Classifications

• • 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
  • 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
  • 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
  • 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
  • C07C45/74—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 combined with dehydration
• • 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
  • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
  • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
  • C07C5/25—Migration of carbon-to-carbon double bonds
  • C07C5/2506—Catalytic processes

Definitions

• the present invention relates to a process for the preparation of hydroformylation products of olefins having at least four carbon atoms in which both a high proportion of olefin-containing feed used linear double-bond linear olefins and the linear C-olefins with internal double bond to hydroformylation is implemented. Furthermore, the invention relates to a process for the preparation of 2-propylheptanol, which comprises such a hydroformylation process.
• Hydroformylation or oxo synthesis is an important industrial process and is used to prepare aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes may optionally be hydrogenated in the same operation with hydrogen to the corresponding oxo alcohols.
• the reaction itself is highly exothermic and generally proceeds under elevated pressure and at elevated temperatures in the presence of catalysts.
• the catalysts used are Co, Rh, Ir, Ru, Pd or Pt compounds or complexes which can be modified to influence the activity and / or selectivity of N- or P-containing ligands.
• plasticizer alcohols of about 6 to 12 carbon atoms which are branched to a low degree (so-called semi-linear alcohols) and to corresponding mixtures thereof.
• These include in particular 2-propylheptanol and alcohol mixtures containing this.
• For their preparation can be, for example, C 4 -hydrocarbon mixtures containing butenes or butenes and butanes, subjected to a hydroformylation and subsequent aldol condensation.
• hydroformylation catalysts with insufficient n selectivity hydroformylation can easily lead not only to the formation of n-valeraldehyde but also to unwanted product aldehydes, thereby economically disadvantageing the entire process.
• phosphorus-containing ligands for the stabilization and / or activation of the catalyst metal in the rhodium-low-pressure hydroformylation.
• Suitable phosphorus ligands are z.
• phosphines, phosphinites, phosphonites, phosphites, phosphoramidites, phospholes and phosphabenzenes are triarylphosphines, such as.
• triphenylphosphine and sulfonated triphenylphosphine since they have sufficient activity and stability under the reaction conditions.
• a disadvantage of these ligands is that generally only very high excess ligands provide satisfactory yields, especially on linear aldehydes, and internal olefins are virtually unreacted.
• catalysts have the advantage of a partial utilization of olefins with internal double bond.
• the phosphite ligands or their derivatives used have the disadvantage that they undergo various degradation reactions under customary hydroformylation and / or distillation conditions. These include, for example, hydrolysis, alcoholysis, transesterification, Arbusov rearrangement, and reaction under O / C and P / O bond cleavage, as described in P.W.N.M. M. Leeuwen, Appl. Cat. A: General 2001, 212, 61.
• the hydroformylation is carried out using cobalt catalysts under high pressure conditions, which also makes it possible to utilize olefins with an internal double bond.
• the n-content of hydroformylation products obtained is comparatively low.
• the process includes a stage that is performed at high pressure. The investment costs for high-pressure processes are significantly higher than for low-pressure processes, so that the process is economically disadvantaged.
• the hydroformylation is carried out as a one-step process, then complete or almost complete conversions of the olefins used to preferably linear hydroformylation products can often not be realized for technical or process-economic reasons. This is especially true for the use of olefin mixtures containing olefins of different reactivity, for example olefins with internal and olefins with terminal double bonds. Therefore, methods have been developed in which the hydroformylation is carried out in two or more reaction stages. In this case, the reactors are present, for example, in the form of a cascade, in which the individual reactors are under different reaction conditions. operating conditions.
• DE-A-100 35 120 and DE-A-100 35 370 describe processes for the hydroformylation of olefins in a two-stage reaction system.
• EP-A-0 562 451 and EP-A-0 646 563 describe processes for preparing mixtures of isomeric decyl alcohols by two-stage hydroformylation of a butene-1 and butene-2-containing olefin mixture, aldol condensation of the resulting aldehyde mixture and subsequent hydrogenation.
• EP-AO 562 451 in the first stage predominantly 1-butene is converted to valeraldehyde with an n-selectivity of greater than 90%, while the unreacted olefins, predominantly 2-butene, in the second reaction stage are added to n-selectivity. and i-valeraldehyde are reacted.
• the second stage gives a valeraldehyde with a relatively low n-content.
• the n-share in total is significantly less than 90%.
• the process includes a stage that is performed at high pressure. The investment costs for high-pressure processes are significantly higher than for low-pressure processes, so that the process is economically disadvantaged.
• WO 02/096843 describes a process for obtaining 1-butene from 2-butenes.
• a hydrocarbon stream containing mainly 2-butenes is subjected to isomerization, and the resulting reaction mixture is subjected to distillation.
• a 1-butene-rich stream is separated from a 2-butene-rich stream and the latter recycled to the isomerization stage.
• this process is uneconomical for a hydrocarbon stream containing significant amounts of 1-butene. Due to the carrying out of the distillation after the isomerization stage, interfering volatile constituents of the feed (eg alkynes) can enter the isomerization reactor where they damage the catalyst or lead to the formation of undesired by-products.
• the process according to the invention should make it possible to utilize as much as possible both the olefins with terminal and those with internal double bond. In addition, it should lead to the highest possible proportion of unbranched hydroformylation products, d. H. have a high n-selectivity.
• the process according to the invention should allow the processing of the hydroformylation products into mixtures of alcohols having 10 or more carbon atoms by means of aldol condensation and hydrogenation.
• the present invention therefore relates to a process for the hydroformylation of olefins having at least four carbon atoms, in which one uses an olefin-containing feed containing a linear C-olefin having a double bond and at least one linear C-olefin with internal double bond, wherein i is an integer of at least 4, and subjecting the olefin-containing feed to hydroformylation to increase the linear double-terminal linear ⁇ -olefin content in the hydroformylation step stream by means of double bond isomerization, by adding the olefin-containing feed
• a first embodiment is a process for the hydroformylation of olefins having at least 4 carbon atoms, in which
• an olefin-containing feed comprising a linear double bond-capped C-olefin and at least one linear C-olefin having an internal double bond, wherein i is an integer of at least 4; subjecting the olefin-containing feed to a separation to give a current enriched in a linear C 1 olefin having a terminal double bond and a stream enriched in a linear C olefin having an internal double bond; at least partially subjecting the current enriched in linear d-olefin having internal double bond to double bond isomerization to increase the linear double-bond linear ⁇ -olefin content; at least partially using the effluent from the double bond isomerization to provide a stream supplied to the hydroformylation.
• the effluent from the double bond isomerization is at least partially combined with the stream obtained from the separation of the olefin-containing feed and enriched in linear double-bond olefin and the combined streams are fed to the hydroformylation.
• the separate streams may be mixed together before entering the hydrofomylation stage.
• the separation of the olefin-containing feed is carried out by distillation and the product obtained in the double bond isomerization with increased content of linear C-olefin with terminal double bond is recycled to the distillation. This recycling is preferably carried out in a part of the distillation apparatus which already has a stream enriched in relation to the olefin-containing feed initially used on linear C-olefin with terminal double bond.
• a second embodiment is a process for the hydroformylation of olefins having at least 4 carbon atoms, in which
• olefin-containing feed containing a linear d-olefin having a terminal double bond and at least one linear d-olefin having an internal double bond, wherein i is an integer of at least 4; subjecting the olefin-containing feed to a hydroformylation, the effluent from the hydroformylation step containing unreacted linear ⁇ -olefin having an internal double bond; separating from the effluent from the hydroformylation step a stream enriched in unreacted linear C-olefin having an internal double bond; at least partially subjecting the separated stream to double bond isomerization to increase the linear double-bond linear ⁇ -olefin content; at least partially feeds the effluent from the double bond isomerization to the hydroformylation step.
• the process according to the invention enables extensive utilization of the linear C-olefins contained in the olefin-containing feed, in particular those having an internal double bond.
• the linear C 1 -olefins contained in the olefin-containing feed are converted by the process according to the invention with high selectivity into linear hydroformylation products.
• an essential aspect of the process of the invention according to the second embodiment is that the effluent from the hydroformylation stage is separated from a stream containing unreacted linear C-olefin having an internal double bond. At least a portion of the separated unreacted linear ⁇ -olefin-containing internal double bond is subjected to double bond isomerization in a separate double bond isomerization step to increase the linear C-olefin content of the terminal double bond.
• process step (II) Since, in process step (II), the olefin-containing feed is first fed to the hydroformylation, the conditions in the hydroformylation stage are therefore generally set in the execution of process step (II) in such a way that the C-olefins present with internal double bond in this Hydroformylation be substantially unreacted.
• the term ⁇ -olefin is here and below for olefin compounds with i carbon atoms.
• the olefin-containing feed contains a linear ⁇ -olefin having a terminal double bond (also referred to herein as ⁇ -olefins) and at least one corresponding linear ⁇ -olefin having an internal double bond, in particular a linear ⁇ - ⁇ -olefin.
• linear d-olefins having a terminal double bond examples include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene, among which 1- Butene, 1-pentene and 1-hexene are preferred.
• the feed contains 1-butene.
• linear C-olefins having an internal double bond examples include 2-butenes, 2-pentenes, 2-hexenes, 3-hexenes, 2-heptenes, 3-heptenes, 4-heptenes, 2-octenes, 2-nonenes, 2-decenes, 2-undecenes, 2-dodecenes and mixtures thereof, among which 2-butenes, 2-pentenes, 2-hexenes, 3-hexenes and mixtures thereof are preferred.
• the feed contains 2-butenes.
• olefin mixtures which contain at least one linear ⁇ -olefin having 4 to 6 carbon atoms.
• olefin mixtures which contain substantially linear C-olefins which have the same value i, ie the same number of carbon atoms, eg. B. 4, 5, 6, 7, 8, 9, 10, 1 1 or 12, have.
• the proportion of linear C, olefins with the same value i is in particular in the range of 50 to 100 wt .-% and especially in the range of 55 to 99.9 wt .-%, each based on the total weight in the hydrocarbon mixture or olefin-containing feed contained mono- or polyethylenically unsaturated hydrocarbons.
• Particularly suitable for use in the process according to the invention are those olefin-containing feeds, in which the proportion of saturated and ethylenically unsaturated hydrocarbons having exactly i carbon atoms together at least 90 wt .-%, z. In the range of 90 to 99.99 wt%, and especially at least 95 wt%, e.g. B. in the range of 95 to 99.9 wt .-%, each based on the total weight of olefin-containing feed.
• the olefin-containing feed used in the process according to the invention is a technically available olefin-containing hydrocarbon mixture.
• olefin mixtures result from hydrocarbon cracking in petroleum processing, for example by cracking, such as fluid catalytic cracking (FCC), thermocracking or hydrocracking with subsequent dehydrogenation.
• a suitable technical olefin mixture is the C 4 cut .
• C 4 cuts are obtainable, for example, by fluid catalytic cracking or steam cracking of gas oil or by steam cracking of naphtha.
• raffinate I obtained after the separation of 1,3-butadiene
• raffinate II obtained after the isobutene separation.
• Another suitable technical olefin mixture is the C 5 cut available from naphtha cleavage.
• Olefin-containing mixtures of hydrocarbons having at least 4 carbon atoms which are suitable for use as olefin-containing feed can furthermore be obtained by catalytic dehydrogenation of suitable industrially available paraffin mixtures.
• suitable industrially available paraffin mixtures For example, it is possible to produce C 4 -olefin mixtures of liquefied natural gas (LPG) and liquefied natural gas (LNG).
• LPG liquefied natural gas
• LNG liquefied natural gas
• the latter in addition to the LPG fraction, additionally comprise relatively large amounts of relatively high molecular weight hydrocarbons (light naphtha) and are thus also suitable for the preparation of C 5 and C 6 olefin mixtures.
• olefin-containing hydrocarbon mixtures which contain monoolefins having at least 4 carbon atoms from LPG or LNG streams succeeds according to customary methods known processes which in addition to the dehydrogenation generally comprise one or more work-up steps. These include, for example, the separation of at least part of the saturated hydrocarbons contained in the aforementioned olefin feed mixtures. For example, these may be reused to produce olefin feeds by cracking and / or dehydrogenation.
• the olefins used in the process according to the invention may also contain a proportion of saturated hydrocarbons which are inert under the hydroformylation conditions according to the invention.
• the proportion of these saturated components is generally at most 60 wt .-%, preferably at most 40 wt .-%, particularly preferably at most 20 wt .-%, based on the total amount of the olefin contained in the hydrocarbon feedstock and saturated hydrocarbons.
• Typical compositions of the aforementioned C 4 - raffinates can be found in the literature z. In EP-AO 671 419 and in Schulz, Herman, "C 4 Hydrocarbons and Derivatives, Resources, Production, Marketing", Springer Verlag 1989.
• a raffinate II suitable for use in the process according to the invention has, for example, the following composition:
• trace gases such as 1, 3-butadiene, propene, propane, cyclopropane, propadiene, methylcyclopropane, vinyl acetylene, pentenes, pentanes, etc. in the range of not more than 1 wt .-%, for. In the range from 0.001 to 1% by weight, in each case based on the total weight of the raffinate II used.
• the proportion of the aforementioned trace gases in the raffinate II is generally in the range from 0.001 to 5% by weight, based on the total weight.
• butenes so are, unless otherwise stated, always includes all butenisomers except isobutene.
• oxygen-containing compounds such as alcohols, aldehydes, ketones or ethers are expediently removed from the olefin-containing hydrocarbon mixture to be used.
• the olefin-containing hydrocarbon mixture with advantage over an adsorbent, such as.
• the concentra- tion of oxygen-containing, sulfur-containing, nitrogen-containing and halogen-containing compounds in the olefin-containing hydrocarbon mixture is preferably not more than 1 ppm by weight and more preferably not more than 0.5 ppm by weight, in each case based on the total weight.
• polyunsaturated hydrocarbon compounds such as diolefins or alkynes are present in the olefin-containing hydrocarbon mixture to be used, they can be removed from the same before use as an olefin-containing feed to an amount of preferably less than 10 ppm by weight, based on the total weight.
• They are preferably by selective hydrogenation, for. B. according to EP-81 041 and DE-15 68 542, more preferably by a selective hydrogenation to a residual content of not more than 5 ppm by weight and most preferably not more than 1 ppm by weight, based on the Total weight.
• Such upstream hydrogenation may be advantageous in particular in process step (II).
• process step (I) it is advantageous to provide such hydrogenation after the double bond isomerization step and before the hydroformylation step. The detailed details will be discussed in more detail in the detailed discussion below of the individual process steps or variants.
• the linear double-terminal linear ⁇ -olefin content is increased in the stream fed to the hydroformylation stage in comparison to its content in the olefin-containing feed used by means of double bond isomerization.
• essentially linear C-olefins having an internal double bond are converted to those having a terminal double bond.
• Suitable substrates for such double bond isomerizations are, in particular, ⁇ -olefins, ie those which have a double bond between the 2-position and the 3-position of the linear chain of 1 carbon atoms. It should be noted, however, that such double bond isomerization reactions are limited by the thermodynamic equilibrium between the individual isomers. This determines the achievable at a given temperature proportion of each linear isomer with terminal double bond.
• the conversion of the 2-butenes to 1-butene by double bond isomerization is favored by higher temperatures.
• the maximum achievable yields of 1-butene (2-butene conversion x selectivity) are in a single reactor passage through the position of the thermodynamic equilibrium at a temperature of 250 0 C to about 16%, at a Temperature of 400 0 C limited to about 23% and at a temperature of 500 0 C to about 30%.
• the yields given are based on the thermodynamic data published in D.
• Carrying out process step (I) generally comprises a C 4 olefin-containing feed having a ratio of 2-butenes to 1-butene in the range from 6: 1 to 0.1: 1 and preferably in the range from 3: 1 to 0, 2: 1.
• the stream supplied to the hydroformylation stage is provided according to the invention by subjecting one part of the olefin-containing feed to double bond isomerization and then feeding it partially or completely to the hydroformylation, while the other Part of the olefin-containing feed partially or completely directly to the hydroformylation feeds.
• the stream fed to the hydroformylation stage is prepared according to the invention by feeding the olefin-containing feed directly to the hydroformylation stage and, moreover, part of the discharge from the hydroformylation stage after subjecting it to double-bond isomerization into the hydroformylation stage.
• the olefin-containing feed is partially subjected to double bond isomerization before the hydroformylation.
• This is z. B. a proportion in the range of 25 to 99 wt .-%, in particular in the range of 35 to 98 wt .-%, and especially in the range of 50 to 95 wt .-%, each based on the total weight of the olefin-containing feed to Double bond isomerization used.
• the part of the olefin-containing feed which is not fed to the double bond isomerization step is partly or completely, preferably essentially completely, for example.
• B a proportion in the range of 50 to 99.9 wt .-%, and preferably in the range of 70 to 99 wt .-%, each based on the total weight of not the double bond isomerization fed portion of the olefin-containing feed, the hydroformylation to.
• the linear C, olefins with terminal double bond contained in the olefin-containing feed are directly suitable for use in the hydroformylation stage.
• these are therefore separated before the isomerization at least partially and preferably as far as possible from the olefin-containing feed, z.
• the largest possible proportion of the linear C, olefins with internal double bond of the Doppel Kunststoffsisomermaschinesyear can be supplied in an easily controllable manner, for.
• This proportion of the olefin-containing feed, which is fed to the isomerization significantly determines the achievable conversion of linear C, olefins having an internal double bond to those having a terminal double bond.
• This total conversion is generally in the range of 50 to 99.9 wt .-%, in particular in the range of 60 to 99.5 wt .-%, and especially in the range of 70 to 99 wt .-%, each based on the total weight on linear C, olefins with internal double bond in the olefin-containing feed.
• the above-mentioned total conversion can also be increased by reacting unreacted linear d-olefins having an internal double bond in the isomerization reaction first and, if appropriate, multiply, for. B. 3, 4, 5 times or more often, the isomerization feeds.
• This can be z.
• Example be carried out so that separated from the discharge from the isomerization linear d-olefins with terminal double bond, z. B. by distillation, and this feeds the hydroformylation.
• a process procedure in which a distillation stage and the isomerization stage are operated parallel to one another has proved to be particularly advantageous.
• the process according to the invention is therefore carried out by subjecting the olefin-containing feed to process step (I), wherein
• Id in the upper part of the distillation column removes a stream enriched in a linear C-olefin having a terminal double bond, the withdrawn stream and carbon monoxide and hydrogen feeds a second reaction zone and reacted in the presence of a hydroformylation.
• the olefin-containing feed is fed to the distillation column usually as a liquid or gaseous, preferably liquid stream.
• the olefin-containing feed can be heated prior to feeding into the distillation column, for. B. to a temperature in the range of more than 20 to 100 0 C.
• the olefin-containing feed of the distillation column at room temperature or slightly above, z. B. in the range of 21 to 40 0 C, too.
• the feed into the distillation column is expediently carried out at one point within the upper two-thirds of the distillation column.
• any distillation column known to those skilled in the art can be used, which can be provided with feeds or outlets in the region of the remaining column body, except at the top and at the bottom of the column.
• Suitable z. B bubble tray columns, packed columns, packed columns or dividing wall columns.
• the distillation column is provided with a number of theoretical shear stages in the range of 30 to 80 and particularly preferably in the range of 40 to 75 executed.
• the reflux ratio is generally set to a value in the range of 5 to 75, and more preferably in the range of 10 to 50.
• the distillation is generally carried out at a pressure in the range of 1 to 50 bar, in particular in the range of 2 to 40 bar and especially in the range of 5 to 20 bar.
• a temperature in the range from 40 to 180 ° C., in particular in the range from 50 to 150 ° C. and especially in the range from 60 to 120 ° C. is generally set in the bottom of the distillation column.
• step Ib) the stream enriched in linear olefins having an internal double bond, in particular ⁇ -olefins, is withdrawn according to the invention in the lower part of the distillation column, preferably in the lower fifth of the distillation column and particularly preferably at the bottom of the column or in the range up to a maximum of 5 theoretical Soils above it.
• z. B a proportion in the range of 25 to 99 wt .-% and in particular in the range of 50 to 95 wt .-%, each based on the total weight of the withdrawn stream, a first reaction zone.
• the supplied stream is reacted in the presence of a double bond isomerization catalyst known per se.
• a double bond isomerization catalyst known per se.
• the isomerization catalyst it must only be able to effect the isomerization of internal olefinic double bonds such as 2-butenes to the corresponding linear olefins with a terminal double bond such as 1-butene.
• basic catalysts or zeolite-based catalysts are used for this purpose; in addition, the isomerization can also take place under hydrogenating conditions on contacts containing noble metal.
• Particularly suitable double-bond isomerization catalysts are earth alkali oxides on aluminum oxide, as described in EP-A 718036; mixture- alumina / silica carriers doped with oxides of alkaline earth metals, boron group metals, lanthanides or elements of the iron group, as described in US 4,814,542; and ⁇ -alumina coated with alkali metals, as described in JP 51-108691. Also suitable are catalysts of manganese oxide on aluminum oxide, described in US Pat. No.
• the aforementioned double bond isomerization catalysts are usually used in the fixed bed, fluidized bed or moving bed. It has been found to be advantageous if the amount of stream passed over the catalyst per unit time is in the range of 0.1 to 40 grams per gram of catalyst per hour.
• a continuous-flow fixed-bed reactor system is preferred. Suitable reactors are z. B. tube reactors, tube bundle reactors, tray reactors, winding reactors or helical reactors.
• the withdrawn in step Ib) from the distillation column stream can be withdrawn gaseous or liquid. If the withdrawn stream is liquid, it must be evaporated before being fed to the first reaction zone.
• the apparatus used for the evaporation is subject to no particular restriction. There are conventional evaporator types such. B. natural circulation evaporator or forced circulation evaporator.
• the gaseous stream Before the gaseous stream passes into the first reaction zone according to step Ib), it must generally be heated to the desired reaction temperature.
• conventional apparatus can be used, for. B. plate heat exchanger or tube bundle heat exchanger.
• the reaction in the first reaction zone is endothermic.
• the isomerization is advantageously carried out at a temperature which ensures a shift of the double bond, in which, however, secondary reactions such as cracking processes, skeletal isomerizations, dehydrogenations and oligomerizations are largely avoided.
• the temperature in the first reaction zone is therefore generally in the range from 100 to 700 ° C., preferably in the range from 150 to 600 ° C., and particularly preferably in the range from 200 to 500 ° C.
• Temperature control can be carried out in a conventional manner known per se.
• the reaction can also be carried out in an adiabatic reaction system. This term is understood in the context of the present invention in the technical and not in the physico-chemical sense.
• the pressure is adjusted so that the current supplied to the first reaction zone is gaseous. It is generally in the range of 1 to 40 bar, preferably in the range of 2 to 30 bar, and more preferably in the range of 3 to 20 bar.
• the isomerization catalyst used for the reaction carbon-containing compounds can be deposited over time, which can lead to deactivation of the catalyst. By burning off these deposits, it is possible to increase the activity of the catalyst again.
• the burning process can be carried out in a separate apparatus or preferably in the apparatus used for the reaction.
• the reactor is designed in duplicate so that one apparatus for the reaction is available alternately and regeneration can take place in the other apparatus.
• the catalyst is generally supplied with a mixture of inert gases such as nitrogen, helium and / or argon with a proportion of oxygen, in particular with a nitrogen / oxygen mixture.
• the proportion of oxygen in the inert gas, in particular nitrogen is generally in the range from 1 to 20% by volume.
• the oxygen content of the mixture may advantageously be changed during the regeneration process. It is preferred with a low oxygen content, for. B. in the range of 1 to 10 vol .-%, begun, which is then increased. This makes it possible to control the amount of heat produced by the exothermic combustion process.
• the regeneration is carried out at elevated temperature, which is usually in the range of 300 to 900 0 C, preferably in the range of 350 to 800 0 C, and more preferably in the range of 400 to 700 ° C.
• the output from the Doppelitatisisomermaschineseck usually has a content of linear C, olefins with internal double bond, z.
• 2-butenes which is compared to the content in the first reaction zone supplied stream by 2 to 50 wt .-% and in particular reduced by 5 to 30 wt .-%, based on the total weight of the same linear C, olefins with internal double bond in the first reaction zone supplied stream.
• step Ic) the discharge from the double bond isomerization stage at one point of the distillation column, which is located above the removal point of the stream withdrawn in step Ib) of the column, is returned to the distillation column.
• the current discharged from the isomerization in the range from 1 to 30 theoretical plates above the withdrawal point of the stream withdrawn in step Ib) can be recycled to the distillation column.
• the feed of the discharge from the Doppelitatisisomer Deutschenstress in the distillation column can be carried out in gaseous or liquid. If the temperature difference between the stream at the outlet of the first reaction zone and the temperature in the interior of the distillation column at the level of the reintroduction is large, e.g. B. more than 20 0 C, it may be useful to cool the discharge from the isomerization. The cooling or condensation takes place using conventional apparatuses known to those skilled in the art.
• step Id a linear C-olefin with terminal double bond, z. B. 1-butene, enriched stream.
• the content of linear d-olefin with terminal double bond, z. B. 1-butene, in the stream taken in step Id) of the column is usually in the range of 60 to 100 wt .-% and in particular in the range of 80 to 99.99% by weight, based in each case on the total of C. Olefins with terminal or internal double bond, z. B. 1-butene and 2-butenes.
• the stream withdrawn in step Id) in the range of 60 to 99.9 weight percent comprises linear olefins having terminal and internal double bond, in the range of 0.01 to 5 weight percent polyunsaturated compounds, in the range of 0 , 01 to 40 wt .-% further compounds such as saturated and / or branched hydrocarbons, especially those with i carbon atoms.
• the current drawn in step Id) thus comprises, for example, In the range of 60 to 99.9% by weight of 1-butene and 2-butenes, in the range of 0.01 to 5% by weight of polyunsaturated compounds, e.g. B. butadienes, and in the range of 0.01 to 40 wt .-% further compounds, for.
• isobutane, n-butane and isobutene are examples of isobutane, n-butane and isobutene.
• the aforementioned polyunsaturated compounds can firstly originate from the olefin-containing feed used, and secondly, they are formed under certain conditions, in particular when choosing particular double bond isomerization catalysts, also during the reaction in the first reaction zone. It has therefore been found to be advantageous to remove the stream withdrawn in step Id) of the distillation column prior to feeding to the second reaction zone of a selective hydrogenation to reduce the content of polyunsaturated compounds, for. As butadienes and alkynes to undergo. Such selective hydrogenation can, as mentioned above, for. B. according to EP-81 041 and DE-15 68 542 are performed. Incidentally, the above applies to this hydrogenation stage in a corresponding manner.
• This stream to be rejected consists essentially of linear C-olefins having an internal double bond, linear ⁇ -olefins having a terminal double bond, saturated hydrocarbons having i, i + 1 and optionally more carbon atoms and optionally polyethylenically unsaturated compounds such as dienes or alkynes.
• 2-butenes in the discharged and discharged partial stream in the range of 80 to 99.99 wt .-% and in particular in the range of 90 to 99.9 wt .-%, each based on the sum of linear d-olefins with internal and terminal double bond, z.
• 2-butenes and 1-butene Carrying out in the bottom of the distillation column separately from a stream for discharging high-boiling compounds, so its content of linear d-olefins with internal double bond, z.
• 2-butenes usually by up to 10 wt .-% compared to the content of the same linear C 1 - olefins with internal double bond, z. B.
• 2-butenes increased in the withdrawn in step Ib) of the column stream.
• the size of the stream taken off at the bottom of the column and its content of linear ⁇ -olefins having an internal double bond depends on the total conversion of the reaction of linear ⁇ - to linear ⁇ -olefins, eg. From 2-butenes to 1-butene, preferably in the range of from 50 to 99.9 wt%, more preferably in the range of from 60 to 99.5 wt%, and most preferably in the range of from 70 to 99 % By weight, based in each case on the total weight of linear ⁇ -olefins having an internal double bond in the olefin-containing feed.
• the proportion of the discharged and discharged stream is at most 5 wt .-%, in particular at most 1 wt .-% and especially at most 0.1 wt .-% and z. B. in the range of 0.001 to 5 wt .-%, in particular in the range of 0.005 to 1 wt.%, Are, in each case based on the total weight of the withdrawn in step Ib) from the distillation column stream.
• a proportion of at most 5% by weight, in particular at most 1 wt .-% and especially at most 0.1 wt .-% makes up and z. B. in the range of 0.001 to 5 wt .-%, in particular in the range of 0.005 to 1 wt.%, In each case based on the total weight of the withdrawn in step Ib) from the distillation column stream.
• the distillation and isomerization carried out in steps Ia) to Id) are designed such that the heat flows for evaporation and heating are combined with the heat flows for cooling and condensing.
• the flow withdrawn in step Id) of the distillation column and enriched in a linear double-bond linear C-olefin is fed to a second reaction zone. Furthermore, this second reaction zone is fed with carbon monoxide and hydrogen. In the second reaction zone, the feed stream is reacted in the presence of a hydroformylation catalyst.
• the second reaction zone (hydroformylation stage) may be one or more stages (reaction stages), eg. B. two or three stages, executed and accordingly comprise one or more, identical or different reactors.
• the second reaction zone or each reaction stage of the second reaction zone is formed by a single reactor. Both the reactors of each individual stage and the reactors forming the various stages may each have the same or different mixing characteristics.
• the reactors can be subdivided one or more times by means of internals. If two or more reactors form one stage of the reaction system of the second reaction zone, they can be interconnected with one another as desired, eg. B. parallel or in series.
• Suitable pressure-resistant reaction apparatuses for the hydroformylation are known to the person skilled in the art. These include the commonly used reactors for gas-liquid reactions, such as. As tubular reactors, stirred tank, gas circulation reactors, bubble columns, etc., which may optionally be divided by internals. Carbon monoxide and hydrogen are usually used in the form of a mixture, the so-called synthesis gas. The composition of the synthesis gas used can vary within wide limits.
• identical or different molar ratios of CO to H 2 can be set in the reactor (s) of the second reaction zone or, if appropriate, in the reactors forming a reaction stage of the second reaction zone.
• the molar ratio of carbon monoxide and hydrogen is generally 1: 1000 to 1000: 1, preferably 1: 100 to 100: 1.
• the temperature in the hydroformylation reaction is generally in a range from about 20 to 200 ° C., preferably from about 50 to 190 ° C., in particular from about 60 to 180 ° C.
• a multistage embodiment of the second reaction zone in a subsequent reaction stage set a higher temperature than in a previous reaction stage, for. B. to achieve the fullest possible conversion of less hydroformylated olefins. If the second reaction zone or a reaction stage thereof comprises more than one reactor, these may also have the same or different temperatures.
• the reaction in the second reaction zone is preferably carried out at a pressure in the range of about 1 to 700 bar, more preferably in the range of 3 to 600 bar, and most preferably in the range of 5 to 50 bar.
• the reaction pressure can be varied in the second reaction zone, depending on the activity of the hydroformylation catalyst used.
• the hydroformylation catalysts described in more detail below allow z. T. a reaction especially in a range of low pressures, such as in the range of about 1 to 100 bar.
• the reactor volume and / or residence time of the second reaction zone are selected to generally react at least about 10 weight percent of the olefins fed, based on the total olefin content of the stream fed to the hydroformylation stage.
• the conversion based on the amount of olefin in the hydroformylation stage is preferably at least 25% by weight in the second reaction zone.
• Suitable hydroformylation catalysts for the second reaction zone are in general the usual transition metal compounds and complexes known to those skilled in the art, which can be used both with and without cocatalysts.
• the transition metal is preferably a metal of the VIII subgroup of the Periodic Table and in particular is Co, Ru, Rh, Pd, Pt, Os or Ir, especially Rh, Co, Ir or Ru.
• alkyl includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched C 1 -C 20 -alkyl, be preferably C 1 -C 2 -alkyl, particularly preferably C 1 -C -alkyl and very particularly preferably C 1 -C 4 -alkyl groups.
• alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2 -Dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl , 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1 Ethyl 2-methylpropy
• alkyl also includes substituted alkyl groups, which are generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent selected from the groups cycloalkyl, aryl, hetaryl, halogen, NE 1 E 2 , NE 1 E 2 E 3+ , COOH, carboxylate, -SO 3 H and sulfonate.
• alkylene in the context of the present invention stands for straight-chain or branched alkanediyl groups having 1 to 4 carbon atoms.
• cycloalkyl in the context of the present invention comprises unsubstituted as well as substituted cycloalkyl groups, preferably C 5 -C 7 -cycloalkyl groups, such as cyclopentyl, cyclohexyl or cycloheptyl, which in the case of a substitution, in general 1, 2, 3, 4 or 5 , preferably 1, 2 or 3 and particularly preferably 1 substituent selected from the groups alkyl, alkoxy and halogen, can carry.
• substituted cycloalkyl groups preferably C 5 -C 7 -cycloalkyl groups, such as cyclopentyl, cyclohexyl or cycloheptyl, which in the case of a substitution, in general 1, 2, 3, 4 or 5 , preferably 1, 2 or 3 and particularly preferably 1 substituent selected from the groups alkyl, alkoxy and halogen, can carry.
• heterocycloalkyl in the context of the present invention comprises saturated, cycloaliphatic groups having generally 4 to 7, preferably 5 or 6, ring atoms in which 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from the elements oxygen, nitrogen and sulfur and which may optionally be substituted, in the case of a substitution, these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1 substituent selected from alkyl, aryl, COOR f , COO " M + and NE 1 e 2, preferably alkyl, can carry.
• heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethyl piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, Morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, Tetrahydrofuranyl, called tetrahydropyranyl, dioxanyl.
• aryl for the purposes of the present invention includes unsubstituted as well as substituted aryl groups, and is preferably phenyl, ToIyI, XyIyI, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthacenyl, particularly preferred zugt for phenyl or naphthyl, said aryl groups in the case of a substitution generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent selected from the groups alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl , -SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , nitro, cyano or halogen can bear.
• heterocycloaromatic groups preferably the groups pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, and the subgroup of the "pyrrole group", these heterocycloaromatic groups in the case of Substitution generally 1, 2 or 3 substituents selected from the groups alkyl, alkoxy, carboxyl, carboxylate, -SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , trifluoromethyl or halogen, can carry.
• pyrrole group in the context of the present invention is a series of unsubstituted or substituted heterocycloaromatic groups which are structurally derived from the pyrrole skeleton and contain a pyrrole nitrogen atom in the heterocycle which is covalently linked to other atoms, for example a pnicogen atom can be.
• pyrrole group thus includes the unsubstituted or substituted groups pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1, 2,3-triazolyl, 1, 3,4-triazolyl and carbazolyl, which in Case of a substitution generally 1, 2 or 3, preferably 1 or 2, more preferably 1 substituent selected from the groups alkyl, alkoxy, acyl, carboxyl, carboxylate, -SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , trifluoromethyl or halogen, can carry.
• a preferred substituted indolyl group is the 3-methylindolyl group.
• bispyrrole group for the purposes of the present invention includes divalent groups of the formula
• the bispyrrole groups may also be unsubstituted or substituted and in the case of a substitution per pyrrole group unit generally 1, 2 or 3, preferably 1 or 2, in particular 1 substituent selected from alkyl, alkoxy, carboxyl, carboxylate, -SO 3 H, Sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , trifluoromethyl or halogen, where in this information to the number of possible substituents, the linkage of the Pyrrol weaknessein- units by direct chemical bonding or mediated by the above-mentioned groups linkage is not considered a substitution.
• Carboxylate and sulfonate in the context of this invention preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function.
• these include z.
• esters with C 1 -C 4 -alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
• These include the primary amides and their N-alkyl and N, N-dialkyl derivatives.
• acyl in the context of the present invention represents alkanoyl or aroyl groups having generally 2 to 11, preferably 2 to 8, carbon atoms, for example the acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, hepta noyl, 2-ethylhexanoyl, 2-propylheptanoyl, benzoyl or naphthoyl group.
• the groups NE 1 E 2 , NE 4 E 5 , NE 7 E 8 , NE 10 E 11 , NE 13 E 14 , NE 16 E 17 NE 19 E 20 , NE 22 E 23 and NE 25 E 26 are preferably N, N-dimethylamino, N, N-diethylamino, N, N- Dipropylamino, N, N-diisopropylamino, N, N-di-n-butylamino, N, N-di-t.-butylamino, N, N-dicyclohexylamino or N, N-diphenylamino.
• Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
• M + stands for a cation equivalent, ie for a monovalent cation or the fraction of a polyvalent cation corresponding to a positive single charge.
• the cation M + serves only as a counterion to the neutralization of negatively charged substituent groups, such as the COO or the sulfonate group, and can in principle be chosen arbitrarily.
• substituent groups such as the COO or the sulfonate group
• alkali metal in particular Na + , K + -, Li + ions or onium ions, such as ammonium, mono-, di-, tri-, tetraalkylammonium, phosphonium, tetraalkylphosphonium or tetraarylphosphonium ions used.
• anion equivalent X " which serves only as a counterion of positively charged substituent groups, such as the ammonium groups, and can be chosen arbitrarily from monovalent anions and the portions of a polyvalent anion corresponding to a negative single charge.
• ions X " such as chloride and bromide.
• Preferred anions are sulfate and sulfonate, for example SO 4 2 " , tosylate, trifluoromethanesulfonate and methylsulfonate.
• the values of x represent an integer of 1 to 240, preferably an integer of 3 to 120.
• Condensed ring systems may be fused (fused) aromatic, hydroaromatic and cyclic compounds.
• Condensed ring systems consist of two, three or more than three rings. Depending on the type of linkage, a distinction is made in condensed ring systems between an ortho-annulation, d. H. each ring has one edge or two atoms in common with each adjacent ring, and a peri-annulation in which one carbon atom belongs to more than two rings.
• Preferred among the fused ring systems are ortho-fused ring systems.
• Preferred complex compounds comprise at least one phosphorus atom-containing compound as ligands.
• the phosphorus atom-containing compounds are preferably selected from among PF 3 , phospholes, phosphabenzenes, mono-, di- and polydentate phosphine, phosphinite, phosphonite, phosphoramidite, phosphite ligands and mixtures thereof.
• the catalysts used according to the invention for the hydroformylation stage can still contain at least one further ligand, which is preferably selected from Halides, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers and mixtures thereof.
• at least one further ligand which is preferably selected from Halides, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers and mixtures thereof.
• catalytically active species of the general formula H x M y (CO) z L q are formed under hydroformylation conditions from the particular catalysts or catalyst precursors used, where M is a metal of subgroup VIII, L is a phosphorus-containing compound and q, x, y, z stand for integers, depending on the valence and type of metal and the binding of the ligand L.
• z and q are independently of one another at least a value of 1, such. B. 1, 2 or 3.
• the sum of z and q is preferably from 1 to 5.
• the complexes may, if desired, additionally have at least one of the further ligands described above.
• the hydroformylation catalysts are prepared in situ in the reactor used for the hydroformylation reaction. If desired, however, the catalysts according to the invention can also be prepared separately and isolated by customary processes. For in situ preparation of the catalysts of the invention can be z.
• Suitable rhodium compounds or complexes are, for. Rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II) or Rhodium (III) carboxylate, rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III), etc.
• Rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II) or Rh
• rhodium complexes are suitable such as rhodium bis-carbonyl acetylacetonate, acetylacetonato-bis-ethyl rhodium (I), etc.
• rhodium bis-carbonyl acetylacetonate or rhodium acetate are used.
• ruthenium salts or compounds are, for example, ruthenium (III) chloride, ruthenium (IV), ruthenium (VI) or ruthenium (VIII) oxide, alkali metal salts of ruthenium oxygen acids such as K 2 RuO 4 or
• KRuO 4 or complex compounds such as. B. RuHCl (CO) (PPh 3 ) 3 .
• metal carbonyls of ruthenium such as trisruthenium dodecacarbonyl or hexaruthenemooctadecacarbonyl, or mixed forms in which CO are partly replaced by ligands of the formula PR 3 , such as Ru (CO) 3 (PPh 3 ) 2
• Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates, such as cobalt acetate, cobalt ethylhexanoate, cobalt naphthanoate, and cobalt caproate -Complex.
• Suitable activating agents are, for. B. Bronsted acids, Lewis acids such as BF 3 , AICI 3 , ZnCl 2 , SnCl 2 and Lewis bases.
• the solvents used are preferably the aldehydes which form in the hydroformylation of the respective olefins, as well as their higher-boiling secondary reaction products, eg. B. the products of aldol condensation.
• suitable solvents are aromatics, such as toluene and xylene, hydrocarbons or mixtures of hydrocarbons, also for diluting the abovementioned aldehydes and the secondary products of the aldehydes.
• Further solvents are esters of aliphatic carboxylic acids with alkanols, for example ethyl acetate or Texanol TM, ethers such as tert-butyl methyl ether and tetrahydrofuran.
• Suitable hydroformylation catalysts for the hydroformylation stage are e.g. In Beller et al., Journal of Molecular Catalysis A, 104 (1995) p. 17-85, which is incorporated herein by reference.
• the catalyst system of the second reaction zone comprises at least one complex of a metal of transition group VIII of the Periodic Table of the Elements with at least one organic phosphorus (III) compound as ligands.
• the organic phosphorus (III) compound is selected from compounds of the general formula PR 1 R 2 R 3 , wherein R 1 , R 2 and R 3 are independently alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the Alkyl radicals 1, 2, 3, 4 or 5 substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, COOH, carboxylate, SO 3 H, sulfonate, NE 1 E 2 , NE 1 E 2 E 3+ X " , halogen, nitro, acyl or cyano may nen, wherein E 1 , E 2 and E 3 are each identical or different radicals selected from Is hydrogen, alkyl, cycloalkyl, or aryl and X "is an anion equivalent, and wherein the cycl
• Suitable organic phosphorus (III) compounds are also chelate compounds of the general formula R 1 R 2 PY 1 -PR 1 R 2 , wherein R 1 and R 2 have the meanings given above and Y 1 is a divalent bridging group.
• the two radicals R 1 , the two radicals R 2 and the two radicals R 3 may each have the same or different meanings.
• the bridging group Y 1 is preferably selected from the groups of the formulas III described below. a to III. t, to which reference is made in its entirety.
• Y 1 is a group of the formula III. a.
• Y 1 is a radical of the formula
• R 1 , R “, R 1 ", R IV , R v and R v ⁇ independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, COOH, carboxylate, SO 3 H, sulfonate, NE 7 E 8 , alkylene-NE 7 E 8 ,
• E 7 and E 8 each represent identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl, wherein two adjacent radicals R 1 to R v ⁇ together with the carbon atoms of the benzene nucleus to which they are attached may also be a fused ring system having 1, 2 or 3 further rings, and
• R d and R e are independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
• Particularly preferred hydroformylation catalysts for use in the second reaction zone are phosphorus-containing rhodium catalysts, as described, for. Under the hydroformylation conditions in situ from a rhodium source and a triarylphosphine, e.g. B. triphenylphosphine, are formed.
• a triarylphosphine e.g. B. triphenylphosphine
• catalysts disclosed in WO 00/56451 based on at least one phosphinamidite ligand.
• those of Veen et al. in Angew. Chem. Int. Ed. 1999, 38, 336 described catalysts based on chelate diphosphines with spines of the xanthene type.
• hydroformylation catalysts described in DE-A-100 23 471 are also suitable.
• the hydroformylation catalysts described in WO 01/58589 are preferably based on phosphorus-containing, diaryl-fused bicyclo [2.2.n] basic bodies.
• Suitable organic phosphorus (III) compounds are, in particular, chelate compounds of the general formula I.
• Y 2 is a divalent bridging group
• R ⁇ , R ⁇ , R ⁇ and R ⁇ independently of one another are alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, the alkyl radicals having 1, 2, 3, 4 or 5 substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy , Cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, thiol, polyalkylene oxide, polyalkylenimine, COOH, carboxylate, SO 3 H, sulfonate, NE 10 E 11 , NE 10 E 11 E 12 X halogen,
• Nitro, acyl or cyano may have, wherein E 10 , E 11 and E 12 each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl, or aryl and X "is an anion equivalent,
• cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals R ⁇ , R ⁇ , R ⁇ and R ⁇ may have 1, 2, 3, 4 or 5 substituents which are selected from alkyl and those previously for the alkyl radicals R ⁇ , R ⁇ , R ⁇ and R ⁇ substituents, or
• X 1, X 2, X 3, X 4, X 5 and X 6 are each independently selected from O, S, SiR ⁇ R ⁇ and NR ⁇ wherein R ⁇ , R ⁇ and R ⁇ independently hydrogen, alkyl, Cycloalkyl, heterocycloalkyl, aryl or hetaryl, and
• d, e, f, g, h and i independently represent 0 or 1.
• the bridging group Y 2 in the formula I is selected from the groups of the formulas III described below. a to lll.t, which is incorporated herein by reference in its entirety.
• the phosphorochelate compounds used as the catalyst system of the second reaction zone are selected from chelate phosphonites, chelate phosphites and chelate phosphoramidites.
• a catalyst system of the second reaction zone are the catalysts described in WO 02/22261 which comprise at least one complex of a metal of transition group VIII with at least one ligand selected from chelate phosphonites and chelate phosphites with xanthene skeleton.
• the pnicogene chelate complexes described in WO 02/083695 based on pnicogen chelate compounds as ligands which have a skeleton of the xanthene or triptycene type.
• the catalysts described in WO 03/018192 with at least one pyrrole-phosphorus compound as ligands are also suitable.
• the catalysts described in the German patent application DE 102 43 138.8 The disclosure of the aforementioned documents is fully incorporated by reference.
• the catalyst system of the second reaction zone preferably comprises at least one complex of a metal of transition group VIII of the Periodic Table of the Elements with at least one phosphorochelate compound of general formula II
• R 4 , R 5 , R 6 and R 7 are independently heteroatom-containing groups which are bonded via an oxygen atom or an optionally substituted nitrogen atom to the phosphorus atom or R 4 together with R 5 and / or R 6 together with R 7 is a divalent form heteroatom-containing group which are bonded to the phosphorus atom via two heteroatoms selected from oxygen and / or optionally substituted nitrogen,
• a and b are independently 0 or 1
• Y 3 is a divalent bridging group having 2 to 20 bridging atoms between the flanking bonds, at least two bridging atoms being part of an alicyclic or aromatic group.
• the individual phosphorus atoms of the phosphorochelate compounds of the formula II are each connected via two covalent bonds with the substituents R 4 and R 5 or R 6 and R 7 , where the substituents R 4 , R 5 , R 6 and R 7 in a first embodiment of heteroatom-containing groups which are bonded via an oxygen atom or an optionally substituted nitrogen atom to the phosphorus atom, wherein R 4 and R 5 or R 6 and R 7 are not joined together.
• R 4 , R 5 , R 6 and R 7 are then preferably pyrrole groups bonded via the pyrrole nitrogen atom to the phosphorus atom Pn.
• the meaning of the term pyrrole group corresponds to the previously given definition.
• R 4 together with R 5 and / or R 6 together with R 7 form a divalent heteroatom-containing group which are bonded to the phosphorus atom via two heteroatoms selected from oxygen and optionally substituted nitrogen.
• the substituent R 4 together with the substituent R 5 and / or the substituent R 6 together with the substituent R 7 can form a bound via the pyrrole nitrogen atoms to the phosphorus atom bispyrrole group.
• the substituent R 4 together with the substituent R 5 and / or the substituent R 6 together with the substituent R 7 form a bridging group bonded via two oxygen atoms to the phosphorus atom.
• Alk is a Ci-C 4 alkyl group
• R 0, R p, R q and R r are each independently hydrogen, CrC 4 alkyl, C r C 4 alkoxy, acyl, halogen, trifluoromethyl, dC are 4 -alkoxycarbonyl or carboxyl.
• the 3-methylindolyl group (skatolyl group) of the formula II.f1 is particularly advantageous.
• Hydroformylation catalysts based on ligands containing one or more 3-methylindolyl group (s) bonded to the phosphorus atom characterized by a particularly high stability and thus particularly long catalyst life.
• Py is a pyrrole group
• I represents a chemical bond or represents O, S, SiR 8 R 1, NR 11 or optionally substituted C 1 -C 10 -alkylene, preferably CR ⁇ R ⁇ ,
• W is cycloalkyloxy or amino, aryloxy or amino, hetaryloxy or amino
• R ⁇ , R ⁇ , R ⁇ , R ⁇ and R ⁇ independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
• Ci-Cio-alkylene for a chemical bond or for O, S, SiR 8 R ⁇ NR 11 or optionally substituted Ci-Cio-alkylene, preferably CR ⁇ R ⁇ , wherein R ⁇ , R ⁇ , R ⁇ , R is ⁇ and R ⁇ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
• R 35 , R 35 ' , R 36 , R 36' , R 37 , R 37 ' , R 38 and R 38' independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, W ' C00R f , W ' C00 ' M + ,
• W ' represents a single bond, a heteroatom, a heteroatom-containing group or a divalent bridging group having 1 to 20 bridging atoms
• R f , E 16 , E 17 , E 18 are each identical or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
• R 9 is hydrogen, methyl or ethyl
• M + is a cation equivalent
• x is an integer from 1 to 240
• I is a chemical bond or a C 1 -C 4 -alkylene group, more preferably a methylene group.
• phosphorus chelate compounds are those of the general formula wherein R 4 and R 5 and / or R 6 and R 7 are each taken together with the pnicogen atom to which they are attached, for a group of general formula ILA
• k and I are independently 0 or 1
• Q together with the phosphorus atom and the oxygen atoms to which it is bonded, represents a 5- to 8-membered heterocycle which is optionally an-mono-, di- or trisubstituted with cycloalkyl, heterocycloalkyl, aryl and / or hetaryl, wherein the fused groups are each independently one, two, three or four substituents selected from alkyl, alkoxy, cycloalkyl, aryl, halogen, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, COOH, carboxylate, SO 3 H, sulfonate, NE 4 E 5 , Alkylene-NE 4 E 5 , nitro and cyano, and / or Q may have one, two or three substituents selected from alkyl, alkoxy, optionally substituted cycloalkyl and optionally substituted aryl, and / or Q is 1, 2 or 3 optionally substituted heteroatoms may be interrupted.
• the phosphorochloridates of the formula II according to the invention thus have at least one phosphine, phosphinite, phosphonite and / or phosphite radical.
• the groups of the formula ILA are preferably bonded to the group Y 3 via an oxygen atom and k and I are 1 (phosphite groups).
• the radical Q preferably represents a C 2 -C 6 -alkylene bridge, which is fused to aryl once or twice and / or which may have a substituent which is selected from alkyl, optionally substituted cycloalkyl and optionally substituted aryl, and / or the may be interrupted by an optionally substituted heteroatom.
• the fused aryls of the radicals Q are preferably benzene or naphthalene.
• Anellissus benzene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2 substituents which are selected from alkyl, alkoxy, halogen, SO 3 H, sulfonate, NE 4 E 5 , alkylene-NE 4 E 5 , Trifluoromethyl, nitro, carboxyl, alkoxycarbonyl, acyl and cyano.
• Anellated naphthalenes are preferably unsubstituted or have in the non-fused ring and / or in the fused ring in each case 1, 2 or 3, in particular 1 or 2 of the substituents mentioned above in the fused benzene rings on.
• alkyl is preferably C 1 -C 4 -alkyl and in particular methyl, isopropyl and tert-butyl.
• Alkoxy is preferably C 1 -C 4 -alkoxy and in particular methoxy.
• Alkoxycarbonyl is preferably C 1 -C 4 -alkoxycarbonyl.
• Halogen is especially fluorine and chlorine.
• the C 2 -C 6 -alkylene bridge of the radical Q is interrupted by 1, 2 or 3, optionally substituted heteroatoms, these are preferably selected from O, S or NR m , where R m is alkyl, cycloalkyl or aryl.
• the C 2 -C 6 -alkylene bridge of the radical Q is interrupted by an optionally substituted heteroatom.
• the C 2 -C 6 -alkylene bridge of the radical Q When the C 2 -C 6 -alkylene bridge of the radical Q is substituted, it preferably has 1, 2 or 3, in particular 1 substituent which is / are selected from alkyl, cycloalkyl and aryl, wherein the aryl substituent 1, 2 or 3 may carry the substituents mentioned for aryl.
• the alkylene bridge Q has a substituent selected from methyl, ethyl, isopropyl, phenyl, p- (C 1 -C 4 -alkyl) phenyl, preferably p-methylphenyl, p- (C 1 -C 4 -alkoxy) phenyl, preferably p-methoxyphenyl , p-halophenyl, preferably p-chlorophenyl and p-trifluoromethylphenyl.
• the radical Q is a Cs-C ⁇ -alkylene bridge which is fused and / or substituted as described above and / or interrupted by optionally substituted heteroatoms.
• the radical Q is a C 3 -C 6 -alkylene bridge which is fused once or twice with benzene and / or naphthalene, the phenyl or naphthyl groups 1, 2 or 3, in particular 1 or 2 of the abovementioned substituents.
• tuenten can carry.
• the radical Q (ie R 4 and R 5 or R 6 and R 7 together) together with the phosphorus atom and the oxygen atoms to which it is attached, represents a 5- to 8-membered heterocycle, wherein Q (R 4 and R 5 or R 6 and R 7 together) is a radical which is selected from among the radicals of the formulas 11.1 to II.5,
• Z 1 is O, S or NR m , where
• R m is alkyl, cycloalkyl or aryl
• Z 1 is a C 1 -C 3 -alkylene bridge which may have a double bond and / or at least one substituent selected from alkyl, cycloalkyl or aryl substituents, the alkyl, cycloalkyl or aryl substituents in turn having a can carry two or three of the substituents mentioned at the outset for these groups, or Z 1 is a C 2 -C 3 -alkylene bridge which is interrupted by O, S or NR m ,
• R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are each independently hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, SO 3 H, sulfonate, NE 19 E 20 , alkylene NE 19 E 20 , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, wherein E 19 and E 20 are independently hydrogen, alkyl, cycloalkyl or aryl.
• Q is a radical of formula 11.1, wherein R 20 , R 21 and R 22 are hydrogen.
• Q is a radical of formula 11.2a
• R ⁇ 0 and R ⁇ 4 for hydrogen, C r C 4 alkyl, C r C 4 alkoxy, SO 3 H, sulfonate, NE 9 E 10 , alkylene-NE -9 ⁇ E-10, preferably hydrogen, dC 4 -Alkyl or C 1 -C 4 -alkoxy, in particular methyl, methoxy, isopropyl or tert-butyl,
• R 21 and R 23 is hydrogen, C r C 4 alkyl, preferably methyl, isopropyl or tert-butyl, Ci-C 4 alkoxy, preferably methoxy, fluoro, chloro or trifluoromethyl stands.
• R 21 can also stand for SO 3 H, sulfonate, NE 9 E 10 or alkylene-NE 9 E 10 .
• Q is a radical of formula 11.3a R21 R 23
• R 20 , R 21 , R 23 and R 24 have the meanings given above for the formula 11.2a,
• R n is hydrogen, C r C 4 alkyl, preferably methyl or ethyl, phenyl, p- (dC 4 alkoxy) phenyl, preferably p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl or p- (trifluoromethyl) phenyl.
• Q is a radical of formula II.4, wherein R 20 to R 29 are hydrogen.
• Q preferably represents a radical of the formula 11.4 in which R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 27 and R 29 are hydrogen and the radicals R 26 and R 28 independently of one another are alkoxycarbonyl, preferably methoxy, ethoxy, n-propyloxy or Isopropyloxycar- bonyl stand.
• Q is a radical of the formula II.5 in which R 20 to R 29 are hydrogen and Z 1 is CR n R n , where R n and R n independently of one another are hydrogen, C 1 -C 4 -alkyl, preferably methyl or Ethyl, phenyl, p- (C 1 -C 4 alkoxy) phenyl, preferably p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl or p- (trifluoromethyl) phenyl.
• Q preferably represents a radical of the formula 11.5 in which R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 27 and R 29 are hydrogen, Z 1 is CR n R n and the radicals R 26 and R 28 independently represent alkoxycarbonyl, preferably methoxy, ethoxy, n-propyloxy or isopropyloxycarbonyl.
• the radicals R 26 and R 28 are ortho to the phosphorus atom or oxygen atom.
• the bridging group Y 3 is selected from groups of the formulas III. a to lll.t
• R 1 , R 1 ' , R “, R” ' , R 111 , R 1 " 1 , R IV , R IV ' , R v , R v ⁇ , R v ", R vm , R ⁇ x , R x , R x ⁇ and R x "independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, SO 3 H, sulfonate, NE 22 E 23 , alkylene-NE 22 E 23 Trifluoromethyl, nitro, alkoxycarbonyl, carboxyl, acyl or cyano in which E 22 and E 23 each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
• Z is O, S, NR 15 or SiR 15 R 16 , where
• R 15 and R 16 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
• Z is a C 1 -C 4 -alkylene bridge which may have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent,
• Z is a C 2 -C 4 alkylene bridge represented by O, S or NR 15 or
• SiR 15 R 16 is interrupted
• a two adjacent radicals R 1 to R v ⁇ together with the carbon atoms of the benzene nucleus to which they are attached may also be a fused ring system having 1, 2 or 3 further rings,
• a 1 and A 2 are each independently O, S, SiR a R b , NR C or CR d R e , wherein
• R a , R b and R c independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
• R d and R e independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl,
• Aryl or hetaryl or the group R d together with another group R d or the group R e together with another group R e form an intramolecular bridge group D
• D is a divalent bridging group of the general formula
• R 9 , R 9 ' , R 10 and R 10 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano,
• R 9 may also together with R 10 represent the bond portion of a double bond between the two carbon atoms to which R 9 and R 10 are bonded, and / or R 9 and R 10 together with the carbon atoms to which they are attached, may also be a 4- to 8-membered carbocyclic or heterocycle which is optionally additionally fi-,, or threefold fused with cycloalkyl, heterocycloalkyl, aryl or hetaryl, the heterocycle and, if present, the fused groups independently of one another can each bear one, two, three or four substituents which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COOR f , COO " M + , SO 3 R f , SCr 3 M + , NE 25 E 26 , Alkylene-NE 25 E 26 , NE 25 E 26 E 27 X alkylene-N E 25 E 26 E 27 X OR f , SR f ,
• R f , E 25 , E 26 and E 27 are each the same or different radicals selected from
• R 9 is hydrogen, methyl or ethyl
• y is an integer from 1 to 120
• the bridging group Y 3 is preferably a group of the formula III. a.
• group III the groups A 1 and A 2 may independently of one another denote O, S, SiR a R b , NR C or CR d R e , where the substituents R a , R b and R c are each, independently of one another, hydrogen Alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, whereas the groups R d and R e independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R d together with another group R d or the group R e together with another group R e can form an intramolecular bridging group D.
• D is preferably a divalent bridging group which is selected from the groups
• R 9 , R 9 ' , R 10 and R 10 independently of one another are hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano, or are joined together to form a C 3 -C 4 -alkylene group and R 11 , R 12 , R 13 and R 14 independently of one another are hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, SO 3 H, sulfonate, NE 1 E 2 , alkylene-N E 1 e 2 e 3+ X can ", aryl or nitro.
• the groups R 9, R 9, R 10 and R 10 represents hydrogen, Ci-Cio-alkyl or carboxylate and the groups R 11, R 12, R 13 and R 14 is hydrogen, C 1 -C 10 -alkyl, halogen, in particular fluorine, chlorine or bromine, trifluoromethyl, C 1 -C 4 -alkoxy, carboxylate, sulfonate or aryl.
• R 9 , R 9 ' , R 10 , R 10 ' , R 11 , R 12 , R 13 and R 14 are hydrogen
• such pnicogen chelate compounds are preferred in which 1, 2 or 3, before preferably 1 or 2, in particular 1 of the groups R 11 , R 12 , R 13 and / or R 14 for a C00 " M + , a SO 3 " M + or a (NE 1 E 2 E 3 ) + X " group where M + and X " are as defined above.
• Particularly preferred bridging groups D are the ethylene group
• R d forms an intramolecular bridging group D with another group R d or R e with another group R e , ie the index c is 1 in this case, it necessarily follows that both A 1 and A 2 together represent a bridging group, preferably a CR d R e group, and the bridging group Y 3 of the formula III.
• a in this case preferably has a triptycene-like or ethanoanthracene-like carbon skeleton.
• those bridge groups Y are preferred in which A 1 is different from A 2 , wherein A 1 is preferably a CR d R e group and A 2 is preferably an O or S group, particularly preferably an oxo group O is.
• Particularly preferred bridging groups Y 3 of formula III. a are thus those which are composed of a triptycene-like, ethanoanthracene-like or xanthene-like (A 1 : CR d R e , A 2 : O) skeleton.
• R 1 , R “, R 1 ", R IV , R v and R v ⁇ preferably selected from hydrogen, alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl and hetaryl.
• R 1 , R “, R 1 ", R IV , R v and R v ⁇ are hydrogen.
• R 1 and R v ⁇ independently of one another are C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.
• R 1 and R VI are selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
• R “, R 1 ", R IV and R v are preferably hydrogen.
• R "and R v independently of one another represent dC 4 -alkyl or C 1 -C 4 -alkoxy.
• R" and R v are selected from methyl, ethyl, isopropyl and tert-butyl.
• R 1, R 1 ', R IV and R VI are hydrogen.
• a two adjacent radicals selected from R 1 , R “, R 1 ", R IV , R V and R V ⁇ are a fused, so fused, ring system, so it is preferably benzene or naphthalene rings.
• Anellieri benzene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2 substituents which are selected from alkyl, alkoxy, halogen, SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , trifluoromethyl, Nitro, COOR f , alkoxycarbonyl, acyl and cyano.
• Anellated naphthalene rings are preferably unsubstituted or have in the non-annealed ring and / or in the fused ring a total of 1, 2 or 3, in particular 1 or 2 of the substituents previously mentioned in the fused benzene rings.
• Y 3 is a group of formula III.
• R IV and R v independently of one another are C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.
• R v and R v are selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
• R 1 , R “, R 1 ", R v ⁇ , R v "and R v ⁇ " are hydrogen.
• Y 3 is preferably a group of the formula III.
• R 1 and R 1 are each independently of one another C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy
• R 1 and R 2 particularly preferably represent tert-butyl.
• R 1" and R VI are each independently alkyl or CrC dC 4 4 - alkoxy.
• Particularly preferred R 1 "and R v ⁇ are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
• Y 3 is preferably a group of the formula III. b, wherein R “and R v " are hydrogen.
• R "and R v " are hydrogen.
• R 1 ", R IV, R V, R VIII and R VIII" In these compounds, R 1, R independently of one another dC 4 alkyl or Ci-C 4 -alkoxy.
• R 1 , R 1 ", R IV , R v , R v ⁇ and R v ⁇ " are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
• Y 3 is preferably a group of the formula III. c, wherein Z is a CrC 4 - alkylene group, in particular methylene.
• R IV and R v are preferably independently of one another C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.
• R IV and R v are preferably independently selected from methyl, ethyl, I- ssoopprrooppyyll ,, aanndd tteerrtt ..-- BBuuttyyll MMeethoxy.
• the radicals R 1 , R “, R 1 ", R v ⁇ , R v "and R v ⁇ " are preferably hydrogen.
• Y 3 is preferably a group of the formula III. c, wherein Z is a C 1 -C 4 -alkylene bridge which has at least one alkyl, cycloalkyl or aryl radical. Z particularly preferably represents a methylene bridge which has two C 1 -C 4 -alkyl radicals, in particular two methyl radicals.
• the radicals R 1 and R VI In these compounds "independently dC 4 alkyl or Ci-C 4 -alkoxy.
• Sonders loading are preferably R 1 and R VIII" are independently selected from methyl, ethyl, isopropyl, tert Butyl and methoxy.
• Y 3 is preferably a group of the formula III.
• R 1 and R x "independently of one another represent dC 4 -alkyl or C 1 -C 4 -alkoxy, in particular R 1 and R x " are independently selected from among methyl, ethyl, isopropyl, tert-butyl, methoxy and Alkoxycarbonyl, preferably methoxycarbonyl.
• Particularly preferred in these compounds are the radicals R "to R x ⁇ for hydrogen.
• Y 3 is preferably a group of the formula III.
• R 1 and R x "independently of one another are C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy
• R 1 and R x " are independently selected from among methyl, ethyl, isopropyl, tert. Butyl and methoxy. Particularly preferred in these compounds are the radicals R "to R x ⁇ for hydrogen.
• Y 3 is preferably a group of the formula III.f in which Z is a C 1 -C 4 -alkylene group which has at least one alkyl, cycloalkyl or aryl substituent. Z particularly preferably represents a methylene group which has two C 1 -C 4 -alkyl radicals, especially two methyl radicals. Especially preferably, the radicals R 1 and R VIII "4 -alkyl or C independently dC 4 alkoxy. In particular, R 1 and R VIII 'in these compounds is independently selected from methyl, ethyl, isopropyl, tert- Butyl and methoxy.
• Y 3 is preferably a group of the formula III. g, wherein R 1 , R 1 ' , R “, R 11' , R 1 " and R 1 " 'are hydrogen.
• Y 3 is preferably a group of the formula III. g, wherein R “and R” together represent an oxo group or a ketal thereof and the remaining radicals are hydrogen. Furthermore, Y 3 is preferably a group of the formula III. h, wherein R 1 , R 1 ' , R “, R 11' , R 1 " and R 1 " 'are hydrogen.
• Y 3 is preferably a group of the formula III. h, wherein R "and R" together represent an oxo group or a ketal thereof and the remaining radicals are hydrogen.
• Y 3 is preferably a group of the formula III. i, wherein R 1 , R 1 ' , R “, R 11' , R 1 ", R 1 " ' , R ⁇ v and R ⁇ v' are hydrogen.
• Y 3 is preferably a group of the formula III. k, wherein R 1 , R 1 ' , R “, R 11' , R 1 ", R 1 " ' , R ⁇ v and R ⁇ v' are hydrogen.
• Y 3 is preferably a group of the formula III. I, wherein R 1 , R 1 ' , R “, R 11' , R '", R'" ' , R ⁇ v and R ⁇ v' are hydrogen.
• Y 3 preferably represents a group of the formula III.m where R 1 , R 1 ' , R “, R 11' , R 1 ", R 1 " ' , R IV and R IV' are hydrogen.
• Y 3 is preferably a group of the formula III. n, wherein R 1 , R 1 ' , R “, R 11' , R 1 ", R 1 " ' , R ⁇ v and R ⁇ v' are hydrogen.
• Y 3 is preferably a group of the formula III.
• one of the radicals R 1 to R IV is C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.
• At least one of the radicals R 1 to R 1 preferably represents methyl, ethyl, isopropyl, tert-butyl or methoxy.
• Y 3 is preferably a group of the formula III. o, wherein R 1 , R “, R 1 " and R ⁇ v are hydrogen.
• Y 3 is preferably a group of the formula III. o, wherein one of the radicals R 1 , R “, R 1 " or R ⁇ v is C r C 4 alkyl or C r C 4 alkoxy. Particularly preferred is then one of the radicals R 1 to R ⁇ v is methyl, ethyl, tert-butyl or methoxy.
• Y 3 is preferably a group of the formula III.
• R 1 and R v ⁇ independently of one another are C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.
• Particularly preferred R 1 and R v ⁇ are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
• Particularly preferred in these compounds are R ", R 1 ", R IV and R v is hydrogen.
• preference is given in the compounds III.
• R 1, R 1 ', R IV and R VI are each independently C r C 4 alkyl or C r C 4 alkoxy.
• R 1 , R 1 ", R IV and R VI are then independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
• Y 3 is preferably a group of the formula III.
• R 1 and R v ⁇ independently of one another are C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.
• Particularly preferred R 1 and R v ⁇ are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
• Particularly preferred in these compounds are R ", R 1 ", R IV and R v is hydrogen.
• R 1 "and R 1 independently of one another are preferably C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy, more preferably R 1 " and R 1V are then independently selected from among methyl, ethyl and isopropyl, tert-butyl and methoxy.
• Y 3 is preferably a group of the formula III. r, III. s or III. t, wherein Z is CH 2 , C 2 H 2 or C 2 H 4 .
• the discharge from the second reaction zone is for workup, z.
• the hydroformylation product in order to isolate, concentrate and / or purify the hydroformylation product, it is usually subjected to a one-stage or multistage separation operation to obtain at least one stream containing the bulk of the hydroformylation product and a stream consisting essentially of unreacted olefins and optionally saturated hydrocarbons.
• Saturated hydrocarbons originate, for example, from the olefin-containing feed used, which may contain these as an admixture, or to a small extent from the hydrogenation of the olefin used.
• streams are optionally obtained, such as synthesis gas-containing exhaust gases, high-boiling by-products of the hydroformylation and / or hydroformylation catalyst-containing streams which - optionally after work-up - are recycled wholly or partly to the second reaction zone or from the process be discharged.
• liquid discharge process a liquid discharge is taken from the second reaction zone (liquid discharge process).
• This liquid discharge contains as essential components:
• hydroformylation product ie the aldehydes which are produced from the linear C 1 -olefins, in particular from those having terminal double bonds contained in the second reaction zone supplied stream
• an inert solvent such as toluene or xylene
• this too is contained in the liquid discharge from the second reaction zone.
• the by-products formed in the hydroformylation for example by aldol condensation, which boil higher than the hydroformylation product, are used as solvents.
• the liquid hydroformylation discharge from the second reaction zone is preferably subjected to a two-stage degassing for working up.
• the first degassing stage may be a rest and / or relaxation stage.
• the liquid hydroformylation discharge from the second reaction zone is transferred to a vessel which is under the pressure of the reaction zone.
• a separation takes place into a first liquid phase and a first gas phase.
• a corresponding device for removing entrained droplets can be provided.
• the liquid hydroformylation discharge from the second reaction zone is particularly preferably subjected to a two-stage expansion for working up.
• the hydroformylation is preferably carried out at a pressure in the range of 5 to 50 bar.
• the liquid hydroformylation discharge from the second reaction zone is preferably expanded in a first expansion stage to a pressure which is 0.1 to 20 bar below the reactor pressure.
• a separation takes place into a first liquid phase and a first gas phase.
• the first liquid phase is expanded in a second expansion stage to a pressure which is lower than the pressure in the first expansion stage.
• a separation into a second liquid phase and a second gas phase takes place.
• the partial relaxation in the first expansion stage can be done for example in a conventional pressure separator.
• the first gas phase obtained consists essentially of synthesis gas and optionally small amounts of unreacted olefin and / or low-boiling components (saturated hydrocarbons).
• the first gas phase can be sent for further use in the process according to the invention or independently thereof in other processes. Thus, for example, it can be returned to the reactor, usually after compression to the reactor pressure, or recycled, depending on the amount, partially or completely to thermal recycling.
• the deposited in the first expansion stage first liquid phase is then discharged usually as a liquid stream from the flash vessel and relaxed in a second expansion stage to a pressure which is lower than the pressure of the first flash stage.
• the pressure is reduced to a pressure in the range of 0.01 to 10 bar, preferably 0.1 to 5 bar.
• the pressure in the second expansion stage is generally around 2 to 20 bar, in particular around 3 to 15 bar, lower than the pressure in the first expansion stage.
• the first liquid phase obtained from the first rest / relaxation stage is separated in the second expansion stage (degassing stage) into a second liquid phase and a second gas phase.
• the second liquid phase contains the by-products boiling higher than the hydroformylation product, the homogeneously dissolved hydroformylation catalyst and a part of the hydroformylation product.
• the second gas phase contains the unreacted olefins, saturated hydrocarbons, and also part of the hydroformylation product.
• the second expansion stage is carried out as a combination of the expansion step (flash) with a thermal separation step.
• This thermal separation step may be, for example, a distillation.
• the second liquid phase and the second gas phase from the second expansion step are preferably conducted in countercurrent and thus brought into particularly intimate contact (stripping).
• the second relaxation step and the thermal separation step may be carried out in separate devices or advantageously in a single device, e.g. B. a so-called "flash / strip column" done.
• the first liquid phase discharged from the first expansion stage can first be expanded in a flash tank.
• the resulting second Gas phase is passed into the bottom or the lower part of a downstream distillation column.
• the (second) liquid phase from the flash vessel is fed to this distillation column above the feed of the gas phase.
• the (second) liquid phase from the flash tank of this distillation column z. B. at or shortly below the head.
• the second liquid phase can be previously heated, for example in a heat exchanger.
• the second liquid phase is heated to a temperature which is about 10 0 C to 120 0 C above the temperature of the liquid phase in the flash tank (in the second expansion stage).
• Suitable columns are the customary distillation columns known to the person skilled in the art, which, for. B. are filled with packing, packages or internals for an intensive gas / liquid exchange.
• the first liquid phase discharged from the first expansion stage is fed into a region above the bottom and below the top of the flash / strip column and thereby expanded
• the feed preferably takes place within the lower half, in particular within the lower third of the flash / strip column, and a liquid stream is withdrawn from the bottom of the flash / strip column and is added to the column at or below the
• the liquid phase withdrawn from the bottom is preferably heated to a temperature which is about 10 ° C. to 120 ° C. above the temperature
• the columns used have in the upper region, in particular within the upper third, preferably internals for an intensive gas / liquid exchange.
• Both in the embodiment of the second expansion stage with separate thermal separation as well as when using a flash / strip column is a the hydroformylation and the hydroformylation higher than the hydroformylation product boiling by-products of hydroformylation containing third liquid phase and the hydroformylation product, the unreacted olefin and saturated Hydrocarbons containing third gas phase.
• the third liquid phase can, if appropriate after removal of the high boilers, in order to avoid their accumulation, be recycled to the first reaction zone.
• the third gas phase obtained in the second relaxation (strip) stage is separated into a fraction containing essentially the hydroformylation product and a fraction containing substantially unreacted olefins and low boiling components.
• the third gas phase can be subjected to a fractional condensation.
• the third gas phase can continue to be completely condensed and then subjected to thermal separation.
• the hydroformylation product is sent for further recovery as described below.
• the fraction containing unreacted olefins and low-boiling components can, after condensation as a liquid stream, be partially fed into the second expansion stage and partially removed from the process or completely discharged.
• this fraction is subjected to an additional workup to separate at least a portion of the inert components (saturated hydrocarbons) present.
• the fraction may for example be subjected to a renewed fractional condensation or a complete condensation with subsequent distillation.
• step Id the processing of the discharge from step Id) is preferably carried out in an additional step Ie), in which one
• Ie1 the generally liquid discharge from the second reaction zone, containing as essential constituents the hydroformylation product, higher than the hydroformylation product boiling by-products, the homogeneously dissolved hydroformylation catalyst, unreacted olefins, saturated hydrocarbons and unreacted synthesis gas, a degassing wherein, optionally, the pressure and / or the temperature relative to the reaction zone are lowered, and wherein a first substantially the unreacted synthesis gas containing gas phase and a first substantially the
• Hydroformylation product by-products boiling higher than the hydroformylation product, the homogeneously dissolved hydroformylation catalyst, unreacted olefins, and liquid phase containing saturated hydrocarbons,
• Ie3 subjects the first liquid phase to a depressurization, the pressure being reduced relative to the first degassing to such an extent that a second unreacted olefins, saturated hydrocarbons and a gas phase containing part of the hydroformylation product and a second higher than the hydroformylation product boiling by-products, the homogeneously dissolved hydroformylation catalyst and a portion of the hydroformylation product containing liquid phase result, Ie4) feeds the second gas phase into the bottom or the lower part of a column and feeds the second liquid phase, optionally after heating, in liquid form above the feed of the gas phase into this column and leads it to the gas phase,
• FIG. 1 A schematic overview of a preferred embodiment of the method according to the invention as described above with reference to step (I) is shown in FIG. Reference is made to the below description of the figures.
• the olefin-containing feed is first subjected to the hydroformylation stage according to the invention before a portion of the discharge therefrom containing linear C-olefin having internal double bonds is fed to the isomerization step.
• Both the reaction in the hydroformylation stage and that in the isomerization stage can be carried out in the same manner as described above for the hydroformylation stage or the isomerization stage when carrying out process step (I), so that in the following description of embodiments with the method step (FIG. II) can be referred to accordingly.
• a common aspect of the various embodiments of the invention with the method step (II) is that the content of educts, products and By-products in the individual streams should be coordinated so that on the one hand unnecessary enrichment of by-products and / or unreacted starting materials in the reaction system is avoided, but on the other hand, an economic implementation of the method is guaranteed.
• the process according to the invention, including the process step (II) is therefore carried out by reacting
• the effluent from the first reaction zone separates the unreacted stream containing linear C-olefin with internal double bond and separates it into two fractions, of which at least one unreacted linear C-olefin with internal double bond;
• Nd returns the discharge from the second reaction zone in step IIa).
• step IIb) the separation of the unreacted linear d-olefin containing internal double bond current from the effluent of step IIa) can be carried out in an analogous manner, as described above in the processing of the discharge from the second reaction zone (hydroformylation stage) according to process step (I) ,
• the steps described there of single or multi-stage degassing or expansion and the separation into different streams can be carried out in the same way.
• the procedure is such that unreacted synthesis from the first reaction zone is removed. segas separates, z. B. by means of a degassing, the hydroformylation catalyst separated, z. B.
• step IIb the current to be separated in step IIb), unreacted linear C-olefin with internal double bond containing stream, which in turn, also in step IIb), is separated into two fractions.
• the unreacted linear d-olefin containing an internal double bond is separated from the effluent from step IIa) in step IIb) by adding
• Hydroformylation product by-products boiling higher than the hydroformylation product, the homogeneously dissolved hydroformylation catalyst, unreacted olefins, and liquid phase containing saturated hydrocarbons,
• Ilb2 supplies the first gas phase to a recovery
• the stream containing unreacted linear ⁇ -olefin having an internal double bond which results from the workup of the discharge resulting from step IIa) in step IIb) essentially comprises unreacted olefins and saturated hydrocarbons.
• This stream is passed to a separation stage for separation into two fractions, of which at least one unreacted linear d-olefin contains internal double bond.
• the separation stage may be designed as a simple flow divider for separation into two fractions, so that the composition of the two fractions obtained is the same.
• one of the two fractions obtained in step IIb) is then fed to step Nc).
• the other, not the step Nc) supplied fraction can be discharged from the process and z.
• B. a thermal utilization can be supplied.
• the amount of the discharged fraction is in the range from 1 to 75% by weight, preferably in the range from 2 to 50% by weight, and more preferably in the range from 5 to 25% by weight, based on the total weight the separated in step IIb), unreacted linear C-olefin containing internal double bond current.
• a particularly preferred embodiment additionally comprises the following step IIb ⁇ a), in which one
• the separation stage in step IIb) for separation into two fractions can be designed such that the stream containing unreacted linear ⁇ -olefin having an internal double bond is split into an olefin-enriched fraction and a fraction depleted in olefins. Of the fractions thus obtained, the depleted of olefins fraction can be discharged from the process and z. B. a thermal utilization can be supplied. The other olefin-enriched fraction is fed to step Nc).
• Such separation of the stream fed to the separation stage into the olefin-enriched and the olefin-depleted fraction can be carried out by passing the stream fed to the separation stage in the separation stage of an extractive distillation, a membrane separation process, a selective absorption separation or a combination of at least two of these measures.
• the aforesaid separation of the unreacted linear ⁇ -olefin having internal double bond-containing stream into an olefin-enriched fraction and an olefin-depleted fraction in step IIb) can be carried out in a specific embodiment by extractive distillation.
• extractive distillations are known to the person skilled in the art.
• the extractive distillation is carried out in a polar solvent, in particular an organic polar solvent or a mixture of such a polar organic solvent with water.
• Suitable polar solvents are, for example, the organic solvents monomethylformamide, dimethylformamide, diethylformamide, dimethylacetamide and N-methylpyrrolidinone and mixtures of one or more thereof with water.
• a decomposition of the components to be extracted may occur, for.
• water is advantageously added to the organic solvent to lower the boiling point of the solvent.
• addition of water may in some cases cause an improvement in selectivity in the extractive distillation.
• N-methylpyrrolidinone water is advantageously added to the organic solvent to lower the boiling point of the solvent.
• Methylpyrrolidinone / water mixtures other extractants are advantageously used.
• CN 1 280 976 describes the use of dimethylformamide in combination with another low-boiling solvent for the separation of butane / butene mixtures.
• solvents or solvent mixtures ethylenically unsaturated compounds such as olefins, z.
• butene usually much better than saturated hydrocarbons, eg. B. butane.
• the extractive distillation is carried out by selectively adding the olefins, eg. B. butene, washes.
• the saturated hydrocarbons, eg. As butane are deducted in this case over the top of the column.
• the charged with olefins solvent stream can then be degassed in a second column (stripper). At the head of the stripper, the butene fraction is removed.
• the aforesaid separation of the unreacted linear ⁇ -olefin containing internal double bond-containing stream into an olefin-enriched fraction and an olefin-depleted fraction in step IIb) may be carried out in a further specific embodiment by a membrane separation process.
• membrane separation processes using membranes which separate olefins from saturated hydrocarbons (paraffins) are known to those skilled in the art.
• Such membranes separate the olefin / paraffin mixture into an olefin enriched fraction which permeates through the membrane, i. H. permeates the membrane and an olefin-depleted fraction that can not permeate through the membrane.
• the former, through the membrane permeating fraction is referred to as permeate, the latter, retained by the membrane fraction as a retentate.
• Different types of membranes can be used.
• Membrane incorporated metal ion such as Ag + or Cu + is effected. Due to a concentration gradient, diffusion of the olefin through the membrane takes place here (see, for example, Chem. Ing. Tech., 2001, 73, 297), where the olefin is either free, if the said metal ions are freely mobile within the membrane ⁇ complex-bonded form or, if said metal ions are not freely movable within the membrane, in a "hopping" mechanism from a metal ion to an adjacent metal ion can move.
• the said metal ions can, for. B. as counterions to bonded to a polymer anionic centers (eg. B. sulfonate or carboxylate groups), for. B.
• the said salt solution is in the pores of a suitable, preferably hydrophilic membrane and / or in the space between two membranes (or membrane systems), of which in the one on the side facing away from said solution, the retention did and in the another is the permeate.
• a continuous or temporary replacement of the solution can advantageously take place.
• Suitable membranes are those in which the separation is based on preferential adsorption and surface diffusion of the olefin into micropores. These membranes may consist of organic or advantageously of inorganic materials. In particular suitable materials are for. B. microporous carbon obtained by thermal treatment of polymeric materials such. As polypropylene or polyimides can be prepared, and ceramic materials with micropores such. B. zeolites.
• Suitable membranes are those which consist of one or more polar polymers, the separation being effected by the fact that the olefins and paraffins to be separated have differences in the solubility and / or in the diffusion coefficient in the polymer.
• Suitable polymers are, for. As polyimides, polyetherimides, polyamides, polyamidoimides, polysulfones, polyethersulfones, polyether ketones, polydialkylsiloxanes and mixtures, copolymers or block copolymers thereof. Polymers in which an ionic or covalent cross-linking of the polymer chains has been carried out have proved to be advantageous.
• the membranes may be embodied as integrally asymmetric or composite membranes in which the actual separation layer effecting the separation is applied to one or more meso and / or macroporous support (s).
• the aforementioned separating layer generally has a thickness of 0.01 to 100 ⁇ m, and preferably 0.1 to 20 ⁇ m.
• the / the meso and / or macroporous carrier consists / consist of one or more organic, especially polymeric materials), z. As carbon, and / or inorganic material (s), in particular ceramic or metal.
• the membranes can z. B. in the form of flat, pillow, capillary, Monokanalrohr- or multi-channel pipe elements are used, which are known to those skilled in the art from other membrane separation processes such as ultrafiltration or reverse osmosis (see, for example BR Rautenbach, membrane processes, fundamentals of the module - and System design, Springer-Verlag, 1997).
• the separating layer is preferably located on the inside or outside of the tube.
• the membranes are generally surrounded by one or more housings of polymeric, metallic or ceramic material, wherein the connection between the housing and the membrane is formed by a sealing polymer (eg elastomer) or inorganic material.
• a sealing polymer eg elastomer
• the membrane separation process can be carried out in one or more membrane apparatuses.
• the supplied stream can flow through the individual membrane apparatuses one behind the other and / or in parallel.
• the structure of the pressure required to carry out the above-described membrane separation process can, for. Example, by compressing a gaseous stream supplied by the skilled person in a known compressor or by conveying a liquid supplied stream by means of those skilled in the known pumps.
• the supplied stream to a pressure in the range of 1 to 200 bar, more preferably in the range of 2 to 50 bar, and most preferably in the range of 4 to 35 bar a.
• Preferred permeate pressures are in the range of 0.01 to 100 bar, more preferably in the range of 0.1 to 50 bar, and most preferably in the range of 1 to 20 bar, wherein the permeate pressure must always be lower than the pressure of the supplied stream .
• the desired temperature can be set by means of apparatuses known per se prior to feeding to the membrane apparatus used, the stream leaving the tempering apparatus and entering the membrane apparatus being liquid, gaseous or two-phase gaseous / liquid. If the stream entering the membrane apparatus is liquid, the special case of so-called pervaporation is given.
• a temperature in the range of -50 to 200 0 C, more preferably in the range of 0 to 120 0 C, and most preferably in the range of 20 to 80 0 C is set for the membrane separation process.
• the membrane separation process can on the one hand be carried out in one stage, ie the permeate from a membrane apparatus or the combined permeates of a plurality of fed by the flow in succession and / or parallel membrane apparatus forms without further treatment of the olefin, z. B. butenes, enriched fraction and the non-permeated portion (retentate) forms the depleted in olefins fraction without further treatment.
• the latter consists essentially of saturated hydrocarbons. It will be understood by those skilled in the art that permeate and retentate may also be reversed in their composition.
• the membrane method can also be configured in two or more stages, wherein in each case the permeate from a preceding stage is used as feed for the respective subsequent stage and the retentate from this (subsequent) stage is added to the feed to the former (previous) stage.
• Such arrangements are known per se and z. In Sep. Be. Technol. 1996, 31, 729.
• the separation of the olefins from the paraffins can in yet another specific embodiment also by selective absorption of the olefins in a ⁇ -complexing, metal ions, for. B. Ag + , Cu + , solution with subsequent desorption of the olefins take place, such as. In Eldridge, Ind. Eng. Chem. Res. 1993, 32, 2208.
• an olefin-enriched fraction consists essentially of saturated hydrocarbons.
• a butane / butene mixture may be separated into a fraction consisting essentially of 2-butenes and a fraction consisting essentially of n-butane and isobutane.
• Another particularly preferred embodiment additionally comprises the following step IIb ⁇ b)
• step Nc separating the unreacted linear C-olefin having an internal double bond, which further contains substantially unreacted linear C 1 olefins having a terminal double bond and saturated hydrocarbons, into an olefin-enriched fraction and an olefin-depleted fraction, of which the olefin-enriched fraction is fed to step Nc) by subjecting that stream to extractive distillation, membrane separation, selective absorption separation or a combination of at least two of these measures.
• step IIb ⁇ b) is preferably carried out in place of the above step IIb ⁇ a).
• the fraction taken from step 11b ⁇ a) may be fed to step Nc), prior to delivery to step Nc), to a separation according to step 11b ⁇ b).
• the fraction not added to step Nc) may be discharged from the process and e.g. B. a thermal utilization can be supplied.
• the olefin-enriched fraction fed to step Nc) usually has an internal double bond linear ⁇ -olefin of at least 25 Wt .-%, in particular at least 50 wt .-%, and especially at least 70 wt .-%, based on the total weight of the olefin-enriched fraction on. Otherwise, it essentially consists of small shares, eg. B. in the range of 0.1 to 25 wt .-%, and in particular in the range of 0.2 to 15 wt .-% of saturated hydrocarbons and / or linear C-olefin with terminal double bond, each based on the total weight of olefins enriched fraction. Other ingredients, eg. B.
• polyunsaturated compounds such as butadienes and alkynes, may optionally be contained in a total of at most 5 wt .-% and in particular at most 1 wt .-%, each based on the total weight of the fraction enriched in olefins.
• the fraction containing unconverted linear d-olefin containing internal double bond obtained from step IIb) and containing step Nc) is either enriched in olefin (in particular according to steps IIb1) to IIb7) and step IIb ⁇ b according to the above-described embodiments. ) or has a content of olefins, which corresponds to the content of olefins in the separated in step IIb), unreacted linear ⁇ -olefin containing internal double bond current (in particular according to steps Ilb1) to Ilb7) and step Nb8a)).
• the fraction fed to step Nc) is fed to a second reaction zone (double bond isomerization) according to the invention.
• the added fraction is reacted in the presence of a double bond isomerization catalyst.
• the design of the second reaction zone (double bond isomerization step) in step Nc) according to process step (II) of the invention reference is made to the above explanations concerning the first reaction zone (double bond isomerization step) according to process step (I) of the invention.
• the reactor types and systems described there, operating parameters such as temperature, pressure, flow rates and residence times, as well as isomerization catalysts, etc. can be used in the same way.
• the discharge from the second reaction zone is recycled to step IIa) according to step Nd).
• the olefin-containing feed is also subjected to such selective hydrogenation before it is fed into step IIa) or before it is fed into the first reaction zone, the discharge from the second reaction zone before being fed to the selective hydrogenation can advantageously be combined with the olefin-containing feed.
• a stream is obtained which is essentially contains the hydroformylation product.
• the hydroformylation product comprises in particular the C l + i-hydroformylation products, ie preferably linear aldehydes having i + 1 carbon atoms.
• This hydroformylation product may be another Auftial. Processing be supplied.
• the product streams obtained can be used immediately for further reaction, eg. B. for the production of propylheptanol, are used. If desired, they can also be subjected to further work-up by customary methods known to the person skilled in the art, such as, for example, B. by distillation, subjected and then processed.
• Another object of the invention is a process for the preparation of 2-propylheptanol, in which
• step iii) subjecting the hydroformylation product obtained in step i) or the n-valeraldehyde-enriched fraction obtained in step ii) to aldol condensation;
• Suitable starting materials for the hydroformylation are, in particular, mixtures of 1-butene with 2-butene and industrially available C 4 -hydrocarbon streams, which
• Butene and / or 2-butene Preferably, the previously described C 4 cuts, which are incorporated herein by reference.
• the hydroformylation catalyst used is a rhodium / triphenylphosphine catalyst or a hydroformylation catalyst, comprising at least one complex of a metal of the VIII.
• Subgroup with at least one ligand of the general formula II With regard to suitable and preferred ligands of the formula II, reference is made to the previous statements.
• the product-enriched streams obtained in step i) are subjected to further separation to obtain a fraction enriched in n-valeraldehyde.
• the separation of the hydroformylation product into an n-valeraldehyde-enriched fraction and an n-valeraldehyde-depleted fraction is carried out by customary methods known to the person skilled in the art.
• the distillation using known separation apparatus such as distillation columns, z. B. tray columns, which may be equipped with bells, sieve plates, trays, valves, etc., if desired, evaporators, such as thin-film evaporator, falling film evaporator, wiper blade evaporator, etc ..
• Cio aldehydes Two molecules of C 5 aldehyde can be condensed to form ⁇ , ⁇ -unsaturated Cio aldehydes.
• the aldol condensation is carried out in a known manner z. B. by the action of an aqueous base, such as sodium hydroxide or potassium hydroxide.
• a heterogeneous basic catalyst such as magnesium and / or alumina, can be used (see, for example, EP-A 792 862). This results in the condensation of two molecules of n-valeraldehyde 2-propyl-2-heptenal.
• step i) If the hydroformylation product obtained in step i) or after the separation in step ii) has further C 5 -aldehydes, such as 2-methylbutanal and optionally 2,2-dimethylpropanal or 3-methylbutanal or traces of other aldehydes, these likewise react in an aldol condensation, in which case the condensation products of all possible aldehyde combinations result, for example 2-propyl-4-methyl-2-hexenal.
• a proportion of these condensation products, eg. B. of up to 30 wt .-%, is an advantageous further processing to softener alcohols suitable 2-propylheptanol-containing Ci 0 -alcohol mixtures not contrary.
• the products of the aldol condensation can be catalytically hydrogenated with hydrogen to Ci 0 - alcohols, such as in particular 2-propylheptanol.
• the catalysts of the hydroformylation are usually suitable at elevated temperature; in general, however, more selective hydrogenation catalysts are preferred, which are used in a separate hydrogenation step.
• Suitable hydrogenation catalysts are generally transition metals, such as. B. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc., or mixtures thereof, to increase the activity and stability on carriers such.
• activated carbon alumina, diatomaceous earth, etc. can be applied.
• Fe, Co and preferably Ni also in the form of the Raney catalysts, can be used as metal sponge with a very large surface area.
• the hydrogenation of the Cio-aldehydes takes place as a function of the activity of the catalyst, preferably at elevated temperatures and elevated pressure.
• the hydrogenation temperature is about 80 to 250 0 C, preferably the pressure is about 50 to 350 bar.
• the crude hydrogenation product may be prepared by conventional methods, e.g. B. by distillation, are worked up to the Cio alcohols.
• the hydrogenation products may be subjected to further separation to give a 2-propylheptanol enriched fraction and a 2-propylheptanol depleted fraction.
• This separation can be carried out by conventional methods known to those skilled in the art, such as. B. by distillation.
• the 2-propylheptanol obtained can be further processed into plasticizers by customary methods known to the person skilled in the art.
• FIG. 1 schematically illustrates a preferred embodiment of the process according to the invention with process step (I).
• the olefin-containing feed 1 is fed to a distillation column 2.
• a distillation column 2 takes a enriched in linear d-olefin with internal double bond stream 3, which is fed to a first reaction zone 4 (double bond isomerization).
• the stream 3 is reacted in the presence of a double bond isomerization catalyst, wherein at least a portion of the linear C, olefins with internal double bond is converted to linear C-olefins with terminal double bond.
• the discharge 5 from the first reaction zone 4 is conducted at a point in the distillation column 2, which is located above the removal point of the stream 3, in the distillation column 2.
• a point in the distillation column 2 takes a enriched in linear C-olefin with internal double bond stream 7, which is discharged from the process.
• a stream 6 enriched in a linear double-bond linear C-olefin is withdrawn, which stream is fed to the selective hydrogenation stage 8.
• polyunsaturated compounds present in the stream 6 are selectively hydrogenated to simply ethylenically unsaturated olefins.
• the discharge 9 from the hydrogenation stage 8 is fed together with carbon monoxide and hydrogen, both fed in via stream 10, and with the discharge 12 from the separation stage 17, which contains recovered hydroformylation catalyst, to a second reaction zone 11 (hydroformylation).
• the second reaction zone 11 the combined streams 9, 10 and 12 are reacted in the presence of a hydroformylation catalyst.
• the product containing the hydroformylation product 13 from the second reaction zone 1 1 is degassed in the separation stage 14.
• the exhaust gas from the separation stage 14 is removed as stream 15.
• the degassed discharge 16 from the separation stage 14 is carried out together with the stream 23 from the separation stage 19, which consists essentially of C-hydrocarbons, the separation stage 17 to. In the separation stage 17 there is a recovery of the hydroformylation catalyst.
• the thus recovered hydroformylation catalyst is passed through the stream 12 back into the second reaction zone 1 1.
• the discharge 18 from the separation stage 17 contains essentially C-hydrocarbons, C + i-hydroformylation products and optionally higher-boiling compounds.
• the discharge 18 is passed to the separation stage 19, in which the C, + i hydroformylation products and optionally the higher-boiling compounds are separated and removed as stream 20.
• the C-hydrocarbons are discharged as stream 21 from the separation stage 19 and partially discharged via stream 22 and partially recycled via stream 23 into the separation stage 17.
• FIG. 2 schematically illustrates a preferred embodiment of the process according to the invention with process step (II).
• the olefin-containing feed 2 is fed together with carbon monoxide and hydrogen, both via stream 3, and with the discharge 6 from the separation stage 5, which recycled hydroformylation catalyst contains, a first reaction zone 1 (hydroformylation) fed.
• the first reaction zone 1 the discharge 15 from the second reaction zone 14 (double bond isomerization), which is enriched in inert d-olefin with a terminal double bond fed.
• the streams 2, 3, 6 and 15 are reacted in the presence of a hydroformylation catalyst.
• the effluent 4 from the first reaction zone contains essentially C, + i- Hydroformylation, optionally higher than the hydroformylation product boiling compounds, the homogeneously dissolved hydroformylation, unreacted ⁇ -olefins, saturated d-hydrocarbons and unreacted synthesis gas.
• the discharge 4 is fed to the separation stage 5, it being expedient to provide a degassing stage beforehand for separating the synthesis gas contained in the discharge 4 (not shown here). In the separation stage 5 there is a recovery of the hydroformylation, advantageously z. Example by means of a flash / strip column.
• the hydroformylation catalyst thus recovered is conducted back into the first reaction zone 1 via the stream 6, it being possible if appropriate in addition to provide a partial separation of by-products from the stream 6 (not shown here).
• the discharge 7 from the separation stage 5 contains essentially -C-n-hydroformylation products, saturated C-hydrocarbons, unreacted ⁇ -olefins, and optionally higher than the hydroformylation product boiling compounds.
• the discharge 7 is passed to the separation stage 8, in which the d + r hydroformylation products and optionally the higher-boiling compounds are separated and removed as stream 9.
• the separation stage 1 1 can here be designed as a simple current divider, so that the composition of the fractions 12 and 13 is the same and only part of the supplied stream 10 is discharged as stream 12 from the process.
• the separation stage 1 1 can be designed here so that the feed stream 10 is separated into an olefin-enriched fraction 13, which is the second reaction zone 14 (double bond isomerization) is fed, and into an olefin-depleted fraction 12, which is discharged.
• Such separation of the feedstream 10 into the olefin-enriched fraction 13 and the olefin-depleted fraction 12 may be accomplished by passing the stream 10 in the separation stage 11 of an extractive distillation, a membrane separation process, a selective absorption separation, or a combination of at least two of these measures.
• the fraction 13 taken from the separation stage 1 1 leads to the second reaction zone 14.
• the fraction 13 is reacted in the presence of a double bond isomerization catalyst.
• the effluent 15 from the second reaction zone 14, which is enriched in a linear d-olefin with a terminal double bond, is recycled to the first reaction zone 1.
• FIG. 3 schematically illustrates an embodiment of the process according to the invention with process step (I), which is explained in detail in Example 1. With respect to the details shown in Fig. 3, reference is therefore made to Example 1. The invention will be further illustrated by the following non-limiting examples.
• a stream 4 (containing 78% of 1-butene and 4% of 2-butene, conversion of 2-butene 90%, based on the raffinate II stream used) is taken off at the top of the distillation column A. At the bottom of the distillation column A, a stream 5 (7 kg / h) is withdrawn, which is combined with stream 4 to stream 6.
• the stream 6 leads to the hydrogenation stage C.
• 5% of the 1-butene contained in stream 6 is isomerized to 2-butene.
• the discharge 9 from the first hydroformylation reactor D (partly liquid 9a, partly gaseous 9b) is conducted together with additional synthesis gas 10 into the second hydroformylation reactor E.
• the discharge 1 1 from the second hydroformylation reactor E (partly liquid 1 1 a, partly gaseous 1 1 b) is separated in the pressure separator F.
• the exhaust gas stream 12 from the pressure separator F is fed to a cooler in order to condense out C 4 hydrocarbons contained in the exhaust gas stream 12.
• the remaining exhaust gas stream 13 is supplied to a combustion.
• the condensed stream 14 is returned to the pressure separator F.
• the degassed discharge 15 from the pressure separator F is led into the lower part of the flasher / stripper G.
• the discharge 15 is fed to the flasher / stripper G via the stream 20 from the hydrocarbon recovery stage H before being fed is and is heated to a temperature of 90 0 C, 8 t / h of C 4 hydrocarbons.
• C 4 hydrocarbons and C 5 hydroformylation products are separated from the catalyst-containing bottoms.
• the stream 12 removed at the bottom of the flasher / stripper G is returned to the first hydroformylation reactor D.
• the feed 16 containing C 4 hydrocarbons and C 5 -Hydroformyl michs leads to the hydrocarbon recovery stage H, where the discharge 16 is separated by distillation.
• the C 5 - hydroformylation products are removed and removed as stream 18 (15 t / h).
• Part of the C 4 hydrocarbons obtained at the top of the distillation column H is discharged via stream 19 (4 t / h).
• the remaining part of the obtained at the top of the distillation column H C 4 hydrocarbons is heated to 90 0 C and stream 20 (8 t / h), together with the stream 15, recycled to the flasher / stripper G.
• Table 1 Table 1
• a crude C 4 stream from a naphtha cracker is completely fed to a selective hydrogenation stage in which polyunsaturated compounds such as 1, 3-butadiene, alkynes and allenes are hydrogenated to alkenes. Subsequently, the isobutene contained therein is largely separated from the discharge from the hydrogenation stage.
• the raffinate stream thus obtained is combined with stream E obtained from the double bond isomerization step to stream A.
• Stream A is reacted with synthesis gas in the hydroformylation stage in the presence of a Rh / triphenylphosphane catalyst.
• 90% of the 1-butene are reacted in the hydroformylation stage.
• Each 3.3% of the 1-butene reacted are isomerized to 2-butenes or hydrogenated to butane.
• 165,000 t / a of C 5 aldehydes are separated off and taken off via stream B.
• Table 2 below shows the individual specified material flows in annual tonnes [t / a].

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