (Si ⁇ 2) and alumina (AI2O3) were obtained commercially from CRI.
  • the supports were impregnated by Pt and/or Pd by means of well-known incipient wetness impregnation.
  • the catalyst acidity is defined as the temperature that is required to achieve 40% yield in isoheptane.
  • Catalysts with strong, weak and no acidity exhibit a temperature requirement of ⁇ 300°C, 310-400 0 C and >400°C, respectively.
  • Table 1 shows clearly that catalysts based on ASA are ⁇ weakly acidic' .
  • catalysts based on ZSM-5, ZSM-12 and Beta zeolites are ⁇ strongly acidic'
  • catalysts based on SiO 2 and Al 2 ⁇ 3 or ⁇ on- acidic' are clearly that catalysts based on SiO 2 and Al 2 ⁇ 3 or ⁇ on- acidic' .
  • the supports were pre-dried at 300 0 C for 1 hour.
  • the required amount of metal solution was calculated and prepared based on the pore volumes of the supports and the desired metal loading such that the total volume of the solution for impregnation was enough to fill 95% +/- 5% of the support pores.
  • the % conversion of the GVL was monitored, providing an indication of the stability of catalyst activity. Also monitored was the percentage of the desired reaction product valeric acid, and various by-products, as an indicator of catalyst selectivity.
  • the stability and selectivity results are summarised in Tables 2 and 3.
  • ASA amorphous silica alumina
  • ZSM-5 zeolites
  • MOR zeolites
  • FR is feed ratio (H 2 /GVL in mol/mol) .
  • Catalysts are defined in terms of the hydrogenation metal/acidic function/inert binder (where present) , with the metal loading given in weight %.
  • the acidic function is a zeolite (H-ZSM-5, H-MWW, H-MOR using the nomenclature published in the atlas of zeolite structure types "W. M. Meier, D. H. Olson, Ch.
  • the inert binder is Si ⁇ 2-
  • amorphous silica-alumina was subjected to a leaching test involving cooking 1 g of amorphous silica-alumina (ASA) shaped as extrudates for approximately one week in 10 g of liquid levulinic acid at 150 0 C. Following this test, integrity of the amorphous silica-alumina was inspected visually and an element analysis of the liquid phase was performed to establish whether there had been material leaching. Results are presented in Table 4 below.
  • ASA amorphous silica-alumina

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

Abstract

La présente invention concerne un procédé pour l'hydrogénation d'un réactif choisi parmi: (a) un lactone à 5 ou 6 chaînons substitué au niveau de l'atome de carbone fermant le cycle et comprenant un proton au niveau d'un atome de carbone adjacent à l'atome de carbone fermant le cycle; (b) un ester d'un acide carboxylique ayant un groupe gamma-carbonyle et un proton au niveau d'un atome de carbone adjacent à l'atome de carbone du groupe carbonyle; et (c) un acide carboxylique ayant un groupe gamma-carbonyle et un proton au niveau d'un atome de carbone adjacent à l'atome de carbone du groupe carbonyle. Ledit procédé comprend la mise en contact du réactif avec un catalyseur en présence d'hydrogène, à une température comprise entre 100 et 3500C et une pression comprise entre 1 et 150 bar (absolue), à condition que la pression soit suffisamment basse pour éviter la condensation du constituant de charge le plus lourd à la température choisie, et que le catalyseur soit un catalyseur hétérogène faiblement acide comportant un métal d'hydrogénation.
EP10740231A 2009-08-07 2010-08-06 Procédé pour l'hydrogénation Withdrawn EP2462100A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10740231A EP2462100A1 (fr) 2009-08-07 2010-08-06 Procédé pour l'hydrogénation

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP09167506 2009-08-07
EP09167497 2009-08-07
PCT/EP2010/061458 WO2011015643A1 (fr) 2009-08-07 2010-08-06 Procédé pour l'hydrogénation
EP10740231A EP2462100A1 (fr) 2009-08-07 2010-08-06 Procédé pour l'hydrogénation

Publications (1)

Publication Number Publication Date
EP2462100A1 true EP2462100A1 (fr) 2012-06-13

Family

ID=43066048

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10740231A Withdrawn EP2462100A1 (fr) 2009-08-07 2010-08-06 Procédé pour l'hydrogénation

Country Status (3)

Country Link
EP (1) EP2462100A1 (fr)
CA (1) CA2769424A1 (fr)
WO (1) WO2011015643A1 (fr)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1240580A (en) 1969-01-27 1971-07-28 Mobil Oil Corp Hydrogenolysis of esters and lactones
NL8103173A (nl) 1981-07-02 1983-02-01 Stamicarbon Werkwijze voor de bereiding van een 5-alkyl-butyrolacton.
US5814112A (en) 1992-06-05 1998-09-29 Battelle Memorial Institute Nickel/ruthenium catalyst and method for aqueous phase reactions
US5883266A (en) 1998-01-16 1999-03-16 Battelle Memorial Institute Hydrogenated 5-carbon compound and method of making
WO2002074760A1 (fr) 2001-03-16 2002-09-26 E.I. Dupont De Nemours And Company Production de 5-methylbutyrolactone a partir de l'acide levulinique
BRPI0519615A2 (pt) 2004-12-23 2009-02-25 Shell Int Research processo para a hidrogenaÇço de um reagente, e, composiÇço combustÍvel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011015643A1 *

Also Published As

Publication number Publication date
CA2769424A1 (fr) 2011-02-10
WO2011015643A1 (fr) 2011-02-10

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