WO2004020423A1 - Integriertes verfahren zur synthese von propylenoxid - Google Patents
Integriertes verfahren zur synthese von propylenoxid Download PDFInfo
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- WO2004020423A1 WO2004020423A1 PCT/EP2003/009616 EP0309616W WO2004020423A1 WO 2004020423 A1 WO2004020423 A1 WO 2004020423A1 EP 0309616 W EP0309616 W EP 0309616W WO 2004020423 A1 WO2004020423 A1 WO 2004020423A1
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- partial stream
- propane
- propene
- hydrogen
- propylene oxide
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- 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 an integrated process for the synthesis of propylene oxide.
- the starting materials of the propylene synthesis are prepared via at least the steps propane dehydrogenation and direct hydrogen peroxide synthesis and converted to propylene oxide.
- propylene oxide has mainly been produced by the chlorohydrin process and by indirect oxidation processes using hydroperoxides.
- the major disadvantages of these two processes are, for example, the wastewater or by-product problem in the chlorohydrin process and the production of cooxidates in large quantities in a process using indirect oxidation.
- the invention was based on the object of providing a further process for the integrated synthesis of propylene oxide.
- the invention thus relates to an integrated process for the synthesis of propylene oxide, which comprises at least the following steps:
- FIG. 1 A preferred embodiment of the procedure, i.e. the essential steps comprising the method are shown schematically in FIG. 1 (FIG. 1).
- the present invention relates to an expanded integrated process for the synthesis of propylene oxide, characterized in that the process comprises at least the following steps:
- FIG. 2 A preferred embodiment of the process control of the extended integrated process for the synthesis of propylene oxide, i.e. the essential steps comprising the method are shown schematically in FIG. 2 (FIG. 2).
- Step (i) or step (a) of the process according to the invention comprises propane dehydrogenation to obtain a substream T (0) which comprises at least propane, propene and hydrogen.
- propane dehydrogenation in question can in principle be carried out in the context of the process according to the invention by all processes known to the person skilled in the art for the dehydrogenation of propane, such as steam cracking or catalytic cracking processes and in particular also catalytic dehydrogenation in the absence or presence of mixtures containing oxygen or oxygen become.
- the dehydrogenation ie the cleavage of a CH bond is generally kinetically disadvantageous compared to the cracking, ie the cleavage of a CC bond
- it is preferably carried out on catalysts which are selective for the dehydrogenation. These are usually of such a nature that a good yield of dehydrogenation products is obtained with the exclusion of oxygen in the temperature range listed above.
- the propylene yield is at least 30 with a propane load on the catalysts of, for example, 1000 h "1 (ie standard liters of propane per liter of catalyst and hour) mol .-%, based on the propane used in a single pass.
- By-products such as methane, ethylene and ethane are only produced in minor quantities.
- the turnover can in principle be increased by lowering the partial pressure of the products. This can be achieved in a simple manner, for example by carrying out the dehydrogenation under reduced pressure and / or by admixing essentially inert diluent gases.
- water vapor is such an inert diluent gas that is preferably used.
- Other diluent gases suitable for propane dehydrogenation are, for example, CO 2 , N 2 and noble gases such as He, Ne and Ar.
- water vapor As a further advantage, dilution with water vapor generally results in reduced coking of the catalyst used, since the water vapor reacts with coke which may form according to the principle of coal gasification. Furthermore, water vapor can easily be partially or completely separated from the product mixture. Accordingly, it is possible within the scope of the present invention to use water vapor as a diluent in the propane dehydrogenation to separate it from the product stream T (0), for example by condensation.
- dehydrogenation catalysts known to the person skilled in the art for this purpose can be used for the propane dehydrogenation in step (i) or step (a).
- examples are catalysts of an oxidic nature, which have chromium oxide and / or aluminum oxide, or those which consist of at least one largely noble metal, e.g. Platinum.
- dehydrogenation catalysts described in the following publications can be used in the context of the present invention: WO 99/46039, US 4,788,371, EP-A 705 136, WO 99/29420, US 5,220,091,
- dehydrogenation catalysts described in the examples of DE 199 37 107 can also be used. These are dehydrogenation catalysts which contain 10 to 99.9% by weight of zirconium dioxide, 0 to 60% by weight of aluminum oxide, silicon dioxide and / or titanium dioxide and 0.1 to 10% by weight of at least one element of the first or second main group, the third or eighth subgroup of the periodic table of the elements containing lanthanum and / or tin, with the proviso that the sum of the weight percent is 100.
- the procedure described in DE 195 30 45 for heterogeneously catalyzed oxydehydrogenation of propane to propene can also be carried out as part of the propane dehydrogenation.
- the propane is converted to propene in a fixed bed or fluidized bed reactor filled with catalyst in the presence of air or an oxygen-containing mixture.
- all of the oxydehydrogenation processes that can be used in the context of the invention can be carried out in at least one reaction vessel filled with catalytically active substance, for example a fixed bed or a fluidized bed reactor.
- the propane is converted to propene on the catalytically active substance used in each case via reaction steps known to the person skilled in the art.
- propane dehydrogenation in the context of the process according to the invention is the Oleflex TM process or processes similar to it.
- the propane used, mixed with pure or recycled hydrogen is comprised of at least one suitable catalyst in at least one reactor - Analyzer bed, converted to propene.
- propane can be partially or almost completely dehydrogenated to propene in the presence of a dehydrogenation catalyst.
- a product gas mixture is formed which, in addition to unreacted propane and the propene formed, contains secondary constituents such as hydrogen, water, further cracked products of the propane, CO and CO 2 .
- the propane dehydrogenation can be carried out with or without an oxygen-containing gas as a co-feed.
- the partial heterogeneously catalyzed dehydrogenation of propane is usually endothermic, i.e.
- the heat / energy required to set the required reaction temperature is supplied to the reaction gas beforehand and / or during the catalytic dehydrogenation.
- the starting material propane can be diluted with hydrogen in the context of the present invention, it being possible for the carbon which is formed to be largely eliminated on the principle of carbon hydrogenation.
- a reactor form suitable for the process in step (i) or step (a) in the context of the present invention is the fixed-bed tube or tube bundle reactor.
- the catalyst is located as a fixed bed in a reaction tube or in a bundle of reaction tubes.
- the propane dehydrogenation can be carried out in the absence of oxygen or, if suitable catalyst formulations are used, also with the addition of oxygen as a co-feed.
- the reaction tubes can be heated in that a gas, for example a hydrocarbon such as methane, is burned in the space surrounding the reaction tubes.
- the gaseous partial stream T (6) resulting from step (iii) can be used entirely or partially burned to generate energy and the energy within the propane dehydrogenation is used, for example, for indirect heating of the reaction tubes in question.
- the catalyst Since the catalyst generally deactivates more or less quickly through coking, depending on the gas load and conversion, it is advantageous to regenerate it at regular intervals.
- the partial stream T (6) resulting from step (iii) can be used for regeneration. Further regeneration processes which can be used according to the invention are described in WO 98/55430 and the prior art cited therein.
- the propane dehydrogenation can be carried out in a moving bed reactor.
- the moving catalyst bed can, for example, be accommodated in a radial flow reactor. In this, the catalyst moves slowly from top to bottom, while the reaction gas mixture flows radially. Since the reactors are operated practically adiabatically in this process, it is expedient to operate several reactors connected in series.
- the inlet mixture Before each reactor, the inlet mixture can be heated to the required reaction temperature by indirect heating. It is also possible to heat the inlet gas mixture in each reactor to the required reaction temperature by burning hydrogen in the presence of supplied oxygen (autothermal procedure).
- autothermal procedure it is advantageous to wholly or partly use the partial stream T (6) or T (6a) resulting from step (iii) to heat the inlet gas mixture or as part of the propane dehydrogenation of step (a) to support an autothermal procedure.
- the catalyst bed Has left the reactor it is fed to the regeneration and then used again.
- the regeneration of the catalyst in the moving bed reactor is usually carried out in a continuous manner. All or part of the spent catalyst is discharged at the end of each reactor, in particular at the end of the last reactor, and at least fed to a subsequent regeneration step. After the regeneration, the catalyst is fed back in at the beginning of each reactor, in particular at the beginning of the first reactor.
- the heterogeneously catalyzed, propane dehydrogenation carried out in a fluidized bed also represents a possible procedure for propane dehydrogenation in the context of the present invention
- the process does not require dilution of the propane.
- two fluidized beds are expediently operated side by side, one of which is generally in the state of regeneration.
- the regeneration of the fluidized beds can be carried out in the context of a preferred embodiment of the integrated process for the synthesis of propylene oxide by recycling the partial stream T (6) resulting from step (iii).
- the heat required for the dehydrogenation is introduced into the reaction system in which the dehydrogenation catalyst is preheated to the reaction temperature.
- the preheating can also be carried out by means of the partial stream T (6) from step (iii) burned entirely or partially for energy.
- step (e) of the extended integrated process for the synthesis of propylene oxide according to the invention is returned in a further step (f) to step (a) comprising the propane dehydrogenation and thus a largely autothermal mode of operation of the propane dehydrogenation allows.
- step (a) comprising the propane dehydrogenation and thus a largely autothermal mode of operation of the propane dehydrogenation allows.
- a hydrogen-containing co-feed can also be added.
- a tray reactor contains one or more successive catalyst beds, which through which the reaction gas flows, preferably radially or axially.
- Such a tray reactor is generally operated with a fixed catalyst bed.
- the fixed catalyst beds are arranged axially in a shaft furnace reactor or in the annular gaps of cylindrical grids placed one inside the other.
- a shaft furnace reactor corresponds to a horde.
- the reaction gas mixture in the tray reactor is subjected to intermediate heating on its way from one catalyst bed to the next catalyst bed, for example by passing it over heat exchanger surfaces heated with hot gases or by passing it through pipes heated with hot fuel gases.
- step (a) the propane dehydrogenation, autothermally.
- an oxygen-containing gas is additionally mixed into the reaction mixture of the propane dehydrogenation in at least one reaction zone and the hydrogen contained in the reaction gas mixture is burned, as a result of which at least some of the heat of dehydrogenation required is generated directly in the reaction mixture in the at least one reaction zone.
- the gaseous, hydrogen-containing partial stream T (6a) obtained in step (e) is completely or partially returned to step (a) and burned.
- step (a) By regulating the amount of oxygen added by means of partial stream T (6a), it is possible to control the reaction temperature within step (a). At the same time, it is possible to control the selectivity of the propane dehydrogenation in step (a) by regulating the amount of hydrogen added by means of partial stream T (6a).
- the amount of oxygen-containing gas added to the reaction gas mixture increases the amount of heat required for the dehydrogenation of the propane to propene, which is generated by the combustion of the hydrogen present in the reaction gas mixture and possibly of hydrocarbons present in the reaction gas mixture and / or of carbon present in the form of coke. regulated.
- oxygen can either as molecular oxygen or as an oxygen-containing gas, u. a. can also be used in a mixture with inert gases.
- molecular oxygen additionally supplied is used in this connection.
- the oxygen-containing gas in question is the partial stream T (6a) resulting from the hydrogen peroxide synthesis in step (e).
- the inert gases and the resulting combustion gases generally have an additional dilution effect and thus promote heterogeneously catalyzed dehydrogenation.
- the hydrogen burned to generate heat can be the hydrogen formed in the hydrocarbon dehydrogenation and the hydrogen additionally added to the reaction gas mixture, for example the hydrogen-containing partial stream T (6a) originating from step (e) in the expanded integrated process for the synthesis of propylene oxide according to the invention.
- the dehydrogenation catalyst and the oxidation catalyst are preferably present in different reaction zones. If the reaction is carried out in several stages, the oxidation catalyst can be present in only one, in several or in all reaction zones.
- the catalyst which selectively catalyzes the oxidation of hydrogen in the presence of hydrocarbons, is preferably arranged at the points where the oxygen partial pressures are higher than at other points in the reactor, in particular in the vicinity of the feed point for the oxygen-containing gas.
- Oxygen-containing gas and / or hydrogen can be fed in at one or more points in the reactor.
- a preferred catalyst which selectively catalyzes the use of hydrogen usually contains oxides or phosphates selected from the group consisting of the oxides or phosphates of germanium, tin, lead, arsenic, antimony and bismuth.
- Another preferred catalyst that catalyzes the combustion of hydrogen contains at least one noble metal from the VLIL subgroup of the Periodic Table of the Elements.
- Examples of such catalysts include described in the following documents: US-A 4,788,371, US-A 4,886,928, US-A 5,430,209, US-A 5,530,171, US-A 5,527,979 and US-A 5,563,314.
- the propane dehydrogenation is preferably carried out in the presence of steam.
- the added water vapor serves as a heat carrier and supports the gasification of organic deposits on the catalysts, which counteracts the coking of the catalysts and increases the service life of the catalyst.
- the organic deposits are converted into carbon monoxide and carbon dioxide.
- the propane dehydrogenation is preferably carried out in the tray process, a largely autothermal and therefore inexpensive process being made possible in the context of the expanded integrated process for the synthesis of propylene oxide by the combustion of the hydrogen supplied by the partial stream T (6a).
- the quality of the propane used is in principle not critical.
- the propane used can be fresh or recycled propane, which may also contain other by-products which do not significantly influence the dehydrogenation process.
- the propane dehydrogenation process can also be carried out continuously or batchwise.
- the partial stream T (0) resulting from this step has at least propene, propane and hydrogen.
- T (0) may also have gases as by-products selected from the group consisting of N, H 2 O, methane, ethane, ethylene, CO and CO 2> individually or as a mixture of two or more from this group.
- the ratio of propane to propene in partial stream T (0) is in the range from 0.1 to 10, preferably 0.5 to 5, particularly preferably 1.0 to 2.0.
- the ratio of hydrogen to propene in partial stream T (0) is in the range from 0 to 1.5, preferably 0.3 to 1.3, particularly preferably about 1.1.
- the hydrogen peroxide synthesis T (6) or T (6a)
- the ratio of hydrogen to propene is preferably 0.4 to 2.0.
- partial or partial flow T (0) is transferred in step (ii) or in step (b) using suitable means known to those skilled in the art, for example line devices in the form of tubes, or in step (b) in the expanded integrated process for the synthesis of propylene oxide.
- partial stream T (0) may be fed to a separation device in an intermediate step following step (i) or step (a).
- the by-products which T (0) may have in the course of the propane dehydrogenation can be separated off in this.
- Step (ii) or step (b) comprises the separation of the partial stream T (0) to obtain at least one gaseous hydrogen-rich partial stream T (2) and a liquid partial stream T (1) which contains at least propene and propane.
- the partial stream T (0) can in principle be separated using any of the methods known to the person skilled in the art and technically possible for the present case, using the respectively suitable devices.
- the separation can be carried out using the device described in DE 100 28 582.1.
- the separation of T (1) from partial stream T (0) via step (ii) or step (b) can be carried out in such a way that the preferably cooled partial stream T (0) is brought into contact with a preferably hydrophobic organic solvent, in which the components propane and propene at least contained in T (1) can preferably be absorbed.
- the at least hydrogen partial stream T (2) represents the exhaust gas of the absorption.
- the absorption can be carried out both in columns and in rotary absorbers. You can work in cocurrent or in countercurrent. Suitable absorption columns are e.g. Tray columns, columns with structured packing and packed columns. Of course, however, trickle and spray towers, granite block absorbers, surface absorbers such as thick-film and thin-film absorbers as well as rotary columns, plate washers, cross-curtain washers and rotary washers can also be used.
- absorbents which appear suitable to the person skilled in the art for this purpose can be used.
- relatively non-polar organic solvents which preferably do not receive any polar groups which act on the outside, for example aliphatic (for example C 8 -C 18 -alkanes), but also aromatic hydrocarbons, for example middle oil fractions from paraffin distillation, or else ethers with bulky groups arranged on the oxygen atom. Mixtures of two or more of the solvents listed are also suitable. Further solvents or solvent mixtures which can be used as absorbents in the context of the invention are listed in DE 100 28 582.1.
- a in the present invention preferably as an absorbent solvent mixture employed comprises diphenyl and diphenyl ether, preferably in the azeotropic composition, in particular from about 25 wt .-% diphenyl (biphenyl) and about 75% by weight of diphenyl ether (Diphyl ®) on.
- partial stream T (0) is preferably separated into partial streams T (1) and T (2) by condensation.
- heat exchangers for example surface condensers or condensers with direct or indirect air cooling, allows the C 3 components of the partial stream T (0) to be fully or partially condensed.
- one or more tube-bundle heat exchangers are preferably used, and the cooling within the heat exchangers can be carried out either with air, water or another suitable medium.
- Partial stream T (0) can thus be fully or partially condensed within step (ii) or step (b).
- step (ii) or step (b) more than 90%, preferably more than 95%, particularly preferably more than 99% of the C 3 components contained in T (0) as Partial stream T (1) separated.
- Partial stream T (1) which has at least the C 3 components propene and propane, is fed to step (iv) or step (c) via suitable line devices known to the person skilled in the art.
- the remaining gas phase, partial stream T (2) in addition to hydrogen as the main component, optionally also contains a variable proportion of C 3 components and, if appropriate, further gaseous, low-boiling components.
- the proportion of C components present in T (2) can be controlled via the conditions in step (ii) or step (b).
- the gas phase in question is transferred as partial stream T (2) via the line devices known to the person skilled in the art in step (iii).
- T (2) is combined with a partial stream T (5a) and transferred in step (e) via line devices known to the person skilled in the art.
- the gaseous partial stream T (2) from step (ii) can have a ratio of hydrogen to C 3 components in a ratio in the range from at least 90 to 95 to 10 to 5, preferably 99 1 and particularly preferably from at least 99.9 to 0.1.
- the liquid substream T (1), which results from step (ii) or step (b) and has at least propene and propane, is in a further step (iv) or step (c) to obtain at least one propane-rich substream T ( 5) and at least one propene-rich substream T (3).
- the partial stream T (1) can be separated by all processes known to the person skilled in the art for this purpose, but preferably by thermal processes such as distillation and / or rectification.
- the separation unit used for this purpose in the context of the invention basically has all the constituents known to the person skilled in the art which are necessary in order to separate substance mixtures by distillation into at least one propane-rich and one propene-rich fraction.
- the partial stream T (1) is preferably separated into a propane-rich and a propene-rich partial stream by rectification.
- the liquid mixture is enriched or separated by mass transfer between the mixture steam flowing in countercurrent and the boiling mixture liquid.
- the rectification is carried out in one or more rectification columns, which essentially consist of tubular separation columns as well as evaporators and a condenser at the upper end (head) of the respective column.
- more than 80%, preferably at least 90%, particularly preferably at least 95% of the propene present in T (l) is mixed with the partial stream T (in step (iv) or step (c) 3) separated.
- This propene-rich partial stream T (3) is fed to the further step (v) or step (g) via suitable line elements.
- the propane-rich partial stream T (5) resulting from step (iv) can be returned to step (i).
- the propane-rich partial stream T (5) may be processed by further processes known to the person skilled in the art before being fed into step (i), for example, the propane in it is enriched before being fed in step (i).
- the present invention also relates to a method of the type described above, the propane-rich partial stream T (5) being fed to step (i).
- the propane-rich partial stream T (5) resulting from step (c) is transferred to step (d) via suitable line devices.
- step (d) the partial stream T (5) is separated into at least the partial streams T (5a) and T (5b).
- the partial stream T (5) is cleaned before the separation in order to separate the by-products which it may contain in addition to propane. This cleaning can be carried out via all methods known to the person skilled in the art for this purpose, e.g. Distillation or absorption processes can be carried out.
- the partial flow T (5) can be separated using all methods available to the person skilled in the art for this purpose, for example by means of the separation using a multi-way valve. Separation with simultaneous purification, for example by means of distillation, is also possible.
- T (5) is separated in step (d) into two partial streams T (5a) and T (5b) containing the same or different amounts of propane.
- Partial stream T (5b) is fed back in step (a) in the context of the present invention via line devices known to the person skilled in the art.
- Partial stream T (5a) can optionally be cleaned again and is then combined with the partial stream T (2) which results from step (b) and has hydrogen and is transferred to step (e).
- Step (iii) or step (e) of the process according to the invention comprises the synthesis of hydrogen peroxide.
- step (iii) using the hydrogen partial stream T (2) and adding oxygen (X in FIG. 1), for example in the form of air implemented, whereby a hydrogen-peroxide-rich partial stream T (4) and a gaseous partial stream T (6) are obtained.
- step (e) the propane-containing partial stream T (5a), which was combined with the hydrogen-containing partial stream T (2), is supplied with an oxygen-containing gas, e.g. Air or of molecular oxygen (X in Fig. 2), reacted, whereby a hydrogen-peroxide-rich partial stream T (4) and a gaseous partial stream T (6a) are obtained.
- an oxygen-containing gas e.g. Air or of molecular oxygen (X in Fig. 2
- oxygen is supplied instead of air. This avoids the accumulation and the associated discharge of potentially disruptive gases.
- hydrogen can also be metered in in a step (iii) or step (e) using a suitable device (Z in FIGS. 1 and 2).
- hydrogen peroxide is produced from the elements by direct synthesis.
- all processes known to the person skilled in the art for the direct synthesis of hydrogen peroxide from the elements can be used.
- the use of the combined partial streams T (2) and T (5a) in step (e) has the advantage that the oxygen quantity in the reaction mixture of the hydrogen peroxide synthesis is reduced below the lower one Explosion limit (4% H 2 to 96% O 2 ) is reached, which increases the safety of the process.
- the propane added by T (5a) thus represents a safe gas cushion for direct hydrogen peroxide synthesis.
- Another related advantage is the resulting increase in the hydrogen concentration to a ratio of oxygen to hydrogen of 1 to 1 or higher. Since the space-time yield of the direct hydrogen peroxide synthesis increases in proportion to the hydrogen concentration, it is within the scope of this Form of the invention possible to spatially reduce the size of the reactor and thus also to reduce operating costs.
- step (e) of the extended process for the synthesis of propylene oxide according to the invention the amount of oxygen and hydrogen in the feed is metered in such a way that a partial stream T (6a) resulting from this step is used for its utilization in the course of the propane dehydrogenation of step ( a) there is an optimal ratio.
- the partial stream T (6a) resulting from step (e) is returned to step (a) and thereby enables the autothermal mode of operation of direct propane synthesis, as described above.
- Examples of possible methods for producing hydrogen peroxide in the context of the present invention are the procedure disclosed in US Pat. No. 4,009,252, in which hydrogen peroxide is formed from hydrogen and oxygen on catalysts containing palladium. This implementation is carried out according to the batch process.
- WO 92/04277 also describes a procedure which can be used in the context of the invention for converting hydrogen with oxygen in a tubular reactor filled with aqueous catalyst suspension to give hydrogen peroxide.
- Another possibility for the production of hydrogen peroxide in the context of the present invention is the continuous process for producing hydrogen peroxide described in US Pat. No. 5,500,202 and EP-A 0 579 109 by reacting H 2 O 2 gas mixtures over a stationary, powdery catalyst in one Trickle bed reactor.
- the safe production of hydrogen peroxide solutions with a hydrogen peroxide content of at least 2.5% by weight is achieved.
- Hydrogen and oxygen are reacted continuously on catalysts, the catalysts containing palladium as the active component and the reaction in water and / or -CC alkanols as the reaction medium on shaped catalyst bodies.
- the shaped catalyst bodies are preferably ordered catalyst packings (monoliths) and / or beds or shaped bodies made of woven fabric, for example woven fabric made of metal.
- oxygen in the form of air.
- the reaction in the context of this process is generally carried out with the reactor flooded.
- Water and / or C 1 -C 3 -alkanols preferably water and / or methanol, serve as the reaction medium.
- the reaction gas which in addition to hydrogen and oxygen can also contain inert gases such as nitrogen or noble gases, generally has an O 2 : H 2 ratio in the range from 1: 100 to 100: 1. It is possible to circulate the reaction gas.
- Reaction gas and reaction medium can be carried out in cocurrent or in countercurrent to one another, preferably in cocurrent, the liquid phase forming the continuous phase and the reaction gas the discontinuous phase.
- a vertical reactor structure (upright reactor) is preferred, in which the reaction gas and reaction medium are preferably passed in cocurrent from bottom to top through the reactor.
- hydrogen can be fed to the reactor via one or more intermediate feeds downstream of the oxygen or air feed point.
- the two-phase reactor discharge can be removed and separated into a hydrogen-peroxide-rich partial stream T (4) and a gaseous partial stream T (6) or T (6a) in a suitable separation vessel.
- the hydrogen peroxide synthesis is carried out in step (iii) in such a way that, even when using hydrogen / oxygen mixtures outside the explosive range (O 2 : H 2 > 20: 1), hydrogen peroxide solutions with a hydrogen peroxide Content above 2.5 wt .-% can be obtained.
- the hydrogen peroxide-rich partial stream T (4) has at least hydrogen peroxide and water. If necessary, partial stream T (4) additionally has halides, acids, alcohols and other organic components as well as sensitizers and promoters for hydrogen peroxide synthesis, for example CO. If necessary, T (4) can be worked up further using methods known to the person skilled in the art.
- the invention also relates to a method of the type described above, partial stream T (4) comprising at least hydrogen peroxide and water.
- the gas phase T (6) can be burned using a suitable compressor or else entirely or partially in a further step (vi) to generate energy and the energy can be used in step (i).
- the present invention also relates to a method as described above, wherein the gaseous partial stream T (6) resulting from step (iii), which has a mixture of hydrogen and oxygen, is completely or partially burned in a further step (vi) for energy generation and the energy is used within step (i).
- step (iii) has less than 4% hydrogen in oxygen or less than 4% oxygen in hydrogen.
- step (vi) The energy thus obtained in step (vi) can be used in step (i) to heat the devices used in the propane dehydrogenation and / or to regenerate the at least one catalyst used in the propane dehydrogenation.
- the present invention also relates to a method as described above, in which the energy recovery in step (i) is carried out individually or in combination by the following steps:
- partial stream T (6) can in principle be entirely or partially recycled in step (iii).
- a partial stream of T (6) is transferred for use in step (i) at times or over the entire course of the process. This procedure is preferably chosen whenever the gaseous partial stream T (6) has more than 0.5%, preferably more than 0.7%, particularly preferably more than 1% of a mixture of hydrogen and oxygen.
- the present invention also relates to a method of the type mentioned above, wherein the gaseous partial stream T (6) resulting from step (iii), which has more than 1% of a mixture of hydrogen and oxygen, is wholly or partly recycled in step (iii) becomes.
- the gaseous partial stream T (6) resulting from step (iii) can be entirely or partially recycled to step (i).
- the advantage of this procedure is that the gaseous partial stream T (6), which in this embodiment has a ratio of H: O 2 in the range of 1: 100 to 100: 1 in addition to C 3 residues, for the regeneration of the in step ( i) catalyst used for propane dehydrogenation can be used.
- the regeneration is basically carried out by completely or partially burning off the organic components deposited on the catalyst surface.
- the present invention also relates to a method as described above, wherein all or part of the gaseous partial stream T (6) resulting from step (iii) is returned to step (i).
- step (iv) or step (c) The partial flow T (3) resulting from step (iv) or step (c) is in step (v) with the partial flow T (4), which results from step (ii) or step (e), in a further step (v) or step (g) implemented to obtain propylene oxide.
- the gas phase T (6a) from step (e) of the process according to the invention can, however, also be returned directly to step (a) in a further step (f).
- the partial stream T (6a) consists of the components propane, oxygen and hydrogen in a molar mixing ratio C 3 : O 2 : H 2 of 1: 0.01-1: 0-2, preferably in a molar mixing ratio C 3 : O 2 : H 2 of 1: 0.03-0.3: 0-0.6 and particularly preferably in a molar mixing ratio C 3 : O 2 : H 2 of 1: 0.04-0.2: 0- 0.4.
- the reaction of the propane-rich substream T (3) with the hydrogen peroxide-rich substream T (4) to obtain propylene oxide can be carried out by all processes known to the person skilled in the art.
- reaction in step (v) or step (g) is preferably the epoxidation of the propene from partial stream T (3) with hydrogen peroxide from partial stream T (4) in the presence of a catalyst to give propylene oxide.
- Epoxidation catalysts used with particular preference in the context of the invention are Ti zeolites with MFI, MEL or MFI / MEL mixed structures, zeolite catalysts referred to as TS-1, TS-2, TS-3 and Ti zeolites with a beta -Zeolite i- somorphic framework structure. Further details regarding the catalysts that can be used, in particular zeolites, are u. a. can be found in DE 100 10 139.2, DE 197 23 950.1 and DE 102 32 406.9 and the prior art cited therein.
- the present invention also relates to a process of the type described above, the reaction in step (v) being the epoxidation of the propene from partial stream T (3) with hydrogen peroxide from partial stream T (4) in the presence of a catalyst to give propylene oxide ,
- the conversion rate to propylene oxide is at least 80%, preferably at least 85%, particularly preferably at least 95%.
- the propylene oxide can be separated from the mixture formed in the reaction in step (v) or step (g) by any method known to the person skilled in the art and, if appropriate, worked up further.
- the separation and processing methods preferred in the context of the present invention are described in DE 198 35 907.1 and DE 100 01 401.1.
- step (v) or step (g) The mixture formed in addition to propylene oxide in step (v) or step (g) can be recycled as a partial stream T (7), which contains at least propane and propene, in whole or in part in step (i) or step (a).
- the present invention also relates to a method of the type described above, step (v) or step (g) giving rise to a partial stream T (7) which comprises at least propane and propene and, if appropriate, with a propane to propene ratio of less than 1 after a further work-up step, all or part of it is returned to step (i) or step (a) or directly to step (iv) or step (c).
- the work-up step in question can be carried out using methods known to those skilled in the art, for example distillation, rectification or membrane separation.
- Tables 1 and 2 below illustrate possible embodiments of the method according to the invention, table 1 relating to the integrated method, which is shown schematically in FIG. 1, and table 2 to the extended integrated method, which is shown schematically in FIG ,
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE50303724T DE50303724D1 (de) | 2002-08-30 | 2003-08-29 | Integriertes verfahren zur synthese von propylenoxid |
US10/526,045 US7173143B2 (en) | 2002-08-30 | 2003-08-29 | Integrated method for synthesis propylene oxide |
CA002496954A CA2496954A1 (en) | 2002-08-30 | 2003-08-29 | Integrated process for the synthesis of propylene oxide |
AU2003266329A AU2003266329A1 (en) | 2002-08-30 | 2003-08-29 | Integrated method for synthesising propylene oxide |
MXPA05002277 MX250839B (es) | 2002-08-30 | 2003-08-29 | Metodo integrado para la sintesis de oxido de propileno. |
EP03790944A EP1537092B1 (de) | 2002-08-30 | 2003-08-29 | Integriertes verfahren zur synthese von propylenoxid |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10240129.2 | 2002-08-30 | ||
DE10240129A DE10240129B4 (de) | 2002-08-30 | 2002-08-30 | Integriertes Verfahren zur Synthese von Propylenoxid |
Publications (1)
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WO2004020423A1 true WO2004020423A1 (de) | 2004-03-11 |
Family
ID=31969013
Family Applications (1)
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---|---|---|---|
PCT/EP2003/009616 WO2004020423A1 (de) | 2002-08-30 | 2003-08-29 | Integriertes verfahren zur synthese von propylenoxid |
Country Status (10)
Country | Link |
---|---|
US (1) | US7173143B2 (de) |
EP (1) | EP1537092B1 (de) |
CN (1) | CN1332955C (de) |
AT (1) | ATE328876T1 (de) |
AU (1) | AU2003266329A1 (de) |
CA (1) | CA2496954A1 (de) |
DE (2) | DE10240129B4 (de) |
MX (1) | MX250839B (de) |
WO (1) | WO2004020423A1 (de) |
ZA (1) | ZA200501665B (de) |
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EP1809587A1 (de) * | 2004-11-11 | 2007-07-25 | Uhde GmbH | Verfahren zur katalytischen dehydrierung von propan zu propylen |
WO2009129355A1 (en) * | 2008-04-18 | 2009-10-22 | Dow Global Technologies Inc. | Integrated process for the production of chlorinated epoxides such as epichlorohydrin |
EP3246323A1 (de) | 2016-05-17 | 2017-11-22 | Evonik Degussa GmbH | Integrierter prozess zur herststellung von propenoxid aus propan |
WO2018197234A1 (en) * | 2017-04-24 | 2018-11-01 | Basf Se | Propene recovery by scrubbing with a solvent/water mixture |
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KR20120060838A (ko) | 2009-08-05 | 2012-06-12 | 다우 글로벌 테크놀로지스 엘엘씨 | 프로필렌 옥사이드의 제조방법 |
TWI523689B (zh) | 2010-03-25 | 2016-03-01 | 陶氏全球科技公司 | 使用預處理環氧催化劑製備環氧丙烷之方法 |
WO2011118823A1 (en) * | 2010-03-26 | 2011-09-29 | Sumitomo Chemical Company, Limited | Method of producing propylene oxide |
JP2011246423A (ja) * | 2010-05-31 | 2011-12-08 | Sumitomo Chemical Co Ltd | オレフィンオキサイドの製造方法 |
CN107428712A (zh) | 2015-01-14 | 2017-12-01 | 赢创德固赛有限公司 | 用于制备氧化丙烯和烷基叔丁基醚的整合方法 |
WO2016113193A1 (en) | 2015-01-14 | 2016-07-21 | Evonik Degussa Gmbh | Integrated process for making propene oxide and an alkyl tert-butyl ether |
MX362989B (es) | 2015-11-26 | 2019-02-28 | Evonik Degussa Gmbh | Proceso para la epoxidacion de una olefina. |
TWI707847B (zh) | 2015-11-26 | 2020-10-21 | 德商贏創運營有限公司 | 丙烯之環氧化方法 |
KR102625924B1 (ko) | 2016-01-19 | 2024-01-16 | 에보닉 오퍼레이션스 게엠베하 | 올레핀의 에폭시화 방법 |
EA035906B1 (ru) | 2016-03-21 | 2020-08-28 | Эвоник Оперейшнс Гмбх | Способ эпоксидирования пропилена |
EP3406603A1 (de) | 2017-05-22 | 2018-11-28 | Evonik Degussa GmbH | Verfahren zur epoxidierung von propen |
CN113387906B (zh) * | 2021-06-30 | 2022-09-06 | 中国石油化工股份有限公司 | 一种丙烷连续生产环氧丙烷衍生物的方法 |
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- 2003-08-29 AU AU2003266329A patent/AU2003266329A1/en not_active Abandoned
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- 2003-08-29 AT AT03790944T patent/ATE328876T1/de not_active IP Right Cessation
- 2003-08-29 EP EP03790944A patent/EP1537092B1/de not_active Expired - Lifetime
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- 2003-08-29 DE DE50303724T patent/DE50303724D1/de not_active Expired - Fee Related
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Cited By (11)
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EP1809587A1 (de) * | 2004-11-11 | 2007-07-25 | Uhde GmbH | Verfahren zur katalytischen dehydrierung von propan zu propylen |
WO2009129355A1 (en) * | 2008-04-18 | 2009-10-22 | Dow Global Technologies Inc. | Integrated process for the production of chlorinated epoxides such as epichlorohydrin |
EP3246323A1 (de) | 2016-05-17 | 2017-11-22 | Evonik Degussa GmbH | Integrierter prozess zur herststellung von propenoxid aus propan |
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CN109219598A (zh) * | 2016-05-17 | 2019-01-15 | 赢创德固赛有限公司 | 由丙烷制备丙烯和氧化丙烯的综合方法 |
RU2717556C1 (ru) * | 2016-05-17 | 2020-03-24 | Эвоник Оперейшнс Гмбх | Объединенный способ получения пропена и пропеноксида из пропана |
CN109219598B (zh) * | 2016-05-17 | 2022-11-29 | 赢创运营有限公司 | 由丙烷制备丙烯和氧化丙烯的综合方法 |
WO2018197234A1 (en) * | 2017-04-24 | 2018-11-01 | Basf Se | Propene recovery by scrubbing with a solvent/water mixture |
KR20190140932A (ko) * | 2017-04-24 | 2019-12-20 | 바스프 에스이 | 용매/물 혼합물과의 스크러빙에 의한 프로펜 회수 |
US11180467B2 (en) | 2017-04-24 | 2021-11-23 | Basf Se | Propene recovery by scrubbing with a solvent/water mixture |
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Also Published As
Publication number | Publication date |
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EP1537092B1 (de) | 2006-06-07 |
DE50303724D1 (de) | 2006-07-20 |
US7173143B2 (en) | 2007-02-06 |
US20050245751A1 (en) | 2005-11-03 |
AU2003266329A1 (en) | 2004-03-19 |
ZA200501665B (en) | 2006-06-28 |
ATE328876T1 (de) | 2006-06-15 |
DE10240129B4 (de) | 2004-11-11 |
DE10240129A1 (de) | 2004-05-19 |
MX250839B (es) | 2007-10-26 |
CN1688560A (zh) | 2005-10-26 |
CA2496954A1 (en) | 2004-03-11 |
CN1332955C (zh) | 2007-08-22 |
EP1537092A1 (de) | 2005-06-08 |
MXPA05002277A (es) | 2005-06-08 |
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