EP0658155A1 - Procede de conversion d'acetals en ethers - Google Patents

Procede de conversion d'acetals en ethers

Info

Publication number
EP0658155A1
EP0658155A1 EP94923325A EP94923325A EP0658155A1 EP 0658155 A1 EP0658155 A1 EP 0658155A1 EP 94923325 A EP94923325 A EP 94923325A EP 94923325 A EP94923325 A EP 94923325A EP 0658155 A1 EP0658155 A1 EP 0658155A1
Authority
EP
European Patent Office
Prior art keywords
acetal
kpa
formula
catalyst
process according
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Withdrawn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
EP94923325A
Other languages
German (de)
English (en)
Other versions
EP0658155A4 (fr
Inventor
Larry M. Cirjak
Wayne R. Kliewer
Rosemary Bartoszek-Loza
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.)
BP Chemicals Ltd
Original Assignee
BP Chemicals Ltd
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 BP Chemicals Ltd filed Critical BP Chemicals Ltd
Publication of EP0658155A1 publication Critical patent/EP0658155A1/fr
Publication of EP0658155A4 publication Critical patent/EP0658155A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/28—Preparation of ethers by reactions not forming ether-oxygen bonds from acetals, e.g. by dealcoholysis
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers

Definitions

  • the present invention relates to a process for converting acetals to ethers. More particularly, this invention relates to a hydrogenation process for converting a 3-alkoxypropionaldehyde dialkyl acetal to the corresponding 1,3-dialkoxypropane in the presence of a supported hydrogenation catalyst.
  • the process is highly selective towards the formation of the foregoing diethers relative to the formation of the corresponding alcohols, alkoxylated alcohols and mono-ethers.
  • R is hydrogen or methyl and R ⁇ is an alkyl, aralkyl, alkoxyalkyl, alkoxyalkenyloxyalkyl or alkoxy-polyalkenyloxy-alkyl radical.
  • the reference indicates that the preferred catalyst is Raney nickel, although other hydrogenation catalysts such as copper- chromium oxide, platinum and palladium black can be used.
  • R"CH(OR' ) (CH 2 CH(OR) ] n CH 2 CH(OR) 2 ⁇ R"CH(OR' ) [CH 2 CH(OR) ] n CH 2 CH 2 OR + ROH
  • each R represents the same or different hydrocarbon radicals chosen from the group consisting of alkyl, aryl and aralkyl radicals, and n is a whole number including 0 and generally less than 10.
  • the reference indicates that Raney nickel is the preferred catalyst but "other metal hydrogenation catalyts (ie, platinum or palladium) or copper, chromium etc.” can be used.
  • a particular aspect of this disclosure is that there is no disclosure of the hydrogenation of a propane ether nor the use of a supported catalyst.
  • R represents a hydrogen atom or a lower alkoxy group
  • Y represents an alkylene group having 2 to 12 carbon atoms
  • n is a positive number of 1 to 6
  • the two groups R(YO) n may, together with the carbon atom to which they are bonded, represent a 1,3-dioxolane ring
  • R 1 and R 2 independently from each other, represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, provided that at least one of R 1 and R 2 represents a hydrogen atom.
  • the catalyst is a "palladium catalyst supported on a carbon carrier in the absence of an acidic substance added".
  • This reference does not disclose the hydrogenation of triethers. Therefore, it cannot be predicted as to what might be the effect of a third ether group in the molecule being hydrogenated.
  • this reference states that, for their hydrogenation reaction, a palladium on carbon catalyst when used in the absence of acid co-catalyst is superior to the same catalyst when used in the presence of an acid co-catalyst.
  • this reference states that, for their hydrogenation reaction, a palladium-on-alumina catalyst in the absence of an acid substance added cannot achieve the excellent improvement shown by palladium on carbon catalyst of that invention. Summary of the Invention
  • This invention is directed to a process for making a 1,3- diether compound represented by the formula:
  • a catalyst composition comprising at least one catalytic metal selected from the group consisting of Pd, Ni, Co, Pt, Rh and Ru and a support material, said support material being one or more selected from the group consisting of silica, alumina, silica- alumina, aluminosilicates and carbon.
  • the acetal reactant hydrogenated has the formula (II) and R in this formula preferably represents an ethyl group.
  • R in this formula preferably represents an ethyl group.
  • Such compounds are known in the art.
  • a compound of formula (II) can be produced by reacting an unsaturated aldehyde, eg acrolein, with an alcohol, R.OH, with at least one acidic reagent for an effective period of time to form the desired acetal.
  • the molar ratio of the aldehyde to alcohol is preferably about 1:1 to 1:20, more preferably about 1:3 to about 1:10.
  • water is also present in the feed to the reaction.
  • concentration of water in the feed can be up to about 35% w/w based on the combined weight of aldehyde and alcohol in the reaction mixture and is preferably from about 1% w/w to about 10% w/w, eg about 5% w/w.
  • the acidic reagent can be a solid.
  • solid acidic reagents include Amberlyst®15 and Amberlyst*35, both of which are available from Rohm & Haas and are strongly acidic cationic macroreticular sulphonated polyvinyl styrenes.
  • acidic reagents that may be used include one or more of mineral acids such as hydrochloric acid, sulphuric acid, sulphonic acid or phosphoric acid; one or more C1-C7 (i) mono- or dicarboxylic acids or (ii) halogenated fatty acids; alkyl and aryl sulphonic acids such as eg methane sulphonic acid and para-toluene sulphonic acid; and ammonium and a ine salts of any of the foregoing mineral or organic acids.
  • the reaction to produce the acetal from the unsaturated aldehyde can be conducted in a batch, continuous or semi-continuous mode in a fixed bed or a slurry reactor.
  • the reaction to produce the acetal is preferably conducted at a temperature in the range of about 0°C to about 120°C, more preferably from about 20°C to about 80°C.
  • the reaction pressure is preferably in the range of about 0 kPa to about 700 kPa, more preferably from about 0 kPa to about 150 kPa.
  • the average residence time of the aldehyde with the acidic reagent is preferably from about 5 minutes to about 20 hours, more preferably from about 15 minutes to about 10 hours.
  • This reaction produces a mixture of products principally containing the unreacted aldehyde and alcohol, the corresponding alkoxyaldehyde and the unsaturated acetal, the desired acetal and water.
  • the desired acetal is separated and the other organic components and some of the water can be recycled to the reactor where the acetal is formed.
  • the acetal is converted to the diether by catalytic hydrogenation.
  • the hydrogenation reaction is suitably carried out at hydrogen pressures of about 650 kPa to about 35,000 kPa, preferably from about 1,500 kPa to about 20,000 kPa, more preferably from about 3,000 kPa to about 17,500 kPa eg from about 4,500 kPa to about 7,500 kPa.
  • the mole ratio of the acetal (II) to hydrogen can be from about 1:1 to about 1:100, and is preferably from about 1:2 to about 1:50.
  • the hydrogenation catalyst composition comprises at least one catalytic metal selected from the group consisting of Pd, Ni, Co, Pt, Rh and Ru on a support material. Pd and Ni are the preferred metals and Pd is especially preferred.
  • the support material for the catalytic metal is one or more selected from the group consisting of silica, alumina, silica-alumina, aluminosilicates and carbon.
  • the carbon where used, can be one of the many forms of carbon eg graphite or activated carbon.
  • the catalytic metal may be deposited or impregnated on the support using conventional mixing or precipitation techniques.
  • the catalyst composition suitably has a catalytic metal content of about 0.05% w/w to about 80% w/w.
  • a relatively less active metal such as eg nickel
  • a relatively more active metal such as palladium
  • the preferred range for the less active catalytic metals is suitably from about 20% w/w to about 80% w/w
  • the preferred range is suitably from about 0.05% w/w to about 20% w/w.
  • the weight ranges quoted above are based solely on the weight of the catalytic metal and the support and does not take into account any water or moisture content associated with either component.
  • Examples of commercially available catalysts that are useful include inter alia (i) Escat®10 (ex Engelhard Industries) which contains 5% w/w of palladium on activated carbon powder and has a surface area of 850 m 2 /g and a moisture content of about 52.5% w/w; (ii) Escat®14 (ex Engelhard Industries) which contains 5% w/w of palladium on activated alumina powder having a surface area of about 125 m 2 /g; and (iii) Ni-3266E (ex Engelhard Industries) which contains a calcium promoted silica/alumina supported metal catalyst having a nickel content of about 50% w/w and a surface area of about 150m 2 /g, and is in the form of 1/16-inch extrudate ⁇ .
  • the reaction may optionally be carried out in the presence of a solvent.
  • solvents include inter alia alcohols, ethers and esters.
  • Polar solvents such as alcohols are preferred although in this case the alcohol used should be such that the oxyalkyl group of the alcohol solvent corresponds to the oxyalkyl group in the desired 1,3-diethyl ether (I).
  • a sufficient amount of solvent can be used to dilute the acetal reactant (II) to the desired concentration to facilitate handling and/or to maintain the reaction mass in solution.
  • the hydrogenation reaction is suitably carried out at a temperature in the range from about 50°C to about 250°C, preferably from about 100°C to about 225°C and more preferably from about 125°C to about 225°C, eg from about 150°C to about 210°C.
  • the hydrogenation of the acetal with hydrogen in the presence of a catalyst composition as described above can be carried out in a slurry reactor, a fixed bed reactor, a spouted bed reactor or any other suitable reactor configuration such as eg a moving bed reactor.
  • the reactants may be in a gaseous phase and/or a liquid phase.
  • the reaction can be carried out in a continuous, semi-continuous or a batch-type mode.
  • the average residence time of the acetal reactant (II) in contact with the catalyst composition during the formation of the corresponding 1,3-diether compound (I) is suitably from about 5 minutes to abaout 30 hours, preferably from about 15 minutes to about 10 hours.
  • one or more of the following compounds may be generated as by-products: a) R.OH b) 3-alkoxy propanol-1 c) 1-propanol and d) alkyl propyl ether
  • the present process has the significant advantage that it is particularly selective towards the formation of the desired 1,3-diether (I) relative to the formation of the by-products (b)-(d) above.
  • the selectivity of the inventive process towards the formation of (I) relative to the formation of the combined amounts of (b)-(d) is at least about 60 mole % and is preferably at least about 90 mole %.
  • a feature of the present invention is that it has the ability to tolerate small amounts of water, eg up to about 30% w/w based on the acetal reactant (II), and anhydrous conditions need not be used. This is a significant advantage since many hydrogenation catalysts such as eg Escat®10 contain water (moisture) .
  • the present invention is further illustrated with reference to the following Examples.
  • the product mixture obtained at the end of the run contains, in addition to ethanol, 88 mole % 1,3-diethoxypropane, 7 mole % 3- ethoxypropanol-1, 3 mole % 1-propanol and 2 mole % ethylpropyl ether.
  • Example 2
  • the product mixture contains in addition to ethanol, 93 mole % 1,3- " diethoxypropane, 5 mole % of 3-ethoxypropanol-l and 2 mole % ethylpropyl ether.
  • Example 4
  • the mixture containing ethanol (40.1% wt), acrolein (0.4% wt), 3-ethoxy- propanol (6.2% wt), acrolein diethyl acetal (0.3% wt), 1,1,3- triethoxypropane (45.1% wt) and water (4.8% wt) is filtered.
  • the filtrate is vacuum distilled to give 1,1,3-triethoxy ⁇ ropane (boiling point 98°C at 40mm Hg) identified by NMR analysis.
  • Examples 6-16 A 500 ml zirconium autoclave equipped with stirrer, baffle cage and ballast vessel is charged with 300 ml of 1,1,3-triethoxypropane and a dry catalyst (which, if moist, is extracted with ethanol to remove any moisture present therein) under a nitrogen atmosphere. Having sealed the autoclave and commenced stirring, an initial charge of hydrogen is introduced such that a hydrogen atmosphere remained present during the period required to allow heating (generally 30 to 60 mins) but not such that the intended operating pressure (shown in the Table 1 below) is exceeded during this time. Once the stipulated operating temperature is attained, the ballast vessel is then employed to make up the hydrogen pressure to the desired value and maintain it at this value for the duration of the reaction.
  • Table 1 summarises the conditions and results of a sequence of Examples 6-16 which are all performed according to the general method outlined above. The following points should be noted.
  • the catalyst charge is calculated on a dry weight per volume basis and the reaction time given is that time which elapsed with the reaction maintained at the stated conditions. Analysis is by gas chromatography calibrated against an internal standard. In Table 1, the following abbreviations have been used:

Landscapes

  • 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)

Abstract

La présente invention se rapporte à un procédé de conversion d'acétals en éthers. Plus particulièrement, l'invention se rapporte à un procédé d'hydrogénation permettant de convertir un acétal de 3-alcoxypropionaldéhyde dialkyle en un 1,3-dialcoxypropane correspondant en présence d'un catalyseur d'hydrogénation sur support. Ce procédé présente une sélectivité élevée pour la formation des diéthers ci-dessus, par rapport à la formation des alcools, alcools alcoxylés et mono-éthers correspondants.
EP94923325A 1993-07-07 1994-07-05 Procede de conversion d'acetals en ethers. Withdrawn EP0658155A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US8797793A 1993-07-07 1993-07-07
US87977 1993-07-07
PCT/US1994/007517 WO1995001949A1 (fr) 1993-07-07 1994-07-05 Procede de conversion d'acetals en ethers

Publications (2)

Publication Number Publication Date
EP0658155A1 true EP0658155A1 (fr) 1995-06-21
EP0658155A4 EP0658155A4 (fr) 1996-01-24

Family

ID=22208380

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94923325A Withdrawn EP0658155A4 (fr) 1993-07-07 1994-07-05 Procede de conversion d'acetals en ethers.

Country Status (5)

Country Link
EP (1) EP0658155A4 (fr)
JP (1) JPH08500368A (fr)
KR (1) KR950703502A (fr)
AU (1) AU7322194A (fr)
WO (1) WO1995001949A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4431994A1 (de) * 1994-09-08 1996-03-14 Degussa Verfahren zur Herstellung von 1,1,3-Trialkoxypropan
GB9506052D0 (en) * 1995-03-24 1995-05-10 Bp Chem Int Ltd Process
KR100483787B1 (ko) * 1995-04-20 2005-06-16 이데미쓰 고산 가부시키가이샤 에테르화합물의제조방법
US5977010A (en) * 1995-06-15 1999-11-02 Engelhard Corporation Shaped hydrogenation catalyst and processes for their preparation and use
GB201717211D0 (en) 2017-10-19 2017-12-06 Bp Plc Etherification process
GB201717210D0 (en) 2017-10-19 2017-12-06 Bp Plc Selective acetalization/etherification process
GB201818905D0 (en) 2018-11-20 2019-01-02 Bp Plc Process for making ethers via enol ethers

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE888999C (de) * 1943-01-13 1953-09-07 Chemische Werke Huels Ges Mit Verfahren zur Herstellung von Diaethern von 1, 3-Glykolen
DE898895C (de) * 1939-06-11 1953-12-07 Degussa Verfahren zur Herstellung von ª‰-Alkoxypropionaldehydacetalen bzw. deren ª‡-substituierten Homologen

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2590598A (en) * 1948-12-07 1952-03-25 Gen Aniline & Film Corp Polyethers and process of preparing the same
US4479017A (en) * 1981-06-29 1984-10-23 Mitsubishi Petrochemical Co., Ltd. Process for producing ether compounds by catalytic hydrogenolysis

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE898895C (de) * 1939-06-11 1953-12-07 Degussa Verfahren zur Herstellung von ª‰-Alkoxypropionaldehydacetalen bzw. deren ª‡-substituierten Homologen
DE888999C (de) * 1943-01-13 1953-09-07 Chemische Werke Huels Ges Mit Verfahren zur Herstellung von Diaethern von 1, 3-Glykolen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9501949A1 *

Also Published As

Publication number Publication date
JPH08500368A (ja) 1996-01-16
EP0658155A4 (fr) 1996-01-24
WO1995001949A1 (fr) 1995-01-19
AU7322194A (en) 1995-02-06
KR950703502A (ko) 1995-09-20

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