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    • 专利摘要:
    The present invention, Hydroformylating an olefin having 6 to 24 carbon atoms at a conversion rate of 20 to 98% (a), (B) removing the catalyst from the resulting liquid reactor discharge, (C) separating the resulting liquid hydroformylation mixture into a low boiling point fraction comprising olefins and paraffins and a bottom fraction comprising aldehydes and / or alcohols, and A process comprising the step (d) of reacting olefins present in the low boiling fraction in a further step comprising processes a), b) and c), characterized in that the bottom fractions of process (c) are combined at all stages. The present invention relates to a method for producing alcohols and / or aldehydes by multistage hydroformylation of olefins having 6 to 24 carbon atoms as a catalyst using cobalt or rhodium.
    公开号:KR20020008020A
    申请号:KR1020010042431
    申请日:2001-07-13
    公开日:2002-01-29
    发明作者:숄츠베른하르트；니를리히프란츠；카이치크알프레트；헤쓰디터；뷔쉬켄빌프리트；비제클라우스-디터；룃트거디르크；프로츠만귀도
    申请人:뮐러 리하르트, 슈베르트페거；옥세노 올레핀케미 게엠베하；
    IPC主号:
    专利说明:

    Multistage process for the preparation of oxo aldehydes and / or alcohols
    [4] The present invention relates to a process for preparing aldehydes having 7 to 25 carbon atoms by multistage hydroformylation of the corresponding olefins using a cobalt or rhodium catalyst.
    [5] As is known, higher aldehydes, in particular higher aldehydes having from 7 to 25 carbon atoms, can be prepared by catalytic hydroformylation (also referred to in the art as the oxo process in the art) of one less carbon olefin. Aldehydes are used, for example, as synthetic precursors for producing carboxylic acids and as fragrances. In the industry, these are often converted to the corresponding alcohols by catalytic hydrogenation, which alcohols are used in particular as intermediates in the preparation of plasticizers and detergents.
    [6] Numerous methods for hydroformylating olefins have been described in the literature. The choice of catalyst system and optimal reaction conditions for carrying out the hydroformylation process depends on the reactivity of the olephine used. The effect of the structure of the olefin used in the hydroformylation process on its reactivity is described, for example, in J. FALBE, "New Syntheses with Carbon Monoxide", Springer Verlag, 1980, Berlin, Heidelberg, New York, pages 95 et seq.
    [7] In general, under certain conventional conditions, the rate of hydroformylation slows down as the number of carbons increases and the degree of branching of the olefins decreases. Thus, the reaction rate of linear olefins can be 10 times faster than branched isomers. In addition, the position of the double bond in the olefin has a critical influence on the reactivity. Olefins with terminal double bonds react much faster than isomers with double bonds inside the molecule. Changes in reactivity of the isomeric octenes are described, for example, in B.L. HAYMORE, A. van HASSELT, R. BECK, Annals of the New York Acad. Sci., 1983, 415, 159-175. A general overview and additional literature are provided [B.CORNILS, W.A.HERRMANN, “Applied Homogeneous Catalysis with Organometallic Compounds”, Vol. 1 & 2, VCH Weinheim, New York, 1996].
    [8] Industrial olefin mixtures used as starting materials for hydroformylation synthesis often contain olefin isomers with very different structures, with different branching and double bond positions, with different molar masses of olefins. This is in particular an olefin mixture prepared by oligomerizing two or more readily available olefins having 2 to 8 carbon atoms or other olefins, or by cooligomerizing such olefins. Possible examples of typical olefin mixtures industrially associated with hydroformylation are tripropene, tetrapropene, dibutene, tributene and tetrabutene.
    [9] In the case of industrially hydroformylation, in addition to high conversion, high selectivity for the optimal use of raw materials is preferred. In order to increase the conversion, for slow reacting olefins a relatively long reaction time and / or a relatively high reaction temperature must be frequently allowed. In contrast, the more reactive olefins are converted to aldehydes under the same reaction conditions in a shorter time. When mixtures of olefins of varying reactivity are hydroformylated together, a relatively long reaction time is required to sufficiently convert olefins that are more difficult to oxidize. However, aldehydes made from olefins that can be more readily converted are formed relatively quickly, and then are present in the reactor with olefins that are more difficult to hydroformylate. In this case, aldehydes undesirably cause a secondary subsequent reaction, for example hydrogenation or condensation reactions or formation of acetals and hemiacetals. Primarily due to changes in the reactivity of the olefin isomers, it is difficult to increase the conversion and selectivity during hydroformylation.
    [10] In addition to the adverse effects on selectivity, there are two additional aspects that ensure that the combined hydroformylation of the olefin mixture in one step does not yield a high conversion. First, a relatively long reaction time for a given capacity (or reactor performance) Requires a relatively large reactor volume. This is particularly disadvantageous because the hydroformylation process is carried out at elevated pressure, and the investment cost for the pressurized reactor increases exponentially with size. Second, the control of the product properties of the aldehyde is limited by, for example, the n / i ratio.
    [11] Two stage hydroformylation processes of olefins are known. EP 562 451 and 0 646 563 describe hydroformylation of mixtures comprising 1- and 2-butenes, in which the first step is carried out with the optional addition of a phase transfer agent or dissolution promoter. The butenes are reacted in a heterogeneous reaction, ie in a multiphase system, and in the second step a homogeneously dissolved catalyst is used. According to EP 0 562 451, a rhodium catalyst is used in both stages, according to EP 0 646 563 a rhodium catalyst is used in the first stage and in the second stage a cobalt catalyst is used. According to EP 0 562 451, olefins which do not react in the first stage, mainly 2-butene, are homoformally hydroformylated in the presence of rhodium as catalyst in the second stage. According to EP 0 646 563, this process is described in which the unreacted olefin in the first stage remains in the reactor in gaseous state with carbon monoxide, hydrogen and butane produced by hydrogenation. This gas optionally undergoes a second hydroformylation step upon compression. The process according to these two documents can be disadvantageous for use in the hydroformylation of higher olefins, ie olefins with 5 or more carbon atoms, because unreacted olefins can be produced from the first stage at a cost feasible due to the relatively high boiling point. This is because it cannot be released in a state.
    [12] British Patent No. 387 657 discloses that the reaction product from the first stage is released in the gaseous state, and after the aldehyde or alcohol is condensed, a portion of the offgas from the first stage comprising the unreacted olefin is subjected to the first stage. The second stage hydroformylation process is passed through the second reactor and the remainder is described. The concept of this process is suitable for hydroformylation of volatile olefins having up to 5 carbon atoms, for example ethylene or propylene. As with the process described above, the vapor pressure of the olefin (and the vapor pressure of the aldehyde) is so low that it is not advantageous to react the higher olefins since the process must be carried out in liquid phase.
    [13] WO 95/08525 describes a two stage hydroformylation process in which the reactor mixture is discharged from the first stage in gaseous state. As claimed in the literature, olefins having 2 to 20 carbon atoms, in particular 2 to 8 carbon atoms, can be reacted by the process. The hydroformylation is catalyzed by rhodium, which is the same in both steps. The examples describe hydroformylation of propylene. According to the process described above, higher olefins having 5 or more carbon atoms may be disadvantageous to convert on a large scale due to the relatively high boiling point of the starting material and the product. Therefore, gaseous transition is undesirable in terms of energy.
    [14] Further variations of the two-stage hydroformylation process are described in German Patent No. 3 232 557. In the first stage, the olefin is hydroformylated using a cobalt catalyst at a conversion rate of 50 to 90%, the cobalt catalyst is separated from the reaction mixture, and the aldehyde formed is introduced into the second hydroformylation stage with the unreacted olefin. . Ligand modified cobalt catalysts used herein not only affect the further hydroformylation of olefins but also affect the hydrogenation of aldehydes to provide alcohols. In addition, the aldehyde produced in the first stage is exposed to a vigorous reaction condition in terms of the energy of the second stage. This leads to subsequent reactions, especially condensation reactions in which high boiling point components are formed.
    [15] Accordingly, it is an object of the present invention to further characterize the high space-time ratio with less conversion of by-products and / or secondary products with high conversion and high selectivity from olefins or olefin mixtures and further room for further adjustment of product properties. It is to provide a method of producing higher oxo aldehydes or the corresponding alcohols while leaving a lot.
    [1] 1 is a view showing a flowchart of process variant 1 according to the present invention,
    [2] 2 is a flowchart illustrating a process variant 2 according to the present invention,
    [3] 3 is a flowchart illustrating a process variant 3 according to the present invention.
    [16] The present invention,
    [17] Hydroformylating an olefin having 6 to 24 carbon atoms at a conversion rate of 20 to 98% (a),
    [18] (B) removing the catalyst from the resulting liquid reactor discharge,
    [19] (C) separating the resulting liquid hydroformylation mixture into a low boiling point fraction comprising olefins and paraffins and a bottom fraction comprising aldehydes and / or alcohols, and
    [20] A process comprising the step (d) of reacting olefins present in the low boiling fraction in a further step comprising processes a), b) and c), characterized in that the bottom fractions of process (c) are combined at all stages. The present invention relates to a method for producing alcohols and / or aldehydes by multistage hydroformylation of olefins having 6 to 24 carbon atoms as a catalyst using cobalt or rhodium.
    [21] The process according to the invention is preferably carried out such that the liquid reactor discharge of the hydroformylation process (a) is in a homogeneous liquid phase. The cobalt or rhodium catalyst is preferably used to dissolve into a homogeneous phase in the liquid reactor discharge of the hydroformylation process (a).
    [22] The unreacted olefin is separated from the formed aldehyde and then the excess synthesis gas or catalyst is removed in one or more separation or distillation processes. Thus, the hydroformylation product from the first step is not applied again under the conditions of the hydroformylation reaction which favors subsequent reactions in one or more further steps.
    [23] Description of Modifications of the Invention
    [24] The process according to the invention can in each case be carried out discontinuously or continuously, preferably in two steps. In the case of continuous, various process variations are possible, such as the two-step method shown in FIGS. This embodiment will be described later as Process Variants 1, 2 and 3. It should be clear that the processes described herein can be applied to methods of two or more steps.
    [25] The crude aldehydes obtained by the process according to the invention comprise formate, condensation products and other high boiling components in addition to the aldehydes and alcohols that are the process products and are post-treated by distillation to separate or first hydrogenate and then distill Alcohol is separated.
    [26] Process variant 1
    [27] The method according to process variant 1 is shown in the flowchart of FIG. 1. The olefin mixture 3, the synthesis gas 2 (carbon monoxide and hydrogen), and the catalyst solution or catalyst precursor 4 are fed to the first hydroformylation reactor 1. The resulting hydroformylation mixture 5 is depressurized, the reduced pressure gas 7 (unconsumed synthetic gas) is removed and the catalyst 4 is removed from the reduced pressure hydroformylation mixture in the first catalyst remover 6. Optionally, a small amount of partial stream is removed and a fresh catalyst is fed from the tower, and then the catalyst 4 is recycled to the first hydroformylation reactor 1. The term catalyst herein also includes precursors of the catalyst, such as cobalt (II) salt solutions. The catalyst-removed hydroformylation mixture 8 is separated from the distillation column 9 into a low boiling point component 10, where the low boiling point component 10 mainly consists of unreacted olefins and a crude aldehyde 11. The low boiling point component 10, the synthesis gas 13 and the catalyst solution 16 are introduced into the second hydroformylation reactor 12. The hydroformylation process of the second stage can be carried out using the same catalyst system (both metal and ligand or their respective concentrations) or using a different catalyst system than the first stage. The hydroformylation mixture 14 is depressurized again from the second hydroformylation reactor 12 and the reduced pressure gas 17 is removed. The reduced hydroformylation mixture 14 is removed from the catalyst 16 in the second catalyst remover 15, and then optionally a small amount of partial stream is removed and a fresh catalyst is fed to the tower and then the catalyst 16 is removed. 2 is recycled to the hydroformylation reactor (12). The catalyst-free hydroformylation mixture 18 can be separated into the low boiling point component 20 in the tower 19, where the low boiling point component 20 consists primarily of saturated hydrocarbons and the crude aldehyde 21. In some cases, some of the low boiling point component 20 may be recycled to the reactor 12 (lines are not shown in FIG. 1).
    [28] A further arrangement of process variant 1 is that the catalyst-free hydroformylation mixture 18 flows together with the crude aldehyde 11 to the hydrogenation reactor 22 without distillation in the tower 19 (line 24). . The crude aldehydes 11 and 21, or 11 and 24 are hydrogenated with hydrogen in the hydrogenation reactor 22 to provide crude alcohol 23, which is optionally worked up in a distillation column (not shown) to give pure alcohol. Can provide. If the aldehyde is the de facto desired product, the crude aldehydes 11 and 21, or 11 and 24 are optionally post-treated in a distillation column (not shown), if necessary, without passing through the hydrogenation reactor 22 to obtain pure aldehyde. Can be provided.
    [29] In process variant 1 of the present invention, each step comprises a hydroformylation process (a), a catalyst removal process (b) and a distillation process (c), provided that the catalyst separated in process (b) is The hydroformylation process of (a) directly or after the treatment and recycle.
    [30] Optionally, process variant 1 can also be carried out so that the final process step does not comprise distillation process (c).
    [31] Process variant 2
    [32] A flow chart of further process variants of the present invention is shown in FIG. The olefin mixture 3, the synthesis gas 2 (carbon monoxide and hydrogen), and the catalyst or precursor 4 thereof are fed to the first hydroformylation reactor 1. The resulting hydroformylation mixture 5 is depressurized, the reduced pressure gas 7 (unconsumed synthetic gas) is removed and the catalyst 4 is removed from the reduced pressure hydroformylation mixture in the first catalyst remover 6. Optionally, a small amount of partial stream is removed and a fresh catalyst is fed from the tower, and then the catalyst 4 is recycled to the first hydroformylation reactor 1. The catalyst removed hydroformylation mixture 8 passes through a distillation column 9. Here, from the second hydroformylation reactor 12, together with the catalyst-free hydroformylation mixture 18, a low boiling point fraction 10 comprising unreacted olefins and inert paraffins and crude aldehyde 19 is separated. After removing the partial stream 11 for removing saturated hydrocarbons (paraffins) and other non-olefin compounds, the low boiling fraction 10 is combined with the synthesis gas 13 and the catalyst 16 to the second hydroformylation reactor 12. Pass through. The resulting hydroformylation mixture 14 is depressurized, the reduced pressure gas 17 is removed, the catalyst 16 is removed from the depressurized hydroformylation mixture in a second catalyst remover 15 and then optionally a small amount of partial stream. After removing the catalyst, the new catalyst is fed to the tower, and the catalyst 16 is recycled to the second hydroformylation reactor 12. The catalyst-free second hydroformylation mixture 18 is fed to the distillation column 9 together with the hydroformylation mixture 8 from the first stage as described above. The crude aldehyde 19 is hydrogenated with hydrogen in the hydrogenation reactor 20 to provide crude alcohol 23. This alcohol can then be optionally worked up in a distillation column (not shown) to give pure alcohol. If the aldehyde is the desired product, the crude aldehyde 19 can be optionally worked up in a distillation column (not shown) without passing through a hydrogenation reactor to provide pure aldehyde.
    [33] The term catalyst herein may include precursors of the catalyst, eg, cobalt (II) salt solutions. The second and further steps can be carried out using the same catalyst system (both metal and ligand or their respective concentrations) or using a different catalyst system than the first step.
    [34] Instead of being removed through the partial stream 11, saturated hydrocarbons may be removed by working up the partial stream of the hydroformylation product 18 from which the catalyst has been removed (not shown). On an industrial scale, this process can be carried out, for example, this partial stream can be separated from the low boiling point component and the aldehyde by distillation, wherein the low boiling point component is removed and the aldehyde is free of the catalyst-free hydroformylation mixture ( 18) or recycle to the crude aldehyde (19).
    [35] In process variant 2 of the present invention, each step comprises a hydroformylation process (a) and a catalyst removal process (b), wherein the combined liquid hydroformylation mixture is subjected to a low boiling point fraction and a bottom fraction in a co-distillation process (c). The catalyst separated in step (b) is recycled directly or after treatment to the hydroformylation step (a) in each step.
    [36] Process variant 3
    [37] Further process variants according to the invention are shown in FIG. 3. The olefin mixture 3, the synthesis gas 2 (carbon monoxide and hydrogen), and the catalyst solution or precursor 4 thereof are fed to the first hydroformylation reactor 1. The resulting hydroformylation mixture 5 is depressurized together with the hydroformylation mixture 14 from the second hydroformylation reactor 12 as combined hydroformylation effluent 15 and decompressed gas 7 ( Unconsumed synthetic gas) is removed. The catalyst is removed from the hydroformylated emissions combined in the catalyst remover 6 to obtain a mixture 8 comprising aldehyde, alcohol and unreacted olefins formed. After optionally a small amount of partial stream is removed and fresh catalyst is fed from the tower, the catalyst 16 is subdivided into two partial streams 4 and 17. The partial stream 4 is recycled to the first hydroformylation reactor 1 and the partial stream 17 is recycled to the second hydroformylation reactor 12. The catalyst-free hydroformylated effluent 8 is separated in the distillation column 9 into a low boiling point component 10 and a crude aldehyde 18. The low boiling fraction 10 comprising unreacted olefins may optionally be followed by the removal of a small amount of partial stream 11 (to remove saturated hydrocarbons or other non-olefinic compounds), followed by synthesis gas 13 and catalyst 17. Together with the second hydroformylation reactor 12. The crude aldehyde 18 is hydrogenated with hydrogen in the hydrogenation reactor 19 to provide crude alcohol 23. This alcohol can then be worked up in a distillation column (not shown) to provide pure alcohol. If the aldehyde is the desired product, the crude aldehyde 18 can be worked up by distillation without passing through the hydrogenation reactor 19 (not shown) to give pure aldehyde.
    [38] Also in Process Variant 3, saturated hydrocarbons can be removed by separately treating the partial streams of the hydroformylation mixture 14, for example, by removing the low boiling point components by distillation.
    [39] In a process variant according to the invention, the combined reactor effluent of all hydroformylation processes (a) is subjected to only one catalyst removal process (b) and one distillation process (c), wherein the process separated from process (b) It is noted that the catalyst is recycled directly or after treatment to the hydroformylation process (a) in each step.
    [40] Also in Process Variant 3, the catalyst used may comprise a precursor of the catalyst, for example a cobalt (II) salt solution.
    [41] In process variant 3, the same catalyst, ie cobalt or rhodium as active catalyst metal, must be used in all hydroformylation processes or steps. However, different catalyst concentrations may be used in different stages or hydroformylation processes thereof.
    [42] In the process according to the invention, some or all of the excess synthesis gas to be separated off can be recycled to the process. Of particular interest is the possibility that can occur when the hydroformylation reactor is operated at different pressures. Emission gas from the reactor operating at higher pressure than in other reactors can be separated off at a higher pressure than the operating pressure of the other reactor, meaning that this emission gas can be used in other reactors without having to be compressed.
    [43] A common aspect of the present invention, or process variants 1 to 3, is that the olefin or olefin mixture is hydroformylated in multiple stages, preferably in two stages, so that in the first stage mainly higher amounts of reactive olefins are converted and in further stages predominantly. Smaller amounts of reactive olefins are converted. Another essential aspect of the present invention is that after the catalyst has been removed, preferably by distillation, the catalyst is removed and then the unreacted olefin present in the low boiling component is removed from the hydroformylation product of the first stage which is released as a liquid. An essential difference between each process variant is the complexity of working up the reaction emissions. Due to the individually operating catalyst cycles, Process Variant 1 allows the use of different catalysts, different catalyst concentrations or different ligand systems in the reactor. In process variant 1, this individual distillation allows for the best removal of the paraffins produced in the process. However, it is possible to reduce one or more distillation processes and separate the emissions from various hydroformylation reactors in only one distillation process (process variant 2). Further reduction in the number of devices required can be achieved by combining the catalyst cycles (process variant 3). Although different catalysts can no longer be used in the process stage, the concentration of catalyst in the reactor can be controlled by the separation ratio of the recycle catalyst (part streams 4 and 17 for the two stage process according to FIG. 3). In addition, reaction conditions such as pressure and temperature can be freely selected independently of each other in each hydroformylation process.
    [44] The reactor in which hydroformylation is carried out may be the same or different for all process steps. Types of reactors that may be used are, for example, bubble towers, loop reactors, jet-nozzle reactors, stirred reactors and tubular reactors, some of which are cascaded and / or equipped with internals.
    [45] Description of starting materials, process conditions and products
    [46] The starting materials used in the process of the invention are olefins or olefin mixtures having 6 to 24 carbon atoms, advantageously 6 to 20, in particular 8 to 20 and having terminal or internal CC double bonds. The mixture consists of olefins having the same, similar (± 2) or significantly different (> ± 2) carbon atoms. The olefins which can be used as starting materials can be used in pure form, as isomer mixtures or as mixtures with further olefins having different carbon numbers, for example: 1-, 2- or 3-hexene, 1-heptene, linear heptene with internal double bonds (2-heptene, 3-heptene, etc.), mixture of linear heptenes, 2- or 3-methyl-1-hexene, 1-octene, linear octene with internal double bonds, Mixture of linear octenes, 2- or 3-methylheptene, 1-nonene, linear nonenes with internal double bonds, mixtures of linear nonenes, 2-, 3- or 4-methyloctene, 1-, 2-, 3-, 4- or 5-decene, 2-ethyl-1-octene, 1-dodecene, linear dodecene with internal double bond, mixture of linear dodecene, 1-tetradecene, linear tetradecene with internal double bond, linear A mixture of tetradecene, 1-hexadecene, a mixture of linear hexadecene and linear hexadecene with internal double bonds. Suitable starting materials are also prepared during the dimerization of propene, mixtures of isomeric hexene (dipropene) produced during dimerization of propene, mixtures of isomeric octenes (dibutene) produced during dimerization of butene, Mixtures of isomeric nonenes (tripropene), mixtures of isomeric dodecenes (tetrapropene or tributene) produced during tetramerization of propene or trimerization of butenes, hexadecene mixtures produced during tetramerization of butenes ( Tetrabutene) and olefin mixtures prepared by co-oligomerizing olefins having different (preferably 2 to 4) carbon numbers after being optionally separated by distillation into fractions having the same or similar carbon number (± 2). Olefins or olefin mixtures prepared by Fischer-Tropsch synthesis can be used. It is also possible to use olefins prepared by olefin interchange or other industrial methods. Preferred starting materials are mixtures of isomeric octenes, nonenes, dodecene or hexadecenes, ie mixtures of oligomers of lower olefins such as n-butene, isobutene or propene. Another very suitable starting material is also oligomers of C 5 -olefins.
    [47] In order to oligomerize butene in a mixture comprising essentially C 8 -olefins, in principle three process variants exist. Oligomerization on acid catalysts has long been known, for example, phosphoric acid or zeolites for industrially used supports. This method essentially produces an isomeric mixture of side chain olefins containing dimethylhexene (WO 92/13818). Also used worldwide is oligomerization using soluble Ni complexes, which are known as the DIMERSOL process. See B. CORNILS, WA HERRMANN, "Applied Homogeneous Catalysis with Organometallic Compounds"; Vol. 1 & 2, VCH, Weinheim, New York 1996]. Process Variant 3 is oligomerization on a nickel fixed bed catalyst, and this method is described in the literature as an octol process. Hydrocarbon Process., Int. Ed. (1986), 65 (2. Sect. 1) page 31-33.
    [48] In order to prepare C 9 -alcohol mixtures particularly suitable for the preparation of plasticizers, preference is given to using C 8 -olefin mixtures obtained from linear butenes by the octol process.
    [49] In the synthesis gas used for hydroformylation, carbon monoxide and hydrogen are usually present in a molar ratio of 1: 4 to 4: 1, preferably in approximately stoichiometric ratios.
    [50] The process of the present invention is carried out using cobalt or rhodium catalysts in the presence or absence of complex stabilizing additives such as organic phosphines or phosphites. In all hydroformylation processes of the process, a rhodium catalyst or cobalt catalyst can be used. In addition, a cobalt catalyst (or rhodium catalyst) may be used in the hydroformylation process (a) in the first step and a rhodium catalyst (or cobalt catalyst) may be used in the hydroformylation process in a further step. An advantage of the process according to the invention is that different catalysts can be used in each step, meaning that different catalysts, for example cobalt / rhodium / cobalt, may be used in two or more steps.
    [51] The choice of catalyst and reaction conditions (catalyst concentration, temperature, pressure, residence time) depends, in particular, on the carbon number and composition of the starting olefin. If a high proportion of terminal hydroformylated olefins is the standard for high quality products for dimerization mixtures of n-butene, for example, known as di-n-butene, then the unmodified cobalt catalyst is positive for the two step process. When used in stages, satisfactory yields can be achieved with very good product quality. When the unmodified cobalt catalyst is used in the first stage and the unmodified rhodium catalyst is used in the subsequent stage, the yield is improved, while the product quality is somewhat behind. If an unmodified rhodium catalyst is used at all stages, further improvements in yield and degradation of product quality occur. If a low proportion of terminal hydroformylated olefins is the standard for high quality products for dimerization mixtures of n-butene, for example, known as di-n-butene, the amount of unmodified rhodium catalyst for the two-stage process When used in stages, very high yields can be achieved with good product quality. Where ligand-modified catalysts are used, especially if rhodium and phosphorus ligands are used, there may be an additional category through which the ligands may be selected, where the terminal or non-terminal position can affect the proportion of hydroformylated olefins. . For a given starting olefin, the optimal number of process steps and the optimum catalyst in the individual hydroformylation process can be easily determined experimentally. The catalyst concentration in the individual steps can be the same or different.
    [52] The temperature and pressure of the various stages of the hydroformylation process can vary widely depending on the catalyst and olefin mixture. The more reactive olefins are preferentially reacted in the first stage, and more active reaction conditions are advantageously used in terms of temperature, catalyst amount and residence time in the hydroformylation process in a further stage.
    [53] Optimal conditions may vary in each case depending on the object. Thus, for example, space-time yields, increased selectivity, or desired product properties, which are achieved overall, can be optimization criteria. In principle, the composition of the starting olefins and the choice of catalyst system and / or reaction conditions depend on whether the possible embodiments of the process according to the invention are economically optimal.
    [54] In the process according to the invention, the olefin conversion in the hydroformylation process of each process step is 20 to 98%, in particular 40 to 80%, particularly preferably 50 to 75% (one pass in each case).
    [55] In the hydroformylation process (a) in a further step subsequent to the first step, the olefin can in each case be reacted at a conversion of at least 50%, preferably 55 to 98%.
    [56] An advantage of the process according to the invention is that different reaction conditions can be set in the hydroformylation reactor. This ensures a balance between the reactivity of the olefin mixture introduced and the hydroformylation conditions. In order to minimize secondary products and by-products, care is taken to react the reactive olefins under mild conditions, for example, so that virtually no secondary products and by-products are produced. Subsequently, in the subsequent reactor, the residual olefin mixture consisting mainly of unreacted olefins is optionally hydroformylated under more stringent conditions. Therefore, it is possible to influence the isomer distribution of aldehydes formed through variable reaction conditions in the reactor.
    [57] The hydroformylation process catalyzed by rhodium and cobalt is largely dependent on its operating parameters. However, the main difference lies primarily in the removal and recycling of different catalysts. These two processes will be described separately below.
    [58] Cobalt Catalyzed Hydroformylation Process
    [59] In cobalt catalyzed hydroformylation of olefins, it is possible to use modified and / or unmodified catalysts which may be the same or different in each step. The hydroformylation process in each of the cobalt catalyzed steps can be carried out as described in German Patent No. 196 54 340. According to the process, the starting material, cobalt salt solution, organic phase and synthesis gas are introduced simultaneously into the reactor in parallel, preferably from below, using a mixing nozzle.
    [60] The cobalt compounds used are preferably cobalt salts such as formate, acetate or carboxylate which are water soluble. Cobalt acetate has been found to be particularly preferred, which is used as an aqueous solution in a cobalt content of 0.5 to 3% by weight, preferably 1.0 to 2.0% by weight, in terms of metals.
    [61] The organic phase comprises the olefin to be hydroformylated and optionally further aldehydes and / or alcohols, the aldehydes or alcohols being preferably reaction products formed during the hydroformylation reaction.
    [62] In the cobalt catalyzed process, it is particularly important to meter the starting material into the reactor. The metering device must ensure the mixing of the phases and the formation of the largest phase exchange area as possible. In the case of cobalt catalyzed hydroformylation, it is advantageous to divide the reactor space of the hydroformylation reactor by incorporating a small number of perforated sheets (minimum = 1) arranged in a direction perpendicular to the flow direction of the reactant and product streams. As a result of cascading the reactor, the backside mixing is greatly reduced compared to a simple bubble column, and the flow behavior is also approximated to the tubular reactor. Such process engineering measures result in both improved yield and selectivity of the hydroformylation process.
    [63] According to the invention, when carrying out the hydroformylation process with a cobalt catalyst, the process is operated under a pressure of 100 to 400 bar at a temperature of 100 to 250 ° C. Temperatures from 140 to 210 ° C. and synthesis gas pressures from 200 to 300 bar have been found to be particularly preferred. The volume ratio of carbon monoxide to hydrogen in the synthesis gas is usually 2: 1 to 1: 2, in particular 1: 1. The synthesis gas is advantageously used in excess, for example at least three times the stoichiometric amount.
    [64] Hydroformylation of the olefins is carried out under a cobalt catalyst in the first step, wherein the more reactive olefins are converted at a temperature of 140 to 195 ° C, preferably 160 to 185 ° C. The olefin conversion in this step is 20 to 90%, preferably 50 to 80%.
    [65] After leaving the reactor of the first stage or first hydroformylation process, the product discharge is depressurized to 10-15 bar and undergoes a cobalt removal process (catalyst removal, symbol 6 in FIG. 1). In the cobalt removal process, cobalt carbonyl complexes are removed from the product emissions (organic phase) in the presence of "process water" using air or oxygen at temperatures between 130 and 190 ° C. Cobalt removal processes are well known and described in detail in the literature [by: J. FALBE, in "New Syntheses with Carbon Monoxide", Springer Verlag (1980), Berlin, Heidelberg, New York, page 158 et seq ].
    [66] The cobalt removal process is preferably carried out in a pressurized container filled with released charges, such as Raschig rings, in which the most possible phase inversion zones are produced. The cobalt free organic product phase is separated from the aqueous phase in the downstream separation container. The “process water” containing the post-extracted cobalt recovered from the organic phase in the form of an aqueous phase, cobalt acetate / formate, is recycled to the oxo reactor of each process step in its entirety or with subsequent removal of fractions, preferably Used as starting material for in situ preparation of cobalt catalyst complexes.
    [67] Precarbonylation, catalyst extraction and actual hydroformylation are preferably carried out in one reactor according to German patent 196 54 340. It is also possible to separate the process steps from one another in terms of apparatus.
    [68] Organic reactor effluents containing unreacted olefins, aldehydes, alcohols, formic acid esters and high boiling components are subjected to a distillation step after the hydroformylation process and the catalyst removal process. Here, the reactor effluent with the cobalt catalyst and excess synthesis gas removed is separated by distillation into crude aldehyde / alcohol (bottom fraction) and low boiling fraction, which, depending on the process variant and the conditions of the hydroformylation process, are reactive. It consists mainly of low unreacted olefins and / or paraffins produced by hydrogenation of olefins.
    [69] The unreacted olefins, which have been removed from the product useful in the distillation process, are then introduced into the subsequent hydroformylation process.
    [70] According to the process of the invention, the cobalt catalyzed hydroformylation process is carried out at a temperature of 160 to 220 ° C., preferably 175 to 195 ° C. in the first step or in a further step following the hydroformylation process. Here, the olefin conversion is aimed at 50% or more, preferably 50 to 95%, more preferably 55 to 98%.
    [71] The multistage process according to the present invention offers the opportunity to adopt the reaction conditions, for example by selecting low cobalt concentrations, to bring the olefin conversion of the first stage to the desired value. In subsequent steps, when the slower reacting olefins are converted, the reaction conditions can be enhanced, for example, by increasing the catalyst concentration.
    [72] The process step according to the invention using a cobalt catalyst is particularly suitable for hydroformylating a mixture of isomeric olefins prepared by oligomerizing propene and butene. Typical oligomerization products which are preferably used as raw material substrates for hydroformylation according to this novel method include di-, tri- and tetrapropene, and di-, tri-, and tetrabutene.
    [73] Rhodium Catalyzed Hydroformylation Process
    [74] In the rhodium catalyzed hydroformylation process, it is possible to use modified and / or unmodified catalysts which may be the same or different in each rhodium catalyzed hydroformylation process.
    [75] These rhodium catalysts can be introduced into the process in the form of active complexes, although it is simpler to produce active catalysts in situ from rhodium compounds which are usually industrially stable and easy to store. Suitable rhodium compounds suitable for this purpose include, for example, rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II) and rhodium (III) carboxylate, rhodium ( II) and rhodium such as rhodium (III) acetate, rhodium (II) octanoate, rhodium (II) nonanoate, rhodium (III) oxide, salts of rhodium (III) acid, triammonium hexachlorodate (III) (II) and rhodium (III) salts. Rhodium complexes such as acetylacetonatocarbonyldium and acetylacetonatobisbisethylenerhodium (I) are also suitable. Rhodium acetate, rhodium octanoate and rhodium nonanoate are particularly suitable.
    [76] Generally, about 1 to 500 mol, preferably 3 to 50 mol of ligand is added per mol of rhodium. New ligands can be added to the reaction at any point in time to keep the free ligands constant.
    [77] The concentration of rhodium in the hydroformylation reactor is 1 to 500 ppm, preferably 5 to 200 ppm.
    [78] The choice of ligand to be added is not limited in the process according to the invention, but depends on the olefin used and the desired product. Preferred ligands are ligands containing nitrogen, phosphorus, arsenic or antimony atoms, with phosphorus ligands being particularly preferred. The ligand can be single or multidentate, and for chiral ligands, racemates, enantiomers or diastereomers can be used. Phosphorus ligands that may be mentioned are, in particular, phosphine, phosphine oxide, phosphite, phosphonite and phosphinite. Examples of phosphines include triphenylphosphine, tris (p-tolyl) phosphine, tris (m-tolyl) phosphine, tris (o-tolyl) phosphine, tris (p-methoxyphenyl) phosphine, tris ( p-fluorophenyl) phosphine, tris (p-chlorophenyl) phosphine, tris (p-dimethylaminophenyl) phosphine, ethyldiphenylphosphine, propyldiphenylphosphine, t-butyldiphenylphosphine, n-butyldiphenylphosphine, n-hexyldiphenylphosphine, c-hexyldiphenylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, triethylphosphine, tri ( 1-naphthyl) phosphine, tri-2-furylphosphine, tribenzylphosphine, benzyldiphenylphosphine, tri-n-butylphosphine, tri-i-butylphosphine, tri-t-butylphosphine , Bis (2-methoxyphenyl) phosphine, neomentyldiphenylphosphine, sulfonated triphenylphosphine [e.g. tris (m-sulfonylphenyl) phosphine, (m-sulfonylphenyl) diphenylphosph Alkali Metal, Alkali Litometal, ammonium or other salts, 1,2-bis (dicyclohexylphosphino) ethane, bis (dicyclohexylphosphino) methane, 1,2-bis (diethylphosphino) ethane, 1,2-bis (2,5-diethylphospholano) benzene [Et-DUPHOS], 1,2-bis (2,5-diethylphospholano) ethane [Et-BPE], 1,2-bis (dimethylphosphino ) Ethane, bis (dimethylphosphino) methane, 1,2-bis (2,5-dimethylphospholano) benzene [Me-DUPHOS], 1,2-bis (2,5-dimethylphospholanoethane [Me -BPE], 1,2-bis (diphenylphosphino) benzene, 2,3-bis (diphenylphosphino) bicyclo [2.2.1] hept-5-ene [NORPHOS], 2,2'-bis (Diphenylphosphino) -1,1'-binafyl [BINAP], 2,2'-bis (diphenylphosphino) -1,1'-biphenyl [BISBI], 2,3-bis (di Phenylphosphino) butane, 1,4-bis (diphenylphosphino) butane, 1,2-bis (diphenylphosphino) ethane, bis (2-diphenylphosphinoethyl) phenylphosphine, 1,1 ' Bis (diphenylphosphino) ferrocene, bis (diphenylphosphino) methane, 1,2-ratio (Diphenylphosphino) propane, 2,2'-bis (di-p-tolylphosphino) -1,1'-vinaphthyl, O-isopropylidene-2,3-dihydroxy-1,4 -Bis (diphenylphosphino) butane [DIOP], 2- (diphenylphosphino) -2'-methoxy-1,1'-binafyl, 1- (2-diphenylphosphino-1-naph Yl) isoquinoline, 1,1,1-tris (diphenylphosphino) ethane, tris (hydroxypropyl) phosphine.
    [79] Particularly preferred phosphine used is triphenylphosphine.
    [80] Examples of phosphites include trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, tri-n-isobutyl phosphite, tri-t- Butyl phosphite, tris (2-ethylhexyl) phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2-tert-butyl-4-methoxyphenyl ) Phosphite, tris (2-tert-butyl-4-methylphenyl) phosphite, tris (p-cresyl) phosphite. In particular, European Patent Nos. 155 508, U.S. Patents 4,668,651, 4,748,261, 4,769,498, 4,774,361, 4,835,299, 4,885,401, 5,059,710, 5,113,022, 5,179,055,5,260,5 Sterically hindered phosphite ligands as described in US Pat. Nos. 5,264,616, 5,288,918, 5,360,938, EP 472 071, EP 518 241 and WO 97/20795. Preference is given in each case to substituted triphenyl phosphites having one or two isopropyl and / or tert-butyl groups on the phenyl ring, preferably in the ortho position relative to the phosphite ester group.
    [81] Examples of phosphonites include methyldiethoxyphosphine, phenyldimethoxyphosphine, phenyldiphenoxyphosphine, 6-phenoxy-6H-dibenz [c, e] [1,2] oxaphosphorin and derivatives thereof Some or all of its hydrogen atoms are substituted with alkyl or aryl radicals or halogen atoms], and WO 98/43935, Japanese Patent No. 09-268152, German Patent 198 10 794, German Patent 199 54 721 and German Patent No. 199 54 510.
    [82] Common phosphonite ligands are described in particular in US Pat. No. 5,710,344, WO 95/06627, US Pat. No. 5,360,938 and Japanese Patent No. Hei 07-082281. Examples thereof include diphenyl (phenoxy) phosphine and derivatives thereof in which some or all of their hydrogen atoms are substituted by alkyl or aryl radicals or halogen atoms, diphenyl (methoxy) phosphine, diphenyl (ethoxy Phosphine and the like.
    [83] The rhodium catalyzed hydroformylation process is usually carried out at a pressure of 1 to 300 bar, preferably 15 to 270 bar. The pressure used depends on the structure of the feed olefin, the rhodium catalyst used and the desired effect. Thus, for example, α-olefins can be converted to corresponding aldehydes in high space-time yields at pressures below 64 bar. Conversely, higher pressures are convenient for olefins with internal double bonds, especially for branched olefins.
    [84] The temperature for the rhodium catalyzed hydroformylation reaction is usually 40 to 180 ° C, preferably 60 to 135 ° C. Temperatures above 100 ° C. provide the technical advantage that the heat released from the reaction can be used to generate steam.
    [85] Following hydroformylation, most of the synthesis gas is removed by pressure drop. The catalyst is removed from the liquid reaction emissions by distillation (catalyst removal process, for example symbols 6 and 15 in FIG. 1), the catalyst and optionally added ligands, stabilizers and the like remain in the distillation residue / as distillation residue. . Therefore, it is advantageous to use a high boiling point inert solvent (higher boiling than the product and starting material) in which the catalyst is dissolved. The catalyst dissolved in the high boiling solvent can be recycled directly to the reaction. It is particularly advantageous to use high boiling byproducts formed in the process as high boiling solvents. Other suitable solvents are high boiling point esters such as 2,2,4-trimethylpentanediol 1,3-monoisobutyrate, which are commercially available as Texanol.
    [86] Various processes can be used to industrially perform the catalyst removal process by distillation. It is desirable to remove the catalyst solution through a falling film, a disconnect or thin film evaporator or a combination of these devices. An advantage of this combination may be, for example, the fact that still part of the synthesis gas and product still dissolved and the remaining starting olefins can be removed in the first stage, followed by the final removal of the catalyst in the second stage. .
    [87] Since hydroformylation of olefins is an exothermic reaction, the heat generated must be removed from the reactor to limit the temperature of the reactor. Too high a temperature usually increases the formation of byproducts and can deactivate the catalyst. It is also desirable to keep the temperature as constant as possible, because often the reaction temperature can directly affect the composition of the product (eg the n / i ratio).
    [88] Dissipation of heat can be through various technical arrangements, for example through reactor walls, integrated capacitors and the like. Industrially, it is advantageous to lower the cost of dissipating heat. However, when olefin mixtures are used, varying the reaction rate can lead to significant heat release, particularly as a result of exotherm in the first stage, since the readily ioxitable components preferentially react here. . The process according to the invention can be adapted to maintain exotherm within a range that is easily industrially controllable, for example by lowering the catalyst concentration or adding an inert solvent, mainly by adopting reaction conditions in the first step.
    [89] Post-treatment of Catalyst-Free Hydroformylation Mixtures
    [90] Reactor effluents from which the catalyst and excess synthesis gas have been removed are separated individually or together into crude aldehyde and low boiling fractions by distillation as shown in FIGS. Depending on the process variant and process step, the low boiling point component consists mainly of unreacted olefins or paraffins formed by hydrogenation of olefins. In addition to aldehydes and alcohols, the bottom product may also include high boiling byproducts such as formate, acetal, saturated and unsaturated ethers, esters, carboxylic acids and condensation products. The catalyst-free hydroformylated effluent may be separated separately from the low boiling point component and the crude aldehyde in one or more distillation (process variant 1) or co-distillation (process variants 2 and 3). The distillation conditions depend on the boiling points of the components and therefore mainly also on the mass per mole of olefin and aldehyde. These conditions are chosen such that a relatively large amount of byproducts are not formed during distillation. Since these by-products arise predominantly from the reaction of aldehydes at elevated temperatures, the distillation process is carried out under reduced pressure so that the temperature in the column can be kept low. However, it is also possible to carry out the distillation process under atmospheric pressure.
    [91] When the reactant emissions of the hydroformylation process are treated in a separate distillation process (process variant 1), the low boiling point component of the first distillation process goes through a subsequent step (generally, the low boiling point component from one step is transferred to the next step). ), The low boiling point component from the final distillation process is removed and optionally partially recycled to the prior hydroformylation step. If reaction emissions from different process steps are post-processed together (process variants 2 and 3), some of the low boiling components may be removed before being introduced into the final stage, or by post-treatment of the partial stream of the emissions from the final stage during the cycle. It is convenient to keep the proportion of paraffin at an acceptable value.
    [92] Therefore, paraffin can be removed in whole or in part from one or more low boiling point fractions.
    [93] In addition to this possibility as described in the low boiling point components and in particular process variants 1 to 3 for removing paraffin from the process, other methods may also be suitably used. When the catalyst removal process and any distillation process are carried out under reduced pressure, part of the low boiling point component and part of the product are removed from the process via a vacuum system. After condensation, the fraction may be discarded, or if the amount is sufficient, it may be useful to recycle (partially) to the process. In addition, depending on the operating conditions, the low boiling fractions and products are disposed of through the excess synthesis gas being separated off, and these low boiling components and products can be separated off (eg by condensation) and optionally recycled or post-treated. have.
    [94] If the crude aldehyde is the desired product they can be worked up step by step or together together by distillation according to known methods to give the product.
    [95] In this case, if the combined bottom fraction from the distillation step (c), or the final distillation step (c) is omitted, the combined bottom fraction in this process and the discharge of the final catalyst removal step (b) are distilled off. It can be worked up or separated off.
    [96] On the other hand, when the alcohol is the desired product, the crude aldehyde is hydrogenated in a conventional manner in gas phase or liquid phase.
    [97] If the combined bottom fraction from distillation process (c), or the final distillation process (c) is omitted, the combined bottom fraction in this process and the emissions of the final catalyst removal process (b) can be hydrogenated.
    [98] For hydrogenation, for example, copper / nickel, copper / chromium, copper / chromium / nickel, zinc / chromium, nickel / molybdenum catalyst can be used. The catalyst can be used without a support, or a hydrogenation active material or precursor thereof can be applied to a support such as, for example, silicon dioxide or aluminum dioxide.
    [99] Preferred catalysts used to hydrogenate the hydroformylation mixture are, in each case, from 0.3 to 15% by mass of copper and nickel as the activator, from 0.05 to 3.5% by mass of chromium and advantageously the support material, preferably aluminum dioxide and 0.01 to 1.6 mass%, preferably 0.02 to 1.2 mass% of the alkali metal component on the silicon phase. Quantitative data indicate that the catalyst is not reduced. The alkali metal component is an optional component.
    [100] The catalyst is advantageously used in the form of low flow resistance, for example in the form of granules, pellets or moldings such as tablets, cylinders, extrudates or rings. They are conveniently activated prior to use, for example by heating in a hydrogen stream.
    [101] Hydrogenation, preferably liquid phase hydrogenation, is generally carried out under a total pressure of 5 to 30 bar, in particular 15 to 25 bar. Gas phase hydrogenation can also be carried out using gas volumes of corresponding sizes at relatively low pressures. If two or more hydrogenation reactors are used, the total pressure of the industrial reactors may be the same or different within the pressure ranges described above.
    [102] During liquid or gas phase hydrogenation, the reaction temperature is usually from 120 to 220 ° C, in particular from 140 to 180 ° C. Examples of such hydrogenation are described in German patent applications 198 42 369 and 198 42 370.
    [103] After hydrogenation, the resulting reaction mixture is worked up by distillation. If desired, the olefins that are separated off can be recycled to the hydroformylation step.
    [104] The following examples are presented to illustrate the invention, but the scope of the application as set forth in the claims is not limited thereto.
    [105] Example 1
    [106] Two-Step Octene Conversion Using Different Catalyst Ligands
    [107] 100 g of 1-octene (> 98%, GC) are converted in a 1 L autoclave at 85 ° C. under 20 bar synthesis gas pressure. The rhodium catalyst is produced from rhodium octanoate and ligand 1 of the following formula (1).
    [108]
    [109] 200 ml of texanol (2,2,4-trimethylpentanediol 1,3-monoisobutyrate) is added to the reaction as an inert high boiling point solvent. The rhodium concentration is adjusted to 40 ppm (based on total mass) and the phosphorus to rhodium ratio (P / Rh) is 20/1. Conversion of olefins is monitored through the amount of synthesis gas adsorbed. After about 90% conversion, virtually no further gas adsorption is observed and the experiment is stopped. According to GC analysis, the conversion is 91%, and the aldehyde formed consists of 95% nonanols. Analysis of residual olefins produces only traces of 1-octene, the main constituents being 2-octene, 3-octene and 4-octene, which are formed by isomerization of 1-octene.
    [110] The experiment is carried out six times and the emissions are combined and distilled. This gives 43 g of octene mixture. They are dissolved in 100 ml of texanol and hydroformylated again at 120 ° C. under a synthetic gas pressure of 50 bar in a 500 ml autoclave. The rhodium concentration is 40 ppm and the ligand added is tris (2,4-di-tert-phenyl) phosphite (P / Rh 20/1). During this reaction, quantitative conversion of olefins is achieved (GC). .
    [111] This example shows that the hydroformylation activity of octenes with internal double bonds is formed in the first stage by the isomerization of n-octene used, although the catalyst system used in the first stage has high normal / iso selectivity. Indicates low [see: PWNM van Leuwen et al., Organometallics 1996, 15, 835-847. However, they can react in the second step under different experimental conditions. Thus, on the one hand they achieve a high selectivity for the desired straight chain nonanol while on the other hand increase the total yield based on the feed material.
    [112] Example 2
    [113] Two-Step Hydroformylation of Di-n-Butene Using Different Catalysts
    [114] In a 3-liter stirred autoclave is loaded about 1000 g of water containing cobalt acetate (cobalt content in terms of metal is about 1 mass%). With stirring (1000 rpm), the mixture is left under conditions where the synthesis gas pressure is 280 bar and the temperature is adjusted to 170 ° C. After 7 hours, the mixture is cooled to 60 ° C. and reduced to 100 bar. Then di-n-butene (14% main component octene, 60% 3-methylheptene, 26% 3,4-dimethylhexene) is added. After stirring for 10 minutes (1000 rpm), the mixture is left for 15 minutes. The aqueous phase is separated off. The di-n-butene phase contains cobalt carbonyl at a concentration of 0.019% by mass in terms of cobalt. The solution is reacted at 170 ° C. at a synthesis gas pressure of 280 bar. Conversion is measured through the amount of synthesis gas absorbed. At 70% conversion, the reaction is stopped. After cooling to 80 ° C. and compacting, cobalt is removed from the reaction mixture by addition of 5% by weight aqueous acetic acid in the presence of air. The cobalt-free organic phase is separated by distillation into residual olefin / small amount of paraffin fraction, aldehyde / alcohol fraction and low boiling point component fraction.
    [115] The remaining olefins (175 g, about 4% main component octene, 52% 3-methylheptene, 44% 3,4-dimethylhexene) are then reacted in a rhodium catalyzed reaction similar to Example 1. The inert solvent added is 200 g of texanol (2,2,4-trimethylpentanediol 1,3-monoisobutyrate), the rhodium concentration is controlled to 200 ppm Rh, and the ligand (tris (2,4-di-tert- The molar ratio of butylphenyl phosphite) to rhodium is 20/1 The pressure is constant at 50 bar and the temperature is 130 ° C.
    [116] After 6 hours, the autoclave is cooled and depressurized, and the emission is separated into residual olefin / small amount of paraffin fraction, aldehyde / alcohol fraction and high boiling point component fraction. The combined aldehyde / alcohol fraction from the two reactions is hydrogenated on Raney nickel to yield an alcohol. The yield of alcohol obtained through two hydroformylation steps and hydrogenation is 87%.
    [117] As such, according to the invention, higher yields are achieved in a two step process than in a single step process (comparative example 6).
    [118] Example 3
    [119] (Improvement of conversion rate, reduction of by-products)
    [120] The experiment is carried out in a small plant consisting of a bubble column reactor, a thin film evaporator and a distillation unit, represented by symbols 1 to 8 in FIG. Such small scale equipment can be used to study essential aspects of carrying out the method in two steps in a laboratory. The olefin to be hydroformylated is introduced at the bottom of the bubble column together with the excess synthesis gas and the catalyst containing high boiling point solvent. Unreacted synthesis gas is removed on the reactor tower. Liquid fractions (remaining olefins, aldehydes, by-products, high boiling point solvents, catalysts) pass through the thin film evaporator, where the aldehydes formed are separated together with the unreacted olefins from the higher boiling point component in which the catalyst is dissolved. It is operated under reduced pressure. The high boiling solvent used is dioctyl phthalate, which is present in the reactor at a rate of 20% by weight. The rhodium concentration in the reactor is 100 ppm rhodium, the ligand added is tris (2,4-di-tert-butylphenyl) phosphite and the P / Rh ratio is 20/1. The bubble column is externally heated to maintain a constant temperature of 120 ° C. via a double jackkit, and the operating pressure is 50 bar of synthesis gas.
    [121] Under the above reaction conditions, 2 kg / h of di-n-butene was set as the olefin feed, and the volume of the bubble column was 2.1 liters. After a constant conversion is achieved, the material stream adjusts the resin over 100 hours. The mixture separated by the thin film evaporator separates the aldehydes formed from the unreacted olefins by distillation. 200 kg of di-n-butene gives 156 kg of aldehyde and 77 kg of olefin, which corresponds to an average conversion of 61.5%. At the same time, 130 g of high boiling by-products are formed, which are concentrated in the catalyst cycle.
    [122] The unreacted olefins in the first stage are reacted again in the second hydroformylation stage in a small plant. The reaction conditions correspond to the conditions of the first step, provided that the feed amount of olefins is reduced to 1 kg / h. The duration of the stationary phase selected is 77 hours during which exactly 77 kg of the olefin obtained from the stationary phase of the first stage are reacted. 65 kg of aldehyde are obtained. At the same time, 310 g of high boiling by-products are formed.
    [123] Summarizing the results of the two stationary periods, 221 kg of aldehyde is obtained from 200 kg of di-n-butene for a total of 177 operating hours. 440 g of high boiling byproducts are obtained from this process.
    [124] Example 4
    [125] (Comparative Example, Single Step Hydroformylation Process)
    [126] Compared to Example 3, 200 kg of di-n-butene are introduced into the small scale plant under the same experimental conditions over 177 hours [1.13 kg (olefins) / h]. A total of 198 kg of aldehyde is formed in this process. At the same time, 490 g of high boiling by-products are formed.
    [127] Comparing Examples 3 and 4, it can be seen that hydroformylation of the olefin in two stages over the same period of time using the same amount of olefin yields at least 23 kg of aldehyde. The result is that by dividing the hydroformylation reaction into two stages, better space-time yields can be obtained compared to the single stage reaction. In addition, it can be seen that in the two-step process, the total production of high-boiling by-products is reduced despite the higher conversion rate calculated in both steps. This is particularly important because the remaining rhodium catalyst is dissolved in the high boiling point component during the workup of the hydroformylation mixture. The more high boiling point components are removed, the more rhodium must be replenished.
    [128] Example 5
    [129] Preparation of nonanol by two stage hydroformylation of di-n-butene
    [130] First step
    [131] In a 5 L high pressure autoclave equipped with a stirrer and an electric heater, 2000 g of di-n-butene (Table 1, composition of the second column) was hydroformylated for 2 hours at 175 ° C. and 280 bar synthesis gas pressure in the presence of a cobalt catalyst. . The catalyst is prepared by treating 640 g of an aqueous cobalt acetate solution containing 1 mass% of cobalt with synthetic gas at 170 ° C. and 280 bar for 7 hours. The cobalt carbonyl formed is cooled and depressurized and then transferred to the organic phase by extraction with 2000 g of di-n-butene and the organic phase is separated from the aqueous phase. The concentration of catalyst in di-n-butene is 0.020% by mass in terms of cobalt metal on the basis of di-n-butene.
    [132] After cooling the hydroformylation mixture to 80 ° C. and reducing the pressure, cobalt is removed by treating it with 5% by weight aqueous acetic acid in the presence of air. The cobalt-free hydroformylation mixture is separated off from the aqueous phase.
    [133] The method is carried out four times under the same conditions. Combine the cobalt-free hydroformylation mixture. 9432 g of hydroformylation mixture are obtained and the composition according to GC analysis is shown in the second column of Table 2. According to this, the conversion of di-n-butene is 67.2% and the selectivity of the useful product is 93.8%, which is a value corresponding to 63.1% yield of the useful product. Herein and hereinafter nonanal, nonanol and its formate are considered useful products.
    [134] 2nd step
    [135] 7500 g of the cobalt-free hydroformylation mixture obtained from the first step is distilled off in the tower to recover the unreacted olefin. The olefin is obtained as a top fraction and the bottom fraction contains useful products and high boiling components. Isomer distribution in the recovered octene mixture is shown in the third column of Table 1. Compared to the new di-n-butenes containing 23% by mass of dimethylhexene, the recovered olefins containing 45% by mass of dimethylhexene contain much more of these unreacted olefins.
    [136] 2000 g of the recovered C 8 -hydrocarbon mixture (91.75% C 8 -olefins and 8.25% C 8 -paraffins) was hydrolyzed at a synthesis gas pressure of 185 ° C. and 280 bar for 3 hours in a 5 L autoclave in the first step. Formylated. The cobalt catalyst is prepared as in the first step and delivered onto the olefin, the concentration of which is based on the olefin and is converted to cobalt metal in an amount of 0.050 mass%.
    [137] The hydroformylation mixture is cooled to 80 ° C. and depressurized as described in the first step and cobalt is removed. This gave 2448 g of a cobalt-free hydroformylation mixture, the results of GC analysis of its composition are shown in the third column of Table 2. The olefin conversion is 91% and the useful product selectivity is 83.7%, which corresponds to a useful product yield of 76.2%.
    [138] The total olefin conversion over both steps ranges from 90.7% to 97.2% useful product selectivity, which corresponds to 88.2% useful product total yield based on the di-n-butene used.
    [139] Example 6
    [140] (Comparative Example, Preparation of Nonanol by Single Step Hydroformylation of Di-n-butene)
    [141] In the 5 L high pressure autoclave used in Example 5, 2000 g of di-n-butene (Table 1, composition of the second column) is hydroformylated for 3 hours at 185 ° C. and 280 bar synthesis gas pressure in the presence of a cobalt catalyst. The catalyst is prepared as in Example 5. The concentration of catalyst in di-n-butene is 0.040 mass% based on di-n-butene and converted to cobalt metal.
    [142] After cooling the hydroformylation mixture to 80 ° C., cobalt is removed by depressurizing and treating with 5% by weight aqueous acetic acid and air. Removal of the aqueous phase yields 2485 g of cobalt-free hydroformylation mixture, the composition of which is determined by GC analysis as shown in the fourth column of Table 2. According to this, the conversion of di-n-butene is useful product selectivity from 88.5% to 92%, which corresponds to product yield 81.4%.
    [143] The conversion, selectivity and yield in the multistage process (Example 5) according to the invention are much better than the single stage process (Example 6).
    [144] Isomer distribution of feed olefins OlefinDi-n-butene (starting material in Example 1 and Example 6) mass%Octene Mixture (Starting Material in Second Step of Example 5) Mass% Dimethylhexene2345 3-methylheptene6250 n-octene155
    [145] Composition of cobalt-free hydroformylated emissions (moisture reduced)Example 5, first step mass%Example 5, 2nd step mass%Example 6 mass% C 8 -olefin27.86.76.4 C 8 -paraffin2.510.83.1 C 9 -aldehyde48.845.252.7 Nonyl Formate2.25.74.2 C 9 -alcohol17.422.926.9 High boiling point1.38.76.7
    [146] The process for preparing aldehydes or alcohols by multistage hydroformylation of olefins according to the invention is much better in terms of the conversion of starting materials and the selectivity and yield of the desired product compared to the single stage process.
    权利要求:
    Claims (19)
    [1" claim-type="Currently amended] Hydroformylating an olefin having 6 to 24 carbon atoms at a conversion rate of 20 to 98% (a),
    (B) removing the catalyst from the resulting liquid reactor discharge,
    (C) separating the resulting liquid hydroformylation mixture into a low boiling point fraction comprising olefins and paraffins and a bottom fraction comprising aldehydes and / or alcohols, and
    A process comprising the step (d) of reacting olefins present in the low boiling fraction in a further step comprising processes a), b) and c), characterized in that the bottom fractions of process (c) are combined at all stages. Wherein the olefins having 6 to 24 carbon atoms are multistage hydroformylated using cobalt or rhodium as catalysts to produce alcohols and / or aldehydes.
    [2" claim-type="Currently amended] The process of claim 1 wherein each step comprises a hydroformylation process (a), a catalyst removal process (b) and a distillation process (c), provided that the catalyst separated in process (b) is hydrolyzed in each step. Recycle to the formylation process (a) either directly or after treatment.
    [3" claim-type="Currently amended] The process of claim 1 wherein each step comprises a hydroformylation process (a), a catalyst removal process (b) and a distillation process (c), provided that the final step does not comprise a distillation process (c) the catalyst separated in b) is recycled directly or after treatment to the hydroformylation process (a) in each step.
    [4" claim-type="Currently amended] The process of claim 1, wherein each step comprises a hydroformylation process (a) and a catalyst removal process (b), wherein the combined liquid hydroformylation mixture is separated into a low boiling point fraction and a bottom fraction in a co-distillation process (c). Wherein the catalyst separated in step (b) is recycled directly or after treatment to the hydroformylation process (a) in each step.
    [5" claim-type="Currently amended] The process of claim 1, wherein the reactor effluents combined through all hydroformylation processes (a) are subjected to only one catalyst removal process (b) and one distillation process (c), with the catalyst separated in process (b). Is recycled directly or after treatment to the hydroformylation process (a) in each step.
    [6" claim-type="Currently amended] 6. The method of any one of claims 1, 2, 4 and 5, wherein the paraffin is partially or completely removed from one or more low boiling fractions.
    [7" claim-type="Currently amended] The process according to any one of claims 1, 2 and 4 to 6, wherein the bottom fractions combined from the distillation process (c) are hydrogenated.
    [8" claim-type="Currently amended] 7. The process according to any one of claims 1, 3 and 6, wherein the bottom fraction combined from the distillation step (c) and the discharge of the final catalyst removal step (b) are hydrogenated.
    [9" claim-type="Currently amended] The process according to any one of claims 1, 2 and 4 to 6, wherein the aldehydes present in the bottom fractions combined from the distillation step (c) are removed by distillation.
    [10" claim-type="Currently amended] The process according to any one of claims 1, 3 and 6, wherein the bottom fraction combined from the distillation process (c) and the aldehyde present in the discharge of the final catalyst removal process (b) are removed by distillation. Way.
    [11" claim-type="Currently amended] The process according to claim 1, wherein in each hydroformylation process (a) a cobalt catalyst is used.
    [12" claim-type="Currently amended] The process according to any one of claims 1 to 10, wherein in each hydroformylation step (a), a rhodium catalyst is used.
    [13" claim-type="Currently amended] The cobalt catalyst is used in the hydroformylation process (a) of the first stage, and the rhodium catalyst is used in the hydroformylation process (a) of the further stage. Way.
    [14" claim-type="Currently amended] The process according to any one of claims 1 to 10, wherein in the hydroformylation process (a) of the first stage, a rhodium catalyst is used, and in the hydroformylation process (a) of the further stage, a cobalt catalyst is used. Way.
    [15" claim-type="Currently amended] The process according to any one of claims 1 to 14, wherein the liquid reactor discharge of the hydroformylation process (a) is a homogeneous liquid phase.
    [16" claim-type="Currently amended] The process according to any one of claims 1 to 15, wherein the cobalt or rhodium catalyst is dissolved in a homogeneous phase in the liquid reactor discharge of the hydroformylation process (a).
    [17" claim-type="Currently amended] The process according to any one of claims 1 to 16, wherein in the hydroformylation process (a) in the subsequent further step of the first step, the olefin is in each case hydroformylated with a conversion of at least 50%.
    [18" claim-type="Currently amended] 18. The process of claim 17, wherein in the hydroformylation process (a) during the subsequent further step of the first step, the olefin is in each case hydroformylated at a conversion of 55 to 98%.
    [19" claim-type="Currently amended] 19. The method of any one of the preceding claims, comprising two steps.
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    KR100729160B1|2007-06-19|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-07-14|Priority to DE10034360A
    2000-07-14|Priority to DE10034360.0
    2001-07-13|Application filed by 뮐러 리하르트, 슈베르트페거, 옥세노 올레핀케미 게엠베하
    2002-01-29|Publication of KR20020008020A
    2007-06-19|Application granted
    2007-06-19|Publication of KR100729160B1
    优先权:
    申请号 | 申请日 | 专利标题
    DE10034360A|DE10034360A1|2000-07-14|2000-07-14|Multi-stage process for the production of oxo aldehydes and / or alcohols|
    DE10034360.0|2000-07-14|
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