WO1998055216A1 - Reactor for carrying out rapid highly exothermic reactions and use thereof - Google Patents

Reactor for carrying out rapid highly exothermic reactions and use thereof Download PDF

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Publication number
WO1998055216A1
WO1998055216A1 PCT/EP1998/003037 EP9803037W WO9855216A1 WO 1998055216 A1 WO1998055216 A1 WO 1998055216A1 EP 9803037 W EP9803037 W EP 9803037W WO 9855216 A1 WO9855216 A1 WO 9855216A1
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Prior art keywords
reactor
reactor according
tubes
feed
openings
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PCT/EP1998/003037
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German (de)
French (fr)
Inventor
Reinhard Langer
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Bayer Aktiengesellschaft
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Publication of WO1998055216A1 publication Critical patent/WO1998055216A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1812—Tubular reactors
    • B01J19/1837—Loop-type reactors
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
    • B01J19/1881—Stationary reactors having moving elements inside resulting in a loop-type movement externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/2435—Loop-type reactors
    • 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
    • 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
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/065—Feeding reactive fluids
    • 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
    • B01J8/1845—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised
    • B01J8/1863—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised followed by a downward movement outside the reactor and subsequently re-entering it
    • 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
    • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
    • B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
    • B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
    • B01J8/228—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement externally, i.e. the particles leaving the vessel and subsequently re-entering it
    • 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
    • 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
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • 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
    • 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
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00256—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the reactor
    • 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
    • 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
    • B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00081—Tubes
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00085—Plates; Jackets; Cylinders
    • 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
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical

Definitions

  • the present invention relates to a reactor for carrying out rapid, highly exothermic reactions in the liquid phase.
  • the reactor essentially consists of a cooled tube bundle. Porous lines are installed in the tubes, via which one of the reactants is metered in, in such a way that the heat of reaction is released uniformly along the tube axis and no areas with too high a starting material concentration arise. 'The reaction medium flows through the reactor tubes in a defined manner
  • the reactor is particularly suitable for the bottom phase hydrogenation of dinitrotoluene
  • Reactors for fast, strongly exothermic conversions require an effective removal of the heat of reaction.
  • the known reactors have complex internals and are also equipped with powerful agitators in order to mix the reactants quickly and to transfer the heat released to the heat exchanger surfaces
  • Solid catalysts can also be deposited in areas of the reactor with poor flow conditions
  • the aim is to design a reactor that allows rapid, highly exothermic reactions to be carried out in a controlled manner in the vicinity of the heat exchanger surfaces and that reliably ensures a uniform flow through the entire reactor
  • the invention relates to a tube bundle reactor for rapid, strongly exothermic reactions consisting of a reactor housing with a bundle of tubes, which are optionally connected to one another radially to their length, as a reaction zone, starting material feed lines, product outlet and heat exchanger, characterized in that a starting material feed line is provided in the tubes the bundle of pipelines running and provided with a multiplicity of openings " , the openings in the pipelines being distributed over the entire length or a long section of the reaction zone
  • the reaction tubes preferably have a catalyst bed
  • the maximum pore opening cross section of the openings in the feed line is in particular 1 mm, preferably 0.7 mm
  • the minimum pore cross section of the openings in the feed line is in particular 1 ⁇ m, preferably 7 ⁇ m
  • the feed line is part of a feed loop with a conveying means, for example a circulating pump and a special heat exchanger
  • the reactor has a pumping loop for the
  • Reaction mixture with a conveying agent at least one further feed line and an outlet for the reaction product on.
  • the conveying agent is, for example, a mammoth pump or a circulating pump
  • a gas supply for gaseous reactants and, if necessary, a mixer element, in particular a static and / or dynamic mixer, are arranged in the area in front of the inlet of the bundle of reaction tubes of the reactor in order to achieve a drafty mixing with the circulating reactants
  • an adiabatic dwell zone adjoins the reaction zone formed from the tubes in the reactor. in which the reaction mixture can react further
  • a feed line for catalyst can be provided in the pumping loop if, for example, catalyst is also pumped around in a suspension in the loop.
  • the line for the reaction product is also arranged in the pumping loop.
  • the product discharge is preferably a settling tank with an outlet or particularly preferably a filtration unit, in particular a unit for cross-flow filtration
  • the invention further relates to the use of the reactor according to the invention for carrying out strongly exothermic reactions, in particular for the hydrogenation of dinitrotoluene
  • Tube bundles surrounded by heat exchangers can be used as are known in principle from the prior art, ie tube bundles containing between 10 and 100,000 tubes, preferably between 100 and 10,000 tubes with an inside diameter of 10 to 100 mm, preferably from 20 to Own 50 mm
  • the pipe length is in particular from 1 to 50 m, preferably from 2 to 20 m, particularly preferably from 3 to 10 m
  • the heat of reaction can be removed by evaporative cooling or by means of a liquid heat carrier; steam is preferably generated directly by evaporative cooling.
  • the heat carrier can move in a heat exchanger surrounding the tubes.
  • the reaction zone can be arranged in the tube-like area between a group of heat exchanger tubes. The heat carrier thus flows through a tube bundle, while the reaction takes place in the interconnected tubular spaces (type linder reactor).
  • the reaction preferably takes place in the tubes and the heat carrier is located in the heat exchanger surrounding the reaction tubes
  • Educt lines can be in contact with the heat transfer wall or are at a distance of 1 to 50 mm, preferably 2 to 25 mm. particularly preferably from 4 to 12 mm from the heat exchanger wall
  • the feed lines In cooled areas of the reactor, the feed lines have pores, in particular
  • the openings are in particular arranged at regular intervals in such a way that there is a pore of 10 to 100,000, preferably 30 to 10,000, particularly preferably 100 to 1000 ml of reaction space. Lines made of metal sintered material with a very large number of pores can also be used
  • the pressure loss when flowing through the pores is in particular such that approximately the same amount of starting material slowly flows out of all pores
  • the educt lines are preferably combined to form an educt circuit, so that there are no regions in the lines in which the educt does not flow or only flows very slowly.
  • the educt circuit also has the advantage that the educt can be cooled In order to be able to flow strongly through the reactor, the majority of the material flowing through the reactor must be returned to the reactor inlet in the preferred variant. This is done in the sense of a loop reactor in which the two ends of the reactor are connected by a line
  • a device for pumping around the contents of the reactor loop must be attached at a suitable location.
  • This can be, for example, a centrifugal pump or a propeller
  • a gas for example hydrogen
  • this gas can simply be injected in front of the tube bundle and is circulated with the liquid, the gas is preferably fed in from below, by swirling or specifically by distributing gas over the reactor tubes on the upper end of the reactor separated from the liquid and fed back to the lower end of the reactor
  • the reactor according to the invention is particularly suitable for the hydrogenation of nitroaromatics.
  • Dinitrotoluene is particularly preferably hydrogenated to toluenediamine
  • the reactor can be operated under normal pressure (ambient pressure) or under elevated pressure, the reactor in the range of 10 3 to 3 • 10 5 hPa is preferred. ⁇ particular DERS preferably from 3 to 10 3 to 10 5 hPa operated The invention is explained in more detail below with reference to the figures, without the invention being restricted thereby in detail
  • FIG. 1 shows a schematic view of the tube bundle reactor according to the invention with starting material circuit and pumping loop 10
  • FIG. 2b shows an enlarged detail from the longitudinal section through the tube 6 according to FIG. 2a to explain the arrangement of the opening 7
  • FIG. 2c shows a cross section through a reaction tube 6 according to FIG. 2a
  • FIG. 3 shows a reaction tube 6 corresponding to FIG. 2a with catalyst bed 8
  • FIG. 4a shows a schematic cross section through a tube bundle 3 according to the invention
  • 4b shows a schematic cross section of a variant of the tube bundle 3 according to the invention
  • 5a shows a schematic longitudinal section through a reactor tube 6 with an internal feed line as part of a feed circuit
  • FIG. 5b An enlarged section of Fig. 5a
  • 5c shows a cross section through the bundle tube 6 according to FIG. 5a
  • FIG. 6 shows a schematic longitudinal section through a reaction tube 6 corresponding to FIG. 5a with catalyst bed 8 7 shows a variant of the reactor arrangement according to FIG. 1 with an additional educt circuit for gaseous educts.
  • FIG. 8 shows a variant of the reactor arrangement according to FIG. 7, in which the gas supply takes place in the vicinity of the inlet of the reactor tubes
  • a bundle 3 of reaction tubes 6 is accommodated in a reactor housing 1 and is surrounded in the area of the reaction zone by a heat exchanger 5 with a condensate supply line 15 and a steam discharge line 16.
  • educt feed tubes 4a, 4b, 4c, 4d run concentrically, according to FIG. 4a.
  • the feed lines 4a to 4d are part of a feed circuit 25 in which a feed pump 14 and a heat exchanger 9 are provided.
  • the starting material consumed in the reaction is supplied via a feed pump 17.
  • the reaction tubes 6 have educt lines 4 provided with an opening in a partial area.
  • the educt flows into the reaction zone of the tube 6 through the large number of openings 7 in the educt line 4 (see FIG. 5b).
  • the reactor 1 with the tube bundle 3 is part of a pumping circuit 10 in which the reaction mixture and the further starting material fed in via the starting material feed line 11 or 11 are circulated. 1 with the help of a circulating pump 13.
  • a cross-flow filter unit 20 is also installed in the circulating circuit in order to be able to remove product obtained from the reaction from the circuit. The product is discharged via the discharge line 12.
  • a simple educt feed 4 is provided in the tubes 6 of the tube bundle instead of the educt circuit 25 instead of the educt circuit 25.
  • FIG 3 shows a schematic longitudinal section through the same arrangement, in which the length of the reaction tube 6 is filled on a catalyst bed 8.
  • FIG. 4b A variant of the arrangement of the reaction tubes 6 according to the invention is shown in FIG. 4b.
  • the spaces between heat exchanger tubes 5 form tubular spaces 6- as reaction zones in which the reactant lines 4 run to feed the reactant.
  • the tubular gaps 6'- are radial to their longitudinal expansion via gaps 27 between the heat transfer tubes 5- connected to each other when the heat exchanger tubes are spaced, as shown in Fig. 4b.
  • FIG. 5a shows a schematic longitudinal section through a reaction tube 6 from an arrangement according to FIG. 1, in which the educt feed line 4 is part of an educt circuit, but only has openings 7 on a partial region of the tube length of tube 6 (see FIG. 5b), according to FIG. 5c a concentric arrangement of the educt feed line 4 is provided
  • the tubes 6 of the tube bundle reactor 1 are provided with a catalyst bed over their entire length
  • the variant of the tube bundle reactor arrangement according to FIG. 7 is suitable for the reaction involving further gaseous starting materials.
  • the arrangement described in Example 1 according to FIG. 1 is supplemented by a further educt circuit 21 for supplying gaseous products, e.g. hydrogen gas.
  • the gas is fed to the gas circuit 21 via the feed line 22 and introduced into the pumping circuit of the reactor at the gas inlet 18 upstream of the mixer 13.
  • the gas is passed through the reaction zone of the tubes 6 with the reaction mixture circulating in the pumping circuit 10 in counterflow to the further starting materials supplied via the tubes 4 and separated from the reaction mixture in a gas separator 19.
  • the separated gas is either fed into the Process returned or at outlet 23 to
  • the inlet for the additional feed gas is attached just before or in the pipe opening of the pipes 6.
  • the gas is carried into the reaction tubes 6 by the density-dependent circulation of the reaction mixture (10) and, as in the arrangement according to FIG. 7, is fed back to the inlet of the reactor via a gas separator 19 and a circulating gas compressor 24 Example 3
  • FIG. 9 shows a simplified reactor arrangement of the tube bundle reactor according to the invention, in which a simple product outlet is provided in the pumping circuit 10 instead of the crossflow filtration provided in the arrangement according to Example 1.
  • the outlet of the reactor bundle 3 is followed by an after-reactor 26 as an adiabatic dwell in which the reaction subsides.
  • the starting materials are introduced into the pumping circuit here, as in Example 1, via open-pore pipelines 4 and via an educt feed line 11.
  • the arrangement has a stationary contact 8, or a catalyst slurry is passed through inlet 11 and outlet 12 with the catalyst being separated off for recycling
  • the reaction can also be carried out homogeneously catalyzed.
  • the catalyst with the material flows must be supplied via the pump 17 or the inlet 11.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

The invention relates to a tube bundle reactor (1) for rapid highly exothermic reactions, consisting of a reactor housing (2) with a bundle (3) of tubes (6) as a reaction zone, said tubes being optionally interconnected radially in relation to their longitudinal extension, eduction pipes (4, 11), a product outlet (12) and a heat exchanger (5). The invention is characterised in that said eduction pipes (4) are configured as pipelines (4a, 4b, 4c, 4d) which are arranged in the tubes (6) of the bundle (3) and which are provided with a plurality of openings (7), said openings (7) in the pipelines (4a, 4b, 4c, 4d) being spread over the entire length of or a section of the length of the reaction zone.

Description

Reaktor zur Durchführung rascher stark exothermer Reaktionen und dessen VerwendungReactor for carrying out rapid, strongly exothermic reactions and their use
Die vorliegende Erfindung betrifft einen Reaktor zur Durchführung rascher stark exothermer Reaktionen in der flussigen Phase. Der Reaktor besteht im Wesentlichen aus einem gekühlten Rohrbündel. In den Rohren sind poröse Leitungen angebracht, über die einer der Reaktanden eindosiert wird, derart, daß entlang der Rohrachse gleichmaßig die Reaktionswarme freigesetzt wird und keine Bereiche mit zu hoher Eduktkonzentration entstehen 'Das Reaktionsmedium durchströmt die Reaktorrohre in einer definiertenThe present invention relates to a reactor for carrying out rapid, highly exothermic reactions in the liquid phase. The reactor essentially consists of a cooled tube bundle. Porous lines are installed in the tubes, via which one of the reactants is metered in, in such a way that the heat of reaction is released uniformly along the tube axis and no areas with too high a starting material concentration arise. 'The reaction medium flows through the reactor tubes in a defined manner
Richtung, wird an dem einen Ende des Rohrbundelreaktors entnommen und gegebenenfalls in einem Umpump-Kreislauf dem anderen Ende wieder zugeführtDirection, is removed from one end of the tube bundle reactor and, if necessary, fed back to the other end in a pumping circuit
Der Reaktor ist besonders geeignet zur Sumpfphasenhydrierung von DinitrotoluolThe reactor is particularly suitable for the bottom phase hydrogenation of dinitrotoluene
Reaktoren für schnelle stark exotherme Umsetzungen verlangen eine effektive Ableitung der Reaktionswarme Die bekannten Reaktoren weisen daher zu diesem Zweck komplexe Einbauten auf und sind ferner mit leistungstarken Ruhrern versehen, um die Reaktanden rasch zu vermischen und die frei werdende Warme auf die Warmetauscherflachen zu übertragenReactors for fast, strongly exothermic conversions require an effective removal of the heat of reaction. For this purpose, the known reactors have complex internals and are also equipped with powerful agitators in order to mix the reactants quickly and to transfer the heat released to the heat exchanger surfaces
Solche Reaktoren sind z B in den Schriften US-A 3 243 268 und EP-A 263 935 beschriebenSuch reactors are described, for example, in US Pat. Nos. 3,243,268 and EP-A 263,935
Die Nachteile der bekannten Reaktoren sind ungleichmäßige Durchstromung der Wärmetauscher und ungleichmäßige Durchmischung der Reaktanden Damit können die Parameter Temperatur und Eduktkonzentration in Teilen des Reaktors ungunstige Werte annehmen, was zu Produkt-Ausbeuteverlust und Schädigung eines beteiligten Katalysators fuhrtThe disadvantages of the known reactors are uneven flow through the heat exchangers and uneven mixing of the reactants. Thus, the parameters of temperature and reactant concentration in parts of the reactor can assume unfavorable values, which leads to loss of product yield and damage to a catalyst involved
Femer können sich feste Katalysatoren in schlecht durchströmten Bereichen des Reaktors ablagern Ziel ist eine Reaktorkonstruktion, die erlaubt, rasch ablaufende, stark exotherme Reaktionen kontrolliert in der Nähe der Warmetauscherflachen ablaufen zu lassen und die zuverlässig eine gleichmäßige Durchströmung des gesamten Reaktors gewährleistetSolid catalysts can also be deposited in areas of the reactor with poor flow conditions The aim is to design a reactor that allows rapid, highly exothermic reactions to be carried out in a controlled manner in the vicinity of the heat exchanger surfaces and that reliably ensures a uniform flow through the entire reactor
Gegenstand der Erfindung ist ein Rohrbundelreaktor für rasche stark exotherme Reaktionen bestehend aus einem Reaktorgehäuse mit einem Bündel von Rohren, die gegebenenfalls radial zu ihrer Langenausdehnung mit einander verbunden sind, als Reaktionszone, Eduktzuleitungen, Produktauslaß und Wärmetauscher dadurch gekennzeichnet, daß eine Eduktzuleitung als in den Rohren der Bündel verlaufende und mit einer Vielzahl von Öffnungen" versehene Rohrleitungen ausgeführt ist, wobei die Öffnungen in den Rohrleitungen über die ganze Lange oder einen Langenabschnitt der Reaktionszone verteilt sindThe invention relates to a tube bundle reactor for rapid, strongly exothermic reactions consisting of a reactor housing with a bundle of tubes, which are optionally connected to one another radially to their length, as a reaction zone, starting material feed lines, product outlet and heat exchanger, characterized in that a starting material feed line is provided in the tubes the bundle of pipelines running and provided with a multiplicity of openings " , the openings in the pipelines being distributed over the entire length or a long section of the reaction zone
Bevorzugt weisen die Reaktionsrohre eine Katalysatorschuttung aufThe reaction tubes preferably have a catalyst bed
Der maximale Porenöffhungsquerschnitt der Öffnungen in der Eduktzuleitung betragt insbesondere 1 mm bevorzugt 0,7 mmThe maximum pore opening cross section of the openings in the feed line is in particular 1 mm, preferably 0.7 mm
Der minimale Porenόfmungsquerschnitt der Öffnungen in der Eduktzuleitung betragt insbesondere 1 μm bevorzugt 7 μmThe minimum pore cross section of the openings in the feed line is in particular 1 μm, preferably 7 μm
In einer bevorzugten Ausführung der Erfindung ist die Eduktzuleitung Teil einer Eduktschleife mit einem Fordermittel, z B einer Umwälzpumpe und einem besonderen WärmetauscherIn a preferred embodiment of the invention, the feed line is part of a feed loop with a conveying means, for example a circulating pump and a special heat exchanger
In einer bevorzugten Ausführung weist der Reaktor eine Umpumpschleife für dieIn a preferred embodiment, the reactor has a pumping loop for the
Reaktionsmischung mit einem Fordermittel, mindestens einer weiteren Eduktzuleitung und einen Auslaß für das Reaktionsprodukt auf Das Fordermittel ist beispielsweise eine Mammutpumpe oder eine UmwälzpumpeReaction mixture with a conveying agent, at least one further feed line and an outlet for the reaction product on. The conveying agent is, for example, a mammoth pump or a circulating pump
Je nach Art der durchzuführenden Reaktion ist es vorteilhaft in der Umpumpschleife desDepending on the type of reaction to be carried out, it is advantageous in the pumping loop of the
Reaktor eine Katalysatorsuspension umlaufen zu lassen Im Bereich vor dem Eingang des Bundeis von Reaktionsrohren des Reaktors ist in einer bevorzugten Variante der Erfindung eine Gaszuführung für gasförmige Reaktanden und ggf zusätzlich ein Mischerelement, insbesondere ein statischer und/oder dynamischer Mischer, angeordnet um eine zugige Durchmischung mit den umlaufenden Reaktanden zu erreichenTo run a catalyst suspension around the reactor In a preferred variant of the invention, a gas supply for gaseous reactants and, if necessary, a mixer element, in particular a static and / or dynamic mixer, are arranged in the area in front of the inlet of the bundle of reaction tubes of the reactor in order to achieve a drafty mixing with the circulating reactants
In einer weiteren Ausführungsform des erfindungsgemäßen Reaktors schließt sich in dem Reaktor an die aus den Rohren gebildete Reaktionszone eine adiabatische Verweilzone an. in der die Reaktionsmischung weiter reagieren kannIn a further embodiment of the reactor according to the invention, an adiabatic dwell zone adjoins the reaction zone formed from the tubes in the reactor. in which the reaction mixture can react further
In der Umpumpschleife kann eine Zuleitung für Katalysator vorgesehen sein, wenn z B Katalysator in einer Suspension in der Schleife mit umgepumpt wird Auch ist die Ableitung für das Reaktionsprodukt in einer bevorzugten Ausführung in der Umpumpschleife angeordnet. Die Produktableitung ist bevorzugt ein Absetztank mit Auslauf oder besonders bevorzugt eine Filtrationseinheit, insbesondere eine Einheit zur QuerstromfiltrationA feed line for catalyst can be provided in the pumping loop if, for example, catalyst is also pumped around in a suspension in the loop. In a preferred embodiment, the line for the reaction product is also arranged in the pumping loop. The product discharge is preferably a settling tank with an outlet or particularly preferably a filtration unit, in particular a unit for cross-flow filtration
Weiterer Gegenstand der Erfindung ist die Verwendung des erfindungsgemäßen Reaktors zur Durchführung stark exothermer Reaktionen, insbesondere zur Hydrierung von DinitrotoluolThe invention further relates to the use of the reactor according to the invention for carrying out strongly exothermic reactions, in particular for the hydrogenation of dinitrotoluene
Als Wärmetauscher umgebene Rohrbundel können solche verwendet werden, wie sie aus dem Stand der Technik grundsätzlich bekannt sind, d h Rohrbundel die zwischen 10 und 100 000 Rohre, bevorzugt zwischen 100 und 10 000 Rohre mit einem Innendurchmesser von 10 bis 100 mm, bevorzugt von 20 bis 50 mm besitzenTube bundles surrounded by heat exchangers can be used as are known in principle from the prior art, ie tube bundles containing between 10 and 100,000 tubes, preferably between 100 and 10,000 tubes with an inside diameter of 10 to 100 mm, preferably from 20 to Own 50 mm
Die Rohrlange betragt je nach Anwendungsfall insbesondere von 1 bis 50 m, bevorzugt von 2 bis 20 m, besonders bevorzugt von 3 bis 10 mDepending on the application, the pipe length is in particular from 1 to 50 m, preferably from 2 to 20 m, particularly preferably from 3 to 10 m
Die Reaktionswarme kann durch Siedekuhlung oder mittels flussiger Warmetrager abgeführt werden, bevorzugt wird durch Siedekühlung direkt Dampf erzeugt. Der Warmeträger kann sich in einem die Rohre umgebenden Wärmetauscher bewegen Alternativ kann die Reaktionszone in dem rohrähnlichen Bereich zwischen einer Schar von Warmeaustauscherrohren angeordnet sein. Dabei fließt also der Warmetrager durch ein Rohrbundel, während die Reaktion in den miteinander verbundenen rohrahnlichen Zwischenräumen ablauft (Typ Lindereaktor) Bevorzugt findet in den Rohren die Reaktion statt und befindet sich der Warmetrager in dem die Reaktionsrohre umgebenden WärmetauscherThe heat of reaction can be removed by evaporative cooling or by means of a liquid heat carrier; steam is preferably generated directly by evaporative cooling. The heat carrier can move in a heat exchanger surrounding the tubes. Alternatively, the reaction zone can be arranged in the tube-like area between a group of heat exchanger tubes. The heat carrier thus flows through a tube bundle, while the reaction takes place in the interconnected tubular spaces (type linder reactor). The reaction preferably takes place in the tubes and the heat carrier is located in the heat exchanger surrounding the reaction tubes
Im erfindungsgemaßen Reaktor befinden sich, wie oben erwähnt, parallel zur Warmeaus- tauscherwand poröse Leitungen, durch die mindestens eines der Edukte fließt DieseIn the reactor according to the invention, as mentioned above, there are porous lines parallel to the heat exchanger wall through which at least one of the starting materials flows
Eduktleitungen können im Kontakt zur Warmetragerwand stehen oder sind in einem Abstand von 1 bis 50 mm, bevorzugt von 2 bis 25 mm. besonders bevorzugt von 4 bis 12 mm von der Warmeaustauscherwand angeordnetEduct lines can be in contact with the heat transfer wall or are at a distance of 1 to 50 mm, preferably 2 to 25 mm. particularly preferably from 4 to 12 mm from the heat exchanger wall
In gekühlten Bereichen des Reaktors besitzen die Eduktleitungen Poren, insbesondereIn cooled areas of the reactor, the feed lines have pores, in particular
Löcher oder Bohrungen als ÖffnungenHoles or holes as openings
Die Öffnungen sind insbesondere in regelmäßigen Abstanden derart angebracht, daß auf eine Pore von 10 bis 100 000, bevorzugt von 30 bis 10 000, besonders bevorzugt von 100 bis 1000 ml Reaktionsraum kommen. Leitungen aus Metallsinterwerkstoff mit einer sehr großen Porenzahl können ebenfalls eingesetzt werdenThe openings are in particular arranged at regular intervals in such a way that there is a pore of 10 to 100,000, preferably 30 to 10,000, particularly preferably 100 to 1000 ml of reaction space. Lines made of metal sintered material with a very large number of pores can also be used
Der Druckverlust beim Durchströmen der Poren ist insbesondere so bemessen, daß aus allen Poren ungefähr die gleiche Menge Edukt langsam ausströmtThe pressure loss when flowing through the pores is in particular such that approximately the same amount of starting material slowly flows out of all pores
Die Eduktleitungen sind wie beschrieben bevorzugt zu einem Eduktkreislauf zusammengefaßt, so daß in den Leitungen keine Bereiche sind, in denen das Edukt nicht oder nur sehr langsam fließt Femer bietet der Eduktkreislauf den Vorteil, daß das Edukt gekühlt werden kann Um den Reaktor stark durchströmen zu können, muß der größte Teil der den Reaktor durchfließenden Materie in der bevorzugten Variante dem Reaktoreingang wieder zugeführt werden. Dies erfolgt im Sinne eines Schleifen-Reaktors, in dem die beiden Reaktorenden mit einer Leitung verbunden sindAs described, the educt lines are preferably combined to form an educt circuit, so that there are no regions in the lines in which the educt does not flow or only flows very slowly. The educt circuit also has the advantage that the educt can be cooled In order to be able to flow strongly through the reactor, the majority of the material flowing through the reactor must be returned to the reactor inlet in the preferred variant. This is done in the sense of a loop reactor in which the two ends of the reactor are connected by a line
In dieser Leitung können sich Vorrichtungen zur Durchführung einer Querstromfiltration befinden, um Feststoffe die im Reaktor verbleiben sollen zurückzuhalten, wahrend das gebildete Produktgemisch ausgeschleust wird Dadurch können heterogene Kontakte im Reaktor zurückgehalten werden Heterogene Katalysatoren können aber auch von einem entnommenem Teilstrom auf konventionelle Art abgetrennt und wieder rezykliert werdenIn this line there can be devices for carrying out a cross-flow filtration in order to retain solids which are to remain in the reactor while the product mixture formed is being discharged.This allows heterogeneous contacts to be retained in the reactor.Heterogeneous catalysts can also be separated from a withdrawn partial stream in a conventional manner and again be recycled
An einer geeigneten Stelle muß eine Vorrichtung zum Umpumpen des Reaktor-Loop- Inhaltes angebracht sein Dies kann z B eine Kreiselpumpe oder ein Propeller seinA device for pumping around the contents of the reactor loop must be attached at a suitable location. This can be, for example, a centrifugal pump or a propeller
Wird als eine Reaktionskomponente ein Gas, z.B Wasserstoff eingesetzt, so kann dieses Gas einfach vor dem Rohrbündel eingedust werden und wird mit der Flüssigkeit im Kreis gefahren, bevorzugt wird das Gas von unten eingespeist, durch Verwirbelung oder gezielt durch eine Gasverteilung auf die Reaktorrohre verteilt am oberen Reaktorende von der Flüssigkeit separiert und wieder dem unteren Reaktorende zugeführtIf a gas, for example hydrogen, is used as a reaction component, this gas can simply be injected in front of the tube bundle and is circulated with the liquid, the gas is preferably fed in from below, by swirling or specifically by distributing gas over the reactor tubes on the upper end of the reactor separated from the liquid and fed back to the lower end of the reactor
Bei einem solchen gepumpten Gaskreislauf kann ggf auf die besondere Pumpe imIn such a pumped gas circuit, the special pump in
Umpump-Kreislauf verzichtet werden, weil das Gas den Flussigkeitskreislauf in Bewegung setzt und antreibtPumping circuit can be dispensed with because the gas sets the liquid circuit in motion and drives it
Der erfϊndungsgemaße Reaktor ist besonders geeignet zur Hydrierung von Nitroaromaten Besonders bevorzugt wird Dinitrotoluol zu Toluylendiamin hydriert Durch die geringenThe reactor according to the invention is particularly suitable for the hydrogenation of nitroaromatics. Dinitrotoluene is particularly preferably hydrogenated to toluenediamine
DNT-Konzentrationen an allen Stellen des Reaktors wird eine besonders geringe Nebenproduktbildung und Katalysatordesaktivierung beobachtetParticularly low by-product formation and catalyst deactivation are observed at DNT concentrations at all points in the reactor
Der Reaktor kann unter Normaldruck (Umgebungsdruck) oder unter erhöhtem Druck betrieben werden, bevorzugt wird der Reaktor im Bereich von 103 bis 3 • 105 hPa. beson¬ ders bevorzugt von 3 -103 bis 105 hPa betrieben Die Erfindung wird nachstehend anhand der Figuren naher erläutert, ohne daß dadurch die Erfindung im Einzelnen eingeschränkt istThe reactor can be operated under normal pressure (ambient pressure) or under elevated pressure, the reactor in the range of 10 3 to 3 • 10 5 hPa is preferred. ¬ particular DERS preferably from 3 to 10 3 to 10 5 hPa operated The invention is explained in more detail below with reference to the figures, without the invention being restricted thereby in detail
In den Figuren zeigen.Show in the figures.
Fig 1 Eine schematische Ansicht des erfindungsgemaßen Rohrbundelreaktors mit Eduktkreislauf und Umpumpschleife 101 shows a schematic view of the tube bundle reactor according to the invention with starting material circuit and pumping loop 10
Fig 2a Ein Teil des Rohrbundelreaktors mit Reaktionsrohr 6 und Eduktzuleitung 4 für einen Reaktor ohne Edukt -Kreislaufführung2a shows a part of the tube bundle reactor with reaction tube 6 and educt feed line 4 for a reactor without educt circulation
Fig 2b Ein vergrößertes Detail aus dem Längsschnitt durch das Rohr 6 nach Fig 2a zur Erläuterung der Anordnung der Öffnung 72b shows an enlarged detail from the longitudinal section through the tube 6 according to FIG. 2a to explain the arrangement of the opening 7
Fig 2c Ein Querschnitt durch ein Reaktionsrohr 6 gemäß Fig. 2a2c shows a cross section through a reaction tube 6 according to FIG. 2a
Fig. 3 Ein Reaktionsrohr 6 entsprechend Fig 2a mit Katalysatorschuttung 83 shows a reaction tube 6 corresponding to FIG. 2a with catalyst bed 8
Fig 4a Einen schematischen Querschnitt durch ein erfindungsgemaßes Rohrbundel 34a shows a schematic cross section through a tube bundle 3 according to the invention
Fig 4b Einen schematischen Querschnitt einer Variante zu dem erfindungsgemaßen Rohrbundel 34b shows a schematic cross section of a variant of the tube bundle 3 according to the invention
Fig 5a Einen schematischen Längsschnitt durch ein Reaktorrohr 6 mit innenliegender Eduktzuleitung als Teil eines Eduktkreislaufs5a shows a schematic longitudinal section through a reactor tube 6 with an internal feed line as part of a feed circuit
Fig 5b Einen vergroßterten Ausschnitt von Fig 5aFig. 5b An enlarged section of Fig. 5a
Fig 5c Einen Querschnitt durch das Bundelrohr 6 gemäß Fig. 5a5c shows a cross section through the bundle tube 6 according to FIG. 5a
Fig 6 Einen schematischen Längsschnitt durch ein Reaktionsrohr 6 entsprechend Fig 5a mit Katalysatorschuttung 8 Fig 7 Eine Variante zu der Reaktoranordnung gemäß Fig 1 mit zusatzlichem Eduktkreislauf für gasförmige Edukte.6 shows a schematic longitudinal section through a reaction tube 6 corresponding to FIG. 5a with catalyst bed 8 7 shows a variant of the reactor arrangement according to FIG. 1 with an additional educt circuit for gaseous educts.
Fig.8 Eine Variante zu der Reaktoranordnung gemäß Fig 7, bei der die Gaszuleitung in der Nahe des Eingangs der Reaktorrohre erfolgt8 shows a variant of the reactor arrangement according to FIG. 7, in which the gas supply takes place in the vicinity of the inlet of the reactor tubes
Fig 9 Eine schematische Reaktoranordnung des Rohrbundel-Reaktors mit Eduktkreislauf und Umpumpschleife sowie einer adiabatischen Verweilzone 26 9 shows a schematic reactor arrangement of the tube bundle reactor with starting material circuit and pumping loop as well as an adiabatic dwell zone 26
BeispieleExamples
Beispiel 1example 1
In dem in Fig. 1 gezeigten Aufbau ist ein Bündel 3 von Reaktionsrohren 6 in einem Reaktorgehäuse 1 untergebracht und im Bereich der Reaktionszone von einem Wärmetauscher 5 mit einer Kondensatzuleitung 15 und einer Dampfableitung 16 umgeben. In den Reaktionsrohren 6 verlaufen Eduktzuleitungsrohre 4a, 4b, 4c, 4d, entsprechend Fig. 4a konzentrisch. Die Eduktzuleitungen 4a bis 4d sind Teil eines Eduktkreislaufes 25, in dem eine Förderpumpe 14 sowie ein Wärmetauscher 9 vorgesehen sind. Über eine Zuleitungspumpe 17 wird in der Reaktion verbrauchtes Edukt nachgeliefert. Die Reaktionsrohre 6 weisen entsprechend Fig. 5a und Fig. 5b in einem Teilbereich mit Öffnung versehene Eduktleitungen 4 auf. Durch die Vielzahl von Öffnungen 7 in der Eduktleitung 4 strömt das Edukt in die Reaktionszone des Rohres 6 ein (siehe Fig. 5b). Der Reaktor 1 mit dem Rohrbündel 3 ist Teil eines Umpumpkreislaufs 10, in dem die Reaktionsmischung und das über die Eduktzuleitung 11 oder 1 1- zugeführte weitere Edukt umgewälzt werden. Der Umlauf wird gefόrdeπ entsprechend Fig. 1 mit Hülfe einer Umwälzpumpe 13. In den Umpumpkreislauf ist femer eine Querstromfiltereinheit 20 eingebaut, um aus der Reaktion erhaltenes Produkt aus dem Kreislauf entfernen zu können. Das Produkt wird abgeführt über die Ableitung 12.In the structure shown in FIG. 1, a bundle 3 of reaction tubes 6 is accommodated in a reactor housing 1 and is surrounded in the area of the reaction zone by a heat exchanger 5 with a condensate supply line 15 and a steam discharge line 16. In the reaction tubes 6, educt feed tubes 4a, 4b, 4c, 4d run concentrically, according to FIG. 4a. The feed lines 4a to 4d are part of a feed circuit 25 in which a feed pump 14 and a heat exchanger 9 are provided. The starting material consumed in the reaction is supplied via a feed pump 17. According to FIGS. 5a and 5b, the reaction tubes 6 have educt lines 4 provided with an opening in a partial area. The educt flows into the reaction zone of the tube 6 through the large number of openings 7 in the educt line 4 (see FIG. 5b). The reactor 1 with the tube bundle 3 is part of a pumping circuit 10 in which the reaction mixture and the further starting material fed in via the starting material feed line 11 or 11 are circulated. 1 with the help of a circulating pump 13. A cross-flow filter unit 20 is also installed in the circulating circuit in order to be able to remove product obtained from the reaction from the circuit. The product is discharged via the discharge line 12.
In einer vereinfachten Ausführung wird entsprechend Fig. 2a anstelle des Eduktkreislaufs 25 eine einfache Eduktzuführung 4 in die Rohre 6 des Rohrbündels vorgesehen.In a simplified embodiment, a simple educt feed 4 is provided in the tubes 6 of the tube bundle instead of the educt circuit 25 instead of the educt circuit 25.
Fig. 3 zeigt einen schematischen Längsschnitt durch die gleiche Anordnung, bei der das Reaktionsrohr 6 auf seine Länge auf einer Katalysatorschuttung 8 gefüllt ist.3 shows a schematic longitudinal section through the same arrangement, in which the length of the reaction tube 6 is filled on a catalyst bed 8.
Eine erfindungsgemäße Variante der Anordnung der Reaktionsrohre 6 ist in Fig. 4b dargestellt. In Fig. 4b bilden die Zwischenräume zwischen Wärmetauscherrohren 5 rohrförmige Zwischenräume 6- als Reaktionszonen, in denen die Eduktleitungen 4 zur Zuleitung des Eduktes verlaufen. Die rohrfόrmigen Zwischenräume 6'- sind radial zu ihrer Längsausdehnung über Zwischenräume 27 zwischen den Wärmeträgerrohren 5 mit- einander verbunden, wenn die Warmetauscherrohre beabstandet sind, wie in Fig 4b dargestellt.A variant of the arrangement of the reaction tubes 6 according to the invention is shown in FIG. 4b. In Fig. 4b, the spaces between heat exchanger tubes 5 form tubular spaces 6- as reaction zones in which the reactant lines 4 run to feed the reactant. The tubular gaps 6'- are radial to their longitudinal expansion via gaps 27 between the heat transfer tubes 5- connected to each other when the heat exchanger tubes are spaced, as shown in Fig. 4b.
Fig. 5a zeigt einen schematischen Längsschnitt durch ein Reaktionsrohr 6 aus einer Anordnung gemäß Fig. 1, bei dem die Eduktzuleitung 4 Teil eines Eduktkreislaufs ist, aber nur auf einem Teilbereich der Rohrlange von Rohr 6 Öffnungen 7 (siehe Fig 5b) aufweist Gemäß Fig 5c ist dabei eine konzentrische Anordnung der Eduktzuleitung 4 vorgesehen5a shows a schematic longitudinal section through a reaction tube 6 from an arrangement according to FIG. 1, in which the educt feed line 4 is part of an educt circuit, but only has openings 7 on a partial region of the tube length of tube 6 (see FIG. 5b), according to FIG. 5c a concentric arrangement of the educt feed line 4 is provided
Im Falle der Variante gemäß Fig 6 sind die Rohre 6 des Rohrbundelreaktors 1 auf ihrer gesamten Länge mit einer Katalysatorschuttung versehenIn the case of the variant according to FIG. 6, the tubes 6 of the tube bundle reactor 1 are provided with a catalyst bed over their entire length
Beispiel 2Example 2
Für die Reaktion unter Beteiligung weiterer gasförmiger Edukte ist die Variante der Rohrbündelreaktoranordnung gemäß Fig 7 geeignet. Hierbei wird die unter Beispiel 1 beschriebene Anordnung gemäß Fig 1 ergänzt durch einen weiteren Eduktkreislauf 21 zur Zuführung von gasformigen Produkten, z.B von Wasserstoffgas. Das Gas wird über die Zuleitung 22 dem Gaskreislauf 21 zugeführt und am Gaseinlaß 18 vor dem Mischer 13 in den Umpumpkreislauf des Reaktors eingebracht. Das Gas wird mit dem im Umpump- kreislauf 10 umlaufenden Reaktionsgemisch im Gegenstrom zu den über die Rohre 4 zugeführten weiteren Edukten durch die Reaktionszone der Rohre 6 geführt und in einem Gasabscheider 19 von der Reaktionsmischung getrennt Das separierte Gas wird entweder über einen Kreisgaskompressor 24 in den Prozeß zurückgeführt oder am Auslaß 23 zuThe variant of the tube bundle reactor arrangement according to FIG. 7 is suitable for the reaction involving further gaseous starting materials. Here, the arrangement described in Example 1 according to FIG. 1 is supplemented by a further educt circuit 21 for supplying gaseous products, e.g. hydrogen gas. The gas is fed to the gas circuit 21 via the feed line 22 and introduced into the pumping circuit of the reactor at the gas inlet 18 upstream of the mixer 13. The gas is passed through the reaction zone of the tubes 6 with the reaction mixture circulating in the pumping circuit 10 in counterflow to the further starting materials supplied via the tubes 4 and separated from the reaction mixture in a gas separator 19. The separated gas is either fed into the Process returned or at outlet 23 to
Reinigungszwecken abgeführtRemoved for cleaning purposes
In der Anordnung gemäß Fig 8 ist der Einlaß für das zusatzliche Eduktgas kurz vor bzw in der Rohrόff ung der Rohre 6 angebracht. Das Gas wird durch die dichte unterschiedsbedingte Umwälzung des Reaktionsgemisches (10) in die Reaktionsrohre 6 mitge- führt und wie bei der Anordnung gemäß Fig 7 über einen Gasabscheider 19 und einen Kreisgaskompressor 24 dem Eingang des Reaktors wieder zugeführt Beispiel 3In the arrangement according to FIG. 8, the inlet for the additional feed gas is attached just before or in the pipe opening of the pipes 6. The gas is carried into the reaction tubes 6 by the density-dependent circulation of the reaction mixture (10) and, as in the arrangement according to FIG. 7, is fed back to the inlet of the reactor via a gas separator 19 and a circulating gas compressor 24 Example 3
Fig. 9 zeigt eine vereinfachte Reaktoranordnung des erfindungsgemäßen Rohrbundelreaktors bei der anstelle der in Anordnung gemäß Beispiel 1 vorgesehene Querstromfiltration ein einfacher Produktauslaß im Umpumpkreislauf 10 vorgesehen ist. In dieser Variante ist aber dem Ausgang des Reaktorbündels 3 ein Nachreaktor 26 als adiabatischer Verweilraum nachgeschaltet, in dem die Reaktion abklingt. Die Edukte werden hier wie in Beispiel 1 über offenporige Rohrleitungen 4 und über eine Eduktzuleitung 1 1 in den Umpumpkreislauf eingeführt.FIG. 9 shows a simplified reactor arrangement of the tube bundle reactor according to the invention, in which a simple product outlet is provided in the pumping circuit 10 instead of the crossflow filtration provided in the arrangement according to Example 1. In this variant, however, the outlet of the reactor bundle 3 is followed by an after-reactor 26 as an adiabatic dwell in which the reaction subsides. The starting materials are introduced into the pumping circuit here, as in Example 1, via open-pore pipelines 4 and via an educt feed line 11.
Wahlweise besitzt die Anordnung einen stationären Kontakt 8 oder es wird ein Kataly- satorslurry über den Einlaß 1 1 und den Auslaß 12 mit zwischengeschalteter Abtrennung des Katalysators zur Recyclierung hindurchgeführtOptionally, the arrangement has a stationary contact 8, or a catalyst slurry is passed through inlet 11 and outlet 12 with the catalyst being separated off for recycling
Die Umsetzung kann auch homogen katalysiert ablaufen. In diesem Fall muß der Katalysator mit den Stoffströmen über die Pumpe 17 oder den Einlaß 11 zugeführt werden. The reaction can also be carried out homogeneously catalyzed. In this case, the catalyst with the material flows must be supplied via the pump 17 or the inlet 11.

Claims

Patentansprücheclaims
1 Rohrbundelreaktor (1) für rasche stark exotherme Reaktionen bestehend aus einem Reaktorgehäuse (2) mit einem Bündel (3) von Rohren (6), die gegebenen- falls radial zu ihrer Längenausdehnung miteinander verbunden sind, als Reaktionszone, Eduktzuleitungen (4, 1 1), Produktauslaß (12) und Wärmetauscher (5) dadurch gekennzeichnet, daß eine Eduktzuleitung (4) als in den Rohren (6) der Bündel (3) verlaufende und mit einer Vielzahl von Öffnungen (7) versehene Rohrleitungen (4a, 4b, 4c, 4d) ausgeführt sind, wobei die Öffnungen (7) in den Rohrleitungen (4a, 4b. 4c, 4d) über die ganze Lange oder einen Längenabschnitt der Reaktionszone verteilt sind1 tube-bundle reactor (1) for rapid, strongly exothermic reactions consisting of a reactor housing (2) with a bundle (3) of tubes (6), which are optionally connected radially to one another as a reaction zone, educt feed lines (4, 1 1 ), Product outlet (12) and heat exchanger (5), characterized in that an educt feed line (4) running in the tubes (6) of the bundles (3) and having a plurality of openings (7) is provided with pipes (4a, 4b, 4c , 4d), the openings (7) in the pipelines (4a, 4b, 4c, 4d) being distributed over the entire length or a length section of the reaction zone
2 Reaktor nach Anspruch 1, dadurch gekennzeichnet, daß die Rohre (6) eine Katalysatorschuttung aufweisen2 reactor according to claim 1, characterized in that the tubes (6) have a catalyst bed
3 Reaktor nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß der maximale Porenöffhungsquerschnitt der Öffnungen (7) 1 mm bevorzugt 0.7 mm beträgt3 reactor according to claims 1 or 2, characterized in that the maximum pore opening cross section of the openings (7) is 1 mm, preferably 0.7 mm
4 Reaktor nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß der minimale4 reactor according to claims 1 to 3, characterized in that the minimum
Porenöffhungsquerschnitt der Öffnungen (7) 1 μm bevorzugt 7 μm betragtPore opening cross section of the openings (7) is 1 μm, preferably 7 μm
5 Reaktor nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Eduktzuleitung (4) Teil einer Eduktschleife 25 mit Fordermittel (14) und Wärmetauscher (9) ist5 reactor according to claims 1 to 4, characterized in that the feed line (4) is part of a feed loop 25 with conveying means (14) and heat exchanger (9)
6 Reaktor nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß der Reaktor eine Umpumpschleife (10) für die Reaktionsmischung mit einem Fordermittel (13), einer Eduktzuleitung (1 1) bzw (1 1)' und einen Produktauslaß (12) aufweist6 reactor according to claims 1 to 5, characterized in that the reactor has a pumping loop (10) for the reaction mixture with a delivery means (13), a starting material feed line (1 1) or (1 1) 'and a product outlet (12)
7 Reaktor nach Anspruch 6, dadurch gekennzeichnet, daß in der Umpumpschleife (10) des Reaktor (1) eine Katalysatorsuspension umlauft Reaktor nach den Ansprüchen 6 bis 7, dadurch gekennzeichnet, daß das Fordermittel (13) eine Mammutpumpe oder eine Umwälzpumpe ist7 reactor according to claim 6, characterized in that in the pumping loop (10) of the reactor (1) circulates a catalyst suspension Reactor according to claims 6 to 7, characterized in that the delivery means (13) is a mammoth pump or a circulating pump
Reaktor nach den Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß im Bereich vor dem Eingang des Rohrbundeis (3) des Reaktors (1) eine Gaszuführung (18) für gasformige Reaktanden und ggf hinter der Gaszuführung (18) zusätzlich ein Mischerelement, insbesondere ein statischer und/oder dynamischer Mischer, angeordnet istReactor according to claims 1 to 8, characterized in that in the area in front of the entrance of the tube bundle (3) of the reactor (1) there is a gas feed (18) for gaseous reactants and, if necessary, an additional mixer element, in particular a static one, behind the gas feed (18) and / or dynamic mixer
Reaktor nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß sich in demReactor according to claims 1 to 9, characterized in that in the
Reaktor (1) an die aus den Rohren (6) gebildete Reaktionszone eine adiabatische Verweilzone (26) anschließtReactor (1) connects to the reaction zone formed from the tubes (6) an adiabatic dwell zone (26)
Reaktor nach den Ansprüchen 1 bis 10, dadurch gekennzeichnet, daß in der Umpumpschleife (10) eine Katalysatorzuleitung bzw Recycherungsleitung (11) und/oder die Produktableitung (12) angeordnet istReactor according to Claims 1 to 10, characterized in that a catalyst feed line or recycling line (11) and / or the product discharge line (12) is arranged in the pumping loop (10)
Reaktor nach Anspruch 1 1, dadurch gekennzeichnet, daß die Produktableitung (12) ein Absetztank mit Auslauf istReactor according to claim 1 1, characterized in that the product discharge (12) is a settling tank with an outlet
Reaktor nach Anspruch 1 1, dadurch gekennzeichnet, daß die Produktableitung (12) eine Filtrationseinheit (20), insbesondere eine Einheit zur QuerstromfiltrationReactor according to claim 1 1, characterized in that the product discharge line (12) is a filtration unit (20), in particular a unit for cross-flow filtration
Verwendung des Reaktors nach den Ansprüchen 1 bis 13 zur Durchführung stark exothermer Reaktionen, insbesondere zur Hvdrierung von Dinitrotoluol Use of the reactor according to claims 1 to 13 for carrying out strongly exothermic reactions, in particular for the hydrogenation of dinitrotoluene
PCT/EP1998/003037 1997-06-04 1998-05-22 Reactor for carrying out rapid highly exothermic reactions and use thereof WO1998055216A1 (en)

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US7109378B2 (en) 2001-08-30 2006-09-19 Air Products And Chemicals, Inc. Monolith catalytic reactor coupled to static mixer
WO2012123469A1 (en) 2011-03-16 2012-09-20 Basf Se Optimized metering of reactants for a process for preparing aromatic amines by hydrogenation of nitroaromatics
US8835688B2 (en) 2011-03-16 2014-09-16 Basf Se Optimized introduction of the starting materials for a process for preparing aromatic amines by hydrogenation of nitroaromatics

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EP2409104B1 (en) * 2009-03-17 2015-11-11 Dow Global Technologies LLC Method of heat exchange
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DE102012206541A1 (en) * 2012-04-20 2013-10-24 Siemens Aktiengesellschaft Method and arrangement for high-temperature electrolysis
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WO2001085332A1 (en) * 2000-05-05 2001-11-15 Deggendorfer Werft Und Eisenbau Gmbh Tubular reactor for carrying out exothermic gas phase reactions
US7109378B2 (en) 2001-08-30 2006-09-19 Air Products And Chemicals, Inc. Monolith catalytic reactor coupled to static mixer
US7595029B2 (en) 2001-08-30 2009-09-29 Air Products And Chemicals, Inc. Monolith catalytic reactor coupled to static mixer
WO2012123469A1 (en) 2011-03-16 2012-09-20 Basf Se Optimized metering of reactants for a process for preparing aromatic amines by hydrogenation of nitroaromatics
US8835688B2 (en) 2011-03-16 2014-09-16 Basf Se Optimized introduction of the starting materials for a process for preparing aromatic amines by hydrogenation of nitroaromatics
US9308515B2 (en) 2011-03-16 2016-04-12 Basf Se Optimized introduction of the starting materials for a process for preparing aromatic amines by hydrogenation of nitroaromatics

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