EP1527058A1 - Procede de separation intermediaire guidee en continu d'oxirane obtenu lors de la synthese d'oxirane exempte de produits de couplage au moyen d'une colonne a membrane - Google Patents

Procede de separation intermediaire guidee en continu d'oxirane obtenu lors de la synthese d'oxirane exempte de produits de couplage au moyen d'une colonne a membrane

Info

Publication number
EP1527058A1
EP1527058A1 EP03765088A EP03765088A EP1527058A1 EP 1527058 A1 EP1527058 A1 EP 1527058A1 EP 03765088 A EP03765088 A EP 03765088A EP 03765088 A EP03765088 A EP 03765088A EP 1527058 A1 EP1527058 A1 EP 1527058A1
Authority
EP
European Patent Office
Prior art keywords
oxirane
hydroperoxide
column
organic compound
dividing wall
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03765088A
Other languages
German (de)
English (en)
Inventor
Peter Bassler
Hans-Georg Göbbel
Joaquim Enrique Teles
Peter Rudolf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1527058A1 publication Critical patent/EP1527058A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the invention relates to a continuously operated process for the intermediate separation of the oxirane formed in the preferably coproduct-free oxirane synthesis by reacting a hydroperoxide with an organic compound, the product mixture formed in the synthesis being separated in a dividing wall column into a light, medium and high boiler fraction and the oxirane being removed the medium boiler fraction at the side take-off point of the column and the hydroperoxide from the high boiler fraction with the bottom of the column.
  • oxiranes can be prepared in one or more stages by reacting suitable organic compounds with hydroperoxides.
  • the multi-stage process described in WO 00/07965 provides that the reaction of the organic compound with a hydroperoxide comprises at least steps (i) to (iii):
  • step (i) reacting the hydroperoxide with the organic compound to obtain a product mixture comprising the reacted organic compound and unreacted hydroperoxide, (ii) separating the unreacted hydroperoxide from the mixture resulting from step (i), (iii) reacting the separated hydroperoxide from step (ii) with the organic compound. Accordingly, the reaction of the organic compound with the hydroperoxide takes place in at least two stages (i) and (iii), the hydroperoxide separated off in stage (ii) being used again in the reaction.
  • the reactions in stages (i) and (iii) are preferably carried out in two separate reactors, preferably fixed bed reactors, the reaction in stage (i) preferably taking place in an isothermal reactor and the reaction in stage (iii) in an adiabatic reactor.
  • this multi-stage process can be used to convert alkenes with hydroperoxides to oxiranes.
  • hydrogen peroxide is preferably used as the hydroperoxide and the organic compound is brought into contact with a heterogeneous catalyst during the reaction.
  • the above process can be used to produce propylene oxide from propylene and hydrogen peroxide.
  • the reaction is preferably carried out in methanol as a solvent.
  • the propylene is mostly used in the "chemical grade" quality level and contains approx. 4% by weight of propane.
  • the hydrogen peroxide conversion in stage (i) reaches about 85% to 90% and in stage (iii) about 95%, based on stage (ii).
  • a hydrogen peroxide conversion of approx. 99% with a propylene oxide selectivity of approx. 94 - 95% can be achieved via both stages.
  • this synthesis is also referred to as oxirane synthesis without co-product.
  • the separation of the hydroperoxide in particular has been optimized since the unreacted hydroperoxide from stage (i) is to be used again in the reaction.
  • the hydroperoxide is preferably removed by distillation via the bottom of a column.
  • the oxirane can be separated off directly from the product mixture in the same column as the hydroperoxide. With this intermediate separation by distillation the oxirane is then removed from the mixture via the top of the column.
  • intermediate separation denotes the separation of the oxirane directly from the reaction mixture, in contrast to the pure distillation, which takes place with the oxirane which has already been separated off.
  • the reaction mixture to be separated by distillation contains, for example, methanol, water, propylene oxide as oxirane, by-products such as, for. B. methoxypropanols, 1,2-propylene diglycol, acetaldehyde, methyl formate, unreacted propylene as an organic compound, propane and hydrogen peroxide as hydroperoxide.
  • the oxirane distilled off via the top of the column according to the prior art is contaminated with low boilers of the abovementioned compounds which are volatile under the distillation conditions, for example with unreacted organic compound. It then usually has to undergo a further purification step, i.e. a pure distillation. This can be done, for example, in a further distillation in a column which is connected in series with the column used as the separation device. This procedure with a distillation of the product of value at least twice requires an increased expenditure on equipment and energy.
  • a process to be operated continuously should be made available, which allows the oxiranes preferably obtained by multistage reaction to be obtained in high purity by intermediate separation with minimal equipment and energy expenditure.
  • the invention therefore relates to a continuously operated process for the intermediate separation of the oxirane formed in the oxirane synthesis by reacting a hydroperoxide with an organic compound, characterized in that the product mixture formed in the synthesis in a dividing wall column into a light, medium and high boiler fraction separated and the oxirane from the medium boiler fraction at the side take-off point and the hydroperoxide from the high boiler fraction are removed with the bottom of the column.
  • the oxirane can be obtained directly from the reaction mixture by intermediate separation in the same column in which the hydroperoxide is also removed by distillation. Furthermore, the oxirane and the hydroperoxide used can be separated from one another under mild conditions and low thermal stress, since in the dividing wall column, only short residence times are necessary in comparison to two columns connected in series. This is extremely advantageous since both compounds are highly reactive and thermally labile components. In comparison to the method described in the prior art, the new method according to the invention therefore leads to reduced expenditure on apparatus and energy and at the same time improved product quality.
  • the dividing wall column is characterized by a particularly low energy consumption and thus offers advantages in terms of energy consumption compared to a conventional column. This is extremely advantageous for industrial use.
  • Distillation columns with side draws and dividing wall also referred to below as dividing wall columns, are already known. They represent a further development of distillation columns that only have a side draw but no dividing wall.
  • the application of the last-mentioned column type is limited, however, because the products removed at the side take-off points are never completely pure.
  • the side product With side decreases in the reinforcement part In the column, which is usually carried out in liquid form, the side product still contains fractions of low-boiling components which are to be removed overhead.
  • the side product still has high boiler components.
  • the use of conventional side draw columns is therefore limited to cases in which contaminated side products are permitted.
  • a partition is attached in the middle area above and below the inlet point and the side removal point, whereby this can be welded tightly or just inserted. It seals the withdrawal section from the inlet section and prevents cross-mixing of liquid and vapor streams across the entire column cross section in this column section. This reduces the number of distillation columns required overall when separating multicomponent mixtures whose components have similar boiling points.
  • This type of column was used, for example, to separate a component stock from methane, ethane, propane and butane (US 2,471,134), to separate a mixture of benzene, toluene and xylene (US 4,230,533) and to separate a mixture of n-hexane, n- Heptane and n-octane (EP 0 122367).
  • Dividing wall columns can also be successfully used to separate azeotropic boiling mixtures (EP 0 133 510).
  • FIG. 1 shows schematically the intermediate separation of the oxirane formed in the oxirane synthesis from the excess hydroperoxide used in one Partition column shown.
  • the reaction mixture originating from oxirane synthesis is introduced into the column via feed Z.
  • said reaction mixture is separated into a low boiler fraction L, which essentially contains unreacted organic compound, into the medium boiler fraction, which contains the oxirane, and into a high boiler fraction S, which essentially contains unreacted hydroperoxide with solvent and water.
  • the oxirane is removed from the side draw for medium boiler M.
  • the organic compound used can be isolated from the low boiler fraction which distills off at the top of the column; . and reacted again with hydroperoxide in the devices provided for this purpose.
  • the medium boiler fraction with the oxirane as a valuable substance is removed in liquid or vapor form at the side take-off point. Both internal and external collecting spaces are suitable for removal from the side removal parts, in which the liquid or condensing steam can be collected.
  • the high boiler fraction which typically contains the hydroperoxide together with the solvent and water used, and is withdrawn via the bottom of the column, can be reacted again with the organic compound in the devices provided for this purpose.
  • the method described in WO 00/07965 and the device for carrying out the method are preferably used for the oxirane synthesis.
  • the device consists of an isothermal fixed bed reactor, a separation device and an adiabatic fixed bed reactor.
  • a system is thus possible with which both the oxirane can be produced continuously, isolated with continuous intermediate separation and unreacted starting materials can be returned to the oxirane synthesis.
  • the organic compound is reacted with the hydroperoxide in the isothermal reactor, and the reaction mixture is separated into the transferred to the wall column, the oxirane and the hydroperoxide being obtained from the high boiler fraction via the side draw.
  • the latter compound is then reacted again with the organic compound in the adiabatic reactor in a second stage.
  • propylene is reacted as an organic compound, this can also be used as a starting material recovered via the top of the column.
  • the process according to the invention is suitable for the preferably continuous intermediate separation of an oxirane from a product mixture which is produced by a process comprising at least steps (i) to (iii):
  • step (i) reacting the hydroperoxide with the organic compound to obtain a product mixture comprising the reacted organic compound and unreacted hydroperoxide, (ii) separating the unreacted hydroperoxide from the mixture resulting from step (i), (iii) reacting the separated hydroperoxide from step (ii) with the organic compound.
  • Conventional dividing wall columns with one or more side draws can be used to carry out the process according to the invention.
  • Such a dividing wall column has, for example, preferably 10 to 70, particularly preferably 15 to 50, particularly preferably 20 to 40 theoretical plates. With this embodiment, the method according to the invention can be carried out particularly cheaply.
  • the upper common section 1 of the inlet and outlet section of the dividing wall column preferably has 5 to 50%, particularly preferably 15 to 30%, and the reinforcing section 2 of the inlet section preferably 5 to 50, particularly preferably 15 to 30%, the stripping section 4 of the inflow section preferably 5 to 50%, particularly preferably 15 to 30%, the stripping section 3 of the removal section preferably 5 to 50%, particularly preferably 15 to 30%, the reinforcement section 5 of the removal section preferably 5 to 50%, particularly preferably 15 to 30%, and the common lower section 6 of the feed and withdrawal section preferably 5 to 50%, particularly preferably 15 to 30%, of the total number of theoretical plates in the column.
  • the sum of the number of theoretical plates of sub-areas 2 and 4 in the feed section is preferably 80 to 110%, particularly preferably 90 to 100%, the sum of the number of separators of sub-areas 3 and 5 in the removal section.
  • the inlet point is preferably arranged 1 to 8, particularly preferably 3 to 5, theoretical plates higher or lower than the side take-off point.
  • the dividing wall column used in the process according to the invention can preferably be carried out both as a packed column with packing or ordered packings and as a tray column.
  • packing or ordered packings For example, sheet metal or fabric packs with a specific surface area of 100 to 1000 m 2 / m 3 , preferably about 250 to 750 m 2 / m 3 , can be used as ordered packs.
  • Such packings offer a high separation performance with a low pressure loss per separation stage.
  • the section of the column subdivided by the dividing wall 7, consisting of the reinforcing part 2 of the inlet part, the stripping part 3 of the removal part, the stripping part 4 of the inlet part and the reinforcing part 5 or parts thereof, is preferably with ordered packings or fillers, and the partition is made heat-insulating in these sections.
  • the mixture obtained in the oxirane synthesis which consists of low boilers L, medium boilers and high boilers S, is then introduced continuously into the column via feed Z. This feed stream is generally liquid.
  • the feed stream may be advantageous to subject the feed stream to pre-evaporation and then to feed it to the column in two phases, ie in gaseous and liquid form or in the form of a gaseous and a liquid stream.
  • This pre-evaporation is particularly useful when the feed stream contains large amounts of low boilers L.
  • the stripping section of the column can be substantially relieved by the pre-evaporation.
  • the feed stream is expediently fed into the feed part in a quantity-controlled manner by means of a pump or via a static feed height of at least 1 m.
  • This addition is preferably carried out via a cascade control in conjunction with the liquid level control of the collecting space of the inlet part.
  • the control is set in such a way that the amount of liquid applied to the reinforcement part 2 cannot drop below 30% of the normal value. It has been shown that such a procedure is important for compensating for disturbing fluctuations in the feed quantity or feed concentration.
  • Control mechanisms for operating dividing wall columns have been described, for example, in Chem. Eng. Technol. 10 (1987) 92-98, Chem.-Ing.-Technol. 61 (1989) No. 1, 16-25, Gas Separation and Purification 4 (1990) 109-114, Process Engineering 2 (1993) 33-34, Trans IChemE 72 (1994) Part A 639- 644, Chemical Engineering 7 (1997) 72-76.
  • the control mechanisms specified in this prior art can also be used for the method according to the invention or can be transferred to it.
  • the control principle described below has proven to be particularly favorable for the continuous intermediate separation of the oxirane from the excess hydroperoxide used. It is able to cope with load fluctuations.
  • the distillate is therefore preferably removed in a temperature-controlled manner.
  • a temperature control is provided in the upper column part 1, which uses the runoff quantity, the reflux ratio or preferably the reflux quantity as the manipulated variable.
  • the measuring point for the temperature control is preferably 3 to 8, particularly preferably 4 to 6, theoretical plates below the upper end of the column.
  • a suitable temperature setting then divides the liquid flowing out of the column part 1 at the upper end of the dividing wall such that the ratio of the liquid flow to the inlet part to that to the removal part is preferably 0.1 to 1.0, particularly preferably 0.3 to 0 , 6, is.
  • the outflowing liquid is preferably collected in a collecting space arranged in or outside the column, from which it is then fed continuously into the column.
  • This collecting space can thus take over the task of a pump supply or ensure a sufficiently high static liquid level, which enables a liquid transfer regulated by actuators, for example valves.
  • actuators for example valves.
  • the vapor flow at the lower end of the partition is adjusted by the choice and / or dimensioning of the partition internals and / or the installation of pressure-reducing devices, for example, orifices, so that the ratio of the Vapor flow in the inlet part to that of the withdrawal part is preferably 0.8 to 1.2, preferably 0.9 to 1.1.
  • a temperature control is also provided in the lower common column part 6, which uses the amount of sump withdrawn as the manipulated variable.
  • the bottom product can thus be removed in a temperature-controlled manner.
  • the measuring point for the temperature control is preferably arranged by 3 to 6, particularly preferably 4 to 6, theoretical plates above the lower end of the column.
  • the above-mentioned level control on the column part 6 with the column sump can be used as a manipulated variable for the side draw quantity.
  • the liquid level in the evaporator is used as the control variable.
  • the differential pressure across the column can also be used as the manipulated variable for the heating output.
  • the distillation is advantageously carried out at a top pressure between 0.5 and 5 bar, preferably between 0.7 and 2 bar. Accordingly, the heating capacity of the evaporator on the column bottom is selected to maintain this pressure range.
  • the resulting distillation temperature is preferably 10 to 60 ° C, particularly preferably 25 to 45 ° C. It is measured at the side deduction point.
  • the process according to the invention is characterized in that the top pressure in the dividing wall column is 0.5 to 5 bar.
  • the process according to the invention is also characterized in that the distillation temperature at the side draw is 10 to 60 ° C.
  • Compliance with the specification for the high boilers in the medium boiler fraction is preferably regulated via the distribution ratio of the amount of liquid at the top end of the partition.
  • the distribution ratio is set so that the concentration of key components for the high boiler fraction in the liquid at the upper end of the partition is 10 to 80% by weight, preferably 30 to 50% by weight, of the value which is to be achieved in the side draw ,
  • the liquid distribution can then be adjusted such that more liquid is fed to the feed section at higher contents of key components of the high boiler fraction and less liquid at lower contents of key components.
  • the specification for the low boilers in the medium boiler fraction is regulated accordingly by the heating power.
  • the heating power in the evaporator is set so that the concentration of key components for the low boiler fraction in the liquid at the lower end of the partition is 10 to 80% by weight, preferably 30 to 50% by weight, of the value which is achieved in the side take-off product shall be.
  • the heating power is thus adjusted such that the heating power increases when the key component content of the low boiler fraction is higher and the heating power is reduced when the key component content of the low boiler fraction is lower.
  • the concentration of low and high boilers in the medium boiler fraction can be determined using standard analysis methods. For example, infrared spectroscopy can be used for detection, the compounds present in the reaction mixture being identified on the basis of their characteristic absorptions. These measurements can be made inline directly in the column. men. However, gas chromatographic methods are preferably used. It is then provided that the upper and lower ends of the partition have sampling options. Thus, liquid or gaseous samples can be taken from the column continuously or at intervals and their composition can be examined. Depending on the composition, the appropriate control mechanisms can then be used.
  • the dividing wall column it is also possible not to combine the feed section and the removal section, which are separated from one another by the dividing wall 7, in one column, but to separate them spatially.
  • the dividing wall column can also consist of at least two columns which are spatially separated from one another, but which must then be thermally coupled to one another.
  • thermally coupled columns exchange steam and liquid with one another, but the energy is supplied only via one column.
  • This special design offers the advantage that the thermally coupled columns can also be operated at different pressures, and an even better setting of the temperature level required for the distillation can be possible than in the conventional dividing wall column.
  • FIGS. 2 and 3 Examples of dividing wall columns in the special design of the thermally coupled columns are shown schematically in FIGS. 2 and 3.
  • FIG. 2 shows a variant in which the energy is supplied via the evaporator V of the column, which is connected downstream of the column via which the product mixture is fed in via the feed Z.
  • the product mixture in the first column is first separated into a low and high boiler fraction, which also contain medium boilers.
  • the resulting fractions are then walked transferred into the second column, the low boiler fraction containing the middle boilers at the upper end and the high boiler fraction containing the middle boilers are fed at the lower end of the second column.
  • the low boilers L are distilled off over the top of the column and isolated via the condenser K.
  • the high boilers S are obtained via the bottom of the column.
  • the cleaned propylene oxide can be removed from the side draw for medium boiler M. Both columns can exchange steam and liquid via d and f.
  • FIG 3 shows a further variant of thermally coupled columns.
  • the energy is supplied via the evaporator V of the column into which the reaction mixture is also fed via the feed Z.
  • the low boilers L are distilled off over the top of this column and condensed with the aid of the condenser K.
  • the high boilers S are obtained with the swamp.
  • Low boilers L enriched with medium boilers are now transferred to the upper part of the downstream column, high boilers S enriched with medium boilers into the lower part of the downstream column.
  • the cleaned propylene oxide can be removed from the side draw for medium boiler M.
  • Both columns can exchange steam and liquid via d and f.
  • the columns according to FIGS. 2 and 3 can also be designed as packed columns with packing elements or ordered packings or as tray columns.
  • packing elements for example, sheet metal or fabric packs with a specific surface area of 100 to 1000 m / m 3 , preferably about 250 to 750 m 2 / m 3 , can be used as ordered packs.
  • Such packings offer high separation performance with low pressure loss per separation stage.
  • the process according to the invention relates to the intermediate separation of propylene oxide, it should be obtained in a purity of preferably at least 95% by weight.
  • concentration of the key components in the low boilers (e.g. acetaldehyde, methyl formate) and the key components in the high boilers (e.g. methanol, water, propylene glycol) in the product should then preferably be below 5% by weight, the sum of Oxirane and key components gives 100 wt .-%.
  • the present invention also relates to a method as described above which is characterized in that the sum of the key components in the purified oxirane is less than 5% by weight, the total sum of oxirane and the components contained in the oxirane being 100% by weight. % results.
  • the starting materials known from the prior art can be used for the oxirane synthesis for the process according to the invention for the continuous intermediate separation of the oxirane formed in the coproduct-free oxirane synthesis in a dividing wall column.
  • Organic compounds which have at least one C-C double bond are preferably reacted.
  • alkenes are mentioned as examples of such organic compounds with at least one C-C double bond:
  • Alkenes containing 2 to 8 carbon atoms are preferably used. Ethene, propylene and butene are particularly preferably reacted. Propylene is particularly preferably reacted.
  • the known hydroperoxides which are suitable for the reaction of the organic compound can be used as the hydroperoxide. Examples of such hydroperoxides are, for example, tert-butyl hydroperoxide or ethylbenzene hydroperoxide.
  • Hydrogen peroxide is preferably used as the hydroperoxide for the oxirane synthesis, it also being possible to use an aqueous hydrogen peroxide solution.
  • the anthraquinone process can be used to produce hydrogen peroxide, according to which practically the entire amount of hydrogen peroxide produced worldwide is produced.
  • This process is based on the catalytic hydrogenation of an anthraquinone compound to the corresponding anthrahydroquinone compound, subsequent reaction of the same with oxygen to form hydrogen peroxide and subsequent separation of the hydrogen peroxide formed by extraction.
  • the catalytic cycle is closed by renewed hydrogenation of the re-formed anthraquinone compound.
  • Catalysts are preferably used which have a porous oxidic material, such as. B. a zeolite. Catalysts are preferably used which comprise a zeolite containing titanium, germanium, tellurium, vanadium, chromium, niobium or zirconium as the porous oxidic material.
  • Zeolites with pentasil-zeolite structure containing titanium, germanium, tellurium, vanadium, chromium, niobium, and zirconium in particular the types with X-ray assignment to ABW, ACO, AEI, AEL -, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ATN, ATO, ATS, ATT, ATV, AWO, AWW, BEA, BIK, BOG, BPH, BRE, CAN, CAS, CFI, CGF, CGS , CHA, CHI, CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV -, EUO, FAU, FER, GIS, GME, GOO, HEU, IFR,
  • Titanium-containing zeolites with the structure of rTQ-4, SSZ-24, TTM-1, UTD-1, ClT-1 or C ⁇ T-5 are also conceivable for use in the process according to the invention. Further titanium-containing zeolites are those with the structure of ZSM-48 or ZSM-12.
  • Ti zeolites with an MFI, MEL or MFI / MEL mixed structure are particularly preferred.
  • the titanium-containing zeolite catalysts which are generally referred to as “TS-1”, “TS-2”, “TS-3”, are very particularly preferred. are referred to, as well as Ti zeolites with a framework structure isomorphic to ⁇ -zeolite.
  • a heterogeneous catalyst which comprises the titanium-containing silicalite TS-1.
  • porous oxidic material per se as a catalyst.
  • a shaped body as the catalyst which comprises the porous oxidic material. All processes according to the prior art can be used to produce the shaped body, starting from the porous oxidic material.
  • noble metals in the form of suitable noble metal components can be applied to the catalyst material.
  • This method is preferably used to produce oxidation catalysts based on titanium or vanadium silicates with a zeolite structure, it being possible to obtain catalysts which contain from 0.01 to 30% by weight of one or more noble metals from the group ruthenium, Rhodium, palladium, osmium, iridium, platinum, rhenium, gold and silver.
  • Such catalysts are described for example in DE-A 196 23 609.6.
  • the moldings can also be assembled. All methods of comminution are conceivable, for example by splitting or breaking the shaped bodies, as are further chemical treatments, as described above, for example.
  • a shaped body or more of it can be regenerated in the process according to the invention after deactivation by a process in which the regeneration is carried out by deliberately burning off the deposits responsible for the deactivation. It is preferably carried out in an inert gas atmosphere which contains precisely defined amounts of oxygen-removing substances.
  • This regeneration process is described in DE-A 197 23 949.8 described. Furthermore, the regeneration processes specified there with respect to the prior art can be used.
  • solvents which completely or at least partially dissolve the starting materials used in the oxirane synthesis can preferably be used as solvents.
  • solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons, esters, ethers, amides, sulfoxides and ketones and alcohols.
  • the solvents can also be used in the form of mixtures. Alcohols are preferably used.
  • methanol as a solvent is particularly preferred.
  • reactors for the oxirane synthesis are not restricted to a single vessel. Rather, it is also possible to use a cascade of stirred tanks, for example.
  • Fixed-bed reactors are preferably used as reactors for the oxirane synthesis.
  • Fixed-bed tube reactors are further preferably used as fixed-bed reactors.
  • an isothermal fixed bed reactor is used as the reactor for stage (i) and an adiabatic fixed bed reactor for stage (iii).
  • the oxiranes used for the process according to the invention are preferably produced in an isothermal fixed bed reactor and an adiabatic fixed bed reactor, the intermediate separation taking place in a dividing wall column.
  • FIG. 4 A dividing wall column with two side draws is sketched in FIG. 4.
  • the lower-boiling oxirane at the upper side-take-off point M1 and the higher-boiling oxirane at the lower side-take-off point M2 are removed from the superimposed side draws.
  • the area of thermal coupling 8 preferably has five to fifty, more preferably fifteen to thirty percent of the total number of theoretical plates in the column.
  • the invention also relates to a device for carrying out a continuously operated process for the intermediate separation of the oxirane formed in the oxirane synthesis by reaction of a hydroperoxide with an organic compound.
  • a preferred embodiment of a device for carrying out a continuously operated process for the intermediate separation of the oxirane formed in the oxirane synthesis by reacting a hydroperoxide with an organic compound is characterized in that the device for producing the oxirane has at least one isothermal and one adiabatic reactor for the process of stages (i) and (iii) and a separation apparatus for stage (ii), the separation device consisting of a dividing wall column with one or two side draws or at least two columns thermally coupled to one another.
  • Horizontal and diagonal or diagonally indicated lines in the columns symbolize packs with packing or ordered packs that may be present in the column.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de séparation intermédiaire, guidé en continu, d'oxirane obtenu lors de la synthèse d'oxirane, par réaction d'un hydropéroxyde avec un composé organique. Le procédé selon l'invention est caractérisé en ce que le mélange de produit obtenu lors de la synthèse est séparé dans une colonne à membrane en une fraction à point d'ébullition bas, une fraction à point d'ébullition moyen, et une fraction à point d'ébullition élevé, l'oxirane est prélevé de la fraction à point d'ébullition moyen sur la zone d'extraction latérale de la colonne, et l'hydropéroxyde est prélevé de la fraction à point d'ébullition élevé avec le produit de bas de colonne.
EP03765088A 2002-07-23 2003-07-22 Procede de separation intermediaire guidee en continu d'oxirane obtenu lors de la synthese d'oxirane exempte de produits de couplage au moyen d'une colonne a membrane Withdrawn EP1527058A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10233383 2002-07-23
DE10233383A DE10233383A1 (de) 2002-07-23 2002-07-23 Verfahren zur kontinuierlich betriebenen Zwischenabtrennung des bei der koppelproduktfreien Oxiransynthese entstehenden Oxirans unter Verwendung einer Trennwandkolonne
PCT/EP2003/007989 WO2004009569A1 (fr) 2002-07-23 2003-07-22 Procede de separation intermediaire guidee en continu d'oxirane obtenu lors de la synthese d'oxirane exempte de produits de couplage au moyen d'une colonne a membrane

Publications (1)

Publication Number Publication Date
EP1527058A1 true EP1527058A1 (fr) 2005-05-04

Family

ID=30128271

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03765088A Withdrawn EP1527058A1 (fr) 2002-07-23 2003-07-22 Procede de separation intermediaire guidee en continu d'oxirane obtenu lors de la synthese d'oxirane exempte de produits de couplage au moyen d'une colonne a membrane

Country Status (9)

Country Link
US (1) US20060014969A1 (fr)
EP (1) EP1527058A1 (fr)
CN (1) CN1671676A (fr)
AU (1) AU2003257488A1 (fr)
CA (1) CA2493273A1 (fr)
DE (1) DE10233383A1 (fr)
MX (1) MXPA05000576A (fr)
WO (1) WO2004009569A1 (fr)
ZA (1) ZA200500606B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI586693B (zh) 2013-07-23 2017-06-11 財團法人工業技術研究院 選擇性氫化共聚物的方法
US9504934B2 (en) 2013-10-27 2016-11-29 Purdue Research Foundation Multicomponent dividing wall columns
CN118176186A (zh) * 2021-11-30 2024-06-11 陶氏环球技术有限责任公司 简化的环氧乙烷纯化方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2471134A (en) * 1946-07-17 1949-05-24 Standard Oil Dev Co Fractionation apparatus
US4230533A (en) * 1978-06-19 1980-10-28 Phillips Petroleum Company Fractionation method and apparatus
DE3314395A1 (de) * 1983-04-21 1984-10-25 Basf Ag, 6700 Ludwigshafen Verfahren zur durchfuehrung von chemischen reaktionen und gleichzeitiger destillativer zerlegung eines produktgemisches in mehrere fraktionen mittels einer destillationskolonne
DE19835907A1 (de) * 1998-08-07 2000-02-17 Basf Ag Verfahren zur Umsetzung einer organischen Verbindung mit einem Hydroperoxid
DE10002514A1 (de) * 2000-01-21 2001-07-26 Degussa Verfahren zur Herstellung von Olefinoxiden in der Gasphase
DE10021624A1 (de) * 2000-05-04 2001-11-08 Basf Ag Trennwandkolonne
FR2810982B1 (fr) * 2000-06-28 2002-09-27 Solvay Procede de fabrication d'oxiranne comprenant la separation de l'oxiranne du milieu reactionnel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004009569A1 *

Also Published As

Publication number Publication date
WO2004009569A1 (fr) 2004-01-29
US20060014969A1 (en) 2006-01-19
CA2493273A1 (fr) 2004-01-29
MXPA05000576A (es) 2005-04-19
AU2003257488A1 (en) 2004-02-09
CN1671676A (zh) 2005-09-21
DE10233383A1 (de) 2004-02-12
ZA200500606B (en) 2006-03-29

Similar Documents

Publication Publication Date Title
EP1526904B1 (fr) Procede de distillation pure operee en continu d'oxiranes, en particulier d'oxyde de propylene
EP1527057B1 (fr) Procede de fabrication continue de propylene glycols
EP1527060B1 (fr) Procede de purification par distillation en continu du 1,2-propylene glycol produit au cours de la synthese d'oxyde de propylene sans co-produits
EP1377562B1 (fr) Procede pour produire un epoxyde
WO2000007965A1 (fr) Procede permettant de transformer un compose organique au moyen d'un hydroperoxyde
EP1268456A1 (fr) Procede pour faire reagir un compose organique avec un hydroperoxyde
EP1527055B1 (fr) Procede de purification par distillation en continu du methanol, solvant employe pour la synthese d'oxyde de propylene
EP1412339B1 (fr) Procede de preparation d'oxyde de propylene
WO2004037803A1 (fr) Procede pour la production en continu d'epoxydes a partir d'olefines et de peroxydes d'hydrogene sur un catalyseur en suspension
EP1527061A1 (fr) Procede de distillation guidee en continu du solvant employe lors de la synthese d'oxirane exempte de produits de couplage
WO2004009569A1 (fr) Procede de separation intermediaire guidee en continu d'oxirane obtenu lors de la synthese d'oxirane exempte de produits de couplage au moyen d'une colonne a membrane
WO2004013116A1 (fr) Procede de production d'oxyde de propylene a l'aide d'un reacteur complementaire comportant plusieurs points d'alimentation et/ou d'exploitation
DE10233386A1 (de) Verfahren zur kontinuierlich betriebenen Reindestillation des bei der koppel-produktfreien Propylenoxidsynthese verwendeten Lösungsmittels Methanol unter gleichzeitiger Abtrennung der Methoxypropanole
EP1620415A1 (fr) Procede de production d'un oxyde d'alcene

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050223

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

17Q First examination report despatched

Effective date: 20050602

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20050602

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20070411