WO2011095566A1 - Dispositif réacteur et procédé pour optimiser la mesure des variations de température dans des réacteurs tubulaires - Google Patents

Dispositif réacteur et procédé pour optimiser la mesure des variations de température dans des réacteurs tubulaires Download PDF

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Publication number
WO2011095566A1
WO2011095566A1 PCT/EP2011/051606 EP2011051606W WO2011095566A1 WO 2011095566 A1 WO2011095566 A1 WO 2011095566A1 EP 2011051606 W EP2011051606 W EP 2011051606W WO 2011095566 A1 WO2011095566 A1 WO 2011095566A1
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WIPO (PCT)
Prior art keywords
catalyst
group
tube
tubes
reaction
Prior art date
Application number
PCT/EP2011/051606
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German (de)
English (en)
Inventor
Harald Dialer
Marvin Estenfelder
Christian GÜCKEL
Gerhard Mestl
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Süd-Chemie AG
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Application filed by Süd-Chemie AG filed Critical Süd-Chemie AG
Priority to CN2011800162284A priority Critical patent/CN103025421A/zh
Priority to DE112011100423T priority patent/DE112011100423A5/de
Publication of WO2011095566A1 publication Critical patent/WO2011095566A1/fr

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Classifications

    • 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
    • B01J8/067—Heating or cooling the reactor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
    • G01K7/42—Circuits effecting compensation of thermal inertia; Circuits for predicting the stationary value of a temperature
    • G01K7/427—Temperature calculation based on spatial modeling, e.g. spatial inter- or extrapolation
    • 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
    • B01J2208/00026—Controlling or regulating the heat exchange system
    • B01J2208/00035—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2208/00044—Temperature measurement
    • B01J2208/00061—Temperature measurement of the reactants
    • 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
    • B01J2208/00654—Controlling the process by measures relating to the particulate material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
    • G01K7/42—Circuits effecting compensation of thermal inertia; Circuits for predicting the stationary value of a temperature
    • G01K2007/422—Dummy objects used for estimating temperature of real objects
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K2213/00—Temperature mapping

Definitions

  • the invention relates to a reactor apparatus having at least a first group G m of pipes comprising at least one normal pipe filled with catalyst bodies K m and a second group G n of pipes comprising at least one thermo pipe provided with a temperature measuring apparatus comprising second catalyst bodies K n is filled, wherein the catalyst body K m , n each in an in
  • the invention relates to a method for providing such a reactor device and a method for
  • a shell-and-tube reactor comprises a plurality of reaction tubes arranged in one
  • Reactor housings are arranged, which of a
  • Heat transfer medium is flowed through.
  • the heat transfer medium flows around the pipes, so that a rapid heat exchange between pipes and heat transfer medium is achieved.
  • a solid catalyst is arranged, the bed of which
  • gaseous educt is flowed through. Since the gas stream is divided into many individual gas streams, each one flow through a single tube, in a reaction in the tube reactor is generally achieved a well reproducible result, since the flow distribution over the
  • a temperature profile can be determined. For example, when starting the reactor, so if a
  • Catalyst which still contains organic binder, burned out and thus activated, it is essential that a certain temperature is not exceeded, so that, for example, sintering operations of the catalyst are largely suppressed.
  • the reaction usually has to be within a very narrow range
  • Temperature range are performed. Furthermore, the age is aging
  • reaction conditions must be readjusted by For example, the reaction temperature or the concentration of a promoter in the gas stream is increased to a
  • thermotubes in which no temperature measurement is made, about 5 to 10 thermotubes are provided, which should allow a representative temperature measurement in the reactor.
  • a thermal tube is a reaction tube which is provided with a device for measuring the temperature. These thermo tubes should reflect the temperature profile of all normal pipes as representative as possible. But this is difficult.
  • a protective tube is usually arranged along the longitudinal axis in the interior of the thermal tube, in which in turn a
  • Temperature sensor is arranged, for example a
  • the protective tube would have to be arranged exactly centric in the thermal tube over its entire length. Any already minimal deviation from the centric-axial position in the direction of the pipe wall leads due to the radial temperature gradient between tube axis and cooled tube wall to significant deviations in the measured
  • thermocouple in a protective tube, which at some locations within the reaction tube of this
  • the catalyst bodies are arranged in the annular gap between the protective tube and the inner surface of the thermal tube. It is usually not possible to arrange the catalyst bodies in the thermal tubes and in the normal tubes in the same way. in the
  • the catalyst bodies in the thermal tubes and the normal tubes have a different bulk density. Also, the flow conditions of the reaction gas in the normal pipe and thermo pipe due to the installation of the
  • thermo tubes The temperatures measured in the thermo tubes can therefore not be directly transferred to the normal tubes, but must first be corrected. This can therefore be directly transferred to the normal tubes, but must first be corrected. This can therefore be directly transferred to the normal tubes, but must first be corrected. This can therefore be directly transferred to the normal tubes, but must first be corrected. This can therefore be directly transferred to the normal tubes, but must first be corrected. This can therefore be directly transferred to the normal tubes, but must first be corrected. This can
  • US 2008 / 0014,127 A1 describes a test method with which the reaction conditions for a catalytic gas phase reaction in a shell-and-tube reactor are determined can.
  • the test conditions are determined on a significantly smaller number of tubes, as in the tube bundle reactor intended for industrial production
  • test reactor which comprises two tubes which are in their
  • the second tube is also filled with catalyst bodies, but additionally contains one
  • Temperature measuring device with which the temperature profile in the tube can be determined.
  • the test reactor is then adjusted to a certain temperature by the two tubes are lapped with a heat transfer medium having a certain temperature. It is then determined the temperature profile in the second tube and the composition of the reaction products in the first tube. The temperature is then changed until the best conditions for the reaction
  • Thermal tube of the reactor results in a product composition in the normal tubes, as they were determined with the test reactor.
  • Tube bundle reactor selected for the measurement of the temperature profile.
  • a tube bundle reactor is used, which is provided with baffles for the heat transfer medium.
  • the temperature profile is measured only in such pipes, which are not connected to a baffle plate.
  • a different bed of catalyst body in normal pipes and thermal tubes is not considered.
  • the mean linear velocity of the gas flow in all tubes is set to the same value.
  • the pressure loss is measured by passing an amount of an inert gas through the tube in question, the amount of gas being chosen to be proportional to the free cross-sectional area of the tube.
  • the amount of FestStoffteilchen which is filled in the normal pipe and in the thermal tube chosen so that the ratio of mass of the solid particles to the free cross-sectional area for normal pipe and thermal tube is the same.
  • a R the amount of active mass in the standard tube
  • a T the amount of active mass in the thermal tube
  • n T the outer diameter of the arranged in the thermal tube
  • Thermowell for the temperature sensor is Thermowell for the temperature sensor.
  • Gas velocity over the catalyst particles can be increased by the use of solid particles of different size and / or Geometry done.
  • solid particles of different size for example, in the thermal tube, a mixture of solid catalyst bodies and from the
  • Full catalysts produced split can be used.
  • the mixture of full catalyst and fine split produced from the full catalyst can not necessarily be filled homogeneously over the entire tube length into the thermal tube.
  • Tube bundle reactor is carried out a further separation, since the finer parts migrate into the lower part of the thermal tube.
  • the invention therefore an object of the invention to provide a reactor device available, in which the thermal tubes reproduce the temperature profile in the normal tube as accurately as possible. This object is achieved with a reactor device with the
  • Embodiments of the reactor device are the subject of the dependent claims.
  • the temperature profile in the normal pipe can be much better represented by the temperature profile in the thermal tube when the activity of the arranged in a certain volume of the pipe section active mass to the inner surface of the tube is set in this section and this ratio for both the normal pipe also set approximately the same for the thermal tube.
  • the modified residence time T m0 d of the reaction gas is defined here as the quotient of mass of active mass in the reactor and the residence time ⁇ of the reaction gas under standard conditions (DIN 1343, 0 ° C, 1013 mbar).
  • the residence time ⁇ is again defined here as the quotient of reactor volume and volume flow of
  • the volume flow is defined as the volume of gas, for example given in Nm 3 , which flows in a unit time, for example one hour, through the reactor, for example a pipe or a boiler.
  • Gas velocity is used as a parameter, but the modified based on the amount of active material
  • linear gas velocity as an adjustment parameter would not account for a different bulk density in the two types of tubes.
  • the reactor device according to the invention thus moves a partial volume of the gas stream with approximately the same
  • Dwell time T m0 d may show a deviation, which is caused by technical tolerances, both in the tubes within a group and between tubes of different groups. Under a substantially same value is therefore a
  • the ratio of the two products is the ratio of the
  • the back pressure on a standard pipe or a thermal pipe measured at a gas flow of 4 Nm 3 / h, according to one embodiment in the range of 1 to 5 bar absolute , according to another embodiment in the range of 1.1 to 1.6 bar absolute .
  • the pressure drop across a standard pipe or a thermal pipe, measured at a gas flow of 4 Nm 3 / h, according to one embodiment is in the range of 80 to 600 mbar, according to another embodiment in the range of 90 to 500 mbar.
  • the ratio of the two products is the ratio of the
  • modified residence time i mod measured in the normal tube
  • modified residence time i mod measured in the thermometer tube
  • the space-time velocity (GHSV) in the normal tubes and the thermal tubes is in one embodiment in the range of 500 to 10,000 h -1 , according to another embodiment in the range of 800 to 4,000 h _1 .
  • the GHSV of a particular tube does not deviate by more than ⁇ 20%, according to another embodiment by not more than ⁇ 10%, and according to another embodiment by not more than ⁇ 5% of the mean of the GHSV (arithmetic mean) across all the tubes of the reactor, off.
  • the pressure drop and the modified residence time ⁇ u m0d are, unlike those defined in the theory of the reaction technique , preferably measured before the reactor goes into operation. This will be an inert gas stream is passed through the individual tube and with this inert gas the pressure drop and the
  • modified residence time ⁇ u m0d determined and adjusted if necessary.
  • the determination is carried out preferably at room temperature, for example in a range of 10 to 40 ° C, in particular at a temperature of 20 ° C.
  • Nitrogen gas or, for example, also compressed air can be used as the inert gas.
  • the reactor device initially corresponds to a conventional tube bundle reactor.
  • the tube bundle reactor comprises in
  • the normal pipes form the group G m of pipes.
  • Thermo tubes are tubes which are charged with catalyst bodies and comprise a measuring device with which the temperature or the temperature profile within the tube can be measured.
  • the thermo tubes form the group G n of tubes.
  • a common tube bundle reactor comprises about 5,000 to 30,000 normal tubes and 3 to 20
  • the tubes are arranged in a boiler, which is flowed through by a heat transfer medium,
  • the tubes are preferably arranged evenly distributed inside the vessel, wherein the distance of the longitudinal axes between adjacent tubes preferably in the range of 20 to 80 mm, according to a
  • Embodiment selected in the range of 35 to 45 mm. Deviations from these ranges are possible.
  • Heat transfer medium flows around the pipes arranged in the boiler so that heat can be supplied to the pipes or heat can be removed from the pipes.
  • the tubes are preferably arranged parallel to one another and usually have a length between 1 m and 8 m, usually 2 to 5 m, for example 3 to 3.5 m up. Deviating dimensions from these areas are possible. In the tubes is one of the
  • Catalyst bodies K mjn formed catalyst bed arranged.
  • the catalyst bed is preferably arranged in a region of the tube which passes through a heat transfer medium
  • the catalyst bed In the longitudinal direction of the tubes, the catalyst bed preferably extends over at least 50%, according to another embodiment over at least 70% and according to another embodiment over at least 80% of the length of the tubes. Usually, the entire length of the tube is not occupied by the catalyst bed, for example, space for mechanical catalyst support, bodies for adjusting the pressure drop or for preheating the reaction gas to
  • the catalyst bed occupies less than 97% of the length of the tube, according to another embodiment, less than 90% of the length of the tube.
  • the heat transfer medium In the heat transfer medium
  • the tubes can open at their two ends in each case in a common gas space, so that the educts from the common gas space flows into the individual, catalyst-charged tubes and flow on the other side of the tube, the reaction products in a common gas space, from which then the Distribution to processing equipment, such as distillation columns or
  • Wash towers can be done.
  • the tubes are made of a material which is stable under the reaction conditions and in particular does not embrittle during operation of the reactor.
  • a suitable one Material for the production of the tubes is, for example, ferritic steel.
  • the tubes have according to a
  • Embodiment an inner diameter of 15 to 50 mm and an outer diameter in the range of 16 to 55 mm. However, dimensions deviating from these ranges are possible. Normal pipes and thermo tubes do not necessarily have the same diameter. In most cases, the thermal tubes are dimensioned with a larger cross section to the
  • the tubes have a wall thickness in the range of 1 to 3 mm.
  • the tubes preferably have a circular cross-section. But it is also possible to use tubes with a different cross-section,
  • All tubes of a group have the same cross-section.
  • the inner diameter of the normal tubes is
  • Inner diameter of the thermal tubes is usually chosen larger.
  • the inner diameter of the thermal tubes is selected in the range of 15 to 50 mm.
  • reaction section S is defined, which preferably has the same dimension in both groups of pipes. In itself, the reaction path
  • Thermo tube and normal tubes are also chosen differently and, for example, in each case the entire length Include catalyst bed.
  • the reaction path is preferably positioned the same for both groups of tubes relative to their gas inlet and gas outlet side, so that in the thermal tubes measurements can be carried out, which is a representative measurement of the temperature profile in the
  • the reaction path S thus comprises a section provided in all tubes, which in each case with corresponding
  • Catalyst bodies is filled and in which an approximately the same temperature profile can be set for all tubes.
  • the similar arrangement of the reaction path S in thermal and normal pipes is advantageous, for example, if the majority of the reaction takes place in the catalyst bed near the gas inlet side, ie the predominant part of the heat development near the gas inlet side in
  • Catalyst bed for example, only an optimization of
  • composition of the reaction products is carried out without a comparable heat of reaction occurs as in the main reaction near the gas inlet.
  • the reaction path S in the normal tube and in the thermal tube should thus comprise approximately the same reaction profile in the catalyst bed.
  • the reaction zone S may comprise the entire filling height of the catalyst bed. But it is also possible to choose a reaction path S, which is smaller than the total distance, which is provided by the catalyst body within a tube in the longitudinal direction, ie ultimately the filling height of the catalyst bed in
  • the reaction distance is preferably selected so that it is at least ten times the radius of the normal tube, preferably at least 100 times the radius of the normal tube equivalent.
  • the reaction path S comprises at least 50%, according to another
  • Embodiment at least 70% and according to another
  • Embodiment at least 90% of the length of the catalyst bed in the tubes.
  • the length of the catalyst bed viewed in the flow direction of the reaction gas, means a section in the tube which is filled with catalyst bodies in all tubes within the reactor.
  • volume section defined in the standard tube or in the thermal tube.
  • the volume section would calculate according to (r N a ) 2 ⁇ ⁇ ⁇ S, where r N a means the inner radius of the normal pipe.
  • r N a means the inner radius of the normal pipe.
  • volume portion has the shape of a hollow cylinder.
  • a wall surface W is defined by the reactor section S in both tubes.
  • the wall surface for the normal pipe is 2nr N a ⁇ S, where r N a is the inner radius of the normal pipe and 2nr T a ⁇ S for the thermal pipe, where r T a is the inner radius of the outer pipe.
  • volume section is filled with catalyst bodies K mjn .
  • the shape and the composition of the catalyst body is initially not subject to any restrictions.
  • the catalyst bodies within a section can be the same
  • Catalyst is used with the same composition. The only requirement is that the im
  • Thermotube introduced catalyst over the length of the
  • Thermotube shows such an activity curve that a temperature profile is generated, as it is approximately produced in the normal tube.
  • a m a catalyst activity in which by the
  • Reaction section S certain volume section in the tube from the first group G m is provided
  • a n a catalyst activity in which by the
  • Reaction section S certain volume section is provided in the tube from the second group G n ,
  • W n an inner surface of the tube from the second group G n , which is determined by the reaction path S, a: a correction factor selected in the range of 0.8 to 1.2.
  • the correction factor a takes into account a deviation of a real reactor from an ideal reactor. In an ideal reactor with an ideal bed of catalyst particles, a would assume the value 1. But because, for example
  • the correction factor a is in a range of 0.9 to 1.1.
  • Catalyst activity A b is calculated according to the equation
  • a x b an active-mass-related activity constant of the first order of a catalyst body K b provided
  • Tube provided active mass
  • a b Determination of Catalyst Activity A b is determined according to a Embodiment proceeded so that a catalyst body is produced with a certain geometry and a certain content of active material. Further, it is believed that the first order reaction proceeds regardless of the order with which the reaction actually proceeds.
  • the product of the rate constant k of a first-order reaction and the average residence time ⁇ corresponds to the first
  • Damköhler number Dai which essentially describes the turnover of a simple reaction in a reactor.
  • the rate constant k is the same for both catalysts.
  • This standardized catalyst body is then diluted in a test reactor with inert bodies so far that the temperature difference between the gas inlet and the
  • Gas outlet side is less than 25 ° C, preferably less than 10 ° C, the reaction under almost isothermal
  • the catalyst body is diluted with inert bodies.
  • the geometry of the catalyst body and the inert body is chosen so that the required low pressure drop is realized.
  • the ratio of inert bodies to catalyst bodies is chosen so that the required conversion is achieved and at the same time the heat development is so low that the required low temperature difference between gas inlet and gas outlet is maintained.
  • a ratio of catalyst bodies to inert bodies of 1: 5 to 1: 10 is preferably selected.
  • the dimensions of the test reactor will vary depending on the considered reaction between 1 and 6 m for the length and between 18 and 32 mm for the diameter of the tube chosen. In fast reactions, a short length is chosen
  • mActive mass the amount of active mass [g] introduced in the test tube; U: the conversion of the educt, whereby this is calculated
  • Reference sales determined. This reference turnover is chosen such that this turnover is in the linear range of
  • Order A * is the active mass of the conversion. For example, a turnover of 85% can be set as a reference. The calculated for a turnover of 85%, for example
  • active mass-related activity constant 1st order is then referred to as active mass-related activity constant 1st order A x b .
  • active mass-related activity constant 1st order A x b is then referred to as active mass-related activity constant 1st order A x b .
  • another value for sales can be set. The value should be however at the
  • the value of the conversion for determining the active mass-related activity constant 1st order A x b is selected within a range which is ⁇ 20% of the conversion at which the reaction in question is technically implemented, the conversion being within a range of the curve of
  • thermo tube include a temperature measuring device, with which the temperature or the temperature profile can be determined in the thermal tube.
  • This can be any measuring devices be used. Preferred are those
  • Temperature sensors are provided with which the temperature can be measured at defined locations of the tube. But it is also possible, for example, a movable
  • the temperature measuring device is designed as arranged along the longitudinal axis of the thermal tube tube, in which at least one temperature sensor is arranged. Through the pipe, the temperature sensor is protected from damage. It is preferably provided that the temperature sensor is designed so that it is in the pipe
  • thermowell thermowell thermowell arranged in the thermowell.
  • the catalyst bodies K m , K n may in themselves have any desired shape, wherein different catalyst bodies can also be combined with one another within a tube. Be within a tube of a catalyst bed
  • Catalyst bodies of different shapes used, but this can during filling to a partial or
  • a homogeneous bed is understood to mean a bed whose bulk density, measured over the length of the relevant pipe, deviates from the mean
  • catalyst bodies of different geometry are used within a common catalyst bed, a homogeneous bed can be achieved by, for example, the differently shaped
  • Catalyst bodies are filled in a particular arrangement or sequence in the pipe in question, so that a
  • Catalyst body K m and the catalyst body K n in the volume section defined by the reaction section S each have a homogeneous shape.
  • the catalyst bodies each have a tube the same properties, ie
  • composition of the active composition the same amount
  • Catalyst body are arranged. Rather, it is generally provided that the catalyst body K m and the
  • Catalyst body K n are different, so for example have a different shape, in the
  • the catalyst bodies K mfn used in the reactor device can be designed as solid catalysts, that is, for example, over their entire volume a homogeneous
  • the catalyst body K m and the catalyst body K n as
  • Supported catalysts in particular as shell catalysts, are formed with a layer of the active composition.
  • the supported catalysts can be designed in the usual way.
  • the supported catalysts may comprise a carrier body which may have any desired shape.
  • the support body may for example have the shape of a ring, a ball or a hollow cylinder.
  • Support bodies in the form of a hollow cylinder are preferred.
  • the support bodies in the form of a hollow cylinder are preferred.
  • Hollow cylinder has a length in the range of 2 to 10 mm, according to one embodiment in the range of 4 to 8 mm. According to one embodiment, the hollow cylinders have a
  • the wall thickness of the hollow cylinder is preferably in the range of 0.5 to 4 mm, according to one embodiment in the range of 1 to 2 mm
  • Exemplary dimensions for suitable hollow cylinders are 8 x 6 x 5 mm, 7 x 7 x 4 mm, 7 x 4 x 4 mm and 6 x 5 x 4 mm
  • hollow cylinders are suitable, the one
  • Carrier body understood.
  • the carrier bodies are preferably constructed of a material which has a very low porosity, for example a porosity of less than 1 ml / 100 g.
  • the carrier bodies may be made of conventional materials, for example porcelain, quartz, magnesium oxide, zinc dioxide, silicon carbide, rutile, alumina (Al 2 O 3 ), aluminum silicate, magnesium silicate (steatite), zirconium silicate or cersilicate or aus
  • the active material may additionally contain other materials,
  • the active mass is a binder.
  • the layer thickness of the applied on the support body shell of the active material is according to one embodiment between 10 and 800 pm and according to another embodiment
  • the layer thickness of the applied on the carrier body shell is preferably low
  • certain volume portion is provided, based on the tube wall area of the section in the range of 0.01 to 1 g / cm 2 , according to one embodiment in the range of 0.02 to 0.08 g / cm 2 is selected. According to one embodiment, both for the
  • Catalyst body of the thermal tubes used the same active mass, the catalyst activity can be adjusted in normal tubes and thermal tubes on the amount of active mass in the tube in question within the by the
  • Pipe wall surface which is for normal pipe and thermal pipe
  • M m the mass of the active mass in which by the
  • Reaction section S certain volume section in the tube from the first group G m is provided
  • M n the mass of the active mass in which by the
  • Reaction section S certain volume section is provided in the tube from the second group G n ,
  • W n an inner surface of the tube of the second group G n , which is determined by the reaction distance S, a: a correction factor, which is selected in the range of 0.8 to 1.2. In one embodiment, a is chosen in the range of 0.9 to 1.1.
  • Asked catalyst activity can according to a
  • Embodiment when using coated catalysts for example, be adjusted by the fact that the active material of the catalyst body K m , K n has a same composition and the activity A b is determined by the layer thickness of the applied on the support body active mass. In this embodiment, therefore, the amount of active material which is provided in the volume section of the tube, determined by the layer thickness of the active composition. A higher one
  • the active mass provided by the catalyst bodies K m , n respectively has the same active mass-related activity constant 1 st order, so that the adjustment of the catalyst activity in the volume section of the pipe determined by the reaction section S is effected via the amount of active mass provided.
  • the activity can also be adjusted by the active mass-related
  • Activity constant 1st order A x b is adjusted.
  • the composition of the active composition can be changed, for example by adding promoters or moderators to the active composition.
  • the concentration of promoters or moderators can be adjusted, for example by adding promoters or moderators to the active composition.
  • Promoters or moderators in the active composition can be chosen differently in the catalyst bodies K m , K n .
  • Activity constant 1st order A x b of the active material lead is achieved by virtue of the fact that the catalyst bodies K m , K n have a different geometry.
  • the catalyst body in the normal tubes and the thermal tubes can have the same shape in both tubes, for example, balls or hollow cylinders, wherein the dimensions of the moldings in the
  • the amount of active material in the volume section determined by the reaction section S can be increased by using smaller balls with the same layer thickness of the active mass. But it is also possible to provide in the determined by the reaction section S volume portions of normal and thermal tube catalyst body, which differ in their shape.
  • shell catalysts are used, wherein the shell catalyst takes the form of a
  • Hollow cylinder has.
  • carrier bodies can be used, which have a smaller inner or
  • Thermal tube and normal tube are chosen completely different, so for example in a tube, the catalyst body having the shape of hollow cylinders while in the other tubes, the catalyst body having the form of balls.
  • the adaptation of the catalyst activity provided in the volume section determined by the reaction section S takes place by adding inert bodies to the catalyst bodies. If identical catalyst bodies are used in the volume sections determined by the reaction section S, the catalyst activity can be adjusted by the fact that the catalyst bodies in one of the tubes are replaced by the addition of
  • the inert bodies can have the same shape as the catalyst bodies or else have a different form from them.
  • the reactor device according to the invention can be designed so that in the normal tubes and the thermal tubes the
  • Thermo tube provided.
  • reaction section S is provided in the tubes of the first group G m and in the tubes of the second group G n , the reaction sections S a respectively defining volume sections in the tubes, and in the volume sections
  • Groups G m and G n in which the respective reaction section S a is arranged are three layers of
  • Catalyst bed comprising a plurality of layers, wherein the catalyst bodies contained in the individual layers are selected differently. This way you can
  • the tubes of the group G m or G n each comprise at least two reaction sections S a , according to a further embodiment, at least three Reaction sections S a and according to yet another
  • Embodiment at least four reaction sections S a .
  • precisely two reaction sections S a in each case exactly exactly three reaction sections S a are arranged in the tubes , and exactly four reaction sections S a are arranged according to a further embodiment.
  • the length of the individual reaction sections S a can be chosen equal or different within a tube.
  • the corresponding reaction sections S a are preferably selected to be the same length, so that a
  • the various reaction sections S a then comprise regions that provide different catalyst activity.
  • the procedure is such that a layer of inert bodies is provided in a first working step for setting the pressure drop of all normal tubes, in particular for increasing the pressure drop.
  • Inert bodies preferably have a different geometry than the catalyst body.
  • a layer of sand can be provided, whereby the pressure drop can be increased. This layer off
  • Inert bodies are preferably provided on the gas exit side of the catalyst bed. If the pressure drop in one of the tubes is to be reduced, it is also possible to proceed in such a way that the length of the catalyst bed arranged in the relevant tube is shortened. The Reaction path S can then optionally be adapted to the shortened catalyst bed.
  • the normal tubes are now set to a certain modified residence time ⁇ u m0d .
  • the modified residence time ⁇ u m0d of the thermal tubes is now adjusted in a second step to this in advance
  • the modified residence time ⁇ u m0d can then be calculated via the amount of gas passed through the catalyst bed of the relevant pipe.
  • Residence time ⁇ u m0d can be adjusted by adding or removing catalyst bodies until the desired
  • the thermal tubes may be corrected, the thermal tubes are filled, controlled and adjusted using the critical parameters determined for the normal tubes.
  • the reactor device can be adapted per se to all reactions that are accessible to heterogeneous catalysis.
  • the reactor apparatus is used for such reactions which are carried out in the gas phase.
  • Shell catalysts can be used.
  • the reactions can be both exothermic and endothermic.
  • Reactor device be discharged when the reaction
  • the reactor device according to the invention is particularly well suited for carrying out exothermic reactions, such as oxidation, dehydrogenation,
  • Examples are the preparation of phthalic anhydride from o-xylene, from acrolein from propene, from acrylic acid from propene / acrolein, from methacrylic acid from methacrolein, from methacrolein i-butene, from acrylonitrile from propene, from formaldehyde from methanol, from ethylene oxide from ethylene or the production of maleic anhydride from butane.
  • Reactor device for the production of phthalic anhydride from o-xylene and / or naphthalene
  • Naphthalene be resorted to.
  • thermal tubes are made according to the reactor apparatus described above.
  • Phthalic anhydride can be carried out in such a way that in the normal tubes or the thermal tubes only a single layer formed from the catalyst bodies
  • phthalic anhydride is preferred to arrange several layers of different catalysts in the tubes, wherein the catalysts of the provided in a tube layers, for example, in their composition and
  • Catalyst body then takes place for each layer according to the principles described above.
  • the catalysts used for the production of phthalic anhydride are preferably based on vanadium pentoxide and Titanium dioxide.
  • the titanium dioxide is generally used in the
  • Anatase modification used and has a specific surface area in the range of 10 to 50 m 2 / g.
  • a specific surface area in the range of 10 to 50 m 2 / g.
  • Components mentioned may contain conventional other components in the active composition, whereby the activity of the active composition
  • composition of the active composition is preferably selected in the following ranges:
  • Compounds may be contained in the active composition, with which the activity of the catalyst can be modified.
  • Such compounds include compounds of the alkali and alkaline earth metals, thallium, antimony, iron, niobium, cobalt, molybdenum, silver, tungsten, tin, lead and bismuth.
  • these elements are usually in the form of their oxides.
  • the proportion of these metals, calculated as the most stable oxide and based on the active composition in its active form, is preferably in the range of 0 to 3 wt .-%, preferably 0 to 2 wt .-%.
  • Oxides may be present alone or in the form of a mixture in the active composition.
  • the missing to 100 wt .-% proportion of the active composition, based on their activated oxidic form, is preferably formed by T1O 2 , which is preferably present in the anatase modification.
  • the T1O 2 preferably has a BET surface area of at least 15 m 2 / g, more preferably a BET surface area of between 15 and 60 m 2 / g, in particular a BET surface area of between 15 and 45 m 2 / g and particularly preferably between 15 and 40 m 2 / g. If the reactor device according to the invention for a
  • the catalyst bodies are preferably provided as shell catalysts.
  • a shell catalyst comprises an inert
  • Carrier which is inert under the reaction conditions. Suitable materials and shapes for the carrier bodies have already been described above.
  • the active composition is applied in the form of a thin layer. The layer thickness of the applied to the carrier body
  • Active composition is preferably in the range of 50 to 500 pm
  • the active material may be applied in the form of a single layer. It is also possible to have two or more layers of the same or different
  • catalyst bodies are preferably arranged in the tubes of the reactor apparatus according to the invention, wherein the individual layers within a tube differ in their activity.
  • the gas inlet side layer has the lowest catalytic activity.
  • the adjoining to the gas outlet side has the lowest catalytic activity.
  • Layers then have an increasing catalytic activity, so that the gas outlet side arranged layer has the highest catalytic activity.
  • Gas outlet side gradually increases, also a different activity profile can be selected.
  • a layer may be provided for the gas inlet side, the catalytic activity of which is higher than the catalytic activity of the layer which adjoins in the direction of the gas outlet side.
  • Reactor device reflects the activity profile, as it is adjusted for example in the normal tube, in
  • the expansion of the individual layers is preferably selected in the range of 30 to 200 cm, the arrangement of the catalyst layers as a whole an expansion in
  • Lengthwise of the tubes of preferably between 2 and 3.50 m.
  • Reaction section S certain volume section is provided a higher active mass content than in the tubes of the other group.
  • the active composition having a higher vanadium content and / or a lower Sb content and / or a lower Cs content.
  • a T1O 2 with a higher BET surface area can also be provided.
  • promoters can be added to the active composition or their proportion can be increased, which increase the activity of the active composition.
  • Carrier body can be increased. However, it is also possible to change the geometry of the carrier body in such a way that the bulk density is increased. Combinations of these measures are also possible.
  • the reactor device according to the invention for the production of acrolein by oxidation of propene and / or acrylic acid from acrolein, or for the production of methacrolein by oxidation of isobutene and / or methacrylic acid from methacrolein
  • Methacrolein be resorted to. The filling of the
  • Thermo tubes may be provided. But it is also possible to arrange several layers of catalysts in the tubes, the composition and thus the activity of the
  • Catalysts in the individual layers is different.
  • both unsupported catalysts and coated catalysts can be used.
  • Catalyst activity can be adjusted when using full catalysts, for example, catalyst bodies with different geometry can be used, so that ultimately the bulk density of the catalyst body in normal and
  • Thermo tubes is different. Alternatively, the
  • Active mass can be diluted with an inert material to adjust the catalyst activity in the respective tube can.
  • catalyst bodies can also be diluted with inert bodies in order to adjust the catalyst activity in the respective tube to a specific value, so that the ratio of the catalyst activity of the standard pipe and the thermal tube is set to the desired value with an otherwise comparable modified residence time T m0 d- Shell catalysts can the
  • Catalyst activity can be adjusted with agents, as described above, so for example by adjusting the layer thickness of the active material layer on the inert support body.
  • a suitable catalyst is described, for example, in DE 23 38 111 C2. This has a composition of the formula Mo ⁇ Bi a Me ⁇ Me ⁇ Me ⁇ Me ⁇ Me ⁇ Zn h O g on which means: Me 1 : In and / or La;
  • Me 2 Fe and / or Cu;
  • Me 3 Ni and / or Co
  • Me 4 at least one element from the group P, B, As, Cr, V and / or W;
  • Me 5 at least one element from the group Cd, Ta, Nb, Ag,
  • b 0.005 to 3, preferably 0.01 to 2;
  • c 0.1 to 8, preferably 0.3 to 6;
  • e 0 to 6, preferably 0.05 to 5;
  • h 0.1 to 10, preferably 0.5 to 6.
  • the dimensioning of the reactor that is, for example, the number of tubes and their dimensions can be selected analogously to the parameters described above.
  • the invention relates to a
  • the reactor apparatus comprises at least a first group G m of pipes comprising at least one normal pipe and a second group G n of pipes comprising at least one thermal pipe provided with a temperature measuring device.
  • catalyst bodies K p are filled so that at least one volume section of the pipe determined by a reaction section S is filled with the catalyst bodies K p ,
  • Reactor device can thus either first the
  • Normal tubes filled and then the filling of the thermal tubes are adapted by providing appropriate catalyst bodies are provided. But it is also possible first to fill the thermal tubes with catalyst bodies, and then to adjust the filling of the normal tubes by appropriate
  • Catalyst body can be selected.
  • the catalyst bodies are preferred for the first
  • catalyst bodies K q are filled, wherein the catalyst bodies K q have an activity such that in a volume section of the pipe from the group G q determined by the reaction section S a catalyst activity A q is obtained, where: W
  • a p a catalyst activity in which by the
  • Tube is provided from the group G p .
  • a q a catalyst activity in which by the
  • Reaction section S certain volume section is provided in a tube from the group G q , W p : an inner surface of the tube from the group G p , which is determined by the reaction path S,
  • W q an inner surface of the tube from the group G q , which is determined by the reaction distance S, a: a correction factor which is in the range of 0.8 to 1.2
  • a 1 d an active mass-related activity constant of the first order of an active composition provided by the catalyst body K d ,
  • M d the mass of the active material provided by the catalyst bodies K d in the volume section of the tube defined by the reaction section S
  • d an index which is selected from p and q and the catalyst body K d in the volume section of the volume defined by the reaction section S. Designated tube.
  • G q generated pressure drop and the modified residence time T mod of the gas is then adjusted according to an embodiment to a substantially same value.
  • the procedure is first of all to determine the pressure drop or the back pressure of all the pipes of the group G p , for example the normal pipes, and thus by adding inert material (pressure increase) or by removing catalyst particles (pressure decrease) adapts all pipes of group G p have substantially the same back pressure or pressure drop, preferably a maximum deviation from Mean value of up to +/- 7%, according to one embodiment of up to +/- 5% is achieved.
  • reaction tubes G q of the other group for example, the thermal tubes with the
  • a substantially equal value is understood to mean a value which does not deviate more than 10%, preferably not more than 5%, from the mean (arithmetic mean), measured over all tubes.
  • the tubes comprise a first group G m of tubes comprising the normal tubes.
  • the second group G n of tubes comprises the thermal tubes.
  • Catalyst bodies is first selected a group of pipes, so either the group G m of pipes, the
  • the selected group of pipes then forms the group G p and the other group of pipes forms the group G q in the sense of the method according to the invention.
  • the normal tubes ie the first group G m of tubes with catalyst bodies are first loaded. All pipes of the group can be loaded. In this embodiment, therefore, the group G m of pipes would form the group G p according to the method according to the invention.
  • reaction distance S determines the catalyst activity provided in the volume of the tube determined by the reaction section S. For this purpose, for example, from the bulk density of the catalyst body in the pipe in question and the proportion of the active mass on
  • the mass of the active mass are calculated, which is provided in the relevant section of the tube. Since the tubes usually have a relatively small cross-section, the bulk density is advantageous in the
  • Active mass can be multiplied by the
  • Order A x d determine the catalyst activity A p . Furthermore, from the length of the reaction path S and the radius of the pipe, the corresponding pipe wall surface W p can be calculated.
  • the correction factor a is set to the value 1 for this purpose.
  • the active substance-related activity constant of the first order of the active material used in this tube can then be the quantity
  • Active mass to be introduced in the corresponding section of the tube so that the above equation is satisfied.
  • This active mass is then introduced into the tube via the corresponding catalyst bodies.
  • the catalyst bodies are selected in such a way that at least that determined by the reaction path S.
  • Volume section of the corresponding tube is filled.
  • Shell catalysts used in the tube can first by means of non-active catalyst bodies, for example, the carrier bodies themselves or by the carrier body
  • Catalyst body can be determined. From this bulk density can then be determined together with the calculated amount of active composition, a catalyst body containing the required amount of active material, which is necessary to provide the desired catalyst activity.
  • Catalyst bodies are filled after their preparation in the corresponding tube.
  • Thermo tubes is the ratio of the mean modified residence time T m0 d of the group of eg 200th
  • Residence time T m0 d is set, which corresponds to the average modified residence time T m0 d of the reference standard pipes, ie the pipes of the group G p .
  • Determination of pressure drop / dynamic pressure and modified Residence time ⁇ u m0d therefore preferably takes place separately for each individual tube.
  • the pressure drop / dynamic pressure and the modified residence time ⁇ u m0d of the gas is preferably determined with an inert gas
  • the column length of the bed of the catalyst body can be shortened. This shortening of the catalyst bed is
  • a section can be provided in the column, which is filled with, preferably inert, bodies which generate a high pressure drop / back pressure.
  • a suitable material is, for example, sand. This inert material will
  • Catalyst bodies is generated. This can be a
  • Pressure drop / back pressure to adjust can be calculated.
  • the catalyst body filled in the tube is first removed again, and then first the corresponding one on the gas outlet side Layer filled from the inert material. On this layer to correct the pressure drop / dynamic pressure are then
  • catalyst bodies of a particular geometry can be used to achieve a desired pressure drop / dynamic pressure.
  • the procedure is preferably that on the gas inlet side the
  • Reactor housing reached about the same level, so that for all tubes a comparable temperature profile in the
  • height adjustment can be achieved by providing supporting bodies which are arranged on the gas outlet side or the lower section of the tube, whereby these correction bodies only have a very small amount
  • the distance between the plane and the upper termination of the filling of a tube is preferably not more than ⁇ 7 cm, according to a further embodiment as ⁇ 5 cm and according to yet another embodiment not more than ⁇ 2 cm.
  • the modified residence time ⁇ u m0d of the gas is adjusted in the manner described above, in a first step by quotient formation, the mean, modified residence time T m0 d of the normal tubes or, if initially a subgroup of normal tubes is selected as reference tubes , the
  • the reactor may after the
  • Filling are still subjected to an activation treatment, during which the catalyst is converted into the active form, for example by burned binder and possibly
  • carbonates, hydroxides or nitrates are converted into the corresponding oxides.
  • the active compounds which of the catalyst bodies in the normal tube or in the thermal tube for
  • the active masses may have different active mass related
  • Activity constants 1st order A x d have, from which then the required amounts of active material in by the
  • Reaction section S specific section of the pipe in question can be calculated.
  • the composition of the active composition can be changed so that the active materials in the normal pipe or thermal tube have a different composition.
  • promoters or moderators of the active composition can be added for this purpose. It is also possible, for example, the BET surface area or the pore volume of the active composition
  • Inert bodies are added. According to a preferred embodiment, it is provided that the same active composition is used both in the normal tubes and in the thermal tubes. This makes it easier to map the temperature profile in the normal tube over a longer period of time in the thermal tube, so that, for example, even after a longer period of operation of the reactor more accurate information about the state of the normal tubes can be given. This is particularly advantageous because in this way too
  • set active mass is set. This can be achieved, for example, by the use of coated catalysts, the amount of active material contained in the shell of the shell catalyst is adjusted accordingly and, for example, the layer thickness of the shell is increased.
  • unsupported catalysts it is possible, for example, to proceed in such a way that one of the catalyst bodies, which are filled into the normal pipe or the thermal pipe, is correspondingly diluted with the aid of an inert filler material. According to another embodiment is in the way
  • the activity of the catalyst body K q is adjusted by adjusting the shape of the catalyst body K q .
  • the catalyst body in the normal tubes in comparison to the catalyst bodies in the thermal tubes so a different geometry. In this way, on the one hand, the bulk density of the
  • Catalyst body on a higher geometric surface so that a larger amount of active material on the
  • hollow cylinders are used which have a greater length or a larger outer or inner diameter
  • hollow tubular catalyst bodies can be used in one of the tubes, which have dimensions of 8 ⁇ 6 ⁇ 5 mm, while in the other group of tubes hollow cylinders with dimensions of 8 ⁇ 6 ⁇ 5, 7 ⁇ 7 ⁇ 4, 6 ⁇ 5 x 4 or 7 x 4 x 4 mm are used (outside diameter x length x inside diameter).
  • the reactor apparatus loaded with used catalyst bodies is first discharged, that is, the used catalyst bodies are first removed from the pipes of group G p and the pipes of group G q .
  • the reactor device is again with Loaded catalyst bodies, proceeding in the manner described above.
  • Phthalic anhydride used by gas phase oxidation of o-xylene and / or naphthalene can be used according to a preferred embodiment in the manner described below.
  • Preparation of phthalic anhydride by gas phase oxidation of o-xylene and / or naphthalene is preferably used as a catalyst body, a shell catalyst.
  • Carrier body are preferably used hollow cylinder of an inert material, on which a layer of the
  • Active material is applied.
  • the active material conventional active materials for the gas phase oxidation of o-xylene or naphthalene to phthalic anhydride can be used.
  • an active composition is used, whose
  • Composition has already been described above.
  • Precursor compounds prepared. Precursor compounds are understood as meaning those compounds which, after, for example, calcination, can be converted into the corresponding catalytically active compounds, in particular the oxides. Such a suspension or solution is often referred to as mash.
  • the solvent preferably water, but also organic solvents, such as
  • the mash can then be applied to the inert carrier body, for example, in a heated coating drum or in a fluidized bed.
  • the layer thickness with which the active composition is applied to the inert support body are determined very accurately.
  • the mash may optionally contain a binder so that the components of the active composition can be bound in a solid film on the inert support body.
  • Binders are, for example, organic polymers, such as
  • the binder used is added in conventional amounts of the catalytically active composition, for example in a proportion of about 0.5 to 30 wt .-%, according to one embodiment in a proportion of 0.5 to 20 wt .-% based on the FestStoffgehalt of catalytically active mass.
  • other common common binder is added in conventional amounts of the catalytically active composition, for example in a proportion of about 0.5 to 30 wt .-%, according to one embodiment in a proportion of 0.5 to 20 wt .-% based on the FestStoffgehalt of catalytically active mass.
  • Components may be included in the mash, for example pore formers.
  • coated carrier body can then be filled into the corresponding tube of the reaction device. There, the binder can then be burned out during the activation of the catalyst. The adjustment of the pressure drop or the dynamic pressure then takes place in the manner described above.
  • Preparation of phthalic anhydride by partial oxidation of o-xylene or naphthalene uses bedstocks of catalyst bodies comprising multiple layers, the layers having a different catalyst activity.
  • Catalyst arrangement three layers, wherein the Gaseintrittsseite layer has the lowest activity and towards the gas outlet side layer has the highest catalyst activity.
  • Catalyst arrangement at least four layers, wherein the closest to the gas inlet side layer has a higher activity than the next, the gas outlet side layer lying.
  • the subsequent layers in the flow direction then show, as already described above, a step-by-step increased activity with respect to the layer arranged upstream in the direction of flow.
  • the active composition of the catalyst bodies of the individual layers has a composition as already described above.
  • the adaptation of the activity may be carried out by taking one or more of the following measures to control the activity of the shift in relation to the one in
  • the measures can be taken individually or in combination
  • the active material of the first layer is silicon
  • Catalyst body of the first catalyst layer between 5 and 25% by weight V 2 0 5 , 0 to 4% by weight Sb 2 0 3 , 0 to 1% by weight Cs, 0 to 3% by weight b 2 0 5 , 0 to 2% by weight
  • the remainder of the active composition consists of at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, especially preferably at least 99% by weight, more preferably at least 99.5% by weight. -% and in particular 100 wt .-% of T1O 2 .
  • the BET surface area of the T1O 2 is between 15 and 45 m 2 / g.
  • such a first catalyst layer has a length fraction of 5 to 25%, particularly preferably 10 to 25%, of the total length of all the catalyst layers present, that is to say the total length of the catalyst bed present.
  • the active composition in the second catalyst layer contains between 1 and 25% by weight of V2O 5 , 0 to 4% by weight of Sb 2 0 3 , 0 to 1% by weight of Cs, 0 to 2% by weight. Nb 2 0 5 and 0 to 2 wt .-% P.
  • the remainder of the active composition consists of T1O 2 in the proportions described in the first catalyst layer.
  • the BET surface area of the T1O 2 is preferably between 15 and 25 m 2 / g.
  • the second catalyst layer comprises a length fraction of about 15 to 60%, preferably 20 to 60%, more preferably 20 to 50% of the total length of all existing
  • the active material of the catalyst of the third catalyst layer contains 1 to 25 wt .-% V 2 0 5 , 0 to 4 wt .-% Sb 2 0 3 , 0 to 1 wt .-% Cs, 0 to 2 wt. % Nb 2 0 5 and 0 to 2 wt% P.
  • the remainder of the active composition consists essentially of T1O 2 in the proportions given in the description of the first catalyst layer. This preferably has in the active composition of the third catalyst layer
  • the third catalyst layer preferably has a length fraction of about 20 to 50% of the total length of all existing catalyst layers.
  • four layers of catalyst bodies are provided in the tubes, wherein the activity provided by the catalyst layers preferably increases from the gas inlet side to the gas outlet side. The first catalyst layer closest to the
  • Gas inlet side preferably, based on the weight of the catalyst body, an active material content of between 5 and 26 wt .-%, preferably between about 7 and 15 wt .-% to.
  • the active composition preferably contains between 1 and 25 wt .-% V 2 0 5 , 0 to 4 wt .-% Sb 2 0 3 , 0 to 1 wt .-% Cs, 0 to 2 wt .-% Nb 2 0 5f 0 to 2 wt .-% P and the rest to 100 wt .-% Ti0 2 .
  • the second catalyst layer preferably contains one based on the weight of the catalyst body
  • Active composition content between 6 and 12 wt .-%, preferably between 6 and 11 wt .-%.
  • the active material of this layer contains
  • the third catalyst layer based on the weight of the catalyst body, an active material content of 5 to 11 wt .-%, in particular 6 to 10 wt .-% have.
  • the active composition of this layer preferably contains 1 and 25 wt .-% V 2 Os, 0 to 4 wt .-% Sb 2 C> 3, 0 to 1 wt .-% Cs, 0 to 2 wt .-% Nb 2 0 5 , 0 to 2 wt .-% of P and the balance to 100 wt .-% Ti0 2 .
  • the fourth catalyst zone comprises, based on the weight of the catalyst body, has an active composition content of between about 7 and 25 wt .-%.
  • the active composition of the fourth layer preferably contains 1 and 25 wt .-% V 2 0 5 , 0 to 4 wt .-% Sb 2 0 3 , 0 to 1 wt .-% Cs, 0 to 2 wt .-% Nb 2 0 5 , 0 to 2 wt .-% P and the remainder to 100 wt .-% Ti0 2 .
  • V 2 0 5 0 to 4 wt .-% Sb 2 0 3
  • 0 to 1 wt .-% Cs 0 to 2 wt .-% Nb 2 0 5 , 0 to 2 wt .-% P and the remainder to 100 wt .-% Ti0 2 .
  • Embodiment contains the active material of the catalyst of the first catalyst layer between 5 to 16 wt .-% V 2 0 5 , 0 to 5 wt .-% Sb 2 0 3 , 0.2 to 0.75 wt .-% Cs, 0 - 1 Wt% P and 0 to 3% by weight 2 0 5 .
  • the remainder of the active composition consists of at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, in particular at least 99% by weight, more preferably at least 99.5% by weight, in particular 100% by weight % of TiC> 2 .
  • a particularly preferred invention
  • Embodiment is the BET surface area of 1O 2 between 15 and about 45 m 2 / g. It is further preferred that such an upstream catalyst layer has a length fraction of 5 to 25%, particularly preferably 10 to 25% of the total length of all catalyst layers present (total length of the catalyst layer)
  • Embodiment contains the active material of the catalyst of the second catalyst layer between 5 to 15 wt .-% V2O 5 , 0 to 5 wt .-% Sb 2 0 3 , 0.2 to 0.75 wt .-% Cs, 0 - 1 wt. -% P and 0 to 2 wt .-% Nb 2 Ü 5 .
  • the remainder of the active composition consists of at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, in particular at least 99% by weight, more preferably at least 99.5% by weight, in particular 100% Wt .-% of T1O 2 .
  • a particularly preferred invention
  • Embodiment is the BET surface area of T1O 2 between 15 and about 25 m 2 / g. Furthermore, it is preferred that such a second catalyst layer has a length fraction of about 15 to 60%, in particular 20 to 60% or 20 to 50% of the total length of all existing catalyst layers (total length of the existing catalyst bed).
  • Embodiment contains the active material of the catalyst of the third catalyst layer 5 to 15 wt .-% V 2 0 5 , 0 to 4 wt .-% Sb 2 0 3 , 0.05 to 0.5 wt .-% Cs, 0 - 1 wt % P and 0 to 2% by weight of Nb 2 0 5 .
  • the remainder of the active composition consists of at least 90% by weight, preferably at least 95% by weight, more preferably
  • the T 1 O 2 has a BET surface area between about 15 and 25 m 2 / g.
  • this third layer occupies a length proportion of about 10 to 30% of the total length of all existing catalyst layers, in particular if at least one further catalyst layer adjoins the third layer. Is it in the third layer to the last, so the
  • Reactor outlet closest location so is a
  • Length fraction for the third layer of 20-50% preferred.
  • Embodiment contains the active material of the catalyst of the fourth catalyst layer 5 to 25 wt .-% V 2 O 5 , 0 to 5 wt .-% Sb 2 0 3 , 0 to 0.2 wt .-% Cs, 0 - 2 wt. % P and 0 to 1 wt .-% b 2 Ü 5 .
  • the remainder of the active composition consists of at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, in particular at least 99% by weight, more preferably at least 99.5% by weight, in particular 100% by weight from ⁇ ⁇ 2.
  • a BET surface area of T 1 O 2 is preferred which is slightly higher than that which lies closer to the gas inlet side
  • Such a fourth catalyst layer occupies a length fraction of about 10 to 50%, particularly preferably 10 to 40% of the total length of all existing catalyst layers.
  • the invention relates to a process for the preparation of at least one product, wherein at least one gaseous educt is fed to a reactor apparatus as described above.
  • the at least one gaseous educt is converted to a catalyst product K m , K n , which are provided in the first and second groups G m , G n of tubes, wherein the reaction conditions for the reaction of the at least one reactant to the at least one product are so selected in that a specific temperature or a specific temperature gradient is set in the thermo tubes of the second group G n of tubes.
  • the reactor device described above is suitable for a variety of reactions, which by a solid
  • Thermo tubes can be displayed, the temperature profile or a temperature at a specific point of the
  • Thermo tube can be used to adjust the conditions in the normal tubes with high accuracy, ie
  • reaction conditions can be tracked, with a new temperature profile is set in the thermal tubes and thus in the normal tubes.
  • reaction conditions are chosen in a conventional manner for the reaction in question, but the
  • Reactor device for the production of phthalic anhydride by partial oxidation of o-xylene
  • a gaseous stream containing o-xylene and / or naphthalene and molecular oxygen, at elevated temperature, in particular between about 250 and 490 ° C passed through the normal tubes or thermotubes.
  • several layers of catalyst bodies are preferably arranged, in particular three or four layers, wherein the catalyst activity of the different layers is preferably chosen differently, in particular preferably
  • the loading of the gas stream with o-xylene or naphthalene is preferably selected in a range of 40 to 100 g / Nm 3 air.
  • the back pressure in the tubes is preferably a bar in the range 1 to 5 para o iut, - preferably 1 to 2 bar abs chosen o iut.
  • Catalyst bed is preferably in the range of 80 to 600 mbar.
  • the reactor device according to the invention is used for the production of maleic anhydride.
  • the educt used is preferably benzene or butane.
  • the reactor apparatus may be used to convert vinyl acetate monomers
  • Ethylene oxide can be used by partial oxidation of ethylene. According to a further embodiment, with the
  • Reactor device also acrolein or
  • Acrylic acid can be prepared by partial oxidation of propene.
  • the reactor device is also suitable for the production of methacrolein and methacrylic acid by gas-phase oxidation of isobutene.
  • Reactor device for the production of formaldehyde by
  • Mesopores are made according to the BJH method according to DIN 66134.
  • the pore radius distribution and the pore volume were determined by mercury porosimetry according to DIN 66133;
  • the particle sizes were determined by laser diffraction using a Fritsch Particle Sizer Analysette 22 Economy (Fritsch, DE) according to the manufacturer's instructions.
  • Sample preparation is carried out in deionized water without addition of auxiliaries 5 minutes by treatment with the sample
  • the BET surface area, the pore radius distribution or the pore volume and the particle size distribution were determined in the characterization of the titanium dioxide in each case at a uncalcined at 150 ° C in a vacuum dried
  • the proportion of active mass (proportion of the catalytically active composition, without binder) relates in each case to the proportion (wt .-%) of the catalytically active composition in the total weight of the
  • Catalyst body including carrier body in the
  • reaction tube with a length of 120 cm and an inner diameter of 24, 8 mm is used. Inside the reaction tube is for the
  • a temperature sensor is arranged, which can be moved along the longitudinal axis, so that over the entire length of the reaction tube, a temperature profile
  • the reaction tube can via a Length of 100 cm to be tempered with a heat transfer medium.
  • reaction tube At the upper end of the reaction tube can over a
  • Mass flow controller a defined air flow in the
  • Reaction tube to be fed.
  • the air stream first passes through a thermostated mixing chamber, in which a defined amount of o-xylene can be injected into the air stream and mixed with it.
  • the pressure drop is monitored by each arranged at the beginning and at the end of the reaction tube pressure gauge.
  • a catalyst bed diluted with inert bodies is introduced, which has a length of 80 cm.
  • the catalyst bed is placed in the isothermal region of the reaction tube.
  • Ammonium dihydrogen phosphate 195.0 g of titanium oxide having a BET surface area of 21 m 2 / g, and 130.5 g of binder (50% dispersion of vinyl acetate / ethylene copolymer in water
  • the catalyst had an active composition content of 8% by weight, the active composition having a composition of 7.5% by weight.
  • Vanadium pentoxide 3.2% by weight antimony trioxide, 0.40% by weight
  • the catalyst bodies are diluted in a mass ratio of 17: 1 (w / w) with steatite inert bodies. Hollow cylinders with the dimensions 5 ⁇ 5 ⁇ 2.5 mm are used as inert bodies. The catalyst bodies and the inert bodies are individually in the
  • Heat transfer medium set to a temperature of 420 ° C.
  • the catalyst is then calcined for 60 hours.
  • Catalyst mass-related space-time velocity of 5 1 / hxm kat (GHSVi), 10 1 / hxm kat (GHSV 2 ), or 15 1 / hxm kat (GHSV 3 ) is set.
  • the heat carrier temperature is set in each case so that an average catalyst temperature of 420 ° C is reached.
  • the reactor is equilibrated for one hour.
  • the reaction gas is analyzed after its exit from the reaction tube to its constituents and the o-xylene Umsat z determined at 420 ° C average catalyst temperature. From the measured o-xylene sales then the
  • the amount of active material m Akt i vmasse was 1.5 g.
  • the o-xylene conversion z is calculated according to
  • the mass-related activity constant is 1.
  • a system which is provided with a receptacle for tubes with a diameter of 20 to 30 mm. 4 m long pipes can be inserted into the receptacle, while a distance of 3.50 m can be thermostated with a salt bath. As normal pipes tubes with an inner diameter of 25 mm or 21 mm are used. To the temperature profile in the
  • Normal tubes to be determined are arranged in the normal tubes along the longitudinal axis of temperature probes fixed at a certain distance. The space requirement of this
  • Thermo tubes are tubes with an inner diameter of 21, 25, 27 or 29 mm, which are provided with an inner tube with an outer diameter of 3, 8 or 10 mm.
  • an inner tube in each case a displaceable in the longitudinal direction of the inner tube temperature probe is arranged.
  • the dimensions of the tubes used are shown in Table 2.
  • a gas inlet At the top of the tubes is a gas inlet, via which a constant flow of gas can be conducted into the tubes by means of a mass flow controller.
  • the gas flow happens before
  • Activity constant 1st order A 1 become test bodies with one Active mass content of 8 wt .-% (normal tube with 25 mm inner diameter) produced. As a carrier body
  • the standard and thermal tubes of the test reactor are filled with the catalyst bodies indicated in Table 2.
  • Adjustment of the modified residence time T m0d is carried out as described above on the calculation of the for a comparable mod. Residence time T m0d required volume flow by means of
  • an air flow is passed from top to bottom through the thermal or the normal pipe, wherein the air flow is set to a flow rate of 4 Nm 3 / h.
  • the air flow is loaded with 30 to 100 g / Nm 3 o-xylene
  • the temperature of the salt bath will be up to 352
  • Thermo tube set to the same value. So it is for the adaptation of thermal and normal pipe exclusively the
  • Residence time x defined as the quotient of reactor volume and volume flow, and not the modified residence time T m0d
  • steatite hollow cylinders of dimensions 8 ⁇ 6 ⁇ 5 mm are used for the normal tube, which have an active mass content of 8%, based on the weight of the catalyst body. Become for the thermal tube
  • the pressure drop in the test reactor was determined at a gas flow rate of 4 Nm 3 / h to 99 mbar, which is a
  • Adj. Ap a adaptation pressure drop
  • Catalyst activity (erf .gem example)
  • a N the catalyst activity in which by the
  • a T the catalyst activity in which by the
  • Reaction section specific volume section is provided in the thermal tube
  • Reaction distance S is determined, a: the correction factor.
  • a 1 the active mass-related activity constant 1.
  • M NfT the amount of the provided by the catalyst bodies in the defined by the reaction section S volume portion of the normal or thermal tube
  • Activity constant 1st order of the active composition A 1 to 480 [l / h * g] determined.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

La présente invention concerne un dispositif réacteur comprenant des tubes normaux et des tubes thermiques dotés d'une sonde de température, lesdits tubes étant remplis respectivement de corps catalyseurs. Afin de permettre la reproduction dans les tubes thermiques du profil de température qui est réglé dans les tubes normaux, les tubes sont remplis respectivement de corps catalyseurs tels que le rapport de l'activité catalytique sur la surface de la paroi de tube dans une section des tubes déterminée par une trajectoire réactionnelle, est égale dans les tubes normaux et les tubes thermiques.
PCT/EP2011/051606 2010-02-03 2011-02-03 Dispositif réacteur et procédé pour optimiser la mesure des variations de température dans des réacteurs tubulaires WO2011095566A1 (fr)

Priority Applications (2)

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CN2011800162284A CN103025421A (zh) 2010-02-03 2011-02-03 反应器装置和用于优化反应器管中温度曲线的测量的方法
DE112011100423T DE112011100423A5 (de) 2010-02-03 2011-02-03 Reaktorvorrichtung und Verfahren zur Optimierung der Messung des Temperaturverlaufs in Reaktorrohren

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DE102010006723.7 2010-02-03
DE102010006723A DE102010006723A1 (de) 2010-02-03 2010-02-03 Reaktorvorrichtung und Verfahren zur Optimierung der Messung des Temperaturverlaufs in Reaktorrohren

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210381910A1 (en) * 2020-06-04 2021-12-09 Gerresheimer Regensburg Gmbh Dummy for Monitoring the Molding Process

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019127788A1 (de) * 2019-10-15 2021-04-15 Clariant International Ltd. Neues Reaktorsystem für die Herstellung von Maleinsäureanhydrid durch katalytische Oxidation von n-Butan

Citations (6)

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Publication number Priority date Publication date Assignee Title
DE2338111C2 (de) 1972-10-12 1982-01-28 Basf Ag, 6700 Ludwigshafen Verfahren zur katalytischen Oxidation von Propylen oder Isobutylen zu Acrolein oder Methacrolein in der Gasphase mit molekularem Sauerstoff
EP0873783A1 (fr) 1997-04-23 1998-10-28 Basf Aktiengesellschaft Dispositif et méthode pour mesure la temperature dans de réacteurs tubulaire
EP1270065A1 (fr) * 2001-06-26 2003-01-02 Nippon Shokubai Co., Ltd. Appareillage pour effectuer des mesures de pression et de température dans des réacteurs tubulaires
EP1484299A1 (fr) 2002-03-11 2004-12-08 Mitsubishi Chemical Corporation Procede d'oxydation catalytique en phase vapeur
US20080014127A1 (en) 2004-05-13 2008-01-17 Mitsubishi Chemical Corporation Pilot test method for multitubular reactor
EP2075058A1 (fr) * 2007-12-20 2009-07-01 MAN DWE GmbH Réacteur à faisceau tubulaire

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2338111C2 (de) 1972-10-12 1982-01-28 Basf Ag, 6700 Ludwigshafen Verfahren zur katalytischen Oxidation von Propylen oder Isobutylen zu Acrolein oder Methacrolein in der Gasphase mit molekularem Sauerstoff
EP0873783A1 (fr) 1997-04-23 1998-10-28 Basf Aktiengesellschaft Dispositif et méthode pour mesure la temperature dans de réacteurs tubulaire
US20020061267A1 (en) * 1997-04-23 2002-05-23 Basf Aktiengesellschaft Apparatus for measuring temperatures in tubular reactors
EP1270065A1 (fr) * 2001-06-26 2003-01-02 Nippon Shokubai Co., Ltd. Appareillage pour effectuer des mesures de pression et de température dans des réacteurs tubulaires
EP1484299A1 (fr) 2002-03-11 2004-12-08 Mitsubishi Chemical Corporation Procede d'oxydation catalytique en phase vapeur
US20080014127A1 (en) 2004-05-13 2008-01-17 Mitsubishi Chemical Corporation Pilot test method for multitubular reactor
EP2075058A1 (fr) * 2007-12-20 2009-07-01 MAN DWE GmbH Réacteur à faisceau tubulaire

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210381910A1 (en) * 2020-06-04 2021-12-09 Gerresheimer Regensburg Gmbh Dummy for Monitoring the Molding Process
US11835397B2 (en) * 2020-06-04 2023-12-05 Gerresheimer Regensburg Gmbh Dummy for monitoring the molding process

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CN103025421A (zh) 2013-04-03
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