WO2008034837A1 - Method for producing 1,2-dichloroethane by catalytic oxichlorination of ethene in a fluidized bed reactor - Google Patents
Method for producing 1,2-dichloroethane by catalytic oxichlorination of ethene in a fluidized bed reactor Download PDFInfo
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- WO2008034837A1 WO2008034837A1 PCT/EP2007/059871 EP2007059871W WO2008034837A1 WO 2008034837 A1 WO2008034837 A1 WO 2008034837A1 EP 2007059871 W EP2007059871 W EP 2007059871W WO 2008034837 A1 WO2008034837 A1 WO 2008034837A1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1872—Details of the fluidised bed reactor
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/32—Packing elements in the form of grids or built-up elements for forming a unit or module inside the apparatus for mass or heat transfer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1836—Heating and cooling the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/34—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with stationary packing material in the fluidised bed, e.g. bricks, wire rings, baffles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
- B01J2208/00132—Tubes
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
- B01J2208/0015—Plates; Cylinders
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/322—Basic shape of the elements
- B01J2219/32203—Sheets
- B01J2219/3221—Corrugated sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/322—Basic shape of the elements
- B01J2219/32203—Sheets
- B01J2219/32213—Plurality of essentially parallel sheets
- B01J2219/3222—Plurality of essentially parallel sheets with sheets having corrugations which intersect at an angle different from 90 degrees
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/322—Basic shape of the elements
- B01J2219/32203—Sheets
- B01J2219/32224—Sheets characterised by the orientation of the sheet
- B01J2219/32227—Vertical orientation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/324—Composition or microstructure of the elements
- B01J2219/32408—Metal
Definitions
- the invention relates to a process for the preparation of 1, 2-dichloroethane by catalytic oxychlorination of ethene in a fluidized bed reactor.
- the oxychlorination of ethene for the preparation of 1, 2-dichloroethane is a known technical process and is usually carried out on a catalyst, in particular a catalyst containing copper in the active composition, preferably copper chloride, and which is preferably supported.
- the reaction is exothermic and is carried out at elevated temperature, typically in the range of 220 to 245 0 C and elevated pressure, typically from 150 to 500 kPas. At these reaction conditions, copper chloride is volatile, with the result that the catalyst activity decreases over time.
- additives which reduce the volatility of copper chloride.
- additives are, for example, alkali metal chlorides, in particular potassium chloride and cesium chloride, alkaline earth metal chlorides, in particular magnesium chloride, chlorides of rare earth metals, in particular cerium chloride or compounds of the platinum group metals, preferably of ruthenium and / or a gold compound.
- a process for oxychlorination in a fluidized bed reactor is described at ww.oxyvinyls.com.
- the reaction is carried out in a fluidized-bed reactor, which typically consists of a cylindrical vessel equipped with a gas distribution system, which ensures uniform fluidization and equal distribution of ethene, hydrogen chloride and oxygen.
- a gas distribution system which ensures uniform fluidization and equal distribution of ethene, hydrogen chloride and oxygen.
- To minimize the discharge of fluidized catalyst particles from the reactor usually cyclone are used.
- the heat of reaction in this case can be done either by evaporation of cooling water or by other heat transfer media, which can be performed in particular by cooling coils.
- Oxychlorination catalysts tend to sticking when used in fluidized beds, which promotes continuity of the reaction, and fluidized catalysts for the oxychlorination of ethene to 1, 2-dichloroethane need not only be optimized for activity and selectivity, but also for sticking "-Free vortex behavior exhibit.
- Such catalyst compositions are proposed, for example, in DE-A 102 04 608.5, containing 3 to 12% by weight of copper as copper salt, 0 to 3% by weight of an alkaline earth metal as alkaline earth metal salt, 0 to 3% by weight of an alkali metal as alkali metal salt and 0.001 to 0.1 wt .-%, preferably 0.005 to 0.05 wt .-%, of at least one metal selected from the group of ruthenium, rhodium, palladium, osmium, iridium and platinum and / or 0.0001 to 0 , 1 wt .-%, preferably 0.001 to 0.05 wt .-% gold, as the corresponding metal salt or tetrachloroauric acid.
- the object is achieved by a process for the preparation of 1, 2-dichloroethane by catalytic oxychlorination of ethene in a fluidized bed reactor, wherein a gaseous reaction mixture containing ethene, hydrogen chloride and oxygen, flows through a heterogeneous, particulate, a fluidized bed catalyst from bottom to top characterized in that internals are arranged in the fluidized bed, which divide the fluidized bed into a plurality of horizontally and a plurality of vertically arranged in the fluidized bed reactor cells, with cell walls that are gas permeable and have the openings having an exchange number of the heterogeneous particulate Ensure catalyst in the vertical direction in the range of 1 to 100 liters / hour per liter of reactor volume.
- the known catalysts for oxychlorination can be used, in particular catalysts containing copper and next to one or more promoters, especially alkali metal chlorides, preferably potassium chloride or cesium chloride, alkaline earth metal chlorides, preferably magnesium chloride and / or chlorides of rare earth metals, preferably Cerium chloride, and / or salts of platinum metals, preferably of ruthenium and / or a gold compound.
- alkali metal chlorides preferably potassium chloride or cesium chloride
- alkaline earth metal chlorides preferably magnesium chloride and / or chlorides of rare earth metals, preferably Cerium chloride, and / or salts of platinum metals, preferably of ruthenium and / or a gold compound.
- the cell walls are gas permeable and have openings which in the vertical direction in the fluidized bed reactor a solid - Allow mass transfer.
- openings can be provided in the cell walls, which allow a solid exchange in the horizontal direction.
- the exchange number is determined by the use of radioactively labeled solid-tracer particles which are introduced into the fluidizing reaction system, such as in: G. Reed “Radioisotope techniques for problem-solving in industrial process plants", Chapter 9 ("Measurement of residence times and residence-time distribution "), p. 112-137, (J.S. Charlton, ed.), Leonard Hill, Glasgow and London 1986, (ISBN 0-249-44171-3). By recording the time and place of these radioactively labeled particles, the solids movement can be determined locally and the exchange number can be deduced (G.
- the residence time of the heterogeneous particulate catalyst in the same can be adapted to the characteristics of each reaction to be performed.
- the backmixing is limited and thus improving the selectivity and the conversion.
- the capacity the reactor can be adjusted as needed.
- the capacity of the reactor according to the invention is thus not limited and can be adapted to the specific needs, for example, for reactions on a large scale.
- the cell material itself occupies only a limited portion of the cross-section of the fluidized bed reactor, in particular only about 1 to 10% of the cross-sectional area of the fluidized bed reactor and therefore does not lead to those in the packers known from the prior art, associated with increased cross-sectional occupancy disadvantages.
- the fluidized bed reactor used in the process according to the invention is, as usual, pressurized with the gaseous starting materials from below via a gas distributor. As the reaction zone passes, the gaseous feedstocks on the heterogeneous particulate catalyst, which is excited by the gas flow to swirl, are partially reacted. The partially reacted feedstocks flow into the next cell, where they are further partially reacted.
- a Feststoffabscheidevorraum is provided which separates entrained catalyst from the gas phase.
- the reacted product leaves the fluidized bed reactor according to the invention at the upper end of the same solids.
- fluidized-bed reactor used in accordance with the invention can additionally be acted upon with liquid educts both from below and from the side. However, these must be able to evaporate directly at their point of addition to ensure the fluidity of the catalyst.
- the cells are not limited in their geometry; it may, for example, be cells with round walls, in particular hollow spheres, or even cells with angular walls. In the case of an angular formation of the walls, it is preferred that the cells have not more than 50 corners, preferably no more than 30 and in particular no more than 10 corners.
- the cell walls in the cells of the internals are gas-permeable, in order to ensure by swirling through the gas phase through the cells, the swirling of the heterogeneous particulate catalyst.
- the cell walls may be formed of a screen fabric or of sheet-like materials, for example, have round or otherwise shaped holes.
- the average mesh size of the mesh fabrics used or the preferred width of the holes in the cell walls is in particular between 50 and 1 mm, more preferably between 10 and 1 mm and particularly preferably between 5 and 1 mm.
- Cross-channel packings are particularly preferably used as internals in the fluidized bed, that is, packings with kinked, gas-permeable metal plates, expanded metal or fabric layers arranged in parallel in the vertical direction in the fluidized bed reactor, with kinked edges forming buckling surfaces with a non-zero angle of inclination to the vertical, and the buckling surfaces of successive metal sheets, expanded metal or fabric layers have the same angle of inclination, but with opposite signs and thereby form cells which are delimited in the vertical direction by constrictions between the bending edges.
- cross-channel packings are packings of the types Mellpack ®, CY or BX from. Sulzer AG, CH-8404 Winterthur or types A3, BSH, B1 or M of Messrs. Monz GmbH, D-40723 Hilden.
- cross-channel packages are formed in the vertical direction between two successive metal sheets, expanded metal or fabric layers, the kinked structuring of the same, cavities, that is, cells, which are limited by bottlenecks between the creases.
- the mean hydraulic diameter of the cells is preferably in the range between 500 and 1 mm, more preferably between 100 and 5 mm and particularly preferred between 50 and 5 mm.
- the average height of the cells is preferably between 100 and 1 mm, more preferably between 100 and 3 mm and particularly preferably between 40 and 5 mm.
- cross-channel packings occupy only a small part of the cross-sectional area of the fluidized-bed reactor, in particular a proportion of about 1 to 10% thereof.
- the inclination angle of the buckling surfaces to the vertical in the range of 10 to 80 °, in particular between 20 and 70 °, more preferably between 30 and 60 °.
- the buckling surfaces in the metal sheets, expanded metal or fabric layers preferably have a buckling height in the range between 100 and 3 mm, particularly preferably between 40 and 5 mm, and a distance of the bottlenecks between the bending edges in the range between 50 and 2 mm, particularly preferably between 20 and 3 mm, on.
- the heat exchangers may for example be plate-shaped or tubular and be arranged vertically, horizontally or inclined in the fluidized bed reactor.
- the heat transfer surfaces can be tailored to the specific reaction; As a result, each reaction can be implemented thermally with the reactor concept according to the invention.
- the cell-forming internals are preferably made of materials with very good thermal conductivity, so that the heat transfer through the cell walls is not hindered.
- the heat transfer properties of the reactor according to the invention correspond to those of a conventional fluidized bed reactor.
- the materials for the cell-forming internals should also have sufficient stability under reaction conditions; In particular, in addition to the resistance to chemical and thermal stresses, the resistance of the material to mechanical attack by the swirling catalyst should also be taken into account.
- metal, ceramic, polymer or glass materials are particularly suitable.
- the internals are preferably designed such that they divide 10 to 90 vol .-% of the fluidized bed into cells.
- the lower region of the fluidized bed is preferably free in the throughflow direction of the gaseous reaction mixture of internals.
- the internals which divide the fluidized bed in cells, o- arranged above the heat exchanger are provided.
- the reactor according to the invention has no disadvantages with respect to segregation and output tendency of the swirling particulate catalyst.
- Figure 1 is a schematic representation of a preferred embodiment of a fluidized bed reactor used in the invention.
- Figure 2 is a schematic representation of a preferred embodiment of inventions used internals.
- the fluidized-bed reactor 1 shown in FIG. 1 comprises a solids-free gas distribution zone 2, internals 3, which form cells 4, with a heat exchanger 5 in the region of the internals 3.
- the reactor widens, and has at least one solids separator 6.
- the arrow 7 indicates the supply of the gaseous starting materials and the arrow 8 indicates the removal of the gaseous product stream. Additional liquid-phase educts can be added laterally, via the dashed arrows 9.
- Figure 2 illustrates a preferred embodiment of internals 3 according to the invention in the form of a cross-channel packing, with bent metal sheets 10 which are arranged parallel to each other in the longitudinal direction, with bending edges 11 which divide the metal sheet 10 into buckling surfaces 12 and wherein two successive metal sheets are arranged in that they have the same angle of inclination but with opposite signs and thereby form cells 4 bounded in the vertical direction by constrictions 13.
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Abstract
The invention relates to a method for producing 1,2-dichloroethane by catalytic oxichlorination of ethene in a fluidized bed reactor, a gaseous reaction mixture containing ethene, hydrogen chloride and oxygen flowing from the bottom to the top of a heterogeneous particulate catalyst that forms the fluidized bed. The invention is characterized in that said fluidized bed comprises insertion elements which divide the fluidized bed into a plurality of horizontal and vertical cells arranged in the fluidized bed reactor, the walls of said cells being permeable to gas and having openings for ensuring the exchange of particles of the heterogeneous particulate catalyst in the vertical direction in the range of between 1 and 100 liter(s)/hour per liter of reactor volume.
Description
Verfahren zur Herstellung von 1 ,2-Dichlorethan durch katalytische Oxichlorierung von Ethen in einem Wirbelschichtreaktor Process for the preparation of 1, 2-dichloroethane by catalytic oxychlorination of ethene in a fluidized bed reactor
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung von 1 ,2-Dichlorethan durch katalytische Oxichlorierung von Ethen in einem Wirbelschichtreaktor.The invention relates to a process for the preparation of 1, 2-dichloroethane by catalytic oxychlorination of ethene in a fluidized bed reactor.
Die Oxichlorierung von Ethen zur Herstellung von 1 ,2-Dichlorethan ist ein bekanntes technisches Verfahren und wird in der Regel an einem Katalysator, insbesondere einem Katalysator, der in der Aktivmasse Kupfer enthält, bevorzugt Kupferchlorid, durchgeführt, und der bevorzugt geträgert ist.The oxychlorination of ethene for the preparation of 1, 2-dichloroethane is a known technical process and is usually carried out on a catalyst, in particular a catalyst containing copper in the active composition, preferably copper chloride, and which is preferably supported.
Die Reaktion ist exotherm und wird bei erhöhter Temperatur, typischerweise im Be- reich von 220 bis 245 0C und erhöhtem Druck, typischerweise von 150 bis 500 kPas, durchgeführt. Bei diesen Reaktionsbedingungen ist Kupferchlorid flüchtig, mit der Folge, dass die Katalysatoraktivität im Laufe der Zeit abnimmt.The reaction is exothermic and is carried out at elevated temperature, typically in the range of 220 to 245 0 C and elevated pressure, typically from 150 to 500 kPas. At these reaction conditions, copper chloride is volatile, with the result that the catalyst activity decreases over time.
Zur Erhöhung der Wirksamkeit von katalytisch aktivem Kupferchlorid auf Trägersub- stanzen wurden Verfahren entwickelt, die neben Kupferchlorid Zusätze enthalten, die die Flüchtigkeit von Kupferchlorid herabsetzen. Derartige Zusätze sind beispielsweise Alkalimetallchloride, insbesondere Kaliumchlorid und Cäsiumchlorid, Erdalkalimetallchloride, insbesondere Magnesiumchlorid, Chloride der Seltenerdmetalle, insbesondere Cerchlorid oder auch Verbindungen der Metalle der Platingruppe, bevorzugt des Rutheniums und/oder eine Goldverbindung.To increase the efficacy of catalytically active copper chloride on carrier substances, processes have been developed which, in addition to copper chloride, contain additives which reduce the volatility of copper chloride. Such additives are, for example, alkali metal chlorides, in particular potassium chloride and cesium chloride, alkaline earth metal chlorides, in particular magnesium chloride, chlorides of rare earth metals, in particular cerium chloride or compounds of the platinum group metals, preferably of ruthenium and / or a gold compound.
Auf der Website der Occidental Petroleum Corporation ist unter ww.oxyvinyls.com ein Verfahren zur Oxichlorierung in einem Wirbelschichtreaktor beschrieben. Die Reaktion wird in einem Wirbelschichtreaktor durchgeführt, der typischerweise aus einem zylind- rischen Behälter besteht, der mit einem Gasverteilungssystem ausgerüstet ist und mit dessen Hilfe eine gleichmäßige Fluidisation sowie die Gleichverteilung der Einsatzstoffe Ethen, Chlorwasserstoff und Sauerstoff gewährleistet wird. Zur Minimierung des Austrage von fluidisierten Katalysatorpartikeln aus dem Reaktor werden üblicherweise Zyklonabscheider eingesetzt. Durch das Wirbeln des Katalysators entsteht ein enger Kontakt zwischen den gasförmigen Reaktanden, Katalysator und Wärmeübertragerflächen, so dass im Reaktor eine gleichförmige Temperaturverteilung gewährleistet wird. Der Reaktionswärme kann hierbei entweder durch Verdampfen von Kühlwasser oder durch andere Wärmeübertragungsmedien erfolgen, die insbesondere durch Kühlschlangen geführt werden können.
Oxichlorierungskatalysatoren neigen beim Einsatz in Wirbelbetten zum Zusammenkleben („sticking"), wodurch die Kontinuität der Reaktion gefördert ist. Wirbelschichtkatalysatoren für die Oxichlorierung von Ethen zu 1 ,2-Dichlorethan müssen daher nicht nur bezüglich Aktivität und Selektivität optimiert werden, sondern auch ein „sticking"-freies Wirbelverhalten aufweisen.On the website of Occidental Petroleum Corporation, a process for oxychlorination in a fluidized bed reactor is described at ww.oxyvinyls.com. The reaction is carried out in a fluidized-bed reactor, which typically consists of a cylindrical vessel equipped with a gas distribution system, which ensures uniform fluidization and equal distribution of ethene, hydrogen chloride and oxygen. To minimize the discharge of fluidized catalyst particles from the reactor usually cyclone are used. By swirling the catalyst, a close contact between the gaseous reactants, catalyst and heat transfer surfaces, so that a uniform temperature distribution is ensured in the reactor. The heat of reaction in this case can be done either by evaporation of cooling water or by other heat transfer media, which can be performed in particular by cooling coils. Oxychlorination catalysts tend to sticking when used in fluidized beds, which promotes continuity of the reaction, and fluidized catalysts for the oxychlorination of ethene to 1, 2-dichloroethane need not only be optimized for activity and selectivity, but also for sticking "-Free vortex behavior exhibit.
Es wurden daher Katalysatorzusammensetzungen entwickelt, die diesbezüglich verbessert sind.Therefore, catalyst compositions have been developed which are improved in this regard.
Derartige Katalysator-Zusammensetzungen sind beispielsweise in DE-A 102 04 608.5 vorgeschlagen, enthaltend 3 bis 12 Gew.-% Kupfer als Kupfersalz, 0 bis 3 Gew.-% eines Erdalkalimetalls als Erdalkalimetallsalz, 0 bis 3 Gew.-% eines Alkalimetalls als Alkalimetallsalz sowie 0,001 bis 0,1 Gew.-%, vorzugsweise 0,005 bis 0,05 Gew.-%, mindestens eines Metalls ausgewählt aus der Gruppe Ruthenium, Rhodium, Palladi- um, Osmium, Iridium und Platin und/oder 0,0001 bis 0,1 Gew.-%, vorzugsweise 0,001 bis 0,05 Gew.-% Gold, als entsprechendes Metallsalz oder Tetrachlorgoldsäure.Such catalyst compositions are proposed, for example, in DE-A 102 04 608.5, containing 3 to 12% by weight of copper as copper salt, 0 to 3% by weight of an alkaline earth metal as alkaline earth metal salt, 0 to 3% by weight of an alkali metal as alkali metal salt and 0.001 to 0.1 wt .-%, preferably 0.005 to 0.05 wt .-%, of at least one metal selected from the group of ruthenium, rhodium, palladium, osmium, iridium and platinum and / or 0.0001 to 0 , 1 wt .-%, preferably 0.001 to 0.05 wt .-% gold, as the corresponding metal salt or tetrachloroauric acid.
Es war demgegenüber Aufgabe der Erfindung, ein Verfahren zur Oxichlorierung von Ethen zu 1 ,2-Dichlorethan zur Verfügung zu stellen, das gegenüber bekannten Verfah- ren weiter verbessert ist.In contrast, it was an object of the invention to provide a process for the oxychlorination of ethene to 1,2-dichloroethane, which is further improved in comparison to known processes.
Die Aufgabe wird gelöst durch ein Verfahren zur Herstellung von 1 ,2-Dichlorethan durch katalytische Oxichlorierung von Ethen in einem Wirbelschichtreaktor, wobei ein gasförmiges Reaktionsgemisch, enthaltend Ethen, Chlorwasserstoff und Sauerstoff, einen heterogenen, partikelförmigen, eine Wirbelschicht ausbildenden Katalysator von unten nach oben durchströmt, das dadurch gekennzeichnet ist, dass in der Wirbelschicht Einbauten angeordnet sind, die die Wirbelschicht in eine Mehrzahl von horizontal sowie eine Mehrzahl von vertikal im Wirbelschichtreaktor angeordneten Zellen aufteilen, mit Zellwänden, die gasdurchlässig sind und die Öffnungen aufweisen, die eine Austauschzahl des heterogenen partikelförmigen Katalysators in vertikaler Richtung im Bereich von 1 bis 100 Litern/Stunde pro Liter Reaktorvolumen gewährleisten.The object is achieved by a process for the preparation of 1, 2-dichloroethane by catalytic oxychlorination of ethene in a fluidized bed reactor, wherein a gaseous reaction mixture containing ethene, hydrogen chloride and oxygen, flows through a heterogeneous, particulate, a fluidized bed catalyst from bottom to top characterized in that internals are arranged in the fluidized bed, which divide the fluidized bed into a plurality of horizontally and a plurality of vertically arranged in the fluidized bed reactor cells, with cell walls that are gas permeable and have the openings having an exchange number of the heterogeneous particulate Ensure catalyst in the vertical direction in the range of 1 to 100 liters / hour per liter of reactor volume.
Als heterogener, partikelförmiger, eine Wirbelschicht ausbildender Katalysator können die bekannten Katalysatoren für die Oxichlorierung eingesetzt werden, insbesondere Katalysatoren enthaltend Kupfer und daneben einen oder mehrere Promotoren, insbesondere Alkalimetallchloride, bevorzugt Kaliumchlorid oder Cäsiumchlorid, Erdalkalimetallchloride, bevorzugt Magnesiumchlorid und/oder Chloride der Seltenerdmetalle, bevorzugt Cerchlorid, und/oder Salze der Platinmetalle, bevorzugt des Rutheniums und/oder eine Goldverbindung.
Es wurde gefunden, dass es wesentlich ist, die Wirbelschicht mittels Einbauten sowohl in horizontaler als auch in vertikaler Richtung in Zellen aufzuteilen, das heißt in von Zellwänden umschlossene Hohlräume, wobei die Zellwände gasdurchlässig sind und Öffnungen aufweisen, die in vertikaler Richtung im Wirbelschichtreaktor einen Fest- Stoffaustausch erlauben. Darüber hinaus können in den Zellwänden Öffnungen vorgesehen sein, die einen Feststoffaustausch in horizontaler Richtung erlauben. Der heterogene partikelförmige Katalysator kann sich somit zwar in vertikaler Richtung und gegebenenfalls auch in horizontaler Richtung durch den Wirbelschichtreaktor bewegen, er wird aber in den einzelnen Zellen im Vergleich zu einer Wirbelschicht ohne diesel- ben zurückgehalten, wobei die oben definierten Austauschzahlen gewährleistet werden.As a heterogeneous, particulate, a fluidized bed-forming catalyst, the known catalysts for oxychlorination can be used, in particular catalysts containing copper and next to one or more promoters, especially alkali metal chlorides, preferably potassium chloride or cesium chloride, alkaline earth metal chlorides, preferably magnesium chloride and / or chlorides of rare earth metals, preferably Cerium chloride, and / or salts of platinum metals, preferably of ruthenium and / or a gold compound. It has been found that it is essential to divide the fluidized bed by means of internals both in the horizontal and in the vertical direction in cells, that is enclosed in cell walls cavities, the cell walls are gas permeable and have openings which in the vertical direction in the fluidized bed reactor a solid - Allow mass transfer. In addition, openings can be provided in the cell walls, which allow a solid exchange in the horizontal direction. Although the heterogeneous particulate catalyst can thus move in the vertical direction and possibly also in the horizontal direction through the fluidized-bed reactor, it is retained in the individual cells without the same compared to a fluidized bed, whereby the above-defined exchange rates are ensured.
Die Austauschzahl wird durch den Einsatz von radioaktiv markierten Feststoff-Tracer- Partikeln bestimmt, die in das wirbelnde Reaktionssystem eingegeben werden, wie beispielsweise in: G. Reed "Radioisotope techniques for problem-solving in industrial process plants", Chapter 9 ("Measurement of residence times and residence-time distribution"), p. 112-137, (J.S. Charlton, ed.), Leonard Hill, Glasgow and London 1986, (ISBN 0-249-44171-3), beschrieben. Über die Aufnahme von Zeit und Ort dieser radioaktiv markierten Partikel kann die Feststoffbewegung lokal bestimmt und die Aus- tauschzahl abgeleitet werden (G. Reed in: "Radioisotope techniques for problem- solving in industrial process plants", Chapter 1 1 ("Miscellanous radiotracer applications", 1 1.1. "Mixing and blending studies"), p. 167-176, (J. S. Charlton, ed.), Leonard Hill, Glasgow and London 1986, (ISBN 0-249-44171-3).The exchange number is determined by the use of radioactively labeled solid-tracer particles which are introduced into the fluidizing reaction system, such as in: G. Reed "Radioisotope techniques for problem-solving in industrial process plants", Chapter 9 ("Measurement of residence times and residence-time distribution "), p. 112-137, (J.S. Charlton, ed.), Leonard Hill, Glasgow and London 1986, (ISBN 0-249-44171-3). By recording the time and place of these radioactively labeled particles, the solids movement can be determined locally and the exchange number can be deduced (G. Reed in: "Radioisotope Techniques for Problem Solving in Industrial Process Plants", Chapter 1 1 ("Miscellanous radiotracer applications "1, 1.1" Mixing and Blending Studies ", pp. 167-176, (JS Charlton, ed.), Leonard Hill, Glasgow and London 1986, (ISBN 0-249-44171-3).
Durch die gezielte Auswahl der Geometrie der Zellen kann die Verweilzeit des heterogenen partikelförmigen Katalysators in denselben an die Charakteristik der jeweils durchzuführenden Reaktion angepasst werden.By selective selection of the geometry of the cells, the residence time of the heterogeneous particulate catalyst in the same can be adapted to the characteristics of each reaction to be performed.
Durch die Reihenschaltung einer Mehrzahl, das heißt insbesondere von 0 bis 100 ZeI- len oder auch von 10 bis 50 Zellen pro Meter Betthöhe, das heißt in vertikaler Richtung, in Richtung der Gasströmung von unten nach oben durch den Reaktor, wird die Rückvermischung begrenzt und damit die Selektivität und der Umsatz verbessert. Durch die zusätzliche Anordnung einer Mehrzahl von, das heißt von 10 bis 100 Zellen oder auch von 10 bis 50 Zellen pro Meter in horizontaler Richtung im Wirbelschichtre- aktor, das heißt von Zellen, die parallel oder in Serie vom Reaktionsgemisch durchströmt werden, kann die Kapazität des Reaktors nach Bedarf angepasst werden. Die Kapazität des erfindungsgemäßen Reaktors ist somit nicht begrenzt und kann dem konkreten Bedarf angepasst werden, beispielsweise auch für Reaktionen im großtechnischen Maßstab.
Indem die Zellen Hohlräume umschließen, die den partikelförmigen heterogenen Katalysator aufnehmen, nimmt das Zellmaterial selbst nur einen begrenzten Teil des Querschnitts des Wirbelbettreaktors ein, insbesondere von nur etwa 1 bis 10 % der Querschnittsfläche des Wirbelschichtreaktors und führt daher nicht zu den bei den Einbau- ten aus dem Stand der Technik bekannten, mit einer erhöhten Querschnittsbelegung verbundenen Nachteilen.By the series connection of a plurality, that is in particular from 0 to 100 cells or even 10 to 50 cells per meter bed height, that is in the vertical direction, in the direction of the gas flow from bottom to top through the reactor, the backmixing is limited and thus improving the selectivity and the conversion. By the additional arrangement of a plurality of, that is, from 10 to 100 cells or even 10 to 50 cells per meter in the horizontal direction in the fluidized bed reactor, that is to say cells which are passed through in parallel or in series by the reaction mixture, the capacity the reactor can be adjusted as needed. The capacity of the reactor according to the invention is thus not limited and can be adapted to the specific needs, for example, for reactions on a large scale. As the cells enclose cavities which receive the particulate heterogeneous catalyst, the cell material itself occupies only a limited portion of the cross-section of the fluidized bed reactor, in particular only about 1 to 10% of the cross-sectional area of the fluidized bed reactor and therefore does not lead to those in the packers known from the prior art, associated with increased cross-sectional occupancy disadvantages.
Der im erfindungsgemäßen Verfahren eingesetzte Wirbelschichtreaktor wird, wie üblich, von unten über einen Gasverteiler mit den gasförmigen Einsatzstoffen beauf- schlagt. Beim Passieren der Reaktionszone werden die gasförmigen Einsatzstoffe an dem heterogenen partikelförmigen Katalysator, der durch die Gasströmung zum Wirbeln angeregt wird, partiell umgesetzt. Die partiell umgesetzten Einsatzstoffe strömen in die nächste Zelle, wo dieselben weiter partiell umgesetzt werden.The fluidized bed reactor used in the process according to the invention is, as usual, pressurized with the gaseous starting materials from below via a gas distributor. As the reaction zone passes, the gaseous feedstocks on the heterogeneous particulate catalyst, which is excited by the gas flow to swirl, are partially reacted. The partially reacted feedstocks flow into the next cell, where they are further partially reacted.
Oberhalb der Reaktionszone ist eine Feststoffabscheidevorrichtung vorgesehen, die mitgeführten Katalysator von der Gasphase trennt. Das umgesetzte Produkt verlässt den erfindungsgemäßen Wirbelschichtreaktor am oberen Ende desselben feststofffrei.Above the reaction zone, a Feststoffabscheidevorrichtung is provided which separates entrained catalyst from the gas phase. The reacted product leaves the fluidized bed reactor according to the invention at the upper end of the same solids.
Darüber hinaus kann der erfindungsgemäß eingesetzte Wirbelschichtreaktor sowohl von unten als auch von der Seite zusätzlich mit flüssigen Edukten beaufschlagt werden. Diese müssen jedoch direkt an ihrer Zugabestelle verdampfen können, um die Wirbelfähigkeit des Katalysators zu gewährleisten.In addition, the fluidized-bed reactor used in accordance with the invention can additionally be acted upon with liquid educts both from below and from the side. However, these must be able to evaporate directly at their point of addition to ensure the fluidity of the catalyst.
Die Zellen sind in ihrer Geometrie nicht eingeschränkt; es kann sich beispielsweise um Zellen mit runden Wänden, insbesondere Hohlkugeln, oder auch um Zellen mit eckigen Wänden handeln. Bei einer eckigen Ausbildung der Wände ist bevorzugt, dass die Zellen nicht mehr als 50 Ecken aufweisen, vorzugsweise nicht mehr als 30 und insbesondere nicht mehr als 10 Ecken.The cells are not limited in their geometry; it may, for example, be cells with round walls, in particular hollow spheres, or even cells with angular walls. In the case of an angular formation of the walls, it is preferred that the cells have not more than 50 corners, preferably no more than 30 and in particular no more than 10 corners.
Die Zellwände in den Zellen der Einbauten sind gasdurchlässig ausgebildet, um durch ein Durchströmen der Gasphase durch die Zellen das Wirbeln des heterogenen partikelförmigen Katalysators zu gewährleisten. Hierzu können die Zellwände aus einem Siebgewebe gebildet sein oder auch aus flächenförmigen Materialien, die beispielsweise runde oder auch anders geformte Löcher aufweisen.The cell walls in the cells of the internals are gas-permeable, in order to ensure by swirling through the gas phase through the cells, the swirling of the heterogeneous particulate catalyst. For this purpose, the cell walls may be formed of a screen fabric or of sheet-like materials, for example, have round or otherwise shaped holes.
Hierbei beträgt die mittlere Maschenweite der eingesetzten Siebgewebe oder die bevorzugte Weite der Löcher in den Zellwänden insbesondere zwischen 50 und 1 mm, weiter bevorzugt zwischen 10 und 1 mm und besonders bevorzugt zwischen 5 und 1 mm.
Besonders bevorzugt werden als Einbauten in die Wirbelschicht Kreuzkanalpackungen eingesetzt, das heißt Packungen mit in vertikaler Richtung im Wirbelbettreaktor parallel zueinander angeordneten geknickten, gasdurchlässigen Metallblechen, Streckmetalloder Gewebelagen, mit Knickkanten, die Knickflächen mit einem von Null verschiede- nen Neigungswinkel zur Vertikalen ausbilden, und wobei die Knickflächen aufeinander folgender Metallbleche, Streckmetall- oder Gewebelagen den gleichen Neigungswinkel, jedoch mit umgekehrtem Vorzeichen aufweisen und dadurch Zellen ausbilden, die in vertikaler Richtung durch Engstellen zwischen den Knickkanten begrenzt werden.In this case, the average mesh size of the mesh fabrics used or the preferred width of the holes in the cell walls is in particular between 50 and 1 mm, more preferably between 10 and 1 mm and particularly preferably between 5 and 1 mm. Cross-channel packings are particularly preferably used as internals in the fluidized bed, that is, packings with kinked, gas-permeable metal plates, expanded metal or fabric layers arranged in parallel in the vertical direction in the fluidized bed reactor, with kinked edges forming buckling surfaces with a non-zero angle of inclination to the vertical, and the buckling surfaces of successive metal sheets, expanded metal or fabric layers have the same angle of inclination, but with opposite signs and thereby form cells which are delimited in the vertical direction by constrictions between the bending edges.
Beispiele für Kreuzkanalpackungen sind die Packungen der Typen Mellpack®, CY oder BX der Fa. Sulzer AG, CH-8404 Winterthur oder die Typen A3, BSH, B1 oder M der Fa. Monz GmbH, D-40723 Hilden.Examples of cross-channel packings are packings of the types Mellpack ®, CY or BX from. Sulzer AG, CH-8404 Winterthur or types A3, BSH, B1 or M of Messrs. Monz GmbH, D-40723 Hilden.
In den Kreuzkanalpackungen bilden sich in vertikaler Richtung zwischen zwei jeweils aufeinander folgenden Metallblechen, Streckmetall- oder Gewebelagen, durch die geknickte Strukturierung derselben, Hohlräume, das heißt Zellen aus, die durch Engstellen zwischen den Knickkanten begrenzt werden.In the cross-channel packages are formed in the vertical direction between two successive metal sheets, expanded metal or fabric layers, the kinked structuring of the same, cavities, that is, cells, which are limited by bottlenecks between the creases.
Der mittlere hydraulische Durchmesser der Zellen, bestimmt mittels radioaktiver Tra- certechnik, und die beispielsweise vorstehend in Verbindung mit der Bestimmung der Austauschzahl angegebenen Literaturstelle beschrieben ist, liegt bevorzugt im Bereich zwischen 500 und 1 mm, weiter bevorzugt zwischen 100 und 5 mm und besonders bevorzugt zwischen 50 und 5 mm.The mean hydraulic diameter of the cells, as determined by radioactive tracer technology, and the reference given, for example, above in connection with the determination of the exchange number, is preferably in the range between 500 and 1 mm, more preferably between 100 and 5 mm and particularly preferred between 50 and 5 mm.
Hierbei wird als hydraulischer Durchmesser in bekannter Weise die vierfache horizontale Querschnittsfläche der Zelle, dividiert durch den von oben betrachteten Umfang der Zelle, definiert.Here, as a hydraulic diameter in a known manner, the fourfold horizontal cross-sectional area of the cell, divided by the viewed from above the circumference of the cell defined.
Die mittlere Höhe der Zellen, gemessen in vertikaler Richtung im Wirbelbettreaktor mittels radioaktiver Tracertechnik, beträgt vorzugsweise zwischen 100 und 1 mm, weiter bevorzugt zwischen 100 und 3 mm und besonders bevorzugt zwischen 40 und 5 mm.The average height of the cells, measured in the vertical direction in the fluidized bed reactor by means of radioactive tracer technology, is preferably between 100 and 1 mm, more preferably between 100 and 3 mm and particularly preferably between 40 and 5 mm.
Die obigen Kreuzkanalpackungen belegen nur einen geringen Teil der Querschnittsflä- che des Wirbelschichtreaktors, insbesondere einen Anteil von etwa 1 bis 10 % derselben.The above cross-channel packings occupy only a small part of the cross-sectional area of the fluidized-bed reactor, in particular a proportion of about 1 to 10% thereof.
Bevorzugt liegen die Neigungswinkel der Knickflächen zur Vertikalen im Bereich von 10 bis 80°, insbesondere zwischen 20 und 70°, besonders bevorzugt zwischen 30 und 60°.
Die Knickflächen in den Metallblechen, Streckmetall- oder Gewebelagen weisen bevorzugt eine Knickhöhe im Bereich zwischen 100 und 3 mm, besonders bevorzugt zwischen 40 und 5 mm, und einen Abstand der Engstellen zwischen den Knickkanten im Bereich zwischen 50 und 2 mm, besonders bevorzugt zwischen 20 und 3 mm, auf.Preferably, the inclination angle of the buckling surfaces to the vertical in the range of 10 to 80 °, in particular between 20 and 70 °, more preferably between 30 and 60 °. The buckling surfaces in the metal sheets, expanded metal or fabric layers preferably have a buckling height in the range between 100 and 3 mm, particularly preferably between 40 and 5 mm, and a distance of the bottlenecks between the bending edges in the range between 50 and 2 mm, particularly preferably between 20 and 3 mm, on.
In die Zellen bildenden Einbauten können für eine gezielte Steuerung der Reaktionstemperatur Wärmeübertrager zwecks Zuführung von Wärme bei endothermen Reaktionen oder Abfuhr von Wärme bei exothermen Reaktionen eingebaut werden. Die Wärmeübertrager können beispielsweise plattenförmig oder rohrförmig ausgebildet sein und im Wirbelschichtreaktor vertikal, horizontal oder geneigt angeordnet sein.In the cells forming internals can be installed for a targeted control of the reaction temperature heat exchangers to supply heat in endothermic reactions or dissipation of heat in exothermic reactions. The heat exchangers may for example be plate-shaped or tubular and be arranged vertically, horizontally or inclined in the fluidized bed reactor.
Die Wärmeübertragungsflächen können auf die konkrete Reaktion abgestimmt werden; dadurch kann jede Reaktion wärmetechnisch mit dem erfindungsgemäßen Reaktorkonzept realisiert werden.The heat transfer surfaces can be tailored to the specific reaction; As a result, each reaction can be implemented thermally with the reactor concept according to the invention.
Die Zellen bildenden Einbauten werden bevorzugt aus Werkstoffen mit sehr guter Wärmeleitfähigkeit hergestellt, so dass der Wärmetransport über die Zellwände nicht behindert wird. Somit entsprechen die Wärmeübergangseigenschaften des erfindungsgemäßen Reaktors denjenigen eines herkömmlichen Wirbelschichtreaktors.The cell-forming internals are preferably made of materials with very good thermal conductivity, so that the heat transfer through the cell walls is not hindered. Thus, the heat transfer properties of the reactor according to the invention correspond to those of a conventional fluidized bed reactor.
Die Werkstoffe für die Zellen bildenden Einbauten sollen darüber hinaus eine ausreichende Stabilität unter Reaktionsbedingungen aufweisen; insbesondere ist neben der Beständigkeit gegenüber chemischen und thermischen Belastungen auch die Beständigkeit des Werkstoffs gegenüber mechanischem Angriff durch den wirbelnden Kataly- sator zu beachten.The materials for the cell-forming internals should also have sufficient stability under reaction conditions; In particular, in addition to the resistance to chemical and thermal stresses, the resistance of the material to mechanical attack by the swirling catalyst should also be taken into account.
Aufgrund der einfachen Bearbeitbarkeit derselben sind Metall-, Keramik-, Polymeroder Glaswerkstoffe besonders geeignet.Due to their ease of processing, metal, ceramic, polymer or glass materials are particularly suitable.
Die Einbauten sind bevorzugt dergestalt ausgebildet, dass sie 10 bis 90 Vol.-% der Wirbelschicht in Zellen unterteilen.The internals are preferably designed such that they divide 10 to 90 vol .-% of the fluidized bed into cells.
Hierbei ist bevorzugt der untere Bereich der Wirbelschicht in Durchströmungsrichtung des gasförmigen Reaktionsgemisches von Einbauten frei.In this case, the lower region of the fluidized bed is preferably free in the throughflow direction of the gaseous reaction mixture of internals.
Besonders bevorzugt sind die Einbauten, die die Wirbelschicht in Zellen aufteilen, o- berhalb der Wärmeübertrager angeordnet. Dadurch kann insbesondere der Restumsatz erhöht werden.
Durch die begrenzte Querschnittsbelegung durch die Zellen bildenden Einbauten weist der erfindungsgemäße Reaktor keine Nachteile hinsichtlich Entmischung und Aus- tragsneigung des wirbelnden partikelförmigen Katalysators auf.Particularly preferably, the internals which divide the fluidized bed in cells, o- arranged above the heat exchanger. As a result, in particular the residual sales can be increased. Due to the limited cross-sectional occupancy of the cells forming internals, the reactor according to the invention has no disadvantages with respect to segregation and output tendency of the swirling particulate catalyst.
Die Erfindung wird im Folgenden anhand einer Zeichnung näher erläutert.The invention will be explained in more detail below with reference to a drawing.
Es zeigen im Einzelnen:They show in detail:
Figur 1 die schematische Darstellung einer bevorzugten Ausführungsform eines erfindungsgemäß eingesetzten Wirbelschichtreaktors, undFigure 1 is a schematic representation of a preferred embodiment of a fluidized bed reactor used in the invention, and
Figur 2 die schematische Darstellung einer bevorzugten Ausführungsform von erfindungsgemäß eingesetzten Einbauten.Figure 2 is a schematic representation of a preferred embodiment of inventions used internals.
Der in Figur 1 dargestellte Wirbelschichtreaktor 1 umfasst eine feststofffreie Gasverteilerzone 2, Einbauten 3, die Zellen 4 ausbilden, mit einem Wärmeübertrager 5 im Bereich der Einbauten 3.The fluidized-bed reactor 1 shown in FIG. 1 comprises a solids-free gas distribution zone 2, internals 3, which form cells 4, with a heat exchanger 5 in the region of the internals 3.
Oberhalb der Reaktionszone erweitert sich der Reaktor, und weist mindestens einen Feststoffabscheider 6 auf. Der Pfeil 7 gibt die Zuführung der gasförmigen Einsatzstoffe und der Pfeil 8 die Abführung des gasförmigen Produktstromes an. Zusätzliche flüs- sigphasige Edukte können seitlich, über die gestrichelten Pfeile 9, zugegeben werden.Above the reaction zone, the reactor widens, and has at least one solids separator 6. The arrow 7 indicates the supply of the gaseous starting materials and the arrow 8 indicates the removal of the gaseous product stream. Additional liquid-phase educts can be added laterally, via the dashed arrows 9.
Figur 2 stellt eine bevorzugte Ausführungsform von erfindungsgemäßen Einbauten 3 in Form einer Kreuzkanalpackung dar, mit geknickten Metallblechen 10, die parallel zueinander in Längsrichtung angeordnet sind, mit Knickkanten 11 , die das Metallblech 10 in Knickflächen 12 unterteilen und wobei zwei aufeinander folgende Metallbleche so angeordnet sind, dass sie den gleichen Neigungswinkel, jedoch mit umgekehrten Vorzeichen aufweisen und dabei Zellen 4 ausbilden, die in vertikaler Richtung durch Engstellen 13 begrenzt werden.
Figure 2 illustrates a preferred embodiment of internals 3 according to the invention in the form of a cross-channel packing, with bent metal sheets 10 which are arranged parallel to each other in the longitudinal direction, with bending edges 11 which divide the metal sheet 10 into buckling surfaces 12 and wherein two successive metal sheets are arranged in that they have the same angle of inclination but with opposite signs and thereby form cells 4 bounded in the vertical direction by constrictions 13.
Claims
1. Verfahren zur Herstellung von 1 ,2-Dichlorethan durch katalytische Oxichlorierung von Ethen in einem Wirbelschichtreaktor (1 ), wobei ein gasförmiges Reaktions- gemisch (7), enthaltend Ethen, Chlorwasserstoff und Sauerstoff, einen heterogenen, partikelförmigen, eine Wirbelschicht ausbildenden Katalysator von unten nach oben durchströmt, dadurch gekennzeichnet, dass in der Wirbelschicht Einbauten (3) angeordnet sind, die die Wirbelschicht in eine Mehrzahl von horizontal sowie eine Mehrzahl von vertikal im Wirbelschichtreaktor (1 ) angeordneten Zellen (4) aufteilen, mit Zellwänden, die gasdurchlässig sind und die Öffnungen aufweisen, die eine Austauschzahl des heterogenen partikelförmigen Katalysators in vertikaler Richtung im Bereich von 1 bis 100 Litern/Stunde pro Liter Reaktorvolumen gewährleisten.1. A process for the preparation of 1, 2-dichloroethane by catalytic oxychlorination of ethene in a fluidized bed reactor (1), wherein a gaseous reaction mixture (7) containing ethene, hydrogen chloride and oxygen, a heterogeneous, particulate, a fluidized bed-forming catalyst of flows through the bottom to the top, characterized in that in the fluidized bed internals (3) are arranged, which divide the fluidized bed into a plurality of horizontally and a plurality of vertically in the fluidized bed reactor (1) arranged cells (4) with cell walls which are gas permeable and have the openings which ensure a replacement number of the heterogeneous particulate catalyst in the vertical direction in the range of 1 to 100 liters / hour per liter of reactor volume.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als Katalysator ein ungeträgerter oder geträgerter Katalysator eingesetzt wird, enthaltend Kupfer und daneben einen oder mehrere Promotoren, insbesondere Alkalimetallchloride, bevorzugt Kaliumchlorid oder Cäsiumchlorid, Erdalkalimetallchloride, bevorzugt Magnesiumchlorid und/oder Chloride der Seltenerdmetalle, bevorzugt Cerchlorid, und/oder Salze der Platinmetalle, bevorzugt des Rutheniums und/oder eine2. The method according to claim 1, characterized in that the catalyst used is an unsupported or supported catalyst containing copper and next to one or more promoters, in particular alkali metal chlorides, preferably potassium chloride or cesium chloride, alkaline earth metal chlorides, preferably magnesium chloride and / or chlorides of rare earth metals, preferably Cerium chloride, and / or salts of platinum metals, preferably of ruthenium and / or a
Goldverbindung.Gold compound.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Öffnungen in den Zellwänden der im Wirbelschichtreaktor (1 ) angeordneten Zellen (4) eine Austauschzahl des heterogenen partikelförmigen Katalysators in horizontaler3. The method according to claim 1 or 2, characterized in that the openings in the cell walls of the fluidized bed reactor (1) arranged cells (4) has an exchange number of the heterogeneous particulate catalyst in the horizontal
Richtung im Bereich von 100 Litern/Stunde pro Liter Reaktorvolumen gewährleisten.Ensure direction in the range of 100 liters / hour per liter of reactor volume.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Öffnungen in den Zellwänden der im Wirbelschichtreaktor (1 ) angeordneten Zellen (4) eine Austauschzahl des heterogenen partikelförmigen Katalysators in vertikaler Richtung im Bereich von 10 bis 50 Litern/Stunde pro Liter Reaktorvolumen und in horizontaler Richtung von 0 oder im Bereich von 10 bis 50 Litern/Stunde pro Liter Reaktorvolumen gewährleisten.4. The method according to any one of claims 1 to 3, characterized in that the openings in the cell walls of the fluidized bed reactor (1) arranged cells (4) has an exchange number of heterogeneous particulate catalyst in the vertical direction in the range of 10 to 50 liters / hour per Ensure reactor volume in the horizontal direction of 0 or in the range of 10 to 50 liters / hour per liter of reactor volume.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Einbauten (3) als Kreuzkanalpackung ausgebildet sind, mit in vertikaler Richtung im Wirbelbettreaktor (1 ) parallel zueinander angeordneten geknickten, gasdurchlässigen Metallblechen, Streckmetall- oder Gewebelagen (10), mit Knickkanten (1 1 ), die Knickflächen (12) mit einem von Null verschiedenen Neigungswinkel zur5. The method according to any one of claims 1 to 4, characterized in that the internals (3) are formed as cross-channel packing, with in the vertical direction in the fluidized bed reactor (1) arranged parallel to each other kinked, gas-permeable metal sheets, expanded metal or fabric layers (10), with buckling edges (1 1), the buckling surfaces (12) with a non - zero angle of inclination to
Vertikalen ausbilden, und wobei die Knickflächen (12) aufeinander folgender Me- tallbleche, Streckmetall- oder Gewebelagen (10) den gleichen Neigungswinkel, jedoch mit umgekehrten Vorzeichen aufweisen und dadurch Zellen (4) ausbilden, die in vertikaler Richtung durch Engstellen zwischen den Knickkanten (1 1 ) begrenzt werden.Form vertical, and wherein the buckling surfaces (12) successive Me- tallbleche, expanded metal or fabric layers (10) have the same angle of inclination, but with opposite signs and thereby form cells (4), which are limited in the vertical direction by bottlenecks between the bending edges (1 1).
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass die Neigungswinkel der Knickflächen (12) zur Vertikalen im Bereich von 10 bis 80°, bevorzugt zwischen 20 und 70°, besonders bevorzugt zwischen 30 und 60°, liegen.6. The method according to claim 5, characterized in that the inclination angle of the buckling surfaces (12) to the vertical in the range of 10 to 80 °, preferably between 20 and 70 °, more preferably between 30 and 60 °.
7. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Einbauten (3) aus einer Schüttung von Hohlkugeln gebildet sind.7. The method according to any one of claims 1 to 3, characterized in that the internals (3) are formed from a bed of hollow balls.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Zellen (4) der Einbauten (3) einen hydraulischen Durchmesser, gemessen mittels radioaktiver Tracertechnik, zwischen 100 und 5 mm, bevorzugt zwischen 50 und8. The method according to any one of claims 1 to 7, characterized in that the cells (4) of the internals (3) has a hydraulic diameter, measured by means of radioactive tracer technology, between 100 and 5 mm, preferably between 50 and
5 mm, aufweisen.5 mm.
9. Verfahren nach einem der Ansprüche 1 bis 6 oder 8, dadurch gekennzeichnet, dass die Zellen (4) der Einbauten (3) eine mittlere Höhe, gemessen in vertikaler Richtung im Wirbelbettreaktor (1 ) mittels radioaktiver Tracertechnik, zwischen9. The method according to any one of claims 1 to 6 or 8, characterized in that the cells (4) of the internals (3) has a mean height, measured in the vertical direction in the fluidized bed reactor (1) by means of radioactive tracer technology, between
100 und 3 mm, bevorzugt zwischen 40 und 5 mm, aufweisen.100 and 3 mm, preferably between 40 and 5 mm.
10. Verfahren nach einem der Ansprüche 1 bis 6, 8 oder 9, dadurch gekennzeichnet, dass die Knickflächen (12) in den Metallblechen, Streckmetall- oder Gewebela- gen (10) eine Knickhöhe im Bereich zwischen 100 und 3 mm, besonders bevorzugt zwischen 40 und 5 mm, und der Abstand der Engstellen zwischen den Knickkanten (11 ) Werte im Bereich zwischen 50 und 2 mm, besonders bevorzugt zwischen 20 und 3 mm, aufweist.10. The method according to any one of claims 1 to 6, 8 or 9, characterized in that the buckling surfaces (12) in the metal sheets, expanded metal or Gewebela- gene (10) has a buckling height in the range between 100 and 3 mm, more preferably between 40 and 5 mm, and the distance of the bottlenecks between the fold edges (11) has values in the range between 50 and 2 mm, particularly preferably between 20 and 3 mm.
1 1. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass in die Einbauten (3) Wärmeübertrager (5) eingebracht sind.1 1. A method according to any one of claims 1 to 10, characterized in that in the internals (3) heat exchanger (5) are introduced.
12. Verfahren nach Anspruch 1 1 , dadurch gekennzeichnet, dass die Wärmeübertrager (5) platten- oder rohrförmig ausgebildet sind.12. The method according to claim 1 1, characterized in that the heat exchanger (5) are plate-shaped or tubular.
13. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, dass die Einbauten (3), die die Wirbelschicht in Zellen (4) aufteilen, oberhalb der Wärmeübertrager angeordnet sind. 13. The method according to claim 11 or 12, characterized in that the internals (3) which divide the fluidized bed in cells (4) are arranged above the heat exchanger.
14. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Einbauten (3) aus Metall-, Keramik-, Polymer- oder Glaswerkstoffen gebildet sind.14. The method according to any one of claims 1 to 12, characterized in that the internals (3) made of metal, ceramic, polymer or glass materials are formed.
15. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass die Einbauten (3) 10 bis 90 Volumenprozent der Wirbelschicht in Zellen (4) unterteilen.15. The method according to any one of claims 1 to 13, characterized in that the internals (3) subdivide 10 to 90 volume percent of the fluidized bed into cells (4).
16. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass der untere Bereich der Wirbelschicht in Durchströmungsrichtung des gasförmigen Reaktionsgemisches (7) von Einbauten (3) frei ist. 16. The method according to claim 14, characterized in that the lower region of the fluidized bed in the flow direction of the gaseous reaction mixture (7) of internals (3) is free.
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EP06120888.0 | 2006-09-19 | ||
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4368173A (en) * | 1979-09-12 | 1983-01-11 | Instituto Mexicano Del Petroleo | Reactor for oxichlorination of ethylene and process therefor |
US5227548A (en) * | 1988-12-20 | 1993-07-13 | Imperial Chemical Industries Plc | Oxychlorination of ethylene to 1,2-dichloroethane |
EP0997187A1 (en) * | 1998-10-28 | 2000-05-03 | Krupp Uhde GmbH | Fluidised bed reactor for the oxychlorination of ethylene, oxygen and HCl |
DE10204608A1 (en) * | 2002-02-05 | 2003-08-07 | Basf Ag | Supported catalyst composition for the oxychlorination of ethylene comprises copper as copper salt and ruthenium, rhodium, palladium, osmium, iridium and/or platinum and/or gold |
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2007
- 2007-09-19 WO PCT/EP2007/059871 patent/WO2008034837A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4368173A (en) * | 1979-09-12 | 1983-01-11 | Instituto Mexicano Del Petroleo | Reactor for oxichlorination of ethylene and process therefor |
US5227548A (en) * | 1988-12-20 | 1993-07-13 | Imperial Chemical Industries Plc | Oxychlorination of ethylene to 1,2-dichloroethane |
EP0997187A1 (en) * | 1998-10-28 | 2000-05-03 | Krupp Uhde GmbH | Fluidised bed reactor for the oxychlorination of ethylene, oxygen and HCl |
DE10204608A1 (en) * | 2002-02-05 | 2003-08-07 | Basf Ag | Supported catalyst composition for the oxychlorination of ethylene comprises copper as copper salt and ruthenium, rhodium, palladium, osmium, iridium and/or platinum and/or gold |
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