EP1562884A1 - Procede de production d'aldehydes a partir d'alcanes - Google Patents

Procede de production d'aldehydes a partir d'alcanes

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Publication number
EP1562884A1
EP1562884A1 EP03810428A EP03810428A EP1562884A1 EP 1562884 A1 EP1562884 A1 EP 1562884A1 EP 03810428 A EP03810428 A EP 03810428A EP 03810428 A EP03810428 A EP 03810428A EP 1562884 A1 EP1562884 A1 EP 1562884A1
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EP
European Patent Office
Prior art keywords
alkanes
alkenes
aldehydes
alcohols
hydrogen
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EP03810428A
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German (de)
English (en)
Inventor
Götz-Peter SCHINDLER
Rocco Paciello
Klaus Harth
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BASF SE
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BASF SE
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    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • 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
    • C07C45/50—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 by oxo-reactions
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • 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
    • C07C29/36—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 with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—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 with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • 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
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • 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
    • Y02P20/10—Process efficiency

Definitions

  • the invention relates to a process for the production of saturated aliphatic C n - aldehydes from C n -i alkanes.
  • the invention further relates to a process for the integrated production of saturated C 1-4 alcohols and C 2n alcohols from C n -alkanes.
  • the invention particularly relates to processes of this type in which propane, butane or C 1 -C 14 -alkanes are used as alkanes.
  • the aldehydes obtained in the hydroformylation can, for example, be hydrogenated directly to the corresponding alcohols.
  • the aldehydes obtained can also be subjected to an aldol condensation and the condensation products obtained can then be hydrogenated to the corresponding alcohols, alcohols having a double carbon number being obtained.
  • the hydroformylation is often carried out as low-pressure hydroformylation in the liquid phase with a catalyst homogeneously dissolved in the reaction medium, for example in the case of
  • olefin mixtures which contain different isomers of the olefins in question.
  • olefin mixtures are obtained from steam crackers.
  • raffinate U which is a C 4 cut from a steam cracker depleted in isobutene and butadiene.
  • Hydrocarbon mixture which must be subjected to a multi-stage work-up before the pure feed olefin for the hydroformylation is available. For example, must
  • Propene from a hydrocarbon mixture of methane, ethane, ethene, acetylene, propane, Propene, butenes, butadiene, C 5 - and higher hydrocarbons can be isolated.
  • the separation of propane and propene requires columns with 10 to 100 trays. Since ethene and propene are usually produced together when cracking naphtha, the production quantity of one product is always linked to the production quantity of the other product.
  • the object of the invention is to put the hydroformylation of olefins on a new raw material basis. It is also an object of the invention to provide a process for the hydroformylation of olefins, with which the hydrocarbons contained in the feed gas stream of the hydroformylation are used as well as possible.
  • the object is achieved by a process for the preparation of saturated aliphatic C n -aldehydes from C n -i-alkanes, where n is a number from 4 to 20, in which
  • a) provides a feed gas stream containing one or more C n -alkanes
  • the C n -alkenes in the presence of the C n -alkanes and optionally the secondary constituents in the presence of a hydroformylation catalyst are at least partially hydroformylated with carbon monoxide and hydrogen to give the C n -aldehydes,
  • the product mixture obtained is separated, giving a stream containing the C n -aldehydes and a C n -ralkanes and, if appropriate, a gas stream containing secondary constituents, e) the gas stream containing the C n - ⁇ alkanes and optionally the secondary constituents is at least partially recycled as a circulating gas stream into the catalytic alkane dehydrogenation (step b)).
  • Suitable alkanes which can be used in the process according to the invention have 3 to 19 carbon atoms, preferably 3 to 14 carbon atoms.
  • Propane, n-butane, isobutane, pentanes, hexanes, heptanes, octanes, nonanes, decanes, undecanes, dodecanes, tridecanes and tetradecanes are therefore preferred as linear n-alkanes or as branched i-alkanes.
  • Propane, n-butane, isobutane and the o-Cu alkanes mentioned are particularly preferred.
  • the mixtures can include isomeric alkanes with the same carbon number or also alkanes with a different carbon number.
  • a mixture of n-butane and isobutane can be used.
  • Higher alkanes for example the C 1 -C 4 -alkanes mentioned, are usually used as a mixture of alkanes of different carbon numbers, for example as a mixture of isomeric decanes, undecanes, dodecanes, tridecanes and tetradecanes.
  • the alkane used in the alkane dehydrogenation can contain minor components.
  • the propane used can contain up to 50% by volume of further gases such as ethane, methane, ethylene, butanes, butenes, propyne, acetylene, H 2 S, SO 2 and pentanes.
  • the crude propane used generally contains at least 60% by volume, preferably at least 70% by volume, particularly preferably at least 80% by volume, in particular at least 90% by volume and very particularly preferably at least 95% by volume of propane.
  • the butane used can contain up to 10% by volume of further gases such as methane, ethane, propane, pentanes, hexanes, nitrogen and water vapor.
  • the alkanes mentioned can be obtained, for example, from natural gas or liquefied petroleum gas (LPG) from refineries.
  • LPG liquefied petroleum gas
  • Propane and butanes are preferably obtained from LPG.
  • the alkane or alkanes are partially dehydrogenated to the corresponding alkenes in the presence of a dehydrogenation catalyst.
  • a product gas mixture is formed which, in addition to unreacted alkanes and the or
  • Alkenes minor components such as hydrogen, water, cracking products of the alkanes, CO and Contains CO 2 .
  • the alkane dehydrogenation can be carried out with or without an oxygen-containing gas as a co-feed.
  • the alkane dehydrogenation can in principle be carried out in all reactor types and procedures known from the prior art. A detailed description of suitable reactor types and modes of operation can be found in "Catalytica® Studies Division, Oxidati ve Deydrogenation and Alternative Deydrogenation Processes, Study Number 4192 OD, 1993, 430 Ferguson Drive, Mountain View, California, 94043-5272 U.S.A.”
  • a suitable reactor form is the fixed bed tube or tube bundle reactor.
  • the catalyst dehydrogenation catalyst and, when working with oxygen as a co-feed, possibly a special oxidation catalyst
  • the catalyst is located as a fixed bed in a reaction tube or in a bundle of reaction tubes.
  • the reaction tubes are usually heated indirectly in that a gas, for example a hydrocarbon such as methane, is burned in the space surrounding the reaction tubes. It is favorable to use this indirect form of heating only for the first approx. 20 to 30% of the length of the fixed bed and to heat the remaining bed length to the required reaction temperature by means of the radiant heat released as part of the indirect heating.
  • Typical reaction tube line diameters are about 10 to 15 cm.
  • a typical dehydrogenation tube bundle reactor comprises approximately 300 to 1000 reaction tubes.
  • the temperature in the interior of the reaction tube is usually in the range from 300 to 700 ° C., preferably in the range from 400 to 700 ° C.
  • the reactor outlet pressure is usually between 0.5 and 8 bar, often between 1 and 2 bar when using a low water vapor dilution (according to the BASF Linde process), but also between 3 and 8 bar when using a high water vapor dilution (according to the so-called “steam active” reforming process "(STAR process) from Phillips Petroleum Co., see US 4,902,849, US 4,996,387 and US 5,389,342).
  • Typical catalyst loads (GHSV) with propane are 500 to 2000 h " ⁇
  • the catalyst geometry can be spherical or cylindrical (hollow or being full.
  • the alkane dehydrogenation can be carried out in a moving bed reactor.
  • the moving catalyst bed can be accommodated in a radial current reactor. In this the catalyst moves slowly from top to bottom while the reaction gas mixture flows radially. This procedure is used, for example, in the so-called UOP-Oleflex dehydrogenation process.
  • the reactors at this If the process is operated virtually adiabatically, it is advisable to operate several reactors in series (typically up to four reactors). Before or in each reactor, the inlet gas mixture is heated to the required reaction temperature by combustion in the presence of supplied oxygen. By using several reactors, large differences in the temperatures of the reaction gas mixture between the reactor inlet and the reactor outlet can be avoided and high overall conversions can nevertheless be achieved.
  • the dehydrogenation catalyst used is generally spherical.
  • the working pressure is typically 2 to 5 bar.
  • the molar ratio of hydrogen to alkane is preferably from 0.1 to 10.
  • the reaction temperatures are preferably 550 to 660 ° C.
  • the alkane dehydrogenation can also, as in Chem. Eng. Be. 1992 b, 47 (9-11) 2313, heterogeneously catalyzed in a fluidized bed, the alkane not being diluted.
  • two fluidized beds are operated side by side, one of which is usually in the state of regeneration.
  • the working pressure is typically 1 to 2 bar, the dehydrogenation temperature usually 550 to 600 ° C.
  • the heat required for the dehydrogenation is introduced into the reaction system by preheating the dehydrogenation catalyst to the reaction temperature.
  • the preheaters can be dispensed with and the required heat can be generated directly in the reactor system by burning hydrogen in the presence of oxygen. If necessary, a hydrogen-containing co-feed can also be added.
  • the alkane dehydrogenation can be carried out in a tray reactor.
  • This contains one or more successive catalyst beds.
  • the number of catalyst beds can be 1 to 20, advantageously 1 to 6, preferably 1 to 4 and in particular 1 to 3.
  • the reaction beds preferably flow radially or axially through the catalyst beds.
  • Such a tray reactor is generally operated with a fixed catalyst bed.
  • the fixed catalyst beds are arranged axially in a shaft furnace reactor or in the annular gaps of cylindrical grids placed one inside the other.
  • a shaft furnace reactor corresponds to a horde.
  • Carrying out the dehydrogenation in a single shaft furnace reactor corresponds to a preferred embodiment.
  • the dehydrogenation is carried out in a tray reactor with 3 catalyst beds. With a driving style without Oxygen as co-feed is subjected to intermediate heating in the tray reactor on its way from one catalyst bed to the next catalyst bed, for example by passing it over heat exchanger surfaces heated with hot gases or by passing it through pipes heated with hot fuel gases.
  • the alkane dehydrogenation is carried out autothermally.
  • an oxygen-containing gas is additionally mixed into the reaction gas mixture of the alkane dehydrogenation in at least one reaction zone and the hydrogen contained in the reaction gas mixture is burned, whereby at least part of the required heat of dehydrogenation is generated directly in the reaction gas mixture in the at least one reaction zone.
  • the amount of the oxygen-containing gas added to the reaction gas mixture is selected so that the combustion of the hydrogen present in the reaction gas mixture and possibly of hydrocarbons present in the reaction gas mixture and or of carbon present in the form of coke generates the amount of heat required for the dehydrogenation of the alkane to the alkene becomes.
  • the total amount of oxygen supplied based on the total amount of the alkane to be dehydrogenated, is 0.001 to 0.5 mol / mol, preferably 0.005 to 0.2 mol / mol, particularly preferably 0.05 to 0.2 mol / mol.
  • Oxygen can be used either as pure oxygen or as an oxygen-containing gas in a mixture with inert gases.
  • the preferred oxygen-containing gas is air.
  • the inert gases and the resulting combustion gases generally have an additional dilution effect and thus promote heterogeneously catalyzed dehydrogenation.
  • the hydrogen burned to generate heat is the hydrogen formed in the hydrocarbon dehydrogenation and, if appropriate, hydrogen additionally added to the reaction gas mixture.
  • Sufficient hydrogen is preferably added such that the molar ratio H 2 / O 2 in the reaction gas mixture is 2 to 10 mol / mol immediately after the feed. This applies to multi-stage reactors for every intermediate feed of hydrogen and oxygen.
  • the hydrogen is burned catalytically.
  • the dehydrogenation catalyst used generally also catalyzes the combustion of hydrocarbons and
  • the process is carried out in the presence of one or more oxidation catalysts which selectively catalyze the combustion of hydrogen to oxygen in the presence of hydrocarbons.
  • the combustion of the hydrocarbons with oxygen to CO and CO 2 takes place only to a minor extent, which has a clearly positive effect on the selectivities achieved for the formation of the alkenes.
  • the dehydrogenation catalyst and the oxidation catalyst are preferably present in different reaction zones.
  • the oxidation catalyst can be present in only one, in several or in all reaction zones.
  • the catalyst which selectively catalyzes the oxidation of hydrogen in the presence of hydrocarbons, is preferably arranged at the points where there are higher oxygen partial pressures than at other points in the reactor, in particular in the vicinity of the feed point for the oxygen-containing gas.
  • Oxygen-containing gas and / or hydrogen can be fed in at one or more points in the reactor.
  • oxygen-containing gas and hydrogen are fed in before each horde except the first horde. In one embodiment, everyone is behind
  • a layer of a special oxidation catalyst is present in the feed point, followed by a layer of the dehydrogenation catalyst.
  • Embodiment there is no special oxidation catalyst.
  • Dehydration temperature is generally 400 to 800 ° C, the outlet pressure in the last
  • Catalyst bed of the tray reactor in general 0.2 to 5 bar, preferably 1 to 3 bar.
  • Exposure to propane (GHSV) is generally 500 to 2000 h “1 , in high-load operation also up to 16000 h “ 1 , preferably 4000 to 16000 h “1 .
  • the dehydrogenation can also be carried out as described in DE-A 102 11 275.
  • a preferred catalyst that selectively catalyzes the combustion of hydrogen contains oxides or phosphates selected from the group consisting of the oxides or
  • Phosphates of germanium, tin, lead, arsenic, antimony or bismuth contains a noble metal of VHI. or I. subgroup.
  • the dehydrogenation catalysts used generally have a support and an active composition.
  • the carrier consists of a heat-resistant oxide or mixed oxide.
  • the dehydrogenation catalysts preferably contain a metal oxide, which is selected from the group consisting of zirconium dioxide, zinc oxide, aluminum oxide, silicon dioxide, titanium dioxide, magnesium oxide, lanthanum oxide, cerium oxide and mixtures thereof, as a carrier.
  • Preferred supports are zirconium dioxide and / or silicon dioxide, mixtures of zirconium dioxide and silicon dioxide are particularly preferred.
  • the active mass of the dehydrogenation catalysts generally contain one or more elements of the VHI. Sub-group, preferably platinum and / or palladium, particularly preferably platinum.
  • the dehydrogenation catalysts can include one or more elements of I. and / or LT. Main group, preferably potassium and / or cesium.
  • the dehydrogenation catalysts can contain one or more elements of the EL subgroup including the lanthanides and actinides, preferably lanthanum and / or cerium.
  • the dehydrogenation catalysts can include one or more elements of HI. and / or IV. Main group, preferably one or more elements from the group consisting of boron, gallium, silicon, germanium, tin and lead, particularly preferably tin.
  • the dehydrogenation catalyst contains at least one element of the VHI.
  • Sub-group at least one element of I. and / or LT.
  • Main group at least one element of the HI. and / or IV.
  • main group at least one element of HI.
  • Subgroup including the lanthanides and actinides.
  • the alkane dehydrogenation is usually carried out in the presence of water vapor.
  • the added steam serves as a heat carrier and supports the gasification of organic deposits on the catalysts, which counteracts the coking of the catalysts and increases the service life of the catalyst.
  • the organic deposits are converted into carbon monoxide and carbon dioxide.
  • the dehydrogenation catalyst can be regenerated in a manner known per se. So steam can be added to the reaction gas mixture or from time to time Gas containing oxygen are passed over the catalyst bed at elevated temperature and the separated carbon is burned off.
  • Alkane dehydrogenation often gives a mixture of isomeric alkenes.
  • a mixture of 1-butene and 2-butene, for example in a ratio of 1: 2 is thus obtained from n-butane.
  • a mixture of 1-butene, 2-butene and isobutene is obtained from a mixture of n-butane and isobutane.
  • An isomerization step can optionally follow.
  • the gas mixture obtained in the alkane dehydrogenation contains minor constituents in addition to the alkenes or the unreacted alkanes. Common secondary components are hydrogen, water, nitrogen, CO, CO 2 , and cracking products of the alkanes used.
  • the composition of the gas mixture leaving the dehydrogenation stage can vary widely depending on the mode of operation of the dehydrogenation. Thus, when the preferred autothermal dehydrogenation is carried out with the addition of oxygen and additional hydrogen, the product gas mixture will have a comparatively high content of water and carbon oxides. In modes of operation without feeding in oxygen, the product gas mixture of the dehydrogenation will have a comparatively high content of hydrogen.
  • the product gas mixture leaving the dehydrogenation reactor contains at least the components propane, propene and molecular hydrogen. In addition, however, it will generally also contain N 2 , H 2 O, methane, ethane, ethylene, CO and CO 2 .
  • the product gas mixture leaving the dehydrogenation reactor will contain at least the constituents 1-butene, 2-butene, isobutene and hydrogen. In addition, however, it will usually also contain N 2 , HO, methane, ethane, ethene, propane, propene, butadiene, CO and CO.
  • the gas mixture leaving the dehydrogenation reactor will be under a pressure of 0.3 to 10 bar and will often have a temperature of 400 to 700 ° C, in favorable cases 450 to 600 ° C.
  • Water can be separated off, for example, by condensation by cooling and / or compressing the product gas stream from the dehydrogenation and can be carried out in one or more cooling and / or compression stages.
  • the Water separation is usually carried out when the alkane dehydrogenation is carried out autothermally or isothermally with the introduction of water vapor (Linde, STAR process) and consequently the product gas stream has a high water content.
  • the or the C n -alkanes and the or the C n -alkenes can be separated from the other secondary constituents in an absorption-Z desorption cycle using a high-boiling absorbent.
  • C n -alkanes and C n -alkenes are absorbed in an inert absorption medium in an absorption stage, an absorption medium loaded with C n -alkanes and C n -alkenes and an offgas containing the secondary components being obtained, and in a desorption stage C "- r alkanes and C n -alkenes released from the absorbent.
  • alkynes, dienes and / or allenes are present in the product gas stream, their content is preferably reduced to less than 10 ppm, in particular to less than 5 ppm. This can be done by partial hydrogenation to alkene, for example as described in EP-A 0 081 041 and DE-A 1 568 542.
  • propyne or all may be contained as minor components in the product gas stream of the propane dehydrogenation.
  • Butine and butadiene may be contained as secondary components in the product gas stream of the butane dehydrogenation. These are preferably subjected to a partial hydrogenation to propene or butene.
  • Suitable catalysts for the partial hydrogenation of butyne and butadiene are disclosed, for example, in WO 97/39998 and WO 97/40000.
  • a catalyst which is insensitive to the alkynes, dienes and allenes mentioned is used in the subsequent hydroformylation stage, the partial hydrogenation can be dispensed with.
  • Suitable catalysts are described, for example, in Johnson et al., Angewandte Chemie Int. Ed. 34 (1995), pp. 1760-61.
  • the C n -alkenes coming from the alkane dehydrogenation are, optionally after separating off secondary constituents and / or partial hydrogenation, in the presence of the unreacted C n -alkanes and in the presence of a hydroformylation catalyst, in part with carbon monoxide and hydrogen to give the corresponding saturated C n - Aldehydes hydroformylated.
  • Synthesis gas ie a technical mixture of carbon monoxide and hydrogen, is usually used for this purpose.
  • the hydroformylation takes place in the presence of catalysts homogeneously dissolved in the reaction medium. In general, compounds or complexes of metals from VHI are used as catalysts.
  • Subgroup, especially Co, Rh, Ir, Pd, Pt or Ru compounds or complexes used, the modified or z. B. can be modified with compounds containing amine or phosphine.
  • the product gas mixture of the alkane dehydrogenation already contains CO and H 2 in certain amounts in addition to alkane and alkene.
  • propene or butenes are hydroformylated.
  • the hydroformylation of propene gives n-butyraldehyde and 2-methylpropanal.
  • Hydroformylation of a 1-butene, 2-butene and optionally isobutene-containing hydrocarbon stream gives Cs aldehydes, i.e. H. n-valeraldehyde, 2-methylbutanal and optionally 3-methylbutanal.
  • the propene or butene hydroformylation is preferably carried out in the presence of a rhodium complex catalyst in conjunction with a triorganophosphine ligand.
  • the triorganophosphine ligand can be a trialkylphosphine, such as tributylphosphine, an alkyldiarylphosphine, such as butyldiphenylphosphine, or an aryldialkylphosphine, such as phenyldibutylphosphine.
  • triarylphosphine ligands such as triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, phenyldinaphthylphosphine, are particularly preferred,
  • Diphenylnaphthylphosphine tri (p-methoxyphenyl) phosphine, tri (p-cyanophenyl) phosphine, tri (p-nitrophenyl) phosphine, p-N, N-dimethylaminophenylbisphenylphosphine and the like. Triphenylphosphine is most preferred.
  • Propene and the butenes are partially hydroformylated.
  • a butene-depleted gas stream is thus obtained, the content of 1-butene of which is reduced compared to the product gas stream of the butane dehydrogenation and which essentially contains the original amounts of 2-butene and isobutene.
  • the ratio of n-valeraldehyde to 2-methylbutanal in the Cs aldehydes obtained is preferably at least 4: 1, in particular at least 8: 1.
  • the preferred hydroformylation of 1-butene over 2-butene and isobutene can be achieved by using a large excess of triorganophosphorus ligands and by carefully controlling the temperatures and partial pressures of the reactants and / or products.
  • the triorganophosphine ligand is preferably used in an amount of at least 100 moles per gram atom of rhodium.
  • the temperature is preferably in the range from 80 to 130 ° C.
  • the total pressure is preferably not more than 5,000 kPa, the partial pressure of carbon monoxide being kept below 150 kPa and the partial pressure of hydrogen in the range from 100 to 800 kPa.
  • a suitable hydroformylation process in which a mixture of butenes is used is described in EP 0 016 286.
  • the hydroformylation can also be carried out in such a way that an almost complete alkene conversion takes place.
  • Suitable catalysts on which both 1-butene and 2-butene are hydroformylated are, for example, the chelate phosphites described in EP-A 0 155 508 or the chelate phosphoramidites described in US Pat. No. 5,710,344.
  • C 1 -C 8 -alkenes are hydroformylated to give C ⁇ -s-aldehydes.
  • an aqueous cobalt (IJ) salt solution is intimately contacted with hydrogen and carbon monoxide to form a hydroformylation-active cobalt catalyst; the cobalt catalyst-containing aqueous phase in at least one reaction zone with the C ⁇ o-C ⁇ 4 - is brought alkenes, hydrogen and carbon monoxide into intimate contact, wherein the cobalt catalyst is extracted into the organic phase and the C 1 0- 4 - alkenes are hydroformylated,
  • the discharge from the reaction zone is treated with oxygen in the presence of acidic aqueous cobalt ( ⁇ ) salt solution, the cobalt catalyst being decomposed to form cobalt ( ⁇ ) salts and these being extracted back into the aqueous phase, the phases then being separated, and
  • Cobalt carboxylates such as cobalt ( ⁇ ) formate, cobalt (IT) acetate or cobalt ethyl hexanoate and cobalt acetylacetonate, are particularly suitable as cobalt (II) salts.
  • the catalyst formation can take place simultaneously with the catalyst extraction and hydroformylation in one step in the reaction zone of the hydroformylation reactor or in an upstream step (precarbonylation).
  • the precarbonylation can advantageously be carried out according to the description in DE-OS 2 139 630.
  • the aqueous solution thus obtained, containing cobalt ( ⁇ ) salts and cobalt catalyst, is then passed into the reaction zone together with the C 10 -C 14 alkenes to be hydroformylated, as well as hydrogen and carbon monoxide.
  • the formation of the cobalt catalyst, the extraction of the cobalt catalyst into the organic phase and the hydroformylation take place in one step in which the aqueous cobalt (U) salt solution and the alkenes in the reaction zone are in intimate contact under hydroformylation conditions to be brought.
  • the starting materials are introduced into the reaction zone in such a way that the phases are mixed well and the phase exchange surface is as large as possible. Mixing nozzles for multiphase systems are particularly suitable for this.
  • the discharge from the reaction mixture is let down and passed to the decarburization stage.
  • the reaction discharge is in the decarburization stage.
  • the C n -aldehydes formed are separated off, a gas stream containing C n -r alkanes and unreacted C n -alkenes being obtained.
  • the C n -aldehydes formed are generally separated off in such a way that the hydroformylation product comprising liquid and gaseous constituents is converted into a C n -aldehyde, C n - ⁇ alkane, unreacted C n -alkenes, unreacted synthesis gas and, if appropriate, more separates gas phase containing non-condensable constituents and a liquid phase, the C n -aldehydes, C n -alkanes and unreacted C n -alkenes are condensed out of the gas phase and the condensate obtained is converted into a liquid stream containing the C "- aldehydes and a C n -r alkanes and the unreacted C n -r alkenes containing gas stream.
  • the most important further non-condensable constituent is nitrogen if the alkane dehydrogenation is carried out autofherm and air is used as the oxygen-containing co-feed.
  • the hydroformylation discharge is preferably separated into a liquid phase and a gas phase in such a way that
  • liquid and gaseous constituents containing hydroformylation which, in addition to the catalyst, essentially the C n -aldehyde, by-products boiling higher than the C n - aldehyde, unreacted C n -r alkenes, C n -r alkanes, unreacted synthesis gas and contains other non-condensable constituents, relaxed in a relaxation vessel,
  • the liquid stream is then heated to a temperature higher than the temperature prevailing in the expansion vessel
  • the essentially liquid discharge from the hydroformylation reactor which generally has a temperature of 50 to 150 ° C. and is generally under a pressure of 2 to 30 bar, is decompressed into a flash vessel.
  • the liquid part of the discharge from the hydroformylation reaction contains as essential constituents the catalyst, the hydroformylation product, i.e. the C n - aldehyde ( s ) produced from the C n -r alkene or alkene mixture used, by-products of the hydroformylation or solvents boiling higher than the hydroformylation product the hydroformylation reaction, unreacted C n-i-alkenes and unreacted because unreactive C n -rAlkane.
  • the hydroformylation product i.e. the C n - aldehyde ( s ) produced from the C n -r alkene or alkene mixture used
  • by-products of the hydroformylation or solvents boiling higher than the hydroformylation product the hydroformylation reaction unreacted C n-i-alkenes and unreacted because unreactive C n -rAlkane.
  • the separation of the liquid hydroformylation output into a catalyst becomes higher than the C n -aldehydes boiling by-products of the hydroformylation reaction, residual amounts of C n -alkenes and C n -aldehydes and, if an additional high-boiling solvent was used in the hydroformylation, this solvent-containing liquid phase and in a major part of the C n -aldehydes, the majority of the unreacted C n _r alkenes, C n - r alkanes and unreacted synthesis gas and, if appropriate, further gas phase containing non-condensable constituents.
  • the liquid phase separated in the expansion vessel is withdrawn as a liquid stream from the expansion vessel and this is heated, for example by means of a continuous-flow heater or heat exchanger, to a temperature which is generally 10 to 80 ° C. above the temperature of the liquid phase in the expansion vessel.
  • the thus heated, liquid stream from the expansion tank is fed to the top or upper part of a column, which is advantageously equipped with packing, packing or internals, and countercurrent to the gas stream introduced in the lower part of the column and drawn off from the upper part of the expansion vessel ,
  • the gas stream is in intimate contact with the heated liquid stream, favored by the large surface area present in the column, the residual amounts of C n -aldehydes and unconverted C n - ⁇ alkenes present in the liquid stream are transferred into the gas stream, so that the via line discharged at the top of the column Gasstom n to C aldehydes and unreacted C n enriched - ⁇ -alkenes, however, the exiting at the bottom of the column liquid stream n to C aldehydes and unreacted C n ⁇ -. alkenes is depleted.
  • the type of separation described is particularly advantageous because of the high alkane content of the hydroformylation output. Because of the high content of non-condensable components, the stripping described is particularly efficient.
  • n to C aldehydes and unreacted C may contain n . ⁇ - alkenes depleted posstechniksstom, consisting essentially of the catalyst and higher boiling by-products of the hydroformylation reaction, and optionally a high-boiling solvent is completely or partly back into returned the hydroformylation reactor.
  • the gas stream enriched at the top of the column with the C n -aldehydes and unreacted C n -alkenes, the additional components C n -r alkanes and unreacted Synthesis gas contains is expediently fed to a condenser for further work-up, in which the C n -aldehydes, unreacted C n - ⁇ alkenes and C n -r alkanes are separated by condensation of unreacted synthesis gas and optionally the further non-condensable constituents.
  • the unreacted syngas can be returned to the hydroformylation reactor.
  • the condensable constituents separated off in the condenser containing the C n aldehydes, unreacted C n ralkenes and C "r alkanes, are introduced into a distillation plant, which can consist of several distillation plants, and into a stream containing the C" aldehydes and a gas stream containing the unreacted C n -r alkenes and Cn-i alkanes separated.
  • the C n -aldehydes can, if appropriate after further purification, then be used for further processing to give other valuable products.
  • the gas stream containing the C n _r alkanes and possibly unreacted C n - ⁇ alkenes is at least partially, preferably completely, recycled as a circulating gas stream into the catalytic alkane dehydrogenation (step b)).
  • a particularly good utilization of the hydrocarbons contained in the feed gas stream of the hydroformylation is achieved by the cycle gas procedure, since unreacted alkanes dehydrate to further alkenes in the dehydrogenation stage and these are subsequently fed to the hydroformylation.
  • the C "- aldehydes obtained can be subjected to an aldol condensation and the products of the aldol condensation can be catalytically hydrogenated to C 2n alcohols.
  • the aldol condensation takes place in a manner known per se, for. B. by the action of an aqueous base such as sodium hydroxide solution or potassium hydroxide solution.
  • a heterogeneous basic catalyst such as magnesium and / or aluminum oxide, can also be used (cf., for example, EP-A 792 862).
  • the product of the aldol condensation is then catalytically hydrogenated with hydrogen.
  • Suitable hydrogenation catalysts are generally transition metals, such as. B. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Rt, Ru etc. or mixtures thereof to increase the activity and stability on supports such.
  • B. activated carbon, aluminum oxide, diatomaceous earth, etc. can be applied.
  • Fe, Co and preferably Ni can also be used in the form of the Raney catalysts as a metal sponge with a very large surface area.
  • the hydrogenation takes place depending on the activity of the catalyst, preferably at elevated temperatures and elevated pressure.
  • the hydrogenation temperature is preferably about 80 to 250 ° C., and the pressure is preferably about 50 to 350 bar.
  • the crude hydrogenation product can by conventional methods, e.g. B. by distillation to the individual alcohols.
  • two molecules of C 4 aldehyde are condensed to unsaturated branched C 8 aldehydes, in particular 2-ethylhexenal, and these are hydrogenated to the corresponding C 8 alcohols, in particular 2-ethyl hexanol.
  • two molecules of C 5 aldehyde are condensed to unsaturated branched o-aldehydes, such as, in particular, 2-propyl-2-heptenal and 2-propyl-4-methyl-2-hexenal, and these are condensed to the corresponding ones Cio-alcohols, such as in particular 2-propylheptanol and 2-propyl-4-methylhexanol, hydrogenated.
  • unsaturated branched o-aldehydes such as, in particular, 2-propyl-2-heptenal and 2-propyl-4-methyl-2-hexenal
  • C n -alkenes which have not been converted in the hydroformylation step can be oligomerized in the presence of the C n -r alkanes on an olefin oligomerization catalyst to give C 2n - 2- alkenes, separated and hydroformylated with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to give C 2n- aldehydes.
  • the C 2n -r aldehydes obtained can be hydrogenated catalytically with hydrogen to give the C 2n -r alcohols.
  • the present invention thus also relates to a process for the integrated production of saturated C 2n alcohols and C 2n -r alcohols from C n _ralkanes, where n is a number from 4 to 20, in which
  • a) provides a feed gas stream containing one or more C n -alkanes, b) the C n -alkanes are subjected to a catalytic dehydrogenation, a product gas stream comprising unreacted C 1 -r alkanes, one or more C n -r alkenes and optionally secondary constituents being obtained,
  • the C 2n -i-aldehydes are hydrogenated catalytically with hydrogen to C 2n -r alcohols
  • the gas stream containing the C n -alkanes and secondary constituents is at least partially recycled as a circulating gas stream into the alkane dehydrogenation (step b)).
  • the hydroformylation step c) is carried out in such a way that there is no substantially complete conversion of the alkenes, further products of value can be obtained from the unreacted alkenes by dimerization, hydroformylation and hydrogenation.
  • C 6 alkene mixtures and from these C 7 aldehydes, such as in particular methylhexanals and further C 7 alcohols, such as in particular methyl hexanols can be obtained.
  • the im Hydroformylation step c) formed C 4 -aldehydes obtained by aldol condensation and hydrogenation, in particular ethylhexanol.
  • a mixture comprising butane and isobutane is catalytically dehydrated and, as described above, the butene hydroformylation is carried out under conditions under which the reaction of 1-butene takes place rapidly, while the hydroformylation of 2-butene and isobutene takes place slowly.
  • a butene-depleted gas stream is obtained, the content of 1-butene of which is reduced compared to the product gas stream of the butane dehydrogenation and which essentially contains the original amounts of 2-butene and isobutene.
  • 2-butene and isobutene are oligomerized to C 8 -alkenes, the resulting product mixture is separated, the C 8 -alkenes obtained are hydroformylated to C 9 -aldehydes such as, in particular, isononanal and hydrogenated catalytically to C 9 alcohols, in particular isononanols.
  • C 9 -aldehydes such as, in particular, isononanal and hydrogenated catalytically to C 9 alcohols, in particular isononanols.
  • 2-propylheptanol and 2-propyl-4-methylhexanol in particular are obtained from the C5-aldehydes formed in the hydroformylation step c) essentially from 1-butene by aldol condensation and hydrogenation.
  • a number of processes are known for dimerizing lower olefins, such as propene, butenes, pentenes and hexenes.
  • each of the known processes is suitable for carrying out the dimerization step of the process according to the invention.
  • Higher olefins can be dimerized, for example, as described in WO 00/56683, WO 00/53347 and WO 00/39058.
  • the olefins can be dimerized using homogeneous or heterogeneous catalysis.
  • An example of a homogeneously catalyzed process is the DLMERSOL process.
  • DIMERSOL process see Revue de 1 'Institut Fran ⁇ ais du Petrol, Vol. 37, No. 5, SeptJOct. 1982, page 639ff
  • lower olefins are dimerized in the liquid phase.
  • precursors of the catalytically active species are, for. B.
  • a disadvantage of the homogeneously catalyzed processes is the complex removal of the catalyst. These disadvantages do not exist with the heterogeneously catalyzed processes.
  • an olefin-containing stream is generally passed over the fixedly arranged heterogeneous catalyst at elevated temperature.
  • the heterogeneous, nickel-containing catalysts that can be used can have different structures, with catalysts containing nickel oxide being preferred.
  • catalysts containing nickel oxide there are known catalysts, such as those used in CT. O'Connor et al., Catalysis Today, Vol. 6 (1990), pages 336-338.
  • supported nickel catalysts are used.
  • the carrier materials can e.g. Example, silica, alumina, aluminosilicates, aluminosilicates with layer structures and zeolites, zirconium oxide, which is optionally treated with acids, or sulfated titanium dioxide.
  • Precipitation catalysts are particularly suitable, which by mixing aqueous solutions of nickel salts and silicates, for. B. sodium silicate with nickel nitrate, and optionally aluminum salts, such as aluminum nitrate, and calcining are available. Furthermore, catalysts can be used which are obtained by incorporating Ni 2+ ions by ion exchange in natural or synthetic layered silicates, such as montmorillonites. Suitable catalysts can also be obtained by impregnating silica, alumina or aluminosilicates with aqueous solutions of soluble nickel salts, such as nickel nitrate, nickel sulfate or nickel chloride, and then calcining.
  • nickel salts and silicates for. B. sodium silicate with nickel nitrate, and optionally aluminum salts, such as aluminum nitrate, and calcining are available.
  • catalysts can be used which are obtained by incorporating Ni 2+ ions by ion exchange in natural or synthetic layered silicates, such as mont
  • Catalysts which essentially consist of NiO, SiO 2 , TiO 2 and / or are particularly preferred
  • ZrO 2 and optionally Al 2 O 3 exist. They lead to a preference for dimerization over the formation of higher oligomers and provide predominantly linear ones
  • a catalyst that acts as an essential active ingredient Contains 10 to 70 wt .-% nickel oxide, 5 to 30 wt .-% titanium dioxide and / or zirconium dioxide, 0 to 20 wt .-% aluminum oxide and the balance silicon dioxide.
  • Such a catalyst can be obtained by precipitation of the catalyst mass at pH 5 to 9 by adding an aqueous solution containing nickel nitrate to an alkali water glass solution which contains titanium dioxide and / or zirconium dioxide, filtering, drying and tempering at 350 to 650 ° C.
  • DE 4 339 713 Reference is made in full to the disclosure of this publication and the prior art cited therein.
  • the catalyst is preferably in lumpy form, e.g. B. in the form of tablets, e.g. B. with a diameter of 2 to 6 mm and a height of 3 to 5 mm, rings with z. B. 5 to 7 mm outer diameter, 2 to 5 mm height and 2 to 3 mm hole diameter or strands of different lengths of a diameter of z. B. 1.5 to 5 mm.
  • Such forms are obtained in a manner known per se by tabletting or extrusion, usually using a tabletting aid, such as graphite or stearic acid.
  • the dimerization on heterogeneous, nickel-containing catalyst is preferably carried out at temperatures from 30 to 280 ° C., preferably from 30 to 140 ° C. and particularly preferably from 40 to 130 ° C. It is preferably carried out at a pressure of 10 to 300 bar, in particular from 15 to 100 bar and particularly preferably from 20 to 80 bar. The pressure is expediently set so that the hydrocarbon stream is liquid or in the supercritical state at the selected temperature.
  • the gas stream containing the C n -alkanes and C n -alkenes is expediently passed over one or more fixed catalysts.
  • Suitable reaction apparatuses for bringing the gas stream into contact with the heterogeneous catalyst are known to the person skilled in the art. Are suitable for. B. shell and tube reactors or shaft furnaces. Because of the lower investment costs, shaft furnaces are preferred.
  • the dimerization can be carried out in a single reactor, and the oligomerization catalyst can be arranged in a single or more fixed beds in the reactor.
  • a reactor cascade consisting of several, preferably two, reactors connected in series can be used to carry out the oligomerization, the dimerization being carried out only up to a partial conversion and the desired final conversion when passing through the reactor or reactors upstream of the last reactor of the cascade is only achieved when the reaction mixture passes through the last reactor in the cascade.
  • the hydroformylation of the C 2n - 2- alkenes to C 2n -r aldehydes following the dimerization can be carried out as described above.
  • the C 2n -r aldehydes can also be separated off as described.
  • the catalytic hydrogenation of the C 2n -aldehydes to the C n - ⁇ alcohols can be carried out as described above in connection with the hydrogenation of the aldol condensation products.
  • the hydroformylation of the C 2n - 2- alkenes to the C 2n -raldehydes and the hydrogenation to the C 2n -r alcohols is carried out in one step without isolation of the aldehydes.
  • a gas stream containing the C n -alkanes, possibly unreacted C n -alkenes and secondary components is obtained, which is at least partially, preferably completely, recycled as a circulating gas stream into the alkane dehydrogenation (step b)).
  • a particularly good utilization of the hydrocarbons contained in the feed gas stream of the process is achieved by the cycle gas procedure.
  • the present invention thus also relates to a process for the integrated production of saturated C 2n -alcohols from C n -ralkanes, where n is a number from 4 to 20, in which
  • a) provides a feed gas atom containing one or more C n .r alkanes
  • the C n -r alkanes are subjected to a catalytic dehydrogenation, a product gas stream containing unreacted C n -r alkanes, one or more C n -r
  • the gas stream containing the C n -alkanes and secondary constituents is at least partially returned as a circulating gas stream to the alkane dehydrogenation (step b)).

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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

L'invention concerne un procédé de production de Cn-aldéhydes aliphatiques saturés à partir de Cn-1-alcanes, n désignant un nombre de 4 à 20. Ledit procédé consiste a) à préparer un flux de gaz utilisé contenant un ou plusieurs Cn-1-alcanes, b) à soumettre les Cn-1-alcanes à une déshydrogénation catalytique, de façon à obtenir un flux de gaz produit contenant des Cn-1-alcanes inaltérés, un ou plusieurs Cn-1-alcènes ainsi que des constituants auxiliaires, c) à procéder à l'hydroformylation des Cn-1-alcènes au moins partiellement en présence des Cn-1-alcanes et éventuellement en présence des constituants auxiliaires ainsi que d'un catalyseur d'hydroformylation avec du monoxyde de carbone et de l'hydrogène pour former lesdits Cn-aldéhydes, d) à séparer le mélange de produits obtenu, de façon à obtenir un flux contenant les Cn-aldéhydes ainsi qu'un flux contenant des Cn-1-alcanes et éventuellement des constituants auxiliaires puis e) à ramener le flux gazeux contenant les Cn-1-alcanes et éventuellement les constituants auxiliaires au moins partiellement en tant que flux de gaz recyclé à l'étape de déshydrogénation catalytique des alcanes (étape b).
EP03810428A 2002-11-04 2003-11-03 Procede de production d'aldehydes a partir d'alcanes Withdrawn EP1562884A1 (fr)

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DE10251262 2002-11-04
DE10251262A DE10251262A1 (de) 2002-11-04 2002-11-04 Verfahren zur Herstellung von Aldehyden aus Alkanen
PCT/EP2003/012201 WO2004041763A1 (fr) 2002-11-04 2003-11-03 Procede de production d'aldehydes a partir d'alcanes

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MY139122A (en) * 2003-10-15 2009-08-28 Shell Int Research Preparation of branched aliphatic alcohols using a process stream from a dehydrogenation-isomerization unit
US8586800B2 (en) * 2009-10-16 2013-11-19 Dow Technology Investments Llc Gas phase hydroformylation process
DE102010030209A1 (de) * 2010-06-17 2011-12-22 Evonik Oxeno Gmbh Energieeffiziente Synthese von aliphatischen Adelhyden aus Alkanen und Kohlendioxid
DE102014203960A1 (de) * 2014-03-05 2015-09-10 Evonik Degussa Gmbh Verfahren zur Herstellung von Aldehyden aus Alkanen und Synthesegas
PL3246303T3 (pl) 2016-05-19 2020-06-01 Evonik Operations Gmbh Wytwarzanie n-pentanalu z mieszanin surowców ubogich w buten
US10227279B2 (en) * 2016-09-12 2019-03-12 Evonik Degussa Gmbh Dehydrogenation of LPG or NGL and flexible utilization of the olefins thus obtained
US10221110B2 (en) 2016-12-08 2019-03-05 Evonik Degussa Gmbh Dehydrogenation of olefin-rich hydrocarbon mixtures
CN111646883A (zh) * 2019-03-04 2020-09-11 内蒙古伊泰煤基新材料研究院有限公司 一种低碳烯烃加氢甲酰化制备醛的方法
DE102019119540A1 (de) * 2019-07-18 2021-01-21 Linde Gmbh Verfahren und Anlage zur Herstellung einer Zielverbindung
DE102019119543A1 (de) * 2019-07-18 2021-01-21 Linde Gmbh Verfahren und Anlage zur Herstellung einer Zielverbindung
EP4015495A1 (fr) * 2020-12-18 2022-06-22 Linde GmbH Procédé et installation de fabrication d'un composé cible
CN115716781A (zh) * 2022-10-27 2023-02-28 万华化学集团股份有限公司 一种丙烷脱氢耦合羰基合成制备丁醛的工艺

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4739124A (en) * 1985-09-16 1988-04-19 Uop Inc. Method for oxygen addition to oxidative reheat zone of ethane dehydrogenation process
US4914249A (en) * 1988-12-29 1990-04-03 Uop Dehydrogenation of dehydrogenatable hydrocarbons
NO300117B1 (no) * 1994-12-22 1997-04-14 Norske Stats Oljeselskap Reaktor for dehydrogenering av hydrokarboner med selektiv oksidasjon av hydrogen
ZA96178B (en) * 1995-01-18 1997-06-30 Exxon Chemical Patents Inc Organic compounds and processes for their manufacture
DE19654340A1 (de) * 1996-12-24 1998-08-06 Huels Chemische Werke Ag Verfahren zur Herstellung von höheren Oxo-Alkoholen
US6436871B1 (en) * 1999-02-22 2002-08-20 Symyx Technologies, Inc. Catalysts for oxidative dehydrogenation
DE10003482A1 (de) * 2000-01-27 2001-08-02 Basf Ag Verfahren zur Herstellung von C9-Alkoholen und Verfahren zur integrierten Herstellung von C9-Alkoholen und C10-Alkoholen
DE10028582A1 (de) * 2000-06-14 2001-12-20 Basf Ag Verfahren zur Herstellung von Acrolein oder Acrylsäure oder deren Gemischen aus Propan
AU2001278449A1 (en) * 2000-06-14 2001-12-24 Basf Aktiengesellschaft Method for producing acrolein and/or acrylic acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004041763A1 *

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CN1735579A (zh) 2006-02-15
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JP2006504777A (ja) 2006-02-09
AU2003276238A1 (en) 2004-06-07
US20060122436A1 (en) 2006-06-08
CN1309695C (zh) 2007-04-11
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