WO2004022515A1 - Procede pour la production en continu de composes carbonyle - Google Patents

Procede pour la production en continu de composes carbonyle Download PDF

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WO2004022515A1
WO2004022515A1 PCT/EP2003/008096 EP0308096W WO2004022515A1 WO 2004022515 A1 WO2004022515 A1 WO 2004022515A1 EP 0308096 W EP0308096 W EP 0308096W WO 2004022515 A1 WO2004022515 A1 WO 2004022515A1
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reaction
column
catalyst
general formula
carbonyl compounds
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PCT/EP2003/008096
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German (de)
English (en)
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Werner Aquila
Walter Dobler
Gerd Kaibel
Christian Miller
Carsten Oost
Manfred Stroezel
Mathias Haake
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Basf Aktiengesellschaft
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Priority to AU2003251465A priority Critical patent/AU2003251465A1/en
Publication of WO2004022515A1 publication Critical patent/WO2004022515A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
    • B01D3/322—Reboiler specifications
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—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
    • C07C45/73—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 hydrogenation

Definitions

  • the present invention relates to a process for the continuous production of higher-chain carbonyl compounds by reacting lower-chain carbonyl compounds with aldehydes over basic or acidic catalysts in a rectification column.
  • the aldol addition of two different aldehydes or an aldehyde with a ketone can only be used preparatively if the aldehyde component does not have an ⁇ -hydrogen atom, so that it can only function as a carbonyl component.
  • This type of reaction is referred to in the literature as the Claisen-Schmidt reaction. Since the aldol addition is a reversible reaction, there is a risk of cleavage back into the starting compounds. Information on the technical implementation of this reaction is not given in Römpp Chemie Lexikon.
  • a process for the preparation of pseudoionone by reacting citral with acetone using LiOH as a catalyst is described in US-4874900.
  • the reaction is then carried out batchwise or continuously at temperatures from -20 to 240 ° C.
  • the pressure is adjusted so that the reaction mixture remains in the liquid phase at the appropriate temperature.
  • the reactants are stirred in a vessel and the catalyst is filtered off after the reaction has ended, while in the continuous mode of operation the premixed reactants are pumped through a column filled with catalyst. In both cases, the reaction mixture is neutralized with CO at the end of the reaction and the excess ketone is distilled off.
  • Patent PL147748 describes a process for the preparation of ionone by condensation of citral and acetone on basic ion exchangers at 56 ° C. Thereafter, acetone and citral are stirred discontinuously in a flask with the catalyst for 5 hours. No details are given in this patent regarding the technical implementation of the reaction. The disadvantage of this process is the very low space-time yields.
  • a method for the aldolization of acetone in a reaction column is described by Podrebarac, Ng and Rempel in Chemtech (May 1997, page 41).
  • the catalyst is installed in the upper part of a distillation column, the acetone is pumped into the column at a point not mentioned and a product mixture of diacetone alcohol, mesityl oxide, acetone and water is drawn off at the bottom.
  • Podrebarac points out that the balance of aldolization of acetone is positively influenced by reactive distillation. In the present invention, however, the formation of condensation products of the ketone is an undesirable side reaction to be avoided.
  • CN1109860-A describes a process for the preparation of diacetone alcohol.
  • acetone is condensed in a reactor and the reaction product is fed into a distillation column in which the acetone is distilled off overhead and in the Reactor is recycled.
  • the reaction product is drawn off at the bottom of the column. This process is therefore a conventional combination of reaction with subsequent distillation and recycling of unreacted starting materials.
  • ZA 9805328-A describes a process for the preparation of methyl isobutyl ketone.
  • acetone and hydrogen are metered into the column in cocurrent below the reaction zone, which consists of a bed of catalyst.
  • the acetone reacts to the mesityl oxide by aldol condensation, which is then hydrogenated to the methyl isobutyl ketone.
  • Below and / or above the reaction zone there are distillation zones.
  • the reaction product is separated off in the distillation zone and drawn off at the bottom, while unreacted acetone is separated off at the top and is returned to the column as reflux.
  • a bifunctional catalyst is installed in the reaction zone, which accelerates both the aldol condensation and the hydrogenation.
  • Ion exchangers zeolites or aluminum oxide with a metal of group VIII or IB, such as nickel, palladium or copper, are mentioned as examples. With this process, selectivities of 61.2% based on acetone are achieved. This selectivity is unsatisfactory for an industrial process.
  • the patent is also limited to directing the reactants in direct current.
  • a process for the aldolization of aldehydes in the presence of a basic catalyst is described in JP 10053552-A.
  • An aldehyde with at least one hydrogen atom in the ⁇ position is then metered into a reaction column with sieve trays. This process can be used, for example, to produce 2-ethylhexenal from n-butyl aldehyde.
  • the dimerization of aldehydes is not the subject of the present invention.
  • DE19605078A1 describes a process for the preparation of a dimerized aldehyde in a reaction column in the presence of an aqueous solution of a basic catalyst.
  • the process is characterized in that the feed aldehyde has one or two hydrogen atoms in the ⁇ position.
  • the aldehyde and an aqueous solution of the basic catalyst are metered in at the same feed point into a reaction column in which the reaction takes place.
  • the unreacted reactant is separated off at the top of the column and some of it is returned to the column.
  • the reaction product is removed from the column on a gaseous side draw together with water. As water forms a miscibility gap with the product, a phase separation vessel is required.
  • aqueous basic catalyst solution and high-boiling compounds are drawn off via the bottom of the column, so that a phase separation is likewise necessary at this point.
  • the phase separations and associated returns in this process are associated with additional investment costs.
  • the recycling of the homogeneous catalyst is complex.
  • DE 3319-430-A claims the production of higher ketones by condensation of methyl ketones and unsaturated aldehydes over mixed metal catalysts in the presence of hydrogen at 100 to 280 ° C. and 10 to 60 bar in a tubular reactor.
  • the catalysts claimed are one Combination of oxides or phosphates of rare earth metals, Mg, Al, Zn or Ti and a Group VIII metal. 5 wt.% Pr0 3 and 0.5 wt.% Pd on aluminum oxide are mentioned as examples.
  • US5254743-A describes the use of Mg, Ca, Ba, Ni, Co, Fe, Cu or Zn oxides on oxides of the elements Al, Ga, Cr, Co, Fe or La with a surface patented of at least 150 m 2 / g.
  • JP-162329 mentions La0 3 , Nd0 3 or Pr 2 0 3 on ⁇ -aluminum oxide as a catalyst for "various" chemical reactions.
  • the discontinuous processes for the aldolization of different carbonyl compounds have the disadvantage of high residence times and therefore low space-time yields, high investment costs and low yields.
  • the reactants are first mixed, passed over a bed of catalyst and the excess ketone is only separated off after the reaction. On the one hand, this leads to increased investment costs and a high thermal load on the products, which is associated with a reduced yield.
  • a reactant in a large excess of over 20 mol / mol must be used to achieve sufficient selectivity.
  • the processes described in the literature for the aldolization of different carbonyl compounds have considerable disadvantages, as explained above.
  • the object of the invention was therefore to provide a new process for the continuous aldolization of different carbonyl compounds with advantageous properties, which no longer has the disadvantages of the prior art and which provides the corresponding products in high selectivities and high space-time yields.
  • the reaction should be able to be carried out continuously in a single reactor, with high product selectivities for both carbonyl compounds being achieved with the shortest possible reaction times. In particular, it should be avoided that a large excess of a reactant is used to achieve high selectivities and that it has to be separated off again after the reaction. Accordingly, a process for the continuous production of carbonyl compounds of the general formula (I) has been found
  • Rl to R4 for hydrogen or for a saturated or unsaturated, branched or unbranched, optionally substituted by one or more methoxy groups aliphatic hydrocarbon radical having 1 to 37 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkylalkyl group 4 to 30 carbon atoms or an aromatic having 6 to 18 carbon atoms, and in which A and B both represent hydrogen, or A or B independently of one another represent a hydroxyl group or can have the same meaning as R 1 to R 4, or A and B together means an additional bond between the C and A atoms,
  • R4 has the meaning given above and R5 can have the same meaning as Rl to R4, and either R4 or R5 is different from Rl or R2,
  • the carbonyl compound of the general formula (II) used in the process according to the invention is particularly preferably one in which R 2 is hydrogen and R 1 is a group of the general formula (IV)
  • n stands for an integer from 1 to 6 and X and Y either both stand for H, or X and Y together means an additional bond between the X and Y-bearing carbon atoms.
  • the method according to the invention can in principle be applied to all aldolization reactions.
  • the process is of particular importance for the aldolization of citral with acetone for the production of pseudoionon and for the production of methylpseudoionon, dirnethylpseudoionon and ethylpseudoionon, since these compounds are important intermediates for the production of vitamin A and fragrances.
  • C 1 -C 3 aliphatic carbon radical for R 1 to R 4 and A and B straight-chain or branched saturated or one or more unsaturated radicals with 1 to 37, preferably with 1 to 20 C atoms, particularly preferably with 1 to 15 C atoms Consider.
  • Examples include methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptenyl, octyl, nonyl, oxyl, 1 Propenyl, 2-propenyl, 2-methyl-2-propenyl, 1-pentyl, l-methyl-2-pentenyl, isopropenyl, 1-butenyl, hexenyl, heptenyl, octenyl, Nonenyl or the decenyl radical.
  • the preferred cycloalkyl radicals for R 1 to R 4 and A and B are C 3 -C 1 -cycloalkyl radicals such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl or cyclodecenyl, which may be one or more C 1 -C 4 - Alkyl, halogen (fluorine, chlorine, bromine, iodine), nitro, cyano, amino, C 1 -C 4 -alkylamino, C 1 -C 4 -dialkylamino, hydroxyl or other atoms or optionally 1 to 3 heteroatoms such as sulfur, nitrogen or oxygen in the ring contain.
  • Cycloalkylalkyl radicals contain a cycloalkyl radical linked to a C 1 -C 2 aliphatic hydrocarbon radical.
  • aryl radicals are, for example, benzyl, aryl, naphthyl or biphenyl.
  • selectivities of over 97% based on the carbonyl compound of the general formula (II) and at the same time over 84% based on the carbonyl compound of the general formula (III) are achieved.
  • the space-time yield is a factor of 3 greater than in the previously known methods.
  • the heat of reaction released during the reaction can be used for distillation and thus energy costs can be saved.
  • Another advantage of the process according to the invention is that the carbonyl compounds of the formulas (II) and (III) can be used in a molar ratio of less than 20 and nevertheless high selectivities with regard to both reactants are achieved.
  • a molar ratio between 5 and 15 is preferably set, the chemically more stable component of the two carbonyl compounds generally forming the excess component.
  • much higher molar ratios have hitherto been required to achieve satisfactory selectivities.
  • An example of this is the conversion of citral with acetone to pseudoionone.
  • reaction product is immediately removed from the reaction mixture, so that subsequent reactions are avoided and the yield is thereby increased.
  • water which may be formed during the reaction can be separated off via the top of the column. This has a positive influence on the equilibrium setting and considerably simplifies the working up of the reaction product by distillation.
  • the concentration profile in the column is preferably adjusted by energy input and reflux ratio so that a belly of the more stable carbonyl compound forms, into which the chemically unstable reactant is metered.
  • the two reactants are conducted in countercurrent for this purpose.
  • the method according to the invention makes it possible to isolate the products of the aldol addition.
  • products of Aldol addition denotes compounds of the formula (I) in which A denotes a hydroxyl group and B can have the same meaning as R1 to R4. Subsequent separation of the addition product from the reaction zone can avoid subsequent aldol condensation or cleavage of the product.
  • the method according to the invention it is also possible to shift the equilibrium to the side of the product of the aldol condensation with elimination of water by appropriate concentration control.
  • the products of the aldol condensation are compounds of the formula (I) in which A and B mean an additional bond.
  • the water formed must be removed continuously from the reaction zone, so that the balance is shifted to the product side.
  • the process according to the invention is possible with the process according to the invention to produce the hydrogenated products of the aldol condensation.
  • the products of the aldol condensation are compounds of the formula (I) in which A and B are hydrogen.
  • a bifunctional catalyst is used in the reaction zone of the reactor, which catalyzes both the aldolization and the hydrogenation, and the reaction is carried out in the presence of hydrogen.
  • the amounts used in the process according to the invention are selected so that a molar ratio of carbonyl compound (II) to carbonyl compound (III) is between 1 and 50, preferably between 5.0 and 15.
  • Pressure and temperature are set so that high reaction rates result with a sufficiently high selectivity.
  • the pressure at the top of the column is preferably set so that the temperature in the bottom is between 50 and 300 ° C., preferably between 80 and 180 ° C.
  • the hydrogen partial pressure is set between 1 and 100 bar, preferably between 1 and 20 bar.
  • the residence time in the reactor system should be between 10 minutes and 10 hours, preferably between 0.5 and 3 hours.
  • aldolization catalysts mentioned in the literature such as, for example, alkali metal oxides, alkaline earth metal oxides, alkali metal hydroxides, alkaline earth metal hydroxides or rare earth metal oxides in pure form, as an aqueous solution or can be used on a carrier.
  • Sodium hydroxide solution and potassium hydroxide solution are preferably used as homogeneous catalysts, since these can be pumped liquid into the fractionation column. It is particularly preferred to use heterogeneous catalysts which can be accommodated in a targeted manner in the reaction zone of the column and thus do not lead to contamination of the product or necessitate neutralization of the reaction product.
  • Preferred catalysts are catalysts containing elements of the lanthanide series, preferably La, Ce and / or Pr, in a concentration of 0.1 to 20% by weight, preferably 1 to 10% by weight, on aluminum oxide, preferably on ⁇ -alumina.
  • the catalyst is used in a concentration of 1 to 99% by volume, based on the empty volume of the reactor, preferably between 10 and 30% by volume.
  • the catalyst is installed on the internals or as internals of a fractionation column or in a residence time container connected in parallel with the column.
  • the process according to the invention is advantageously carried out in such a way that the carbonyl compound of the general formula (II), the carbonyl compound of the general formula (III) and, if appropriate, the catalyst via the feeds (3), (2) and (1) to the internals as Reaction column acting fractionation column (4) metered. It is advantageous, but not mandatory, if the higher-boiling reactants are fed separately or continuously together with the catalyst above the lower-boiling reactant into the fractionation column (4), thus forcing a countercurrent of the reactants. It may be advantageous to meter the lower-boiling reactants into the column (4) in gaseous or superheated form, since then a split in the bottom (19) of the column at high temperatures and the formation of by-products are avoided.
  • the pressure at the top of the column (23) is adjusted so that the temperature in the bottom (19) is between 100 and 300 ° C, preferably between 130 and 180 ° C. Depending on the material system, this can be done with a vacuum pump (10) and / or a pressure control device (11).
  • the reaction of the carbonyl compound of the formula (II) with the carbonyl compound of the formula (III) takes place on the internals (21) of the fractionation column (4).
  • the superimposed distillation continuously removes the carbonyl compound of the formula (I) from the reaction equilibrium and the reaction zone and reaches the bottom (19) of the Fractionation column and is withdrawn via stream (14).
  • the water formed by the reaction is also continuously removed from the reaction zone.
  • the superimposed distillation thus, on the one hand, has a positive influence on the reaction equilibrium and, on the other hand, prevents subsequent reactions and thus high selectivities.
  • the reaction product collects in the bottom (19) of the column (4) and is drawn off via the bottom stream (14) by means of a pump (16) together with any unreacted reactants and high-boiling by-products.
  • a part of the bottom stream (14) is evaporated with an evaporator (18) and fed into the column via the vapor line (15). This creates the vapor required for the distillation.
  • the raw product is made over the
  • This workup can consist, for example, of a downstream evaporator, with which the crude product is freed from low boilers, in particular from unreacted reactants. It is possible to remove low-boiling
  • Components additionally feed an inert gas (30) into the bottom of the column.
  • the workup can also be carried out directly in subsequent columns, preferably in dividing wall columns.
  • the unreacted reactants are preferably returned to the column.
  • the lower-boiling reactant if appropriate together with low-boiling by-products, accumulates in the case of aldol additions. This is fed via line (7) into the condenser (8), condensed out and fed back into the column via line (12), optionally after a partial flow has been discharged via line (13).
  • the internal reflux in the column can be used to set a high concentration of the low-boiling reactant, if required, without setting a high molar ratio of the reactants to be fed in.
  • the water of reaction formed leaves the column together with any unreacted reactants and / or low boilers formed as a by-product during the reaction via the top stream (7) and reaches the condenser (8) in which the condensable constituents of this vapor stream be condensed out.
  • Part of the condensate is returned to the column as reflux (12) and the other part (13) is drawn off.
  • the distillate (13) When carrying out aldol condensations, the distillate (13) generally consists of water and low boilers or of an azeotrope of water and one of the reactants, which is passed on for further processing.
  • the azeotrope acetone / water is obtained at the top of the column and is separated in a subsequent column. If a heteroazeotrope occurs at the top of the column, the water of reaction can be discharged in a targeted manner using a phase separation vessel. It is also possible to discharge the water over the column sump and to drive the column as with the Aldol addition.
  • a corresponding catalyst preferably a Pd / Pr / AlO 3 catalyst
  • hydrogen is fed into the column via the stream (29).
  • the hydrogen is separated off via the top (23) of the column and returned to the column using a compressor (10).
  • the reaction column (4) generally consists of several zones with different functions. In the column internals of the reaction zone (21) between the feed points (2) and (3) of the column (4), the reactants are essentially reacted with simultaneous removal of the resulting products by distillation. Separation zones (20, 22) which are provided with distillative separation elements are generally located above and / or below the segment (21). In the lower separation zone (20), the reaction product is largely separated from the water which may be formed and from the low-boiling components, in particular from the low-boiling reactant added at point (3). The upper separation zone (22) ensures that the reactant added at the upper feed point (2) does not get into the distillate. The separation zones (20) and (22) are generally advantageous, but not absolutely necessary.
  • trays with a long residence time of the liquid such as valve trays, preferably bubble trays or related types such as tunnel trays or Thormann trays, are advantageously installed.
  • metal mesh packs or sheet metal packs with an ordered structure or packed beds as column internals. If heterogeneous catalysts are used, this can be accommodated on the trays or as a catalyst bed be installed in the reaction zone (21).
  • catalyst-containing packings such as Montz MULTIPAK or Sulzer KATAPAK, or to introduce the catalyst into the column in the form of packing.
  • catalytically active distillation packs or fabric bags filled with catalyst so-called Bales or Texas tea bags).
  • the catalyst is used in a concentration of 1 to 50% by volume, based on the empty volume of the column, preferably between 10 and 30% by volume.
  • Partial streams (25) are returned to the column (4).
  • the containers can be filled with heterogeneous catalyst. Additional catalyst and / or reactants can optionally be metered into the containers (26) with the aid of a feed line (24). The heating of the container (26) makes sense.
  • column internals with a large number of separation stages such as metal mesh packs or sheet metal packs with an ordered structure, such as Sulzer Melapak, Sulzer BX, Montz Bl types or Montz A3 types, are preferably used.
  • fractionation columns are advantageously used which have internals 10 to 100 of the trays described in more detail above, preferably between 10 and 40 trays. It is advantageous to work in such a way that the higher-boiling reactants are introduced into the upper part of the column and the lower-boiling reactants into the lower part of the column. It has proven to be particularly advantageous if 0 to 50 trays, preferably 5 to 20 trays, in the separation zone (22) above the feed stream (2) for the higher-boiling reactants, 0 to 100 trays, preferably 5 to 30 trays, in the reaction zone and 0 to 50, preferably 5 to 20 trays, in the lower part of the column (20) below the feed stream (3), be provided. The same applies to the so-called theoretical plates in other column internals.
  • Example 1 Production of pseudo ionone by aldolization of acetone and citral
  • the experimental apparatus consisted of a heatable 2 liter stainless steel reaction flask equipped with a stirrer, on which a distillation column (length: 1.2 m, diameter: 50 mm) was placed. The column was in the lower area
  • the column was equipped with thermocouples at regular intervals, so that the temperature could be measured at every 3rd to 4th theoretical stage, except in the bottom and at the top of the column.
  • the concentration profile in the column could be determined with the help of appropriate sampling points.
  • the reactants were metered into the column from feed containers standing on scales with a mass flow-controlled pump.
  • the evaporator (18) which was heated to 124 ° C with the aid of a thermostat, had a hold-up between 50 and 150 ml during operation, depending on the dwell time.
  • the bottom stream (17) was level-controlled from the evaporator with a pump conveyed into a container standing on a scale.
  • the top stream (7) of the column was condensed out in a condenser (8) which was operated with a cryostat. Part (13) of the condensate ran through a return divider into a feed tank standing on a balance, while the other part (12) was fed as return to the column.
  • the apparatus was equipped with a pressure regulator (11) and designed for a system pressure of 20 bar. All incoming and outgoing material flows were continuously monitored with a PLS nuously recorded and registered. The apparatus was operated in 24-hour operation (stationarity).
  • the bottom stream of the column was 183.9 g / h of crude product with 62.14% by weight of acetone, 0.71% by weight of water, 0.45% by weight of mesityl oxide, 0.95% by weight of diacetone alcohol, 9 , 14% by weight of citral, 24.43% by weight of pseudoionone and 2.18% by weight of high boilers.
  • 80.8 g / h of distillate consisting of 95.8% by weight of acetone and 4.2% by weight of water were drawn off.
  • Pseudoionone with a selectivity of 97.3% based on citral and 84.4% based on acetone was obtained.
  • the yield was 66.7% based on citral.
  • the space-time yield was about 330 g / (l * h).
  • Example 2 Production of pseudo ionone with separation of the water overhead
  • the experimental apparatus consisted of a distillation column (length: 1.8 m, diameter: 50 mm) with a thin-film evaporator.
  • the column was in the lower area (separation zone (20)) with segments of a structured tissue pack of the type Sulzer DX (total height: 125 cm) and in the upper area (separation zone (22)) with 3 segments of a structured tissue pack of the type Sulzer EX (total height: 15 cm) filled.
  • the reaction zone (21) in the middle area of the column was filled with a bed of 600 g of the catalyst. Strands of 1% Pr on ⁇ -Al 2 0 3 were used as the catalyst, which were prepared by impregnating ⁇ -Al0 with an aqueous solution of Pr nitrate and then calcining.
  • the reaction zone (21) in the middle area of the column was filled with a bed of 600 g of the catalyst.
  • Strands of 1% Pr on ⁇ -Al 2 0 3 were used as the
  • the column was equipped with thermocouples at regular intervals so that the temperature could be measured at every 3rd to 4th theoretical stage, except in the bottom and at the top of the column.
  • the concentration profile in the column could be determined with the help of appropriate sampling points.
  • the reactants were metered into the column from feed containers standing on scales with a mass flow-controlled pump.
  • the evaporator (18) which was heated to 113 ° C. with the aid of an electrical heater, had a hold-up between 50 and 150 ml during operation, depending on the dwell time.
  • the bottom stream (17) was level-regulated from the evaporator with a pump conveyed a container standing on a scale.
  • the top stream (7) of the column was condensed out in a condenser (8) which was operated with a cryostat. Part (13) of the condensate ran through a return divider into a feed tank standing on a balance, while the other part (12) was fed as return to the column.
  • the apparatus was equipped with a pressure regulator (11) and designed for a system pressure of 20 bar. All incoming and outgoing material flows were continuously recorded and registered with a PLS throughout the test. The apparatus was operated in 24-hour operation (stationarity).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour la production en continu de composés carbonyle à chaîne longue par réaction de composés carbonyle à chaîne courte avec des aldéhydes sur des catalyseurs basiques ou acides dans une colonne de rectification.
PCT/EP2003/008096 2002-08-15 2003-07-24 Procede pour la production en continu de composes carbonyle WO2004022515A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003251465A AU2003251465A1 (en) 2002-08-15 2003-07-24 Continuous method for the production of carbonyl compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002138140 DE10238140A1 (de) 2002-08-15 2002-08-15 Kontinuierliches Verfahren zur Herstellung von Carbonylverbindungen
DE10238140.2 2002-08-15

Publications (1)

Publication Number Publication Date
WO2004022515A1 true WO2004022515A1 (fr) 2004-03-18

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AU (1) AU2003251465A1 (fr)
DE (1) DE10238140A1 (fr)
WO (1) WO2004022515A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825538A (zh) * 2020-07-13 2020-10-27 万华化学集团股份有限公司 一种连续化生产假性紫罗兰酮的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110496414B (zh) * 2019-09-19 2021-04-27 福州大学 合成二丙酮醇的连续反应精馏装备及其工艺

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4431844A (en) * 1981-04-08 1984-02-14 Basf Aktiengesellschaft Preparation of polyunsaturated ketones
US5667644A (en) * 1995-02-13 1997-09-16 Mitsubishi Chemical Corporation Method for producing a dimerized aldehyde
WO1999065851A1 (fr) * 1997-06-18 1999-12-23 Catalytic Distillation Technologies Production de mibk au moyen de la technologie par distillation catalytique
US6069261A (en) * 1995-11-04 2000-05-30 Rwe-Dea Aktiengesellschaft Fur Mineraloel Und Chemie Method of chemically reacting substances in a reaction column
EP1164119A2 (fr) * 2000-06-15 2001-12-19 Basf Aktiengesellschaft Procédé pour la préparation de cétones supérieures à partir d' aldéhydes insaturés
WO2003047748A1 (fr) * 2001-12-06 2003-06-12 Basf Aktiengesellschaft Oxydes metalliques supportes servant de catalyseurs de condensations aldoliques
WO2003047747A1 (fr) * 2001-12-06 2003-06-12 Basf Aktiengesellschaft Dispositif et procede de mise en oeuvre de distillations reactives a catalyse heterogene notamment destinees a la fabrication de pseudoionone

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4431844A (en) * 1981-04-08 1984-02-14 Basf Aktiengesellschaft Preparation of polyunsaturated ketones
US5667644A (en) * 1995-02-13 1997-09-16 Mitsubishi Chemical Corporation Method for producing a dimerized aldehyde
US6069261A (en) * 1995-11-04 2000-05-30 Rwe-Dea Aktiengesellschaft Fur Mineraloel Und Chemie Method of chemically reacting substances in a reaction column
WO1999065851A1 (fr) * 1997-06-18 1999-12-23 Catalytic Distillation Technologies Production de mibk au moyen de la technologie par distillation catalytique
EP1164119A2 (fr) * 2000-06-15 2001-12-19 Basf Aktiengesellschaft Procédé pour la préparation de cétones supérieures à partir d' aldéhydes insaturés
WO2003047748A1 (fr) * 2001-12-06 2003-06-12 Basf Aktiengesellschaft Oxydes metalliques supportes servant de catalyseurs de condensations aldoliques
WO2003047747A1 (fr) * 2001-12-06 2003-06-12 Basf Aktiengesellschaft Dispositif et procede de mise en oeuvre de distillations reactives a catalyse heterogene notamment destinees a la fabrication de pseudoionone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PODREBARAC G G ET AL: "More uses for catalytic distillation", CHEMTECH, WASHINGTON, DC, US, vol. 27, no. 5, May 1997 (1997-05-01), pages 37 - 45, XP008015170, ISSN: 0009-2703 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825538A (zh) * 2020-07-13 2020-10-27 万华化学集团股份有限公司 一种连续化生产假性紫罗兰酮的方法
CN111825538B (zh) * 2020-07-13 2022-08-05 万华化学集团股份有限公司 一种连续化生产假性紫罗兰酮的方法

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DE10238140A1 (de) 2004-02-26

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