DE102005051401A1 - Preparation of acrolein/acrylic acid comprises supplying gas mixture stream A to zone A, supplying propane gas stream to obtain product gas mixture; dividing product stream A into two component streams; feeding a stream to zone B - Google Patents

Abstract

Preparation of acrolein/acrylic acid from propane comprises supplying reaction gas mixture input stream A to a reaction zone A; supplying dehydrogenated propane gas stream to obtain a product gas mixture; removing the product mixture stream A; dividing the product gas mixture stream A into component streams (I) and (II); feeding the component stream (II) in a second reaction zone B into an oxidative reactor, in which propylene in stream (II) is oxidized to form a product gas mixture B containing e.g. acrolein/acrylic acid as final product and separating the final product. Preparation of acrolein and/or acrylic acid from propane comprises supplying a reaction gas mixture input stream A (which is produced by merging at least four different gaseous initial streams 1, 2, 3 and 4) to the inlet of the first reaction zone A by at least a catalyst bed; optionally further supplying partially, heterogeneously catalyzed dehydrogenated propane gas stream to the mixture to obtain a product gas mixture containing propane and propylene; removing the obtained product gas mixture stream A from the first reaction zone A by discharge opening; dividing the product gas mixture stream A into two component streams (I) and (II) with identical composition, where the component stream (I) is fed back as gaseous initial stream 1 into the first reaction zone A in a first gas cycle operation and the component stream (II) is optionally led into the first separation zone A, to separate partial or large quantity of different propane and propylene components and to produce a residual product gas mixture stream A1 containing propane and propylene; feeding the component stream (II) or the product gas mixture in a second reaction zone B into at least an oxidative reactor, in which the propylene contained in the component stream (II) or in the product gas mixture stream A1 is subjected to selective heterogeneously catalyzed partial gaseous phase oxidation with molecular oxygen to form a product gas mixture B containing acrolein and/or acrylic acid as final product, optionally unconverted propane and propylene, and surplus molecular oxygen; removing the product gas mixture stream B from the reaction zone B; separating the final product, where the residual gas containing unconverted propane and propylene, and molecular oxygen is fed back as gaseous initial stream 2 in a second gas cycle operation into the reaction zone A (when the gaseous initial streams 2, 3 and 4 and optionally a gaseous stream different from the 1 are merged to a single propelled jet gaseous mixture stream); and subsequently operating the mixture with gaseous propelled jet mixture stream as propelled jet of a jet pump, which comprises a jet nozzle, a mixing path, a diffuser and a suction intake socket; where the direction of the propulsion of the propelled jet by the jet nozzle over a mixing path and the diffuser, points towards the inlet of the first reaction zone A and the suction effect of the suction intake socket, points towards the direction of the discharge opening of the first reaction zone A leading to the product gas mixture stream A and the component stream (I) is sucked through the negative pressure produced in the suction intake socket along with the splitting up of the product gas mixture A into the two component stream, and is transported with simultaneous mixing of propelled jet by the mixing path over the diffuser and the obtained reaction gas mixture input stream A is left into the inlet of the first reaction zone A; the gaseous initial streams 1, 2 and 3 is a propane, the gaseous initial stream 4 is a molecular hydrogen and the gaseous initial stream 3 is a fresh propane; the first gaseous initial stream 2 and 3 and optionally stream 1 and stream 4 are combined in an arbitrary sequence to a single gaseous mixture stream and stream 4 is added to the gaseous initial mixture stream under the formation of the gaseous propelled jet mixture stream.

Description

• A) dem Einlass in eine erste Reaktionszone A einen Reaktionsgasgemischeingangsstrom A zuführt, der durch Zusammenführung von wenigstens vier voneinander verschiedenen gasförmigen Ausgangsströmen 1, 2, 3 und 4 mit der Maßgabe erzeugt wurde, dass die drei gasförmigen Ausgangsströme 1, 2 und 3 Propan enthalten, der gasförmige Ausgangsstrom 4 molekularer Wasserstoff und der gasförmige Ausgangsstrom 3 Frischpropan ist, den Reaktionsgasgemischeingangsstrom A in der Reaktionszone A durch wenigstens ein Katalysatorbett führt, an welchem, gegebenenfalls unter Zufuhr weiterer Gasströme, durch partielle heterogen katalysierte Dehydrierung des Propan ein Propan und Propylen enthaltender Produktgasgemischstrom A gebildet wird, den Produktgasgemischstrom A durch den Auslass aus der ersten Reaktionszone A aus selbiger herausführt und dabei in zwei Produktgasgemisch A-Teilströme 1 und 2 mit identischer Zusammensetzung aufteilt und den Produktgasgemisch A-Teilstrom 1 in erster Kreisgasfahrweise als gasförmigen Ausgangsstrom 1 in die erste Reaktionszone A rückführt, den Produktgasgemisch A-Teilstrom 2 gegebenenfalls in eine erste Trennzone A führt, um in selbiger von in ihm enthaltenen, von Propan und Propylen verschiedenen Bestandteilen eine Teilmenge oder mehr abzutrennen, und dadurch einen verbleibenden, Propan und Propylen enthaltenden, Produktgasgemischstrom A' zu erzeugen,
• B) den Produktgasgemischstrom A-Teilstrom 2 oder den Produktgasgemischstrom A' in einer zweiten Reaktionszone B zu Beschickung wenigstens eines Oxidationsreaktors verwendet und in dem wenigstens einen Oxidationsreaktor das im Produktgasgemisch A-Teilstrom 2 oder im Produktgasgemischstrom A' enthaltene Propylen einer selektiven heterogen katalysierten partiellen Gasphasenoxidation mit molekularem Sauerstoff zu einem Acrolein, oder Acrylsäure, oder deren Gemisch als Zielprodukt, nicht umgesetztes Propan und gegebenenfalls nicht umgesetztes Propylen sowie überschüssigen molekularen Sauerstoff enthaltenden Produktgasgemischstrom B unterwirft, den Produktgasgemischstrom B aus der Reaktionszone B herausführt und in ei ner zweiten Trennzone B im Produktgasgemischstrom B enthaltenes Zielprodukt abtrennt und von dem dabei verbleibenden, nicht umgesetztes Propan, molekularen Sauerstoff sowie gegebenenfalls nicht umgesetztes Propylen enthaltenden Restgas wenigstens eine nicht umgesetztes Propan, molekularen Sauerstoff und gegebenenfalls nicht umgesetztes Propylen enthaltende Teilmenge in zweiter Kreisgasfahrweise als gasförmigen Ausgangsstrom 2 mit der Maßgabe in die Reaktionszone A rückführt, dass man die gasförmigen Ausgangsströme 2, 3 und 4 sowie gegebenenfalls zusätzliche vom gasförmigen Ausgangsstrom 1 verschiedene gasförmige Ausgangsströme zu einem gasförmigen Treibstrahlgemischstrom vereinigt und anschließend mit dem gasförmigen Treibstrahlgemischstrom als Treibstrahl eine Strahlpumpe, die eine Treibdüse, eine Mischstrecke, einen Diffusor und einen Saugstutzen umfasst, betreibt, wobei die Förderrichtung des durch die Treibdüse über die Mischstrecke und den Diffusor entspannten Treibstrahls in den Einlass der ersten Reaktionszone A sowie die Saugwirkung des Saugstutzens in Richtung des den Produktgasgemischstrom A führenden Auslass der ersten Reaktionszone A weist und dabei durch den im Saugstutzen erzeugten Unterdruck unter Aufteilung des Produktgasgemischstroms A in die beiden Teilströme 1 und 2 den Produktgasgemisch A-Teilstrom 1 ansaugt, bei gleichzeitiger Vermischung mit dem Treibstrahl durch die Mischstrecke über den Diffusor transportiert und den dabei gebildeten Reaktionsgasgemischeingangsstrom A in den Einlass der ersten Reaktionszone A entlässt.

The present invention relates to a process for the preparation of acrolein, or acrylic acid or a mixture thereof of propane, wherein

• A) the inlet into a first reaction zone A, a reaction gas mixture input stream A supplied by merging at least four mutually different gaseous output streams 1 . 2 . 3 and 4 was generated with the proviso that the three gaseous output currents 1 . 2 and 3 Propane contained, the gaseous output current 4 molecular hydrogen and the gaseous output stream 3 Fresh propane is the reaction gas mixture input stream A in the reaction zone A by at least one catalyst bed leads to which, optionally with the supply of additional gas streams, by partial heterogeneously catalyzed dehydrogenation of propane, a propane and propylene containing product gas mixture stream A, the product gas mixture stream A through the outlet of the first reaction zone A leads out of selbiger and thereby in two product gas mixture A partial streams 1 and 2 divided with identical composition and the product gas mixture A partial stream 1 in the first cycle gas mode as gaseous output current 1 returns to the first reaction zone A, the product gas mixture A partial stream 2 optionally, passing into a first separation zone A to separate a subset or more of the same from propane and propylene components contained therein and thereby to produce a remaining product gas mixture stream A 'containing propane and propylene,
• B) the product gas mixture stream A partial stream 2 or the product gas mixture stream A 'used in a second reaction zone B to feed at least one oxidation reactor and in the at least one oxidation reactor that in the product gas mixture A partial stream 2 or Propylene contained in the product gas mixture stream A 'a selective heterogeneously catalyzed partial gas phase oxidation with molecular oxygen to an acrolein, or acrylic acid, or their mixture as the target product, unreacted propane and optionally unreacted propylene and excess molecular oxygen containing product gas mixture stream B, the product gas mixture stream B from the reaction zone B and in egg ner second separation zone B in the product gas mixture stream B contained target product and separated from the remaining, unreacted propane, molecular oxygen and optionally unreacted propylene containing residual gas containing at least one unreacted propane, molecular oxygen and optionally unreacted propylene Subset in second cycle gas mode as gaseous output current 2 with the proviso in the reaction zone A that leads to the gaseous output streams 2 . 3 and 4 and optionally additional from the gaseous output stream 1 combines different gaseous output streams to a gaseous propellant jet mixed stream and then with the gaseous propellant jet stream as propulsion jet a jet pump, which comprises a motive nozzle, a mixing section, a diffuser and an inlet, operates, wherein the conveying direction of the relaxed by the motive nozzle via the mixing section and the diffuser propellant jet in the inlet of the first reaction zone A and the suction of the suction nozzle in the direction of the product gas mixture stream A leading outlet of the first reaction zone A and thereby by the negative pressure generated in the suction under distribution of the product gas mixture stream A in the two partial streams 1 and 2 the product gas mixture A partial stream 1 aspirates, with simultaneous mixing with the propulsion jet transported through the mixing section via the diffuser and the resulting reaction gas mixture input stream A discharges into the inlet of the first reaction zone A.

Acrylic acid is as a partial oxidation product of propylene, a significant monomer, as such or in the form of its alkyl esters for the production of z. As adhesives or water superabsorbent polymers Is used (see, for example, WO 02/055469 and WO 03/078378). acrolein is a significant intermediate, for example for manufacturing of glutardialdehyde, methionine, folic acid and acrylic acid.

method for the preparation of acrolein and / or acrylic acid in which the propylene produced by partial heterogeneously catalyzed dehydrogenation from propane and in the presence of unreacted (inert) propane as an ingredient a partial oxidation mixture of a heterogeneously catalyzed partial Gas phase oxidation with molecular oxygen to acrolein and / or acrylic acid subjecting product gas mixtures subject are known (see. z. For example, DE-A 102 45 585 and cited in this document state of the technique).

In contrast to the exothermic heterogeneously catalyzed oxydehydrogenation, which is enforced by oxygen present and in which intermediate free hydrogen is not formed (which is too dehy entrenched hydrogen is directly torn as water (H ₂ O) or detectable, it should be understood in this document under a heterogeneously catalyzed dehydrogenation a ("conventional") dehydrogenation whose heat of reaction is endothermic unlike the oxydehydrogenation ( as a subsequent step, an exothermic hydrogen combustion may be involved in the heterogeneously catalyzed dehydrogenation) and in which at least intermediate free molecular hydrogen is formed, which generally requires different reaction conditions and different catalysts than for oxydehydrogenation.

In Similarly, in this document under fresh propane propane understood that neither dehydration in the reaction zone A, still at a partial oxidation of propylene to acrolein and / or acrylic acid in the Reaction zone B has participated. Preferably, it has at all not yet participated in any chemical reaction. Usually will it may be crude propane, preferably the specification according to DE-A 102 46 119 and DE-A 102 45 585, and that usually in small quantities also different from propane Contains components. Such crude propane is described, for example, in DE-A 10 2005 022 798 Method available.

Usually become the above-mentioned methods of the prior art so performed that of the after product separation from the product gas mixture the partial oxidation remaining, unreacted propane, molecular Oxygen and optionally unreacted propylene containing Residual gas, at least one unreacted propane, molecular oxygen and optionally unreacted propylene-containing subset in Kreisgasfahrweise in the heterogeneously catalyzed dehydrogenation returns.

there has already been proposed (e.g., DE-A 10 2004 032 129 and DE-A 10 2005 013 039), that a mixture of water vapor, fresh propane and such cycle gas as the reaction mixture input gas of the heterogeneously catalyzed dehydrogenation of the propane fed to the propylene becomes. Here, the heterogeneously catalyzed propane dehydrogenation appropriate as Horden reactor be realized in which the catalyst beds in cheaper Way are arranged radially or axially one behind the other. Conveniently, In such a tray reactor, the fixed catalyst bed type is used. Advantageously, the number of Katalysatorbetthorden in such a horde reactor at three. The stand recommends this technology, the heterogeneously catalyzed partial propane dehydrogenation to perform autothermally. For this purpose, the reaction gas mixture is passed behind the first Catalyst bed and between the first in the flow direction fixed catalyst bed subsequent fixed catalyst beds to a limited extent molecular Added oxygen (eg in the form of air). That way, usually catalyzed by the dehydrogenation catalysts themselves, a limited Combustion during the heterogeneously catalyzed propane dehydrogenation formed molecular hydrogen (and optionally in at most small amount of propane) whose exothermic heat of the Dehydration temperature is substantially maintained.

In Comparative Examples 1, 3 and 4 of DE-A 10 2004 032 129 and in the exemplary embodiment of DE-A 10 2005 010 111, such a heterogeneously catalyzed partial propane dehydrogenation in the tray reactor (3 catalyst bed grades) is simulated by three dehydrogenation tube reactors connected in series. Instead of such a series connection of tube reactors can in these comparative examples or in this embodiment, but also a tray reactor according to the accompanying 1 and 2 used (each with 3 catalyst fixed bed grades).

In the tray reactor type according to 1 the catalyst bed ( 2 ) flows through from the outside to the inside. On the other hand, according to the type of horde reactor 2 the respective catalyst bed ( 2 ) flows through from the inside to the outside. The addresses ( 1 ) are each for the reaction gas mixture input gas, ( 3 ) indicates the air feed and ( 4 ) are mixing elements.

In addition, the following reactor data, based on a propane flow of 72280 kg / h in the reaction gas mixture input gas, and a total air feed of 3496 kg / h are appropriate:

When Catalyst is in each case the catalyst of the corresponding Comparative example or the embodiment to use. The same applies the reaction temperatures and the composition of the reaction gas mixture input gas.

Preferred reactor construction material is suitable for all reactor parts Sihaltiger stainless steel or steel, z. B. type 1.4841.

When Catalyst is in each case the catalyst of the corresponding Comparative example or the embodiment to use. The same applies the reaction temperatures and the composition of the reaction mixture input gas. Preferred reactor construction material is suitable for all reactor parts Si-containing stainless steel or steel, z. B. type 1.4841.

It is useful the partial heterogeneously catalyzed dehydrogenation of propane thereby operated essentially on the three catalyst hordes so operated, that the conversion of the propane fed into the reactor, based on one-time reactor passage, about 20 mol .-% is. The achieved selectivity of propylene formation is included regularly 90 mol .-%. The maximum revenue contribution of a single horde wanders with increasing operating time in the flow direction from the front to rear. As a rule, the catalyst feed is regenerated, before the flow direction third horde provides the maximum revenue contribution. With advantage regeneration when the coking of all hordes is identical Extent reached Has.

It is favorable in general for the above-described heterogeneously catalyzed partial dehydrogenation of propane if the total catalyst charge (sum over all beds) with the total amount of propane and propylene is ≥ 500 Nl / l ·h and ≦ 20000 Nl / l ·h ( typical values are 1500 Nl / l · h to 2500 Nl / l · h). The maximum reaction temperature within an individual fixed catalyst bed is advantageously maintained at 500 ° C to 600 ° C. With particular advantage, the reaction gas mixture input gas in the above-described heterogeneously catalyzed partial propane dehydrogenation in the tray reactor only from Fresh propane and recirculated from the partial oxidation in the dehydrogenation cycle gas resulting from the partial oxidation containing a sufficient amount of water vapor to cause a satisfactory service life of Dehydrierkatalysatorbetten. That is to say, the comparative examples and the example can also be carried out in the described tray reactors if the addition of the extra water vapor in the dehydrogenation is dispensed with. Moreover, the statements made in DE-A 10 2005 009 885, DE-A 10 2005 010111, DE-A 10 2005 009 891, DE-A 10 2005 013 039 and DE-A 10 2004 032 129 on such procedures apply , The amount of reaction gas mixture in standard liters (= N1, the volume in liters which the corresponding reaction gas mixture amount would assume under normal conditions (0 ° C., 1 bar)) is also understood in this document to mean the loading of a catalyst bed catalyzing a reaction step per hour through one liter of catalyst bed (eg fixed catalyst bed). The load can also be related to only one component of the reaction gas mixture. Then it is the amount of this component in Nl / lh which is passed through one liter of the catalyst bed per hour (pure inert material beds are not counted as fixed catalyst bed).

adversely the described method of the prior art is that almost all catalysts that catalyze the dehydrogenation of propane, also the combustion (complete Oxidation of propane and propylene to carbon oxides and water vapor) catalyze propane and propylene with molecular oxygen and molecular oxygen normally but already in the heterogeneously catalyzed partial dehydrogenation of propane recycled cycle gas from the partial oxidation is included. This is due to the fact that for the sake of a increased Catalyst life in heterogeneously catalyzed partial oxidation the molecular oxygen, measured by the stoichiometry of the partial oxidation, usually in excess is used. The catalyzed combustion reaction of this molecular Oxygen with propane contained in the reaction mixture input gas and / or propylene reduces the selectivity of propene formation in the frame the heterogeneously catalyzed partial propane dehydrogenation.

It was therefore already proposed (see DE-A 102 11 275), in the context of a multi-stage production of acrolein and / or acrylic acid Propane heterogeneously catalyzed partial propane dehydrogenation so perform, in that the product gas taken from the dehydrogenation zone is divided into two parts identical composition divides to only one of the two subsets to supply the partial oxidation, while the other subset as part of the reaction gas mixture input gas is recycled to the dehydrogenation. The circulating gas contained in this from the dehydrogenation itself molecular hydrogen, should then that in the reaction gas mixture input gas contained propane and optionally propylene before in this Input gas also protect contained molecular oxygen. This Protection is based insist that they are usually heterogeneous by the same catalysts catalyzed combustion of molecular hydrogen to water over the Full combustion of propane and / or propylene is kinetically preferred.

In DE-A 102 11 275 is already the Dehydrierkreisgasführung means of the jet pump principle (it is also referred to as a loop method designated). Furthermore, in this document the possibility is addressed, the Reaction gas mixture in the propane dehydrogenation additionally molecular Add hydrogen. about the requirement of molecular hydrogen in the propellant jet for the Metering jet pump in certain feed hierarchy is silent DE-A 102 11 275.

The DE-A 10 2004 032 129 and DE-A 10 2005 013 039 suggest that the repatriation of the from the heterogeneously catalyzed partial oxidation, molecular oxygen-containing, circulating gas not in the reaction gas mixture input gas for the to carry out heterogeneously catalyzed partial propane dehydrogenation. Rather, the repatriation is only still a certain Dehydrierumsatz in the reaction gas mixture the dehydration. It is also in DE-A 10 2004 032 129 also suggested, in advance of this recycling the reaction gas mixture the dehydration in addition add external molecular hydrogen. Furthermore, it will too in DE-A 10 2004 032 129 the loop procedure for the dehydrogenation propagated. Propulsion jet is exclusively from the partial oxidation recycled gas recirculated to the dehydrogenation.

However, this mode of operation is disadvantageous insofar as the externally added molecular hydrogen is still conducted in a significant subset thereof as part of the product gas mixture from the dehydrogenation into the partial oxidation, without its protective potential having been extensively used beforehand. Furthermore, the jet pump also brings the partial amount of the product gas mixture from the partial dehydrogenation to an elevated pressure, which is discharged into the partial oxidation. However, prior to partial oxidation, additional compression of the corresponding reaction gas mixture starting gas by means of a separate compressor is normally required in each case to reduce the pressure associated with the partial oxidation compensate for loss. Under pressure, the conversion of the product gas mixture stream A partial stream is usually 2 carried out in the product gas mixture stream A '. Against this background, a pressure load on the jet pump, which is associated as described, is not very expedient.

The DE-A 10 2005 009 885 recommends against this background in the exemplary embodiment II a loop procedure in which the reaction gas mixture input gas for the heterogeneously catalyzed partial dehydrogenation of the propane composed is from recycled gas, which is recycled from the partial oxidation, from fresh propane, from external molecular hydrogen, from a minimal amount on external water vapor and from the dehydrogenation itself recycled circulating gas (on the external water vapor could also be waived). The propulsion jet is a mixture of fresh propane, external molecular hydrogen, recycled gas from the partial oxidation and external steam used. With regard to a dosing order to be kept in propulsion jet production, DE-A 10 2005 009 is silent 885 off. This is because that the applicant at the time, to which the operated Stainless steel test facility was new, no indication of the requirement had a special Zudosierungsabfolge. Meanwhile, however, has changed shown that over a longer period of operation in stainless steel or conventional steel equipment (i.e. h., generally made of steel) in the smallest amounts applying rust the combustion of molecular hydrogen with molecular oxygen catalyzed. This is disadvantageous insofar as the heat of combustion formed thereby at least partially not where it is needed, namely in endothermic dehydration. Rather, she fizzles herself envisaged adiabatic dehydration at least partially, as a ideal adiabatic reaction device is not feasible. This conditioned either the need for a supply of external heat, with the usually undesirable on the heat transfer surfaces cracking processes the hydrocarbons involved are involved or result dehydrogenation conversions which are significantly reduced. Both are disadvantageous.

The Object of the present invention was therefore to provide an improved Process for the preparation of acrolein, or acrylic acid or To provide their mixture of propane, the described Disadvantages either no longer, or at best only in a reduced Form has.

• A) dem Einlass in eine erste Reaktionszone A einen Reaktionsgasgemischeingangsstrom A zuführt, der durch Zusammenführung von wenigstens vier voneinander verschiedenen gasförmigen Ausgangsströmen 1, 2, 3 und 4 mit der Maßgabe erzeugt wurde, dass die drei gasförmigen Ausgangsströme 1, 2 und 3 Propan enthalten, der gasförmige Ausgangsstrom 4 molekularer Wasserstoff und der gasförmige Ausgangsstrom 3 Frischpropan ist, den Reaktionsgasgemischeingangsstrom A in der Reaktionszone A durch wenigstens ein Katalysatorbett führt, an welchem, gegebenenfalls unter Zufuhr weiterer Gasströme, durch partielle heterogen katalysierte Dehydrierung des Propan ein Propan und Propylen enthaltender Produktgasgemischstrom A gebildet wird, den Produktgasgemischstrom A durch den Auslass aus der ersten Reaktionszone A aus selbiger herausführt und dabei in zwei Produktgasgemisch A-Teilströme 1 und 2 mit identischer Zusammensetzung aufteilt und den Produktgasgemisch A-Teilstrom 1 in erster Kreisgasfahrweise als gasförmigen Ausgangsstrom 1 in die erste Reaktionszone A rückführt, den Produktgasgemisch A-Teilstrom 2 gegebenenfalls in eine erste Trennzone A führt, um in selbiger von in ihm enthaltenen, von Propan und Propylen verschiedenen Bestandteilen eine Teilmenge oder mehr abzutrennen, und dadurch einen verbleibenden, Propan und Propylen enthaltenden, Produktgasgemischstrom A' zu erzeugen,
• B) den Produktgasgemischstrom A-Teilstrom 2 oder den Produktgasgemischstrom A' in einer zweiten Reaktionszone B zur Beschickung wenigstens eines Oxidationsreaktors verwendet und in dem wenigstens einen Oxidationsreaktor das im Produktgasgemisch A-Teilstrom 2 oder im Produktgasgemischstrom A' enthaltene Propylen einer selektiven heterogen katalysierten partiellen Gasphasenoxidation mit molekularem Sauerstoff zu einem Acrolein, oder Acrylsäure, oder deren Gemisch als Zielprodukt, nicht umgesetztes Propan und gegebenenfalls nicht umgesetztes Propylen sowie überschüssigen molekularen Sauerstoff enthaltenden Produktgasgemischstrom B unterwirft, den Produktgasgemischstrom B aus der Reaktionszone B herausführt und in einer zweiten Trennzone B im Produktgasgemischstrom B enthaltenes Zielprodukt abtrennt und von dem dabei verbleibenden, nicht umgesetztes Propan, molekularen Sauerstoff sowie gegebenenfalls nicht umgesetztes Propylen enthaltenden Restgas wenigstens eine nicht umgesetztes Propan, molekularen Sauerstoff und gegebenenfalls nicht umgesetztes Propylen enthaltende Teilmenge in zweiter Kreisgasfahrweise als gasförmigen Ausgangsstrom 2 mit der Maßgabe in die Reaktionszone A rückführt, dass man die gasförmigen Ausgangströme 2, 3 und 4 sowie gegebenenfalls zusätzliche vom gasförmigen Ausgangsstrom 1 verschiedene gasförmige Ausgangsströme zu einem gasförmigen Treibstrahlgemischstrom vereinigt und anschließend mit dem gasförmigen Treibstahlgemischstrom als Treibstrahl eine Strahlpumpe, die eine Treibdüse, eine Mischstrecke, einen Diffusor und einen Saugstutzen umfasst, betreibt, wobei die Förderrichtung des durch die Treibdüse über die Mischstrecke und den Diffuser entspannten Treibstrahls in den Einlass der ersten Reaktionszone A sowie die Saugwirkung des Saugstutzens in Richtung des den Produktgasgemischstrom A führenden Auslass der ersten Reaktionszone A weist und dabei durch den im Saugstutzen erzeugten Unterdruck unter Aufteilung des Produktgasgemischstroms A in die beiden Teilströme 1 und 2 den Produktgasgemisch A-Teilstrom 1 ansaugt, bei gleichzeitiger Vermischung mit dem Treibstrahl durch die Mischstrecke über den Diffusor transportiert und den dabei gebildeten Reaktionsgasgemischeingangsstrom A in den Einlass der ersten Reaktionszone A entlässt, gefunden, das dadurch gekennzeichnet ist, dass man zunächst die gasförmigen Ausgangsströme 2 und 3 sowie gegebenenfalls zusätzliche, von den gasförmigen Ausgangsströmen 1 und 4 verschiedene gasförmige Ausgangsströme in beliebiger Abfolge zu einem gasförmigen Ausgangsgemischstrom vereinigt und erst dem gasförmigen Ausgangsgemischstrom unter Ausbildung des gasförmigen Treibstrahlgemischstroms den gasförmigen Ausgangsstrom 4 beifügt.

Accordingly, a process for producing acrolein, or acrylic acid or its mixture of propane, wherein

• A) the inlet into a first reaction zone A, a reaction gas mixture input stream A supplied by merging at least four mutually different gaseous output streams 1 . 2 . 3 and 4 was generated with the proviso that the three gaseous output currents 1 . 2 and 3 Propane contained, the gaseous output current 4 molecular hydrogen and the gaseous output stream 3 Fresh propane is the reaction gas mixture input stream A in the reaction zone A by at least one catalyst bed leads to which, optionally with the supply of additional gas streams, by partial heterogeneously catalyzed dehydrogenation of propane, a propane and propylene containing product gas mixture stream A, the product gas mixture stream A through the outlet of the first reaction zone A leads out of selbiger and thereby in two product gas mixture A partial streams 1 and 2 divided with identical composition and the product gas mixture A partial stream 1 in the first cycle gas mode as gaseous output current 1 returns to the first reaction zone A, the product gas mixture A partial stream 2 optionally, passing into a first separation zone A to separate a subset or more of the same from propane and propylene components contained therein and thereby to produce a remaining product gas mixture stream A 'containing propane and propylene,
• B) the product gas mixture stream A partial stream 2 or the product gas mixture stream A 'used in a second reaction zone B for charging at least one oxidation reactor and in the at least one oxidation reactor that in the product gas mixture A partial stream 2 or Propylene contained in the product gas mixture stream A 'a selective heterogeneously catalyzed partial gas phase oxidation with molecular oxygen to an acrolein, or acrylic acid, or their mixture as the target product, unreacted propane and optionally unreacted propylene and excess molecular oxygen containing product gas mixture stream B, the product gas mixture stream B from the reaction zone B and in a second separation zone B in the product gas mixture stream B contained target product and separated from the remaining unreacted propane, molecular oxygen and optionally unreacted propylene-containing residual gas at least one unreacted propane, molecular oxygen and optionally not set propylene-containing subset in the second cycle gas mode of operation as a gaseous output stream 2 with the proviso in the reaction zone A that leads to the gaseous output currents 2 . 3 and 4 and optionally additional from the gaseous output stream 1 combines different gaseous output streams to a gaseous propellant jet mixed stream and then with the gaseous propellant mixed stream as propulsion jet, a jet pump, which includes a motive nozzle, a mixing section, a diffuser and an inlet, operates, wherein the conveying direction of the relaxed through the motive nozzle via the mixing section and the diffuser propellant jet in the inlet of the first reaction zone A and the suction of the suction nozzle in the direction of the product gas mixture stream A leading outlet of the first reaction zone A and thereby by the negative pressure generated in the suction under distribution of the product gas mixture stream A in the two partial streams 1 and 2 the product gas mixture A partial stream 1 sucks, transported with simultaneous mixing with the propulsion jet through the mixing section via the diffuser and the resulting reaction gas mixture input stream A discharges into the inlet of the first reaction zone A, found, which is characterized in that first the gaseous output streams 2 and 3 and optionally additional, from the gaseous output streams 1 and 4 different gaseous output streams combined in any sequence to form a gaseous starting mixture stream and only the gaseous starting mixture stream to form the gaseous propellant jet mixture stream, the gaseous output stream 4 accompanied.

apart from the characterizing part, the inventive method as in the EP-A 117,146, US-A 3,161,670, DE-A 33 13 573, WO 01/96270, DE-A 103 160 39, DE-A 10 2005 013 039, DE-A 10 2004 032 129, DE-A 102 11 275, DE-A 102 45 585, DE-A 10 2005 009 891, DE-A 10 2005 010 111, DE-A 10 2005 022 798 and DE-A 10 2005 009 885 appropriate procedures are carried out.

According to the invention, the addition of the gaseous output stream preferably takes place 4 to the gaseous starting mixture stream (forming the motive jet mixture stream) within the shortest possible time. Furthermore, the addition of the gaseous output stream takes place 4 to the gaseous starting mixture stream (forming the motive jet mixture stream) such that from the time of formation of the motive jet mixture stream to the time the reaction gas mixture input stream A reaches the first catalyst bed of the reaction zone A with dehydrogenation catalyst, not more than 30 seconds, preferably not more than 20 or 10 seconds, advantageously not more than 7 seconds, more preferably not more than 5 seconds, most preferably not more than 3 seconds, and most preferably not more than 1, 0.5 or 0.1 seconds ,

As a method for the separation of target product contained in the product gas mixture stream B, in principle all methods known in the art in this regard come into consideration for the process according to the invention. They are essentially characterized in that one converts the target product, for example by absorptive and / or condensing measures from the gaseous to the condensed phase. As an absorption agent come z. As water, aqueous solution and / or organic solvents into consideration. As part of this "condensation" of the target product normally remains a not in the condensed phase transient residual gas, which includes the relatively difficult to be condensed components of the product gas mixture stream B. These are usually especially those components whose boiling point at atmospheric pressure (1 bar) ≤ -30 ° C (their total content of the residual gas is generally ≥ 70% by volume, frequently ≥ 80% by volume and in many cases ≥ 90% by volume) .This primarily includes unreacted propane, excess product remaining in the product gas mixture stream B. In addition, the residual gas is usually inert diluent gases such as N ₂ , CO ₂ , noble gases (He, Ne, Ar, etc.), CO and to a lesser extent also acrylic acid, acrolein and / or H ₂ O (the water vapor content of the residual gas can be up to 25 vol .-%, often up to 20 vol .-%, or up to 10 vol .-%, but often below 10 vol .-% or below r 5 vol.%). This aforementioned residual gas forms (based on the amount of propane contained therein) normally the main amount (usually at least 80%, or at least 90%, or at least 95% or more) of the residual gas formed in the separation zone B and is therefore in this document, inter alia also referred to as main residual gas.

According to the invention, at least one unreacted propane, molecular oxygen, and optionally unreacted propylene containing subset of this residual gas (main residual gas) in Kreisgasfahrweise as gaseous output stream 2 be recycled to the reaction zone A. According to the invention, the total amount of this residual gas in the reaction zone A is often useful as gaseous output stream 2 recycled.

Especially when the condensation of the target product by absorption by means of an organic solvent takes place, falls in the separation zone B usually at least a second unreacted propane and optionally unreacted propylene containing residual Gas (based on propane contained therein is its amount in Compared to the main residual gas quantity normally much lower). This is due to the fact that the forming condensed phase to some extent not converted propane and optionally unreacted propylene receives.

in the further course of the extractive, distillative, crystallizing and / or desorptive separation of the target product from the condensed Phase, this unreacted propane and, where appropriate Propylene usually as part of at least one other Gas phase recovered and in the method according to the invention preferably also recycled to the reaction zone A.

This can z. B. in a mixture with the main residual gas (in this document then called total residual gas). It can also be in the form of independent in the reaction zone A to be recycled gas flows respectively. Of course can this return in the reaction zone A as a further gaseous output stream respectively. These stand-alone returnee gas flows can free of oxygen, or also containing oxygen (secondary residual gas) (For example, if he stripping by air or at the head of a by means of air as a polymerization inhibitor rinsed rectification column accrues).

Both main residual gas, total residual gas and secondary residual gas form in the sense of this invention as a gaseous output stream 2 in the reaction zone A traceable unreacted propane, molecular oxygen and optionally unreacted propylene containing residual gas. Unreacted propane obtained in the separation zone B and any unconverted propylene-containing residual gas which is free of molecular oxygen can, according to the invention, be mixed with main residual gas and / or secondary residual gas (ie, eg as constituent of total residual gas). B. as part of the gaseous output stream 2 and / or independently (in this case, it is not recycled to the reaction zone A in the context of the invention residual gas) are recycled to the reaction zone A. In the latter case, this feedback without any restriction, ie, z. B. also take place as a further gaseous output stream. In particular, when in the process according to the invention in a first separation zone A from the product gas mixture A partial stream 2 substantially all contained in it, separate from propane and propylene components and then used the resulting product gas mixture stream A 'to feed the at least one oxidation reactor, is In the process according to the invention, essentially the total amount of unreacted propane obtained in the separation zone B and optionally unreacted propylene-containing gas streams are returned to the reaction zone A, preferably as a component of total residual gas as a gaseous output stream 2 , Subsets could (as described for example in DE-A 10 2004 032 129) but optionally also for other purposes, such as. B. for power generation and / or synthesis gas production and / or as a diluent gas in the reaction zone B continue to be used. In general, however, in the case described above, at least half or two-thirds (ie, 50% by volume or 66.6% by volume), preferably at least three quarters, and very particularly preferably the total amount of the abovementioned occurring in the separation zone B. (Each individually with respect to the main and / or secondary or total) residual gas in the reaction zone A, according to the invention preferably as part of the gaseous output stream 2 , return. If in the separation zone B only an unreacted propane, molecular oxygen and unreacted propylene containing residual gas flow to (this is often the case), this is, especially if in the process according to the invention in a first separation zone A from the product gas mixture A partial stream 2 essentially all contained in it, separate from propane and propylene components and then the resulting product gas mixture stream A 'used to charge at least one oxidation reactor, according to the invention preferably completely (optionally less one guided into the reaction zone B as a diluent partial amount of identical composition) as gaseous output current 2 recycled to the reaction zone A. However, it can then be divided into two subsets of identical composition and, as described above, only a partial amount as gaseous output stream 2 returned to the reaction zone A and the other subset can be used elsewhere. If more than one such residual gas stream precipitates in the separation zone B, these residual gas streams (as already mentioned) can be jointly (for example, combined) according to the invention as a gaseous output stream 2 be recycled to the reaction zone A. Of course, the return of these residual gas streams in the reaction zone A but also be done individually. Also, a subset of the residual gas is not a gaseous output stream 2 but only along the reaction path of the heterogeneously catalyzed dehydrogenation of propane in the reaction zone A in the reaction zone A are recycled. Under the reaction path of the heterogeneously catalyzed dehydrogenation of the propane in the ERS th reaction zone A while the flow path of the propane contained in the reaction gas mixture input stream A through the reaction zone A in dependence on the dehydrogenating reaction (the order in the heterogeneously catalyzed dehydrogenation) of this propane.

Normally exists as gaseous output current 2 in the inventive method recycled residual gas in the inventive method to ≥ 70 vol .-%, often ≥ 80 vol .-% and often to ≥ 90 vol .-%, usually to ≥ 95 vol .-%, or to ≥ 98 vol. -% of constituents whose boiling point at normal pressure (1 bar) is ≤ -30 ° C.

In particular, when in the process according to the invention in a first separation zone A from the product gas mixture A partial stream 2 essentially all components contained in it, separated from propane and propylene and then the resulting product gas mixture stream A 'used to charge at least one oxidation reactor, comprising the composition of the gaseous output stream 2 typically:
0 to 2 vol.%, Often 0 to 1 vol.%, Often 0 to 0.5 vol.% Propene;
0 to 2 vol.%, Often 0 to 1 vol.%, Often 0 to 0.5 vol.% Acrolein;
0 to 0.5 vol.%, Often 0 to 0.1 vol.%, Often 0 to 0.05 vol.% Of acrylic acid;
0 to 4 vol.%, Often 0 to 2 vol.%, Often 0 to 1.5 vol.% CO _x ;
10 to 50% by volume, often 20 to 30% by volume of propane;
0 to 70 vol.%, Often 40 to 70 vol.% N ₂ ;
1 to 10 vol.%, Often 2 to 5 vol.%, Often 2.5 to 3.5 vol.% O ₂ and> 0 to 15 vol.% H ₂ O.

Often the gaseous output current 2 in the inventive method, a temperature of 50 to 200 ° C, or from 70 to 130 ° C and a pressure of 1.5 to 5 bar, preferably from 3 to 4 bar.

Typical temperatures for the gaseous output stream 3 are at 0 to 50 ° C, often at 5 to 20 ° C, at pressures of 3 to 6 bar or 4 to 5 bar.

According to the procedure of the invention, the gaseous output stream 4 This is to be understood in this document gas flows, either only of molecular hydrogen or at least 50 vol%, preferably at least 60 vol .-%, or at least 70 vol .-%, or at least 80% by volume, or at least 90% by volume, or at least 95% by volume or at least 98% by volume or at least 99% by volume of molecular hydrogen and in the respective In this document, the term "inert gas" is to be understood more generally to mean a reactant gas constituent which essentially behaves as inert under the conditions of the corresponding reaction (in the above-mentioned case of heterogeneously catalyzed dehydrogenation) and considers each inert reactant constituent per se - remains more than 95 mol .-%, preferably more than 99 mol .-% chemically unchanged.Examples of such inert gases are N ₂ , noble gases, CO ₂ or water vapor.

Expedient according to the invention, the gaseous output current 4 in the inventive method, a temperature of 20 to 100 ° C, often 40 to 60 ° C and a pressure in the range of 1 to 5 bar.

An inventive method is advantageous in which 60 to 90 mol .-%, preferably 75 to 85 mol .-% of the molecular hydrogen contained in the reaction gas mixture inlet stream A the product gas mixture A partial stream 1 (gaseous output current 1 ) and the remaining 10 to 40 mol%, or 15 to 25 mol .-% of the gaseous output stream 4 ,

As about the gaseous output currents 1 to 4 In addition to gaseous output streams is especially water vapor or spray of finely divided water droplets into consideration. Conveniently, such, for example, gaseous output current 5 from steam, a temperature of 100 to 200 ° C, often 120 to 160 ° C, and a pressure of 1 bar to 4 bar.

According to the invention, such a gaseous starting stream consisting of water vapor is obtained 5 integrate in the gaseous starting mixture stream in the process according to the invention, before the gaseous output stream to the latter 4 adds.

The aforementioned integration is carried out expedient so that one to the gaseous output stream 2 first the gaseous output current 5 and to the resulting gaseous mixture, the gaseous output stream 3 adds.

The resulting starting mixture stream is advantageously only then by an indirect heat led exchanger to selbigem in the product gas mixture A partial stream 2 to cool (eg from 500 to 600 ° C to 150 to 350 ° C) and at the same time to heat the output stream (eg from 20 to 200 ° C, to 350 to 530 ° C). The presence of water vapor reduces the risk of coking associated with heating. Then, according to the invention, the combination of the gaseous output stream takes place 4 with the initial mixture stream brought to temperature as described to form the motive jet mixture stream. The latter according to the invention advantageously has a temperature of 350 to 550 ° C and a pressure of 2 to 5 bar.

The co-use of water vapor as a gaseous output stream 5 is particularly advantageous for the catalyst lifetime in the heterogeneously catalyzed partial dehydrogenation, as will be described below. According to the invention, however, it is advantageous to use such a gaseous output stream 5 avoid as possible and it in the gaseous output stream 2 contained with advantage, leaving from the occurring during the partial oxidation reaction water formation steam. Water vapor contents in the reaction gas mixture input stream A from 1 to 20 or to 15 or to 10 vol .-%, frequently 4 to 6 Vol .-%, have proved to be useful according to the invention.

In particular, when in the process according to the invention the product gas mixture A partial stream 2 in a less preferred variant of the invention used as such for feeding the at least one oxidation reactor, it is expedient according to the invention to separate from the residual gas accumulating in the separation zone B at least a portion of the constituents other than propane, molecular oxygen and optionally propylene present therein to form the gaseous output stream 2 is used.

Appropriate Separations are z. In EP-A 117 146, US-A 3,161,670, DE-A 33 13 573, DE-A 103 16 039 and in DE-A 102 45 585 described.

For the process according to the invention, it is favorable within the context of the loop procedure to be used in reaction zone A if the amount of product gas mixture A partial stream 1 , Based on the total amount of the product gas mixture stream A, 25 to 75 vol .-% and 30 to 70 vol .-%, preferably 40 to 60 vol .-% and particularly preferably 50 vol .-%.

The propane conversion during the passage of the reaction gas mixture input stream A, which according to the invention preferably only from the gaseous output streams 1 . 2 . 3 and 4 and optionally a gaseous output stream 5 constituted by water vapor can in the process of the invention (based on the single passage of the reaction gas mixture input stream A through the reaction zone A and based on the total amount contained in the reaction gas mixture input stream A fresh propane and from the gaseous output stream 2 originating propane) is 20 to 30 mol%. However, the process according to the invention is particularly favorable when the abovementioned propane conversion is 30 to 60 mol%, preferably 35 to 55 mol% and particularly preferably 35 to 45 mol%.

For the realization of the aforementioned propane conversions, it is favorable to carry out the partial heterogeneously catalyzed propane dehydrogenation in the reaction zone A at a working pressure of 0.3 to 10 bar, or advantageously up to 3 bar. The presence of water vapor makes it possible, via the heat capacity of the water, to compensate for the effect of dehydrogenation on the endothermic effect and, on the other hand, dilution with steam reduces the educt and product partial pressure, which has a favorable effect on the equilibrium state of the dehydrogenation. Such a dilution effect can also be caused by the concomitant use of other inert gases (eg N ₂ , CO _2, etc.) as further gaseous output streams. However, water vapor, as already mentioned, additionally has a beneficial effect on the catalyst lifetime in the reaction zone A.

• 1 = Treibstrahlgemischstrom
• 2 = Produktgasgemisch A-Teilstrom 2
• 3 = Katalysatorfestbett
• 4 = Treibdüse
• 5 = Mischrohr
• 6 = Diffusor

3 shows two possible embodiments of such a reaction zone A (which in 3 given diameter have the dimension "mm"), where the numeric addresses mean:

• 1 = Motive jet mixed flow
• 2 = Product gas mixture A partial flow 2
• 3 = Fixed catalyst bed
• 4 = Motive nozzle
• 5 = Mixing tube
• 6 = Diffuser

The motive jet mixture flow can be z. B. 148 t / h, a temperature of 486 ° C and a Pressure of 3.11 bar or 3.51 bar have. The product gas mixture A partial stream 2 is in a similar manner also 148 t / h and z. B. typically have a temperature of 600 ° C and a pressure of 2.3 bar.

D. h., The pressure on the suction side may be 2.3 bar. This corresponds to a total circulation of 296 t / h. As a catalyst z. For example, stranded rings with a diameter of 1.5 mm and a length of typically 3 to 7 mm according to Example 4 of DE-A 102 19 879 can be used (total amount: eg 30 t). The bulk density of the same in the fixed catalyst bed can, for. B. at 1200 kg / m ³ (loose) to 1350 kg / m ³ (fixed). Immediately before the catalyst bed, a pressure of typically 2.71 bar would then be present.

The essential contents of the reaction gas mixture input stream A are typical: propene > 0 to 25, often 1 to 10, often 2 to 7% by volume; acrolein 0 to 1, often 0 to 0.5, often 0 to 0.25 vol .-%; acrylic acid 0 to 0.25, often 0 to 0.05, often 0 to 0.03% by volume; CO _x 0 to 5, often 0 to 3, often 0 to 2 vol .-%; propane 5 to 50, preferably 10 to 20% by volume; nitrogen 30 to 80, preferably 50 to 70% by volume; oxygen > 0 to 5, preferably 1.0 to 2.0% by volume; H ₂ O ≥0 to 20, preferably 5.0 to 10.0% by volume; H ₂ 0.5 to 10, preferably 1 to 5 vol .-%.

As a general rule However, as already stated, the lowest possible water vapor contents in the reaction gas mixture input stream A preferred and desired. With increasing in the reaction zone A sought propane conversion grows the requirement for a significant amount of water vapor in the Reaction gas mixture input stream A to satisfactory service life to ensure the dehydrogenation catalysts.

Cheap is it for the method according to the invention, if the molar ratio from containing molecular hydrogen to molecular contained Oxygen in the reaction gas mixture input stream A is about 2: 1. The molar ratio of contained molecular hydrogen to be contained propane while in the reaction gas mixture input stream A usually at the same time ≤ 5. The molar relationship of water vapor contained in the reaction gas mixture input stream A. propane contained therein is used in the process according to the invention often ≥ 0.05 to 2 or to 1 amount.

With Advantage is the process of the invention the reaction zone A designed so that the product gas mixture stream A unreacted propane and desired propylene in the molar relationship Propene to propane of 0.2 or 0.3 to 0.5 (optionally to 0.66) contains.

Basically the partial heterogeneously catalyzed propane dehydrogenation in the reaction zone A (quasi) adiabatic and thereby be carried out endothermically. It is the Reaction gas mixture input stream A with a temperature of 450 ° C to 700 ° C (or from 550 to 650 ° C) led to at least one catalyst bed. At the adiabatic passage by the same (there is both a fluidized bed and a fixed bed into consideration; a fixed catalyst bed is preferred according to the invention) the reaction gas mixture will normally be due to hydrogen combustion first heat and then depending on sales and dilution around 30 ° C up to 200 ° C cooling down. Lower reaction temperatures allow longer life of the used Catalyst bed. higher Promote reaction temperatures increased Sales.

application point becomes appropriate the heterogeneously catalyzed propane dehydrogenation in the reaction zone A as a horde reactor realize.

This contains spatial successively more useful as a dehydrogenation catalyzing catalyst bed. The number of catalyst beds can 1 to 20, expedient 2 to 8, but also 3 to 6 amount. Let with increasing Hordenzahl Increased increasingly easier propane conversions to reach. The catalyst beds are preferably radial or axial arranged one behind the other. Application technology is appropriate applied in such a tray reactor, the fixed catalyst bed type.

in the In the simplest case, the fixed catalyst beds are in a shaft furnace reactor axially or in the annular gaps of centric nestled arranged cylindrical gratings. However, it is also possible that Ring gaps in segments one above the other to arrange and the gas after radial passage in a segment in the next about that or underlying segment.

In expedient manner the reaction gas mixture input stream A is on its way from a catalyst bed to the next Catalyst bed, for example by passing over heated with hot gases heat exchanger surfaces (z. B. ribs) or by passing through heated with hot fuel gases pipes, subjected in the Horden reactor of a Zwischenerhitzung (material suitably Si-containing steels, especially stainless steels, z. B. of type 1.4841).

Becomes the Horden reactor in the rest operated adiabatically, it is for as described, propane conversions ≤ 30 mol%, especially when used the catalysts described in DE-A 199 37 107, in particular the exemplary embodiments, sufficiently, the reaction gas mixture input stream A to a temperature from 450 to 550 ° C preheated to pass into the dehydrogenation reactor and within the tray reactor to keep in this temperature range. That is, the entire propane dehydrogenation is so at extremely low Temperatures to realize what the service life of the fixed catalyst beds as a particularly cheap proves. For higher propane conversions the reaction gas mixture input stream A is expedient to higher temperatures preheated into the dehydrogenation reactor (these can be up to to 700 ° C amount) and within the tray reactor in this elevated temperature range held.

It is even more clever to carry out the above described intermediate heating directly (autothermal mode). To this end, molecular oxygen is normally added to the reaction gas mixture stream both behind the first catalyst bed (viewed in the direction of flow) and between the subsequent catalyst beds. Thus, (usually catalysed by the dehydrogenation catalysts themselves) a limited combustion of the reaction gas mixture contained in the course of the heterogeneously catalyzed propane dehydrogenation and / or the reaction gas mixture added molecular hydrogen (possibly accompanied by a small extent propane combustion) (it may also be useful in terms of application, to insert catalyst beds in the tray reactor, which are charged with catalyst, which catalyzes the specific (selectively) the combustion of hydrogen (as such catalysts are, for example, those of the writings US 4,788,371 . US 4,886,928 . US 5,430,209 . US 5,530,171 . US 5,527,979 and US 5,563,314 into consideration; For example, such catalyst beds may be housed in alternating manner with the Dehydrierkata lysator-containing beds in the tray reactor). Preferably, according to the invention, molecular hydrogen is added from the outside only to form the reaction gas mixture input stream A. The released heat of reaction thus enables quasi-autothermal (the gross carbonization is essentially zero) a nearly isothermal mode of operation of heterogeneously catalyzed propane dehydrogenation. With increasing selected residence time of the reaction gas in the catalyst bed as a propane dehydrogenation at a decreasing or substantially constant temperature is possible, which allows particularly long catalyst life.

In general, an oxygen feed as described above should be carried out so that the oxygen content of the reaction gas mixture, based on the amount of molecular hydrogen contained therein, 0.5 to 50 or 30, preferably 10 to 25 vol .-% (these relations are also favorable for the corresponding contents in the reaction gas mixture input stream A). In this case, both pure molecular oxygen or inert gas, for example CO, CO ₂ , N ₂ and / or noble gases, dilute oxygen, but in particular air (preferably only air is used as the oxygen source) are considered as oxygen source. The resulting combustion gases generally additionally dilute and thus promote heterogeneously catalyzed propane dehydrogenation. This applies in particular to the water vapor formed during combustion.

The Isothermia of heterogeneously catalyzed propane dehydrogenation can be thereby further improve that one in the Horden reactor in the spaces between the catalyst beds closed, but before its filling conveniently but not necessarily evacuated, installations (for example, tubular) attaches. These fittings Contain suitable solids or liquids above one evaporate or melt at a certain temperature while consuming heat and condense again where this temperature falls below and heat release.

The reaction gas mixture input stream A advantageously contains, in particular in the case of such an autothermal mode of operation as described: 15 to 25 vol.% Propane, 2 to 6% by volume propylene, 5 to 20% by volume Steam, 2 to 10 vol.% molecular hydrogen, 40 to 75 vol.% molecular nitrogen, and > 0 to 3 vol.% molecular oxygen.

Typical loads of the total amount of dehydrogenation catalyst (sum over all beds) with reaction gas mixture input stream A according to the invention 250 to 5000 h ^-1 (in high load mode also up to 40,000 h ^-1 ), preferably 10,000 to 25,000 Nl / l · h, more preferably 15,000 to 20,000 Nl / lh. The corresponding charges with propane are typically 50 to 1000 h ^-1 (in high load mode also up to 40 000 h ^-1 ), preferably at 2000 to 5000 Nl / l · h, particularly preferably 3000 to 4000 Nl / l · h.

The inventive procedure allows in the reaction zone A, even at high propane conversions Propylenbildungsselektivitäten of 95 mol% and more.

The reaction mixture A (the dehydrogenation reactor) removed product gas mixture A partial stream 2 is in accordance with the reaction conditions selected for the heterogeneously catalyzed propane dehydrogenation generally at a pressure of 0.3 to 10 bar, preferably 1 to 3 bar, and often has a temperature of 450 to 650 ° C and up to 750 ° C, often a temperature of 500 to 600 ° C on. In general, it comprises propane, propene, H _2, N _2, H ₂ O, methane, ethane (the latter two resulting mostly due to thermal decomposition of a small amount of propane), ethylene, butene-1, other butenes such as isobutene, other Ca hydrocarbons such as n-butane, isobutane, butadiene, etc., CO and CO ₂ , as a rule but also oxygenates such as alcohols, aldehydes and carboxylic acids (normally having ≦ 9 C atoms). Furthermore, in small quantities from the gaseous output stream 2 containing ingredients.

While EP-A 117 146, DE-A 33 13 573 and US-A 3,161,670 recommend the product gas mixture A partial stream 2 to use for charging the at least one oxidation reactor, it is considered advantageous for the inventive method, from which the required propylene-containing product gas mixture A partial stream 2 prior to its use as a propene source for the subsequent propene partial oxidation, separate at least a portion of the constituents other than propane and propylene contained therein. The requirements of DE-A 102 11 275 should be observed.

It be at this point first still recorded that for the heterogeneous invention catalyzed propane dehydrogenation in principle all in the prior art known dehydrogenation catalysts come into consideration. They leave roughly divide into two groups. Namely in those that are more oxidic Nature are (for example, chromium oxide and / or alumina) and in those that consist of at least one on one, usually oxidic, carrier isolated, usually comparatively noble, metal (for Example platinum) exist. Among other things, so all dehydrogenation catalysts used in WO 01/96270, EP-A 731077, the DE-A 10211275, DE-A 10131297, WO 99/46039, US-A 4,788 371, EP-A-0 705 136, WO 99/29420, US-A 4 220 091, US-A 5 430 220, US-A 5,877,369, EP-A-0 117 146, DE-A 199 37 196, the DE-A 199 37 105 and DE-A 199 37 107 are recommended. In particular can both the catalyst according to Example 1, Example 2, Example 3, and Example 4 of DE-A 199 37 107 used become.

there are dehydrogenation catalysts containing 10 to 99.9% by weight Zirconia, 0 to 60 weight percent alumina, silica and / or Titanium dioxide and 0.1 to 10 wt .-% of at least one element of first or second main group, an element of the third subgroup, an element of the eighth subgroup of the Periodic Table of the Elements, Lanthanum and / or tin contain, with the proviso that the sum of the weight percentages 100 wt .-% results.

Especially also suitable in the examples and comparative examples Dehydrogenation catalyst used in this document.

As a general rule For example, the dehydrogenation catalysts may be catalyst strands (diameter typically 1 to 10 mm, preferably 1.5 to 5 mm; Length typically 1 to 20 mm, preferably 3 to 10 mm), tablets (preferably the same dimensions as in the strands) and / or catalyst rings (outer diameter and length each typically 2 to 30 mm or to 10 mm, wall thickness expediently 1 to 10 mm, or to 5 mm, or to 3 mm).

In As a rule, the dehydrogenation catalysts (especially those in this Example font used and those in DE-A 19937107 recommended (in particular the exemplary catalysts of this DE-A) so that they can both the dehydration of propane and to catalyze the combustion of propane and molecular hydrogen capital. The hydrogen combustion proceeds both in comparison to the dehydrogenation of propane and compared to its combustion in the case of a competitive situation at the catalysts much faster.

Further come to heterogeneously catalyzed propane dehydrogenation in principle all known in the art reactor types and process variants into consideration. Descriptions of such process variants included for example, all concerning the dehydrogenation catalysts quoted prior art writings and the prior art cited at the beginning of this document.

A comparatively comprehensive description of dehydrogenation processes suitable according to the invention also includes Catalytica® ^® Studies Division, Oxidative Dehydrogenation and Alternative Dehydrogenation Processes, Study Number 4192 OD, 1993, 430 Ferguson Drive, Mountain View, California, 94043-5272 USA.

Advantageously according to the invention, at least 50% by volume, preferably at least 75% by volume, more preferably at least 90% by volume and most preferably at least 95% by volume of the partial stream in the product gas mixture A will be used 2 separated, separate from propane and propylene, components before the same is used as a propene source for the partial oxidation of the process according to the invention.

Basically, you can do that all in DE-A 10 2004 032 129, DE-A 10 2005 013 039, DE-A 10 2005 009 891, DE-A 10 2005 010 111, DE-A 10 2005 009 885, DE-A 10 2005 028 798 and DE-A 102 45 585 described separation variants become.

An expedient for the needs according to the invention possibility is, for example, the preferably cooled (preferably to temperatures of 10 to 100 or 70 ° C) product gas mixture A partial stream 2 , z. B. at a pressure of 0.1 to 50 bar, preferably 5 to 15 bar and a temperature of z. B. 0 to 100 ° C, preferably 20 to 40 ° C, with a (preferably high-boiling) organic solvent (preferably a hydrophobic), in which propane and propylene (compared to the other constituents of the product gas mixture A partial stream 2 expediently preferred) to bring into contact (eg by simply passing through). Subsequent desorption, rectification and / or stripping with a gas which is inert with respect to the subsequent propylene partial oxidation and / or requires a reactant in this partial oxidation (for example air or another mixture of molecular oxygen and inert gas) can be used for the propane and Propylene recovered in a mixture in purified form and this mixture are used for the partial oxidation as a propylene source (preferably as described in Comparative Example 1 of the German application DE-A 10 2004 032 129 described procedure). The optionally molecular hydrogen-containing exhaust gas of such absorption can be subjected to, for example, a pressure swing adsorption and / or membrane separation (eg according to DE-A 10235419) and then, the separated hydrogen as a constituent of the reaction gas mixture input stream A (as gaseous output stream 4 ) co-use.

Indeed is the C3 hydrocarbons / C4 hydrocarbons separation factor in the above separation method comparatively limited and for in DE-A 10245585 described needs often not sufficient.

When alternative for the separation step described above via absorption is for the purposes according to the invention therefore often a pressure swing adsorption or a pressure rectification preferred.

In principle, all absorbents which are capable of absorbing propane and propylene are suitable as absorbents for the absorptive separation described above. The absorbent is preferably an organic solvent which is preferably hydrophobic and / or high boiling. Advantageously, this solvent has a boiling point (at a normal pressure of 1 atm) of at least 120 ° C, preferably of at least 180 ° C, preferably from 200 to 350 ° C, especially from 250 to 300 ° C, more preferably from 260 to 290 ° C. Conveniently, the flash point (at a normal pressure of 1 bar) is above 110 ° C. Generally suitable as absorbent relatively non-polar organic solvents, such as aliphatic hydrocarbons, which preferably contain no polar group acting outward, but also aromatic hydrocarbons. In general, it is desirable that the absorbent has the highest possible boiling point with the highest possible solubility for Propane and propylene has. Examples which may be mentioned as absorbents are aliphatic hydrocarbons, for example C ₈ -C ₂₀ alkanes or alkenes, or aromatic hydrocarbons, for example, middle oil fractions from the Paraffindestillation or ethers with bulky (sterically demanding) groups on the O atom, or mixtures thereof, wherein this may be added a polar solvent, such as, for example, the 1,2-dimethyl phthalate disclosed in DE-A 43 08 087. Also suitable are esters of benzoic acid and phthalic acid with straight-chain alkanols containing 1 to 8 carbon atoms, such as n-butyl benzoate, benzoic acid, ethyl benzoate, dimethyl phthalate, diethyl phthalate, and so-called heat transfer oils, such as diphenyl, diphenyl ether and mixtures of diphenyl and diphenyl ether or their chlorinated derivatives and triaryl alkenes, for example, 4-methyl-4'-benzyl diphenylmethane and its isomers 2-methyl-2'-benzyldiphenylmethane, 2-methyl-4'-benzyldiphenylmethane and 4-methyl-2'-benzyl diphenylmethane and mixtures of such isomers. A suitable absorbent is a solvent mixture of diphenyl and diphenyl ether, preferably in the azeotropic composition, in particular from about 25 wt .-% diphenyl (biphenyl) and about 75 wt .-% of diphenyl ether, for example the commercially available Diphyl ^® (z. B. obtained from Bayer Aktiengesellschaft). Frequently, this solvent mixture contains a solvent such as dimethyl phthalate in an amount of 0.1 to 25 wt .-%, based on the total solvent mixture added. Particularly suitable absorbents are also octanes, nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, heptadecans and octadecanes, with tetradecanes in particular having proven to be particularly suitable. It is favorable if the absorbent used on the one hand fulfills the above-mentioned boiling point, but on the other hand has a molecular weight which is not too high. Advantageously, the molecular weight of the absorbent is ≦ 300 g / mol. Also suitable are the paraffin oils having 8 to 16 carbon atoms described in DE-A 33 13 573. Examples of suitable commercial products are products sold by Haltermann, such as Halpasols i, such as Halpasol 250/340 i and Halpasol 250/275 i, as well as printing ink oils under the names PKWF and Printosol. Preference is given to aromatics-free commercial products, eg. B. those of the type PKWFaf. If they contain a low content of residual aromatics, this can advantageously be reduced by rectification and / or adsorption in advance of the described use and be pressed to values significantly below 1000 ppm by weight. In continuous operation, the composition of the absorbent will change due to the process accordingly.

The performance of absorption is not particularly limited. All methods and conditions customary to the person skilled in the art can be used. Preferably, the product gas mixture is A partial stream 2 at a pressure of 1 to 50 bar, preferably 2 to 20 bar, more preferably 5 to 15 bar, and a temperature of 0 to 100 ° C, in particular from 20 to 50 or 40 ° C, brought into contact with the absorbent. The absorption can be carried out both in columns and in quenching apparatuses. It can be done in cocurrent or in countercurrent (is preferred). Suitable absorption columns are, for example tray columns (having bubble and / or sieve trays), columns with structured packings (for example, sheet metal packings with a specific surface area of 100 to 1000, or up to 750 m ² / m ^3, for example Mellapak ^® 250 Y) and Packed columns (filled, for example, with Raschig fillers). However, it is also possible to use trickle and spray towers, graphite block absorbers, surface absorbers such as thick-film and thin-layer absorbers, dishwashers, cross-flow scrubbers and rotary scrubbers. In addition, it may be beneficial to let the absorption take place in a bubble column with and without internals.

The Separation of the propane and propylene from the absorbent can by stripping, flash evaporation and / or distillation respectively.

The Separation of the propane and propylene is carried out by the absorbent preferably by stripping and / or desorption. The desorption can in usual Way over a pressure and / or temperature change carried out be, preferably at a pressure of 0.1 to 10 bar, in particular 1 to 5 bar, stronger preferably 1 to 3 bar, and a temperature of 0 to 200 ° C, in particular 20 to 100 ° C, stronger preferably 30 to 70 ° C, more preferably 30 to 50 ° C. One for the stripping suitable gas is for example steam, preferably however, are in particular oxygen / nitrogen mixtures, for example Air. When using air or oxygen / nitrogen mixtures, where the oxygen content is over 10 vol%, it may be useful before and / or during the Stripping process to add a gas that reduces the explosion area. Especially suitable for it are gases with a specific heat capacity ≥ 29 J / mol · K at 20 ° C, such as methane, Ethane, propane (preferred), propene, benzene, methanol, ethanol, as well as Ammonia, carbon dioxide, and water. C4 hydrocarbons are preferred according to the invention as such additives however to avoid. Bubble columns are also particularly suitable for stripping and without fittings.

The separation of propane and propylene from the absorbent may also be via a distillate tion or rectification, wherein the skilled worker familiar columns can be used with packages, packing or corresponding internals. Preferred conditions in the distillation or rectification are a pressure of 0.01 to 5 bar, in particular 0.1 to 4 bar, more preferably 1 to 3 bar, and a temperature (in the bottom) of 50 to 300 ° C, in particular 150 up to 250 ° C.

A obtained by stripping from the absorbent for the reaction zone B of the method according to the invention in principle suitable propylene source can be used before Charging the partial oxidation of yet another process step supplied be used to For example, the losses of co-stripped absorbent (eg separation in demisters and / or depth filters) and the partial oxidation to be carried out according to the invention at the same time to protect against absorption or the release effect between C3 / C4 hydrocarbons to further improve. Such Separation of the absorbent can according to all known in the art Procedural steps take place. One in the context of the method according to the invention preferred embodiment such a separation is z. As the quenching of the output current from the stripping device with water. In this case, the absorbent becomes washed out of this loaded output stream with water and the output current is simultaneously charged with water (small amounts of water have a beneficial effect on the activity the catalysts for the partial oxidation according to the invention out). This laundry or the quenching can z. B. at the top of a desorption column over a Liquid collecting tray by spraying carried out by water or in a separate apparatus.

to support of the separation effect can in the quench space, the quench surface enlarging internals be installed, as the expert of rectifications, absorptions and Desorptionsen ago known.

water is in this respect a preferred detergent, as it is in the following Partial oxidation does not normally interfere significantly. After this the water is the absorbent from the laden with propane and propylene Output stream has washed out the water / absorbent mixture fed to a phase separation and the treated, low-volume, output stream, directly according to the invention to be carried out Partial oxidation fed become.

In an advantageous manner for the process according to the invention, in particular when the propylene / propane mixture is stripped from the absorbate by means of air, generally usable reaction gas starting mixtures which are directly usable for the partial oxidation can be obtained. In the event that their propane content should not satisfy the invention, fresh propane may be added to them prior to their use for the inventive partial oxidation of the propylene present. About the residual gas (the gaseous output current 2 ) The same is then conveniently recycled to the heterogeneously catalyzed dehydrogenation (as a component of the reaction gas mixture input stream A). To the appropriate amount of propane, then the supply of fresh propane flow through the gaseous off 3 be mitigated. In an extreme case, the supply of fresh propane required in the heterogeneously catalyzed propane dehydrogenation can be completely eliminated if this supply of fresh propane completely takes place before the partial oxidation of the propylene into the reaction gas starting mixture in question, from where it then passes as the remaining constituent in the residual gas only after passing through the Partial oxidation to be carried out according to the invention is fed to the reaction gas mixture input stream A for the heterogeneously catalyzed propane dehydrogenation. If appropriate, a fresh propane feed can also be carried out in a C ₃ separation which may be present between heterogeneously catalyzed dehydrogenation and propylene partial oxidation (for example as stripping gas).

These it can be a two-stage partial oxidation of propylene to acrylic acid a part or the whole Supply of fresh propane also in the starting reaction gas mixture for the second Stage of the partial oxidation take place (however, this is Reaction gas starting mixture sometimes already then not explosive, if this qualification already on the starting reaction gas mixture for the first stage of partial oxidation was true). This is mainly because of that advantageous because the unwanted Side reaction of propane to propionaldehyde and / or propionic acid all from the first partial oxidation stage (propylene → acrolein) under their conditions. It is also advantageous, a Frischpropanzufuhr to the first and to the second partial oxidation stage substantially evenly distributed.

By this possibility of the supply of fresh propane into the starting reaction gas mixture for the partial oxidation stages, the composition of these reaction gas starting mixtures can not be designed to be explosive. Optionally, a partial amount of residual gas for this purpose can be recycled directly into the propylene and / or Acroleinpartialoxidation. If necessary, a mixture of Fresh propane and residual gas can be used for this purpose. Decisive for the answer to the question, whether or not the starting reaction gas mixture is explosive for a partial oxidation stage, is whether in the starting reaction gas mixture under certain starting conditions (pressure, temperature) a combustion initiated by a local ignition source (eg glowing platinum wire) ( Inflammation, explosion) spreads or not (see DIN 51649 and the examination description in WO 04/007405). If it spreads, the mixture should be called explosive here. If not spread, the mixture in this document is classified as non-explosive. If the reaction gas starting mixture is not explosive, this also applies to the reaction gas mixtures formed in the course of the partial oxidation of propylene according to the invention (compare WO 04/007405).

In However, the rule is in the process according to the invention, only the Reaction gas mixture input stream A fresh propane added included.

This However, the invention also relates to method embodiments in which you do that for the procedure needed Fresh propane at most partially (eg, only 75%, or only 50%, or only 25%) of the reaction gas mixture input stream A and at least partially (usually the residual amount, if necessary the total amount) of the starting reaction gas mixture (s) Partial oxidation supplies. Furthermore can proceed as described in WO 01/96170, the one integral part of this application forms.

In in a known manner runs the heterogeneously catalyzed gas phase partial oxidation of propylene to acrylic acid with molecular oxygen basically in two along the Reaction coordinate of successive steps, of which the first leads to acrolein and the second from acrolein to acrylic acid.

This Reaction process in two successive steps open in a known manner the possibility the inventive method at the stage of acrolein (the stage of predominant acrolein formation) abort and perform the target product separation at this stage, or the method according to the invention to the majority Acrylic acid formation continue and then carry out the target product separation.

Leading the inventive method to the majority Acrylic acid formation, it is advantageous according to the invention the process is two-stage, d. H. arranged in two consecutive To carry out oxidation steps, where expediently in each of the two oxidation states, the fixed catalyst bed to be used and preferably also the other reaction conditions, such. As the temperature of the fixed catalyst bed, in an optimizing manner be adjusted.

Though capital the for the catalysts of the first oxidation state (propylene → acrolein) particularly suitable as active compositions containing the elements Mo, Fe, Bi Multimetal oxides, to some extent also the second oxidation state (Acrolein → acrylic acid) catalyze, but be for the second oxidation step normally prefers catalysts, whose active material contains at least one element Mo and V Multimetal is.

In order to the method to be carried out according to the invention is suitable the heterogeneously catalyzed partial oxidation of propylene over fixed catalyst beds, their catalysts as active mass at least one of the elements Mo, Fe and Bi containing multimetal have, in particular as one-step process for the preparation of acrolein (and optionally Acrylic acid) or as the first reaction stage for the two-stage preparation of acrylic acid.

The realization of the one-stage heterogeneously catalyzed partial oxidation of propylene to acrolein and optionally acrylic acid or the two-stage heterogeneously catalyzed partial oxidation of propylene to acrylic acid using a reaction gas starting mixture produced according to the invention can be described in detail as in EP-A 70 07 14 (first reaction stage; described therein, but also in a corresponding countercurrent procedure of salt bath and reaction gas starting mixture via the tube bundle reactor), EP-A 70 08 93 (second reaction stage, as described there, but also in a corresponding countercurrent procedure), WO 04/085369 (in particular this document is an integral part this document) (as a two-stage process), WO 04/85363, DE-A 103 13 212 (first reaction stage), EP-A 1 159 248 (as a two-stage process), EP-A 1 159 246 (second reaction stage), EP -A 1 159 247 (as a two-stage process), DE-A 199 48 248 (as a two-stage process), D E-A 101 01 695 (single-stage or two-stage), WO 04/085368 (as a two-stage process), DE 10 2004 021 764 (two-stage), WO 04/085362 (first reaction stage), WO 04/085370 (second reaction stage), WO 04/085365 (second reaction stage), WO 04/085367 (two-stage), EP-A 990 636, EP-A 1 007 007 and EP-A 1 106 598.

This applies in particular to all embodiments contained in these documents. They can be carried out as described in these documents, but with the difference that the reaction gas starting mixture for the first reaction stage (propylene to acrolein) is a reaction gas starting mixture produced according to the invention 2 is used. As regards the other parameters, the procedure is as in the exemplary embodiments of the cited documents (in particular the fixed catalyst beds and reactant loading of the catalyst test beds). If two stages are used in the abovementioned exemplary embodiments of the prior art and a secondary oxygen (secondary air) feed takes place between the two reaction stages, this is carried out in a corresponding manner, but adjusted in amount such that the molar ratio of molecular oxygen to acrolein in the feed mixture the second reaction stage corresponds to that in the embodiments of said writings. An inventive reaction gas starting mixture for the heterogeneously catalyzed partial gas phase oxidation z. B. in a simple manner obtainable by reacting the product gas mixture A partial stream 2 or the product gas mixture stream A 'adds as much molecular oxygen as is required for the partial oxidation. This feed can take place as pure molecular oxygen or else as a mixture of molecular oxygen and of inert gas (or else only in the presence of inert gas). As such a mixture, air is preferred according to the invention. According to the invention, it is essential that this oxygen feed takes place in such a way that the product gas mixture B contains unreacted molecular oxygen.

In usually the molar ratio of the starting gas mixture for the partial oxidation contained molecular oxygen to in the starting reaction gas mixture for the partial oxidation contained propylene ≥ 1 and ≤ 3.

For the respective Reaction stage particularly suitable Multimetalloxidkatalysatoren are widely described above and well known to those skilled in the art. For example EP-A 25 34 09 on page 5 refers to corresponding US patents.

Cheap catalysts for the respective oxidation state is also disclosed in DE-A 4 431 957, DE-A 10 2004 025 445 and DE-A 4 431 949. This applies in particular for those the general formula I in the two aforementioned earlier writings. Particularly advantageous catalysts for the respective oxidation state disclose the writings DE-A 103 25 488, DE-A 103 25 487, DE-A 103 53 954, DE-A 103 44 149, DE-A 103 51 269, DE-A 103 50 812 and DE-A 103 50 822.

For the reaction stage according to the invention the heterogeneously catalyzed gas phase partial oxidation of propylene to acrolein or acrylic acid or their mixture, are in principle all Mo, Bi and Fe containing Multimetal oxide compositions as active mass into consideration.

This In particular, the multimetal oxide active materials are the general ones Formula I of DE-A 199 55 176, the Multimetalloxidaktivmassen the general formula I of DE-A 199 48 523, the Multimetalloxidaktivmassen of the general formulas I, II and III of DE-A 101 01 695, the multimetal oxide active compositions the general formulas I, II and III of DE-A 199 48 248 and Multimetal oxide active compounds of the general formulas I, II and III DE-A 199 55 168 and the multimetal oxide active compositions mentioned in EP-A 7 00 714.

Also suitable for this reaction stage are the Mo, Bi and Fe-containing multimetal oxide catalysts described in Research Disclosure No. 497012 of 29.08.2005, DE-A 100 46 957, DE-A 100 63 162, DE-C 3 338 380, DE -A 199 02 562, EP-A 15 565, DE-C 2 380 765, EP-A 8 074 65, EP-A 27 93 74, DE-A 330 00 44, EP-A 575897, US-A 4438217, DE-A 19855913, WO 98/24746, DE-A 197 46 210 (those of the general formula II), JP-A 91/294239, EP-A 293 224 and EP-A 700 714 are disclosed. This applies in particular to the exemplary embodiments in these documents, among which those of EP-A 15565, EP-A 575897, DE-A 197 46 210 and DE-A 198 55 913 are particularly preferred. Of particular note in this context are a catalyst according to Example 1c from EP-A 15 565 and a catalyst to be prepared in a corresponding manner, the active composition but the composition Mo ₁₂ Ni _6.5 Zn ₂ Fe ₂ Bi ₁ P _0.0065 K _{0, 06} O _x · 10SiO ₂ . Further mention should be made of the example with the consecutive no. 3 from DE-A 198 55 913 (stoichiometry: Mo ₁₂ Co ₇ Fe ₃ Bi _0.6 K _0.08 Si _1.6 O _x ) as hollow cylinder full catalyst of the geometry 5 mm × 3 mm × 2 mm (outer diameter × height × inner diameter) and the multimetal II - full catalyst according to Example 1 of DE-A 197 46 210. Further, the multimetal oxide catalysts of US-A 4,438,217 should be mentioned. The latter applies in particular when these hollow cylinders have a geometry of 5.5 mm × 3 mm × 3.5 mm, or 5 mm × 2 mm × 2 mm, or 5 mm × 3 mm × 2 mm, or 6 mm × 3 mm × 3 mm, or 7 mm × 3 mm × 4 mm (outer diameter × height × inner diameter). Other possible kata Analyzer geometries in this context are strands (eg, 7.7 mm in length and 7 mm in diameter, or 6.4 mm in length and 5.7 mm in diameter).

A multiplicity of the multimetal oxide active compositions which are suitable for the step of propylene to acrolein and optionally acrylic acid can be obtained under the general formula IV Mo ₁₂ Bi _a Fe _b X ¹ _c X ² _d X ³ _e X ⁴ _f O _n (IV) in which the variables have the following meaning:
X ¹ = nickel and / or cobalt,
X ² = thallium, an alkali metal and / or an alkaline earth metal,
X ³ = zinc, phosphorus, arsenic, boron, antimony, tin, cerium, lead and / or tungsten,
X ⁴ = silicon, aluminum, titanium and / or zirconium,
a = 0.5 to 5,
b = 0.01 to 5, preferably 2 to 4,
c = 0 to 10, preferably 3 to 10,
d = 0 to 2, preferably 0.02 to 2,
e = 0 to 8, preferably 0 to 5,
f = 0 to 10 and
n = a number determined by the valence and frequency of the elements other than oxygen in IV,
subsume.

she are available in a manner known per se (see, for example, DE-A 4 023 239) and are customary in substance to spheres, rings or cylinders shaped or in Shape of shell catalysts, d. h., coated with the active composition preformed, inert support bodies used. Of course you can but also be used in powder form as catalysts.

In principle, active compounds of the general formula IV can be prepared in a simple manner by producing an intimate, preferably finely divided, stoichiometrically composed, dry mixture of suitable sources of their elemental constituents and calcining this at temperatures of 350 to 650 ° C. The calcination can be carried out both under inert gas and under an oxidative atmosphere such. As air (mixture of inert gas and oxygen) and also under a reducing atmosphere (eg., Mixture of inert gas, NH ₃ , CO and / or H ₂ ) take place. The calcination time can be several minutes to several hours and usually decreases with temperature. Suitable sources of the elemental constituents of the multimetal oxide active compositions IV are those compounds which are already oxides and / or those compounds which can be converted into oxides by heating, at least in the presence of oxygen.

In addition to the oxides, suitable starting compounds in particular are halides, nitrates, formates, oxalates, citrates, acetates, carbonates, amine complexes, ammonium salts and / or hydroxides (compounds such as NH ₄ OH, (NH ₄ ) ₂ CO ₃ , NH ₄ NO ₃ , NH ₄ CHO ₂ , CH ₃ COOH, NH ₄ CH ₃ CO ₂ and / or ammonium oxalate, which can disintegrate and / or decompose into gaseous compounds at the latest during later calcination, can be additionally incorporated into the intimate dry mixture) ,

The intimate mixing of the starting compounds for the preparation of multimetal oxide active materials IV can be done in dry or wet form. It happens in dry Form, the starting compounds are expediently as finely divided Powder used and after mixing and optionally compacting subjected to calcination. Preferably, the intimate mixing takes place but in wet form. Usually be the starting compounds in the form of an aqueous solution and / or suspension mixed together. Especially intimate dry mixtures are then obtained in the described mixing method, if only from in dissolved Form present sources of elementary constituents becomes. As a solvent Water is preferably used. Subsequently, the resulting aqueous mass dried, the drying process preferably by spray drying the aqueous Mixture with outlet temperatures of 100 to 150 ° C takes place.

The multimetal oxide of the general formula IV can be used for the step "propylene → acrolein (and optionally acrylic acid)" formed both in powder form and to certain catalyst geometries, wherein the shaping can be carried out before or after the final calcination. For example, from the powder form of the active composition or its uncalcined and / or partially calcined solid precursors by compression to the desired catalyst geometry (eg., By tableting, extrusion or extrusion) can be prepared unsupported catalysts, where appropriate aids such. As graphite or stearic acid as lubricants and / or molding aids and reinforcing agents such as microfibers of glass, asbestos, silicon carbide or potassium titanate can be added. Instead of graphite but also hexagonal boron nitride can be used as an aid in shaping, as recommended by DE-A 10 2005 037 678. Suitable Vollkatalysatorgeometrien are z. B. solid cylinder or hollow cylinder with an outer diameter and a length of 2 to 10 mm. In the case of the hollow cylinder, a wall thickness of 1 to 3 mm is appropriate. Of course, the full catalyst may also have spherical geometry, wherein the ball diameter may be 2 to 10 mm.

A especially cheap Hollow cylinder geometry is 5 mm × 3 mm × 2 mm (outer diameter × length × inner diameter), especially in the case of full catalysts.

Of course you can the shape of the powdered Active mass or its powdery, yet non-calcined and / or partially calcined, precursor material also by application carried out on preformed inert catalyst support. The coating the carrier body to Preparation of the coated catalysts is usually in one suitable rotatable container executed as it is z. B. from DE-A 29 09 671, EP-A 293 859 or from EP-A 714 700 is known. Conveniently, is applied to the coating of the carrier body to be applied Moistened powder mass and after application, for. B. by means of hot air, dried again. The layer thickness of the applied to the carrier body Powder mass is expediently in the range 10 to 1000 μm, preferably in the range 50 to 500 microns and more preferably in the range 150 to 250 microns, selected.

When support materials can usual porous or nonporous Aluminas, silica, thoria, zirconia, silicon carbide or silicates such as magnesium or aluminum silicate are used. They are behaving the method of the invention underlying target reaction is generally substantially inert. The carrier bodies can be regular or irregular shaped being regularly shaped Carrier body with clearly formed surface roughness, e.g. Spheres or hollow cylinders are preferred. Suitable is the Use of substantially non-porous, surface rough, spherical carriers Steatite whose diameter is 1 to 10 mm or 8 mm, preferably 4 to 5 mm. But is also suitable for the use of cylinders as a carrier body whose Length 2 up to 10 mm and their outer diameter 4 to 10 mm. In the case of suitable according to the invention Rings as a carrier body lies the wall thickness over it usually at 1 to 4 mm. According to the invention preferred to be used annular Own carrier body a length from 2 to 6 mm, an outer diameter from 4 to 8 mm and a wall thickness of 1 to 2 mm. Suitable according to the invention are above all rings of geometry 7 mm × 3 mm × 4 mm (outside diameter × length × inside diameter) as a carrier body. The Fineness of the surface of the carrier body to be applied catalytically active oxide masses will of course be of the desired shell thickness adapted (see EP-A 714 700).

For the step from propylene to acrolein (and optionally acrylic acid) to be used Multimetalloxidaktivmassen are also compounds of general formula V, [Y ¹ _{a '} Y ² _b' O _{x '} ] _p [Y ³ _c' Y ⁴ _{d '} Y ⁵ _e' Y ⁶ _{f '} Y ⁷ _g' Y ² _{n '} O _y' ] q (V) in which the variables have the following meaning:
Y ¹ = only bismuth or bismuth and at least one of the elements tellurium, antimony, tin and copper,
Y ² = molybdenum or molybdenum and tungsten,
Y ³ = an alkali metal, thallium and / or samarium,
Y ⁴ = an alkaline earth metal, nickel, cobalt, copper, manganese, zinc, tin, cadmium and / or mercury,
Y ⁵ = iron or iron and at least one of the elements chromium and cerium,
Y ⁶ = phosphorus, arsenic, boron and / or antimony,
Y ⁷ = a rare earth metal, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and / or uranium,
a '= 0.01 to 8,
b '= 0.1 to 30,
c '= 0 to 4,
d '= 0 to 20,
e '> 0 to 20,
f '= 0 to 6,
g '= 0 to 15,
h '= 8 to 16,
x ', y' = numbers which are determined by the valence and frequency of the elements other than oxygen in V, and
p, q = numbers whose ratio p / q is 0.1 to 10,
containing three-dimensionally extended areas of the chemical composition Y ¹ _{a '} Y ² _b' O _{x '} , delimited from their local environment due to their different composition from their local environment, whose largest diameter (longest passing through the center of gravity of the area direct connection of two on the surface (Interface) of the area of points) 1 nm to 100 microns, often 10 nm to 500 nm or 1 micron to 50 or 25 microns, is.

Especially advantageous according to the invention suitable multimetal V are those in which Y ¹ is only bismuth.

Among these, those which are of the general formula VI, (Bi _{a ''} Z ² _{b ''} O _{x ''} ] _{p ''} [Z ² ₁₂ Z ³ _{c ''} Z ⁴ _{d ''} Fe _{e ''} Z ⁵ _{f ''} Z ⁶ _{g ''} Z ⁷ _{h ''} O _y'' ] _q'' (VI), in which the variables have the following meaning:
Z ² = molybdenum or molybdenum and tungsten,
Z ³ = nickel and / or cobalt,
Z ⁴ = thallium, an alkali metal and / or an alkaline earth metal,
Z ⁵ = phosphorus, arsenic, boron, antimony, tin, cerium and / or lead,
Z ⁶ = silicon, aluminum, titanium and / or zirconium,
Z ⁷ = copper, silver and / or gold,
a '' = 0.1 to 1,
b '' = 0.2 to 2,
c '' = 3 to 10,
d "= 0.02 to 2,
e "= 0.01 to 5, preferably 0.1 to 3,
f '' = 0 to 5,
g '' = 0 to 10,
h '' = 0 to 1,
x '', y '' = numbers determined by the valency and frequency of the element other than oxygen in VI,
p ", q" = numbers whose ratio p "/ q" is 0.1 to 5, preferably 0.5 to 2,
wherein those masses VI are particularly preferred, in which Z ² _{b "} = (tungsten) _b" and Z ² ₁₂ = (molybdenum) ₁₂ .

Furthermore, it is advantageous if at least 25 mol% (preferably at least 50 mol% and particularly preferably 100 mol%) of the total fraction [Y ¹ _{a '} Y ² _b' O _{x '} ] _p ([Bi _a'' Z ² _{b "} O _x" ] _{p "} ) of the multimetal oxide materials V (multimetal oxide materials VI) which are suitable according to the invention in the multimetal oxide compositions V (multimetal oxide compositions VI) which are suitable according to the invention in the form of three-dimensionally extended chemical substances which are different from their local environment because of their local environment Composition of delimited, areas of the chemical composition Y ¹ _{a '} Y ² _b' O _{x '} [Bi _a'' Z ² _b'' O _x'' ] are present, the largest diameter in the range 1 nm to 100 microns.

Regarding the shaping applies with respect Multimetal oxide V-catalysts in the multimetal oxide materials IV catalysts said.

The Preparation of Multimetal Oxide Compounds V-Active Compounds is, for. In EP-A 575 897 and in DE-A 198 55 913 described.

The The above-recommended inert support materials include i.a. also as inert materials for dilution and / or delimitation of corresponding fixed catalyst beds, or as their protective and / or the gas mixture heating pre-feed into consideration.

For the second Step (the second reaction step), the heterogeneously catalyzed Gas-phase partial oxidation of acrolein to acrylic acid, come, As already stated, in principle all Mo and V-containing multimetal oxide materials as active masses for The necessities Catalysts into consideration, for. B. those of DE-A 100 46 928.

A variety of the same, for. B. those of DE-A 198 15 281, can be found under the general formula VII, Mo ₁₂ V _a X ¹ _b X ² _c X ³ _d X ⁴ _e X ⁵ _f X ⁶ _g O _n (VII) in which the variables have the following meaning:
X ¹ = W, Nb, Ta, Cr and / or Ce,
X ² = Cu, Ni, Co, Fe, Mn and / or Zn,
X ³ = Sb and / or Bi,
X ⁴ = one or more alkali metals,
X ⁵ = one or more alkaline earth metals,
X ⁶ = Si, Al, Ti and / or Zr,
a = 1 to 6,
b = 0.2 to 4,
c = 0.5 to 18,
d = 0 to 40,
e = 0 to 2,
f = 0 to 4,
g = 0 to 40 and
n = a number which is determined by the valence and frequency of the elements other than oxygen in VII,
subsume.

Preferred embodiments within the active multimetal oxides VII according to the invention are those which are covered by the following meanings of the variables of general formula VII:
X ⁶ = W, Nb, and / or Cr,
X ² = Cu, Ni, Co, and / or Fe,
X ³ = Sb,
X ⁴ = Na and / or K,
X ⁵ = Ca, Sr and / or Ba,
X ⁶ = Si, Al, and / or Ti,
a = 1.5 to 5,
b = 0.5 to 2,
c = 0.5 to 3,
d = 0 to 2,
e = 0 to 0.2,
f = 0 to 1 and
n = a number determined by the valence and frequency of the elements other than oxygen in VII.

However, very particularly preferred multimetal oxides VII according to the invention are those of the general formula VIII Mo ₁₂ V _{a '} Y ¹ _b' Y ² _{c '} Y ⁵ _f' Y ⁶ _{g '} O _n' (VIII) With
Y ¹ = W and / or Nb,
Y ² = Cu and / or Ni,
Y ⁵ = Ca and / or Sr,
Y ⁶ = Si and / or Al,
a '= 2 to 4,
b '= 1 to 1.5,
c '= 1 to 3,
f '= 0 to 0.5
g '= 0 to 8 and
n '= a number which is determined by the valence and frequency of the elements other than oxygen in VIII.

The suitable according to the invention Multimetal oxide active materials (VII) are known per se, for. B. in DE-A 43 35 973 or in EP-A 714 700 disclosed manner available.

In principle, suitable for the step "acrolein → acrylic acid" suitable Multimetalloxidaktivmassen, especially those of the general formula VII, in a simple manner be prepared by suitable sources of their elemental constituents an intimate, preferably finely divided, their stoichiometry correspondingly composed, dry mixture and this calcined at temperatures of 350 to 600 ° C. The calcination can be carried out both under inert gas and under an oxidative atmosphere such. As air (mixture of inert gas and oxygen) as well as under a reducing atmosphere (eg., Mixtures of inert gas and reducing gases such as H ₂ , NH ₃ , CO, methane and / or acrolein or said reducing acting gases per se) performed become. The calcination time can be several minutes to several hours and usually decreases with temperature. Suitable sources of the elemental constituents of the multimetal oxide active compounds VII are those compounds which are already oxides and / or those compounds which can be converted into oxides by heating, at least in the presence of oxygen.

The intimate mixing of the starting compounds for the preparation of multimetal oxide materials VII can be done in dry or wet form. Is it done in dry form, so the starting compounds are suitably used as finely divided powder and after mixing and optionally Compacting subjected to calcination. Preferably, this is done intimate mixing but in wet form.

Usually be the starting compounds in the form of an aqueous solution and / or suspension mixed together. Especially intimate dry mixtures are then obtained in the described mixing method, if only from in dissolved Form present sources of elementary constituents becomes. As a solvent Water is preferably used. Subsequently, the resulting aqueous mass dried, the drying process preferably by spray drying the aqueous Mixture with outlet temperatures of 100 to 150 ° C takes place.

The resulting Multimetalloxidmassen, in particular those of the general Formula VII, can for the Acrolein oxidation both in powder form and to certain catalyst geometries be used, wherein the shaping before or after the final Calcination can be done. For example, from the powder form of Active mass or its uncalcined precursor mass by compaction to the desired Catalyst geometry (eg by tabletting, extruding or Extrusion) Vollkatalysatoren be prepared, where appropriate Aids such. As graphite or stearic acid as a lubricant and / or Molding aids and reinforcing agents such as glass microfibers, asbestos, silicon carbide or potassium titanate can be added. Suitable Vollkatalysatorgeometrien are z. B. solid cylinder or Hollow cylinder with an outer diameter and a length from 2 to 10 mm. In the case of the hollow cylinder is a wall thickness of 1 to 3 mm appropriate. Of course you can the full catalyst also have spherical geometry, wherein the ball diameter 2 to 10 mm (eg 8.2 mm or 5.1 mm).

Of course you can the shape of the powdered Active mass or its powdery, yet uncalcined, precursor material also be carried out by applying to preformed inert catalyst support. The coating of the carrier body for Preparation of the coated catalysts is usually in a suitable rotatable container executed as it is z. B. from DE-A 2 909 671, EP-A 293 859 or from EP-A 714 700 is known.

Conveniently, is used to coat the carrier body applied powder compound moistened and after application, z. B. by means of hotter Air, dried again. The layer thickness of the applied to the carrier body Powder mass is expediently in the range 10 to 1000 μm, preferably in the range 50 to 500 microns and more preferably in the range 150 to 250 microns, selected.

As carrier materials, it is possible to use customary porous or non-porous aluminum oxides, silicon dioxide, thorium dioxide, zirconium dioxide, silicon carbide or silicates, such as magnesium silicate or aluminum silicate. The carrier bodies may be regularly or irregularly shaped, with regularly shaped carrier bodies having a distinct surface roughness, e.g. As balls or hollow cylinder with chippings, are preferred. Suitable is the use of substantially nonporous, surface rough, spherical steatite supports whose diameter is 1 to 10 mm or 8 mm, preferably 4 to 5 mm. That is, suitable ball geometries may have diameters of 8.2 mm or 5.1 mm. However, it is also suitable to use cylinders as support bodies whose length is 2 to 10 mm and whose outer diameter is 4 to 10 mm. In addition, in the case of rings as a carrier body, the wall thickness is usually 1 to 4 mm. Preferably to be used annular support body have a length of 2 to 6 mm, an outer diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm. Particularly suitable are rings of geometry 7 mm × 3 mm × 4 mm (outer diameter × length × inner diameter) as Trä gerkörper. The fineness of the catalytically active oxide masses to be applied to the surface of the carrier body is, of course, adapted to the desired shell thickness (cf EP-A 714 700).

Favorable for the step "acrolein → acrylic acid" to be used Multimetalloxidaktivmassen are also compounds of general formula IX, [D] _p [E] _q (IX). in which the variables have the following meaning:
D = Mo ₁₂ V _{a "} Z ¹ _b" Z ² _{c "} Z ³ _d" Z ⁴ _{e "} Z ⁵ _f" Z ⁶ _{g "} O _x" ,
E = Z ⁷ ₁₂ Cu _{h "} H _i" O _{y "}
Z ¹ = W, Nb, Ta, Cr and / or Ce,
Z ² = Cu, Ni, Co, Fe, Mn and / or Zn,
Z ³ = Sb and / or Bi,
Z ⁴ = Li, Na, K, Rb, Cs and / or H
Z ⁵ = Mg, Ca, Sr and / or Ba,
Z ⁶ = Si, Al, Ti and / or Zr,
Z ⁷ = Mo, W, V, Nb and / or Ta, preferably Mo and / or W.
a '' = 1 to 8,
b '' = 0.2 to 5,
c '' = 0 to 23,
d '' = 0 to 50,
e '' = 0 to 2,
f '' = 0 to 5,
g '' = 0 to 50,
h '' = 4 to 30,
i '' = 0 to 20 and
x '', y '' = numbers which are determined by the valence and frequency of the element different from oxygen in IX and
p, q = numbers other than zero whose ratio p / q is 160: 1 to 1: 1,
and which are obtainable by using a multimetal oxide composition E Z ⁷ ₁₂ Cu _{h "} H _i" O _{y "} (E), in finely divided form vorbildet (starting material 1) and then the preformed solid starting material 1 in an aqueous solution, an aqueous suspension or in a finely divided dry mixture of sources of elements Mo, V, Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , which the aforementioned elements in the stoichiometry D Mo ₁₂ V _{a "} Z ¹ _b" Z ² _{c "} Z ³ _d" Z ⁴ _{e "} Z ⁵ _f" Z ⁶ _{g "} (D) contains (starting material 2), in the desired ratio p: q incorporated, which optionally dried resulting aqueous mixture, and the dry precursor material thus calcined prior to or after drying to the desired catalyst geometry at temperatures of 250 to 600 ° C.

Prefers are the Multimetalloxidmassen IX, in which the incorporation of Preformed solid starting material 1 in an aqueous starting material 2 at a temperature <70 ° C is carried out. A detailed description of the preparation of multimetal oxide compositions VI catalysts contain z. For example, EP-A 668 104, DE-A 197th 36 105, DE-A 100 46 928, DE-A 197 40 493 and DE-A 195 28 646.

Regarding the shaping applies with respect Multimetal oxide materials IX catalysts that in the case of the multimetal oxide materials VII catalysts said.

For the step "acrolein → acrylic acid" in excellent Suitable multimetal oxide catalysts are also those of DE-A 198 15 281, in particular with Multimetalloxidaktivmassen the general formula I of this document.

Advantageous be for the step from propylene to acrolein full-catalyst rings and for the step from Acrolein to acrylic acid Shell catalyst rings used.

Carrying out the parital oxidation of the process according to the invention, from propylene to acro lein (and optionally acrylic acid) can be treated with the described catalysts z. B. in a one-zone multi-contact fixed bed reactor, as described in DE-A 4 431 957. In this case, reaction gas mixture and heat transfer medium (heat exchange medium) viewed over the reactor can be conducted in cocurrent or in countercurrent.

Of the Reaction pressure is usually in the range of 1 to 3 bar and the total space load of the fixed catalyst bed with reaction gas (exit) mixture 2 is preferably 1500 to 4000 or 6000 Nl / l · h or more. The propylene load (the propylene load of the fixed catalyst bed) is typically 90 to 200 Nl / l · h or up to 300 Nl / l · h or more. Propylene loads above 135 Nl / lh or ≥ 140 Nl / lh, or ≥ 150 Nl / lh, or ≥ 160 Nl / l · h are particularly preferred according to the invention preferred, since the reaction gas starting mixture according to the invention as a result of the presence of unreacted propane, a favorable one Hotspot behavior conditional (all the above also applies regardless of the specific choice of the fixed bed reactor).

Preferably, the single-zone multiple contact tube fixed bed reactor is supplied with the feed gas mixture from above. As a heat exchange agent is advantageously a molten salt, preferably consisting of 60 wt .-% potassium nitrate (KNO ₃ ) and 40 wt .-% sodium nitrite (NaNO ₂ ), or from 53 wt .-% potassium nitrate (KNO ₃ ), 40 wt .-% Sodium nitrite (NaNO ₂ ) and 7 wt .-% sodium nitrate (NaNO ₃ ) used.

On the Reactor can be considered As already stated, molten salt and reaction gas mixture both be conducted in DC and in countercurrent. The molten salt itself is preferably meandering around guided the contact tubes.

• – zunächst auf einer Länge von 40 bis 80 bzw. bis 60% der Kontaktrohrlänge entweder nur Katalysator, oder ein Gemisch aus Katalysator und Inertmaterial, wobei letzteres, bezogen auf die Mischung, einen Gewichtsanteil von bis zu 30 bzw. bis zu 20 Gew.-% ausmacht (Abschnitt C);
• – daran anschließend auf einer Länge von 20 bis 50 bzw. bis 40% der Gesamtrohrlänge entweder nur Katalysator, oder ein Gemisch aus Katalysator und Inertmaterial, wobei letzteres, bezogen auf die Mischung, einen Gewichtsanteil von bis zu 40 Gew.-% ausmacht (Abschnitt B); und
• – abschließend auf einer Länge von 10 bis 20% der Gesamtrohrlänge eine Schüttung aus Inertmaterial (Abschnitt A), die vorzugsweise so gewählt wird, dass sie einen möglichst geringen Druckverlust bedingt.

If the contact tubes are flown from top to bottom, it is advisable to charge the catalyst tubes from the bottom to the top as follows (for the flow from bottom to top, the feed sequence is suitably reversed):

• - First on a length of 40 to 80 or 60% of the contact tube length either catalyst only, or a mixture of catalyst and inert material, the latter, based on the mixture, a weight fraction of up to 30 or up to 20 wt. % (Section C);
• - Thereafter, over a length of 20 to 50 or 40% of the total tube length, either catalyst, or a mixture of catalyst and inert material, the latter, based on the mixture, a weight fraction of up to 40 wt .-% makes (Section B); and
• - Finally, over a length of 10 to 20% of the total tube length, a bed of inert material (Section A), which is preferably chosen so that it causes the lowest possible pressure loss.

Prefers section C is undiluted.

The aforementioned Loading variant is particularly useful if as catalysts such according to Research Disclosure No. 497012 dated 29.08.2005, or according to Example 1 of DE-A 100 46 957 or according to example 3 of DE-A 100 46 957 and as an inert material rings of steatite with the geometry 7 mm × 7 mm × 4 mm (outer diameter × height × inner diameter) be used. With regard to the salt bath temperature, this applies in DE-A 4 431 957.

The execution the partial oxidation according to the invention, from propylene to acrolein (and optionally acrylic acid) with the described catalysts but also z. B. in a two-zone Vielkontaktrohr fixed bed reactor carried out are, as DE-A 199 10 506, DE-A 10 2005 009 885, DE-A 10 2004 032 129, DE-A 10 2005 013 039 and DE-A 10 2005 009 891 and DE-A 10 2005 010 111 describes. In both above described cases (And more generally in the process of the invention) is the achieved Propene conversion in a single pass normally at values ≥ 90 mol%, or ≥ 95 mol% and the selectivity acrolein formation at values ≥ 90 mol%. Advantageously according to the invention the partial oxidation according to the invention from propene to acrolein, or acrylic acid or a mixture thereof in EP-A 1159244 and very particularly preferably as in WO 04/085363 as well as in WO 04/085362.

The Documents EP-A 1159244, WO 04/085363 and WO 04/085362 are known as integral part of this document.

D. h., The invention to be carried out partial oxidation of propylene particularly advantageous on a fixed catalyst bed with increased propylene loading carry out, which has at least two temperature zones.

This will be z. For example, refer to EP-A 1159244 and WO 04/085362.

A typical composition of the reaction gas starting mixture for the partial oxidation of propylene to acrolein can comprise in the process according to the invention: 5 to 9 vol.% propylene, 8 to 18% by volume molecular oxygen, 6 to 30 vol.% Propane and 32 to 72 vol.% molecular nitrogen.

The execution of the second step in the case of a two-stage partial oxidation from propylene to acrolein, viz the partial oxidation of acrolein to acrylic acid, can with the described Catalysts z. B. be carried out in a one-zone Vielkontaktrohr fixed bed reactor, as described in DE-A 44 31 949. Reaction gas mixture and Heat transfer medium over the Reactor considered to be run in DC. Usually will the product gas mixture of the preceding propylene partial oxidation according to the invention to acrolein in principle as such (optionally after intercooling (this can indirectly or directly by z. B. secondary air addition) of the same), that is, without secondary component removal, into the second reaction stage, i.e. led to the acrolein partial oxidation.

The molecular oxygen required for the second step, the acrolein partial oxidation, can already be present in the reaction gas starting mixture for the propylene partial oxidation according to the invention for the acrolein. However, it can also be partially or completely added directly to the product gas mixture of the first reaction stage, ie the propylene partial oxidation according to the invention to acrolein (this is preferably done as (secondary) air, but can also be in the form of pure oxygen or mixtures of inert gas or oxygen ). Regardless of the procedure, the feed gas mixture (the starting reaction gas mixture) of such a partial oxidation of the acrolein to acrylic acid advantageously has the following contents: 4 to 8 vol.% acrolein, 2.25 or 4.5 to 9 vol.% molecular oxygen, 6 to 30 vol.% Propane, 32 to 72 vol.% molecular nitrogen and 5 to 15 vol.% Steam.

The aforementioned reaction gas starting mixture preferably has the following contents: 5 to 8 vol.% acrolein, 2.75 or 5.5 to 9 vol.% molecular oxygen, 10 to 25 vol.% Propane, 40 to 70 vol.% molecular nitrogen and 5 to 15 vol.% Steam.

Most preferably, the abovementioned Reaktionsgsgasausgangsgemisch following contents: 5 to 8 vol.% Acrolein (preferably 6 to 7% by volume), 3 or 6 to 9 vol.% molecular oxygen, 10 to 20% by volume Propane (preferably 10 to 16% by volume), 50 to 65 vol.% molecular nitrogen and 7 to 13 vol.% Steam, wherein the preferred ranges apply independently, but with advantage be realized simultaneously.

As in the first reaction stage (propylene → acrolein) is also in the second reaction stage (acrolein → acrylic acid) the reaction pressure usually in the range of 1 to 3 bar, and the total space load of the fixed catalyst bed with reaction gas (exit) mixture is preferably from 1500 to 4000 or 6000 Nl / l · h or more. The acrolein load (the acrolein loading of the fixed catalyst bed) is typically 90 to 190 Nl / lh, or to 290 Nl / l · h or more. Acrolein load above 135 Nl / lh, or ≥ 140 Nl / lh, or ≥ 150 Nl / l · h, or ≥ 160 Nl / l · h are particularly preferred, since the invention to be enzusetzende Reaction gas starting mixture due to the presence of propane also a cheap one Hotspot behavior conditionally.

Of the Acroleinumsatz, based on a single pass of the reaction gas mixture through the fixed catalyst bed, it is expedient to use ≥90 mol% and the associated selectivity of acrylic acid formation ≥ 90 mol%.

Preferably, the single-zone multiple contact tube fixed bed reactor is also supplied with the feed gas mixture from above. As a heat exchange agent, a salt melt, preferably from 60% by weight of potassium nitrate (KNO ₃ ) and 40% by weight of sodium nitrite (NaNO ₂ ) or of 53% by weight of potassium nitrate (KNO ₃ ) is expediently also used in the second stage. 40 wt .-% sodium nitrite (NaNO ₂ ) and 7 wt .-% sodium nitrate (NaNO ₃ ) consisting used. Viewed over the reactor, as already stated, molten salt and reaction gas mixture can be conducted both in cocurrent and countercurrent. The molten salt itself is preferably guided meander-shaped around the catalyst tubes.

• – zunächst auf einer Länge von 50 bis 80 bzw. bis 70% der Kontaktrohrlänge entweder nur Katalysator oder ein Gemisch aus Katalysator und Inertmaterial, wobei letzteres, bezogen auf die Mischung, einen Gewichtsanteil von bis zu 30 (bzw. 20) Gew.-% ausmacht (Abschnitt C);
• – daran anschließend auf einer Länge von 20 bis 40% der Gesamtrohrlänge entweder nur Katalysator, oder ein Gemisch aus Katalysator und Inertmaterial, wobei letzteres, bezogen auf die Mischung, einen Gewichtsanteil von bis zu 50 bzw. bis zu 40 Gew.-% ausmacht (Abschnitt B); und
• – abschließend auf einer Länge von 5 bis 20% der Gesamtrohrlänge eine Schüttung aus Inertmaterial (Abschnitt A), die vorzugsweise so gewählt wird, dass sie einen möglichst geringen Druckverlust bedingt.

If the contact tubes are flown from top to bottom, it is advisable to feed the contact tubes from bottom to top as follows:

• Either initially catalyst or a mixture of catalyst and inert material over a length of 50 to 80 or up to 70% of the catalyst tube length, the latter, based on the mixture, having a weight fraction of up to 30 (or 20)% by weight (Section C);
• - Thereafter, over a length of 20 to 40% of the total tube length, either catalyst only, or a mixture of catalyst and inert material, the latter, based on the mixture, a weight fraction of up to 50 and up to 40 wt .-% makes ( Section B); and
• - Finally, on a length of 5 to 20% of the total tube length, a bed of inert material (Section A), which is preferably chosen so that it causes the lowest possible pressure loss.

Prefers section C is undiluted. As is generally the case with heterogeneously catalyzed gas phase partial oxidation from acrolein to acrylic acid (especially at high acrolein loadings of the catalyst bed and high water vapor contents of the feed gas mixture), can Section B also consists of two consecutive catalyst dilutions exist (for the purpose of minimizing hotspot temperature and hotspot temperature sensitivity). From bottom to top first with up to 30 (or 20) wt .-% inert material and subsequently with> 20 wt .-% to 50 or to 40 wt .-% inert material. The section C is then preferred undiluted.

For a flow of the Contact tubes from bottom to top, is the contact tube feed in expediently vice versa.

The aforementioned Loading variant is particularly useful if as catalysts such according to the preparation example 5 of DE-A 100 46 928 or those according to DE-A 198 15 281 and as an inert material Steatite rings with the geometry 7 mm × 7 mm × 4 mm or 7 mm × 7 mm × 3 mm (each Outside diameter × height × inside diameter) be used. With regard to the salt bath temperature, this applies in DE-A 443 19 49. It is usually chosen so that the scored Acrolein conversion in a single pass normally ≥ 90 mol%, or ≥ 95 mol% or ≥ 99 mol%.

The execution Partial oxidation of acrolein to acrylic acid, can with the described Catalysts but also z. B. be carried out in a two-zone multi-contact fixed bed reactor, as described in DE-A 199 10 508. For acrolein sales this applies mentioned above. Also in the case of performing a as above Acroleinpartialoxidation described as the second reaction stage a two-stage propylene oxidation to acrylic acid in a two-zone multi-contact fixed bed reactor to produce the feed gas mixture (reaction gas starting mixture) appropriate immediately the product gas mixture of the directed to the first step partial oxidation (if applicable after indirect or direct (eg by Supply of secondary air) intercooling the same) (as already described above). The for required the acrolein partial oxidation Oxygen is preferably as air (but possibly also as pure molecular oxygen or as a mixture of molecular Oxygen and an inert gas) is added and z. B. the product gas mixture of the first step of the two-stage partial oxidation (propylene → acrolein) immediately added. But he can also, as already described, already in the reaction gas starting mixture for the first reaction stage be included.

In a two-stage partial oxidation of propylene to acrylic acid with immediate reuse of the product gas mixture of the first stage of the partial oxidation to feed the second stage of the partial oxidation, one will generally use two one-zone multiple contact tube fixed bed reactors (at high reactant loading of the catalyst bed, as is generally true). a Gleichstromfahrweise between reaction gas and salt bath (heat carrier) over the tube bundle reactor considered preferred) or two Zweizo one after the other. A mixed series connection (one-zone / two-zone or vice versa) is also possible.

Between The reactors may be an intercooler, if necessary Inert fillings included can, which can exercise a filter function. The salt bath temperature of multi-contact tube reactors for the first step of the two-stage partial oxidation of propylene to acrylic acid is usually 300 to 400 ° C. The salt bath temperature of multi-contact tube reactors for the second Step of the partial oxidation of propylene to acrylic acid, the Partial oxidation of acrolein to acrylic acid, is usually 200 to 350 ° C. In addition, will the heat exchange agents (preferably molten salts) normally in such amounts by the relevant multi-contact tube fixed bed reactors guided, that the difference between their input and their output temperature usually ≤ 5 ° C. As already mentioned, can however, both steps of the partial oxidation of propylene to acrylic acid also as described in DE-A 101 21 592 in a reactor on a Charging be done.

It be mentioned again, that a part of the reaction gas starting mixture for the first step ("propylene → acrolein") from the partial oxidation can be coming residual gas.

in this connection it is, as already said, a molecular oxygen containing gas which, after the target product separation (acrolein and / or acrylic acid separation) from the product gas mixture of the partial oxidation remains and partially as inert diluent gas in the feed for the first and / or optionally second step of the partial oxidation from propylene to acrolein and / or acrylic acid can be recycled.

Preferably, such propane, molecular oxygen and optionally unreacted propylene-containing residual gas according to the invention, however, advantageously only as a gaseous output stream 2 recycled to the heterogeneously catalyzed propane dehydrogenation in the reaction zone A.

All in all forms a tube bundle reactor within which the catalyst feed along the individual Change contact tubes with completion of the first reaction step accordingly (such Two-stage propylene partial oxidations in the so-called "single reactor" teach, for example, the EP-A 91 13 13, EP-A 97 98 13, EP-A 99 06 36 and DE-A 28 30 765) the simplest form of realization of two oxidation states for the two Steps of partial oxidation of propylene to acrylic acid. Possibly In this case, the feed of the catalyst tubes with catalyst an inert material bed interrupted.

Preferably However, the two oxidation states are in the form of two consecutively switched tube bundle systems realized. these can are in a reactor, the transition from a tube bundle to other tube bundle from a not in the contact tube accommodated (appropriately walkable) fill is formed from inert material. While the contact tubes in the Usually be lapped by a heat transfer medium, this does not reach an inert material bed attached as described above. Advantageously, therefore, the two catalyst tube bundles in spatially separate reactors accommodated. As a rule, this is between the two Tube reactors an intercooler, an optional acrolein afterburning in the product gas mixture, which leaves the first oxidation zone to reduce. The reaction temperature in the first reaction stage (propylene → acrolein) is usually at 300 to 450 ° C, preferably at 320 to 390 ° C. The reaction temperature in the second reaction stage (acrolein → acrylic acid) is usually at 200 to 370 ° C, often at 220 to 330 ° C. Of the Reaction pressure is in both oxidation zones appropriate 0.5 to 5, advantageously 1 to 3 bar. The load (Nl / l · h) of Oxidation catalysts with reaction gas is in both reaction stages often 1500 to 2500 Nl / l · h or up to 4000 Nl / l · h. The load of propylene can be 100 to 200 or 300 and more Nl / lh lie.

in principle can designed the two oxidation states in the process of the invention be like z. In DE-A 198 37 517, DE-A 199 10 506, DE-A 199 10 508 and DE-A 198 37 519 is described.

In Both reaction stages have an excess of molecular oxygen relative to the reaction stoichiometric required amount advantageous to the kinetics of the respective Gas phase partial oxidation and on the catalyst life.

In principle, the heterogeneously catalyzed gas-phase partial oxidation of propylene to acrylic acid to be carried out according to the invention can also be carried out as follows, even in a single single-zone tube bundle reactor. Both reaction steps take place in an oxidation reactor which is charged with one or more catalysts whose active composition is a multimetal oxide containing the elements Mo, Fe and Bi, which is able to catalyze the reaction of both reaction steps. Of course, this catalyst feed can also change continuously or abruptly along the reaction coordinate. Of course, in one embodiment of a two-stage partial oxidation of propylene to acrylic acid according to the invention in the form of two series-connected oxidation stages from the first oxidation stage leaving the product gas mixture in selbigem contained, formed in the first oxidation stage as by-product, carbon monoxide and water vapor, if necessary, before forwarding to the second oxidation stage be partially or completely separated. Preferably, according to the invention, one will choose a procedure which does not provide such a separation.

As sources for an oxygen intermediate feed carried out between the two oxidation stages, as already mentioned, in addition to air (preferably) both pure molecular oxygen and inert molecular gas diluted with inert gas such as CO ₂ , CO, noble gases, N ₂ and / or saturated hydrocarbons are considered.

By Metering of z. B. cold air to the product gas mixture of the first Partialoxidaitonsstufe can in the context of the method according to the invention also on direct way a cooling off be effected before it as part of a starting reaction gas mixture for the second partial oxidation stage is used.

According to the invention advantageous the partial oxidation of acrolein to acrylic acid takes place as in EP-A 11 59 246, and most preferably as in WO 04/085365 and described in WO 04/085370. According to the invention preferred is used as acrolein-containing reaction gas starting mixture However, a starting reaction gas mixture is used, which is the product gas mixture a first-stage partial oxidation according to the invention from propylene to acrolein, which was optionally supplemented with so much secondary air that The relationship from molecular oxygen to acrolein in the resulting reaction gas starting mixture in each case 0.5 to 1.5. The documents EP-A 1159246, WO 04/08536 and WO 04/085370 are known as integral part of this document.

that is, the partial oxidation according to the invention from acrolein to acrylic acid let yourself perform advantageous on a fixed catalyst bed with increased Acroleinbelastung, the has at least two temperature zones.

All in all If a two-stage partial oxidation of propylene to acrylic acid is preferred as in EP-A 1 159 248 or in WO 04/085367 or WO 04/085369 described described.

Of the the partial oxidation to be carried out according to the invention (After the first and / or second reaction stage) leaving product gas mixture stream B is in the case of a production of acrolein and / or acrylic acid in the Usually composed essentially of the target product acrolein or acrylic acid or its mixture with acrolein, unreacted molecular Oxygen (looking at the life of the catalysts used is it cheap if the oxygen content in the product gas mixture of both partial oxidation stages is still at least 1.5 to 4 vol .-%), propane, unreacted Propylene, molecular nitrogen, by-produced and / or as a diluent gas co-used steam, by-produced and / or as a diluent gas co-used carbon oxides, and small amounts of other lower Aldehydes, lower alkanecarboxylic acids (eg, acetic acid, formic acid and propionic acid) as well as maleic anhydride, Benzaldehyde, aromatic carboxylic acids and aromatic carboxylic acid anhydrides (e.g., phthalic anhydride and benzoic acid), optionally further hydrocarbons, such as. B. C4 hydrocarbons (eg butene-1 and possibly other butenes), and other inert Diluent gases.

The target product can be separated off from the product gas mixture B in a manner known per se in a second separation zone B (for example by partial or complete and optionally fractional condensation of the acrylic acid or by absorption of acrylic acid in water or in a high-boiling hydrophobic organic solvent or by Absorption of acrolein in water or in aqueous solutions of lower carboxylic acids and subsequent work-up of the condensates and / or absorbates: According to the invention, the product gas mixture B is preferably fractionally condensed, cf., for example, EP-A 1 388 533, EP-A 1 388 532, DE-A 102 35 847, EP-A 792 867, WO 98/01415, EP-A 1 015 411, EP-A 1 015 410, WO 99/50219, WO 00/53560, WO 02/09839, DE -A 102 35 847, WO 03/041833, DE-A 102 23 058, DE-A 102 43 625, DE-A 103 36 386, EP-A 854 129, US-A 4,317,926, DE-A 198 37 520, DE-A 196 06 877, DE-A 190 50 1325, DE-A 102 47 240, DE-A 197 40 253, EP-A 695 736, EP-A 982 287, EP-A 1 041 062, EP-A 1 171 46, DE-A 43 08 087, DE -A 43 35 172, DE-A 44 36 243, DE-A 199 24 532, DE-A 103 32 758 and DE-A 199 24 533). An acrylic acid removal can also be carried out as described in EP-A 982 287, EP-A 982 289, DE-A 103 36 386, DE-A 101 15 277, DE-A 196 06 877, DE-A 197 40 252, DE-A 196 27 847, EP-A 920 408, EP-A 1 068 174, EP-A 1 066 239, EP-A 1 066 240, WO 00/53560, WO 00 / 53561, DE-A 100 53 086 and EP-A 982 288 are made. Preferably, as in 7 WO / 0196271 or as described in DE-A 10 2004 032 129 and their equivalent patents described separated. Favorable separation methods are also the processes described in the publications WO 04/063138, WO 04/35514, DE-A 102 43 625 and DE-A 102 35 847. The further processing of a crude acrylic acid thereby obtained can, for. As described in the publications WO 01/77056, WO 03/041832, WO 02/055469, WO 03/078378 and WO 03/041833.

common Feature of the aforementioned separation method is (as already mentioned mentioned), that at the top of the respective separating internals containing Separation column, in the lower part of the product gas mixture B, usually after prior direct and / or indirect cooling thereof, normally a residual gas flow remains, which are essentially those components contains the product gas mixture B, the boiling point at normal pressure (1 bar) is ≤ -30 ° C (i.e., the hardly condensable or volatile Components).

in the lower part of the separation column usually fall the heavier volatile Constituents of the product gas mixture B, including the respective target product, in condensed phase.

The Residual gas components are primarily propane, if necessary in the partial oxidation unreacted propylene, molecular Oxygen as well as often the other in-use diluent gases used in the partial oxidation, such as As nitrogen and carbon dioxide. Water vapor can vary depending on applied separation process in the residual gas only in traces or in Be contained in amounts of up to 20 vol .-% or more.

Of this main residual gas according to the invention is usually at least one (preferably residual gas composition having) propane, molecular oxygen and optionally unreacted propylene containing subset (preferably the total amount, but possibly also only half, or two thirds, or three quarters of this total) as a gaseous output stream 2 recycled to the reaction zone A. However, residual gas fractions can also be recycled to one or both stages of the partial oxidation and / or burnt for the purpose of generating energy.

Of course, as described in this document and in EP-A 117 146, US-A 3,161,670, DE-A 33 13 573 and DE-A 103 16 039, advance use of residual gas as a gaseous output stream 2 From the residual gas in particular propane, propylene and molecular oxygen different components are separated.

In the work-up of the condensed phase (for the purpose of separation of the target product), other residual gases may be incurred, since it will normally be attempted to recycle the total amount of unreacted propane contained in the product gas mixture B into the reaction zone A and recover it as part of the target product separation. These usually still contain propane and possibly propylene, but often no molecular oxygen more. Usually they are combined with the main residual gas to a total residual gas as a gaseous output stream 2 recycled to the reaction zone A. But it is also a separate recovery or return to the reaction zone A of such other residual gases possible.

By the preferably complete Return of the Total residual gas can thus be continuous in continuous operation Conversion of propane to acrylic acid and / or acrolein.

Essential is doing that by the described feedback and by the operation of the invention the reaction zone A in the latter a conversion of fresh propane to propylene can be reached with almost 100% selectivity.

The Advantageousness of such a procedure is both in lower (<30 mol%) as well as at high (≥ 30 mol%) dehydrogenation conversions (Based on a single pass through the reaction zone A). In general, it is favorable according to the invention, if the hydrogen content in the reaction gas mixture input stream A in a at least stoichiometric relationship (in terms of an oxygen combustion to water) to the amount of oxygen contained in it stands.

At This point is again stated that the separation of acrylic acid from a product obtained according to the invention Product gas mixture B preferably takes place in such a way that the previously optionally by direct and / or indirect cooling cooled product gas mixture B in a separation-effective internals-containing column under side draw a crude acrylic acid (eg, in itself) ascending fractionally condensed and / or with water or aqueous solution as exemplified by WO 2004/035514 and DE-A 102 43 625 describe. The withdrawn crude acrylic acid is preferred below subjected to a suspension crystallization and the resulting Acrylsäuresuspensionskristallisat preferably by means of a wash column of residual mother liquor separated. Advantageously, as the washing liquid, the melt of in the wash column pre-separated acrylic acid crystals used. Further is the wash column prefers one with forced transport of the crystal bed. Particularly preferred is a hydraulic or a mechanical wash column. In detail, the description WO 01/77056, WO 03/041832 and WO 03/041833 become. D. h., Preferably, remaining mother liquor in the fractional condensation recycled (see. also EP-A 10 15 410). The minor component outlet is normally below side exhaust of crude acrylic acid as purge stream.

Under Use of only one crystallization stage is so acrylic acid with a purity ≥ 99.8% by weight available, which are outstanding for the production of superabsorbents based on poly-Na-acrylate.

I. General experimental setup the reaction zone A and their operation

The heterogeneously catalyzed partial propane dehydrogenation is carried out in a tray loop reactor according to 4 performed, to which the numerical addresses refer in the following.

A vertical tubular reactor ( 11 ) (Diameter: 80 mm) is equipped with a thermal insulation ( 10 ) provided in a support heater ( 9 ). The temperature of the support heater is 500 ° C. In the center of the tube reactor is a central tube (diameter: 20 mm) which contains a sleeve for a tensile thermocouple and a sleeve for a step thermocouple. In addition, it contains in the tubular reactor leading lines through which reaction gas samples could be taken from the tube reactor, as well as in the tubular reactor leading lines through which air can be injected into the tubular reactor.

The tube reactor contains three hordes ( 5 . 6 . 7 ) consisting of three identical, applied to a stainless steel wire mesh beds of inert material (bed height: 100 mm) and a mixture (bed height: 165 mm) of dehydrogenation catalyst and steatite (1.5 to 2.5 mm diameter) in the bulk volume ratio 1: 1 , The total chute is thus 265 mm each.

The dehydrogenation catalyst is a Pt / Sn alloy promoted with the elements Cs, K and La in oxidic form and deposited on the outer and inner surfaces of ZrO ₂ .SiO ₂ mixed oxide carrier strands (average length (Gauss distributed in the range of 3 mm to 6 mm, 6 mm diameter: 2 mm) in elemental stoichiometry (mass ratios including support) Pt _0.3 Sn _0.6 La _3.0 Cs _0.5 K _0.2 (ZrO ₂ ) _88.3 (SiO ₂ ) _7.1 (catalyst precursor preparation and activation to the active catalyst as in Example 4 of DE-A 10219879).

In front Each catalyastor horde is fitted with a mixing element.

The product gas mixture A emerging from the last horde 12 ) is divided into two halves of identical composition. One half ( 2 ) (the product gas mixture A partial stream 1 ) as a constituent of the reaction gas mixture input stream A ( 4 ) returned to the dehydrogenation. The other half ( 1 ) (the product gas mixture A partial stream 2 ) led out of the dehydrogenation zone (the reaction zone A).

The reaction gas mixture input stream A ( 4 ) consists of the gaseous output stream 1 ( 2 ) and from the gaseous starting mixture stream ( 3 ) composed of water vapor, residual gas from the partial oxidation, fresh propane and molecular hydrogen. This output mixture stream ( 3 ) is propulsion jet of a jet pump, which the product gas mixture stream A ( 12 ) as described and the reaction gas mixture input stream A ( 4 ) generated.

The total catalyst load (without inert material) of all hordes with propane is always 350 Nl / l · h.

Of the Input pressure of the reaction gas mixture input stream A is enclosed 2.3 bar. Its temperature is 500 ° C. Of the Pressure loss over the dehydrogenation reactor is about 200 mbar. Before the second and before the third catalyst bed (in Flow direction) is the reaction gas mixture air (500 ° C, reaction pressure) zugedüst. The Quantity is calculated so that the highest temperature in each case subsequent catalyst bed 575 to 580 ° C is.

II. General experimental setup the heterogeneously catalyzed two-stage partial oxidation of propylene to acrylic acid and their operation

experimental arrangement

First reaction stage:

• Abschnitt 1: 50 cm Länge Steatitringe der Geometrie 7 mm × 7 mm × 4 mm (Außendurchmesser × Länge × Innendurchmesser) als Vorschüttung.
• Abschnitt 2: 140 cm Länge Katalysatorbeschickung mit einem homogenen Gemisch aus 20 Gew.-% (alternativ 30 Gew.-%) an Steatitringen der Geometrie 5 mm × 3 mm × 2 mm (Außendurchmesser × Länge × Innendurchmesser) und 80 Gew.-% (alternativ 70 Gew.-%) Vollkatalysator aus Abschnitt 3.
• Abschnitt 3: 160 cm Länge Katalysatorbeschickung mit ringförmigem (5 mm × 3 mm × 2 mm = Außendurchmesser × Länge × Innendurchmesser) Vollkatalysator gemäß Beispiel 1 der DE-A 10046957 (Stöchiometrie: [Bi₂W₂O₉ × 2WO₃]_0,5[Mo₁₂Co_5,5Fe_2,94Si_1,59K_0,08O_x]₁). Alternativ kann hier auch einer der Katalysatoren BVK1 bis BVK11 aus Research Disclosure Nr. 497012 vom 29.08.2005 eingesetzt werden.

A reaction tube (V2A steel, 30 mm outer diameter, 2 mm wall thickness, 28 mm inner diameter, length: 350 cm, and a centered in the reaction tube tube thermal tube (10 mm outer diameter) for receiving a thermocouple with the temperature in the reaction tube over its entire length determined can be) is loaded from top to bottom as follows:

• Section 1: 50 cm long steatite rings of geometry 7 mm × 7 mm × 4 mm (outer diameter × length × inner diameter) as a pre-fill.
• Section 2: 140 cm length of catalyst charge with a homogeneous mixture of 20% by weight (alternatively 30% by weight) of steatite rings of geometry 5 mm × 3 mm × 2 mm (outer diameter × length × inner diameter) and 80% by weight (alternatively 70% by weight) of unsupported catalyst from Section 3.
• Section 3: 160 cm length catalyst charge with annular (5 mm × 3 mm × 2 mm = outer diameter × length × inner diameter) unsupported catalyst according to Example 1 of DE-A 10046957 (stoichiometry: [Bi ₂ W ₂ O ₉ × 2WO ₃ ] _{0 5} [Mo ₁₂ Co _5.5 Fe _2.94 Si _1.59 K _0.08 O _x ] ₁ ). Alternatively, one of the catalysts BVK1 to BVK11 from Research Disclosure No. 497012 of 29.08.2005 can be used here.

From top down are the first 175 cm by means of a counter-current pumped salt bath A thermostated. The second will be 175 cm thermostated by means of a countercurrently pumped salt bath B.

Second reaction stage:

• Abschnitt 1: 20 cm Länge Steatitringe der Geometrie 7 mm × 7 mm × 4 mm (Außendurchmesser × Länge × Innendurchmesser) als Vorschüttung.
• Abschnitt 2: 90 cm Länge Katalysatorbeschickung mit einem homogenen Gemisch aus 25 Gew.-% (alternativ 30 Gew.-%) Steatit-Ringen der Geometrie 7 mm × 3 mm × 4 mm (Außendurchmesser × Länge × Innendurchmesser) und 75 Gew.-% (alternativ 70 Gew.-%) Schalenkatalysator aus Abschitt 4.
• Abschnitt 3: 50 cm Länge Katalysatorbeschickung mit einem homogenen Gemisch aus 15 Gew.-% (alternativ 20 Gew.-%) an Steatit-Ringen der Geometrie 7 mm × 3 mm × 4 mm (Außendurchmesser × Länge × Innendurchmesser) und 85 Gew.-% (alternativ 80 Gew.-%) Schalenkatalysator aus Abschnitt 4.
• Abschnitt 4: 190 cm Länge Katalysatorbeschickung mit ringförmigem (7 mm × 3 mm × 4 mm = Außendurchmesser × Länge × Innendurchmesser) Schalenkatalysator gemäß Herstellungsbeispiel 5 der DE-A 10046928 (Stöchiometrie: Mo₁₂V₃W_1,2Cu_2,4O_x).

A reaction tube (V2A steel, 30 mm outer diameter, 2 mm wall thickness, 28 mm inner diameter, length: 350 cm, and a centered in the reaction tube tube thermal tube (10 mm outer diameter) for receiving a thermocouple with the temperature in the reaction tube over its entire length determined can be) is loaded from top to bottom as follows:

• Section 1: 20 cm length steatite rings of geometry 7 mm × 7 mm × 4 mm (outer diameter × length × inner diameter) as a feed.
• Section 2: 90 cm length of catalyst feed with a homogeneous mixture of 25 wt% (alternatively 30 wt%) steatite rings of geometry 7 mm x 3 mm x 4 mm (outside diameter x length x inside diameter) and 75 wt. % (alternatively 70% by weight) coated catalyst from section 4.
• Section 3: 50 cm length of catalyst charge with a homogeneous mixture of 15% by weight (alternatively 20% by weight) of steatite rings of geometry 7 mm x 3 mm x 4 mm (outer diameter x length x inner diameter) and 85 wt. % (alternatively 80% by weight) coated catalyst from section 4.
• Section 4: 190 cm length catalyst charge with annular (7 mm × 3 mm × 4 mm = outer diameter × length × inner diameter) coated catalyst according to Preparation Example 5 of DE-A 10046928 (stoichiometry: Mo ₁₂ V ₃ W _1.2 Cu _2.4 O _x ).

From top to bottom, the first 175 cm are thermostated by means of a countercurrently pumped salt bath C. The second 175 cm are thermo by means of a countercurrently pumped salt bath D. statisiert.

III. Process for the preparation of acrylic acid from propane (the stationary operating state is described) in one new pilot plant

The first catalyst bed of a tray reactor as described in I is fed with a reaction gas mixture input stream A which is composed as follows (% by volume based on total gas): Vol .-% acrylic acid 0.01 acetic acid 0,015 water 9.23 1-butene 0.01 isobutene 0.02 propane 18.46 propylene 3.98 Ethan 1.16 ethylene 0.22 CO ₂ 2.34 CO 0.26 N ₂ 59.7 O ₂ 1.62 CH ₄ 0.12 H ₂ 2.83

• – 41,9 Vol.-% Restgas aus der Partialoxidation (gasförmigem Ausgangsstrom 2) das folgende Gehalte aufweist:

Vol.-% Acrylsäure 0,02 Essigsäure 0,04 H₂O 2,73 iso-Buten 0,01 Acrolein 0,05 Propan 17,30 Propylen 0,32 Ethan 1,20 Ethylen 0,22 CO₂ 2,41 CO 0,61 N₂ 71,21 O₂ 3,87

• – 3,9 Vol.-% Frischpropan (gasförmiger Ausgangsstrom 3), das folgende Gehalte aufweist:

Vol.-% Propan 98,91 iso-Butan 0,05 Propylen 0,1 Ethan 0,92 Ethylen 0,01

• – 1,02 Vol.-% molekularem Wasserstoff (gasförmiger Ausgangsstrom 4)
• – 2,03 Vol.-% Wasserdampf und (gasförmiger Ausgangsstrom 5)
• – 51,15 Vol.-% Dehydrierkreisgas (Produktgasgemisch A-Teilstrom 1 bzw. gasförmiger Ausgangsstrom 1)

It is generated from (in the order residual gas (23 ° C, 3.1 bar), fresh propane, (25 ° C, 4 bar), hydrogen (25 ° C, 8 bar), water vapor (200 ° C, 2.5 bar), Dehydrierkreisgas (600 ° C, 1.9 bar)):

• - 41.9 vol .-% residual gas from the partial oxidation (gaseous output stream 2 ) has the following contents:

Vol .-% acrylic acid 0.02 acetic acid 0.04 H ₂ O 2.73 isobutene 0.01 acrolein 0.05 propane 17.30 propylene 0.32 Ethan 1.20 ethylene 0.22 CO ₂ 2.41 CO 0.61 N ₂ 71.21 O ₂ 3.87

• - 3.9 vol .-% fresh propane (gaseous output stream 3 ), which has the following contents:

Vol .-% propane 98.91 isobutane 0.05 propylene 0.1 Ethan 0.92 ethylene 0.01

• - 1.02 Vol .-% molecular hydrogen (gaseous output stream 4 )
• - 2.03 vol .-% water vapor and (gaseous output stream 5 )
• - 51.15 vol .-% Dehydrierkreisgas (product gas mixture A partial stream 1 or gaseous output current 1 )

Residual gas, fresh propane, hydrogen and water vapor are combined in the order mentioned to the motive jet mixed stream and by indirect heat exchange with the product gas mixture A substream 2 brought to 500 ° C, 2.3 bar.

The resulting product gas mixture A partial stream 2 is composed as follows: Vol .-% H ₂ O 11.84 isobutene 0.01 propane 14.32 propylene 7.52 Ethan 1.21 ethylene 0.26 CO ₂ 2.61 N ₂ 58.41 O ₂ 0.23 H ₂ 3.55

The in the product gas mixture A partial flow 2 contained propane and propylene is absorptively separated by absorption in technical tetradecane from the company Haltermann, DE type PKWF 4/7 af as an absorbent and stripped by air to obtain the following feed gas for the partial oxidation (thereby, as in DE-A 10 2004 032 129 described method), which has the following contents: Vol .-% H ₂ O 2.39 tetradecane 0.01 isobutene 0.01 propane 15.15 propylene 7.95 Ethan 1.10 ethylene 0.20 CO ₂ 1.05 N ₂ 56,99 O ₂ 15.16

• U^P _A, der Propenumsatz am Ende der Reaktionszone A, beträgt 64,5 mol.-%.
• U^P _B, der Propenumsatz am Ende der Reaktionszone B, beträgt 94,9 mol.-%.

With this feed gas mixture (it is outside the explosion range), the described first partial oxidation reaction stage is charged. The propylene loading of the fixed bed catalyst feed is chosen to be 185 Nl / lh. The pressure at the entrance of the first reaction stage is 3.1 bar. T _A = 322 ° C; T _B = 328 ° C;
The product gas mixture leaving the first reaction stage has the following contents: Vol .-% acrylic acid 0.46 acetic acid 0.14 H ₂ O 10.65 1-butene 0.01 acrolein 6.99 propane 15.16 propylene 0.17 Ethan 1.10 ethylene 0.20 CO ₂ 1.62 CO 0.23 N ₂ 57,02 O ₂ 6.25

• U ^P _A , the propene conversion at the end of the reaction zone A, is 64.5 mol .-%.
• U ^P _B , the propene conversion at the end of the reaction zone B, is 94.9 mol .-%.

As much air (25 ° C) is metered into the product gas mixture of the first stage that the ratio of acrolein: 0 ₂ in the resulting mixture is 6.85.

The second reaction stage is then charged directly with this mixture (T = 231.7 ° C.).
The acrolein loading of the fixed catalyst bed is 152 Nl / lh.
T _C = 263 ° C; T _D = 269 ° C. The pressure at the inlet of the second reaction stage is 2.1 bar.

• U^A _C, der Acroleinumsatz am Ende der Reaktionszone C, beträgt 68,1 mol.-%.
• U^A _D, der Acroleinumsatz am Ende der Reaktionszone D, beträgt 99,3 mol.-%.

The product gas mixture leaving the second reaction stage has the following contents: Vol .-% acrylic acid 6.72 acetic acid 0.22 H ₂ O 11.06 formaldehyde 0.14 acrolein 0.05 formic acid 0.03 maleic anhydride 0.06 benzoic acid 0.01 propane 14.62 propylene 0.28 Ethan 1.02 ethylene 0.18 CO ₂ 2.03 CO 0.52 N ₂ 59.86 O ₂ 3.20 propionic 0.0032

• U ^A _C , the acrolein at the end of the reaction zone C, is 68.1 mol .-%.
• U ^A _D , the acrolein conversion at the end of the reaction zone D, is 99.3 mol .-%.

In flows through both reaction stages the reaction gas mixture, the two catalyst tubes from top to bottom.

The Content analyzes are carried out by means of gas chromatographic analysis.

The acrylic acid is separated from the product gas mixture as in the exemplary embodiments of DE-A 10 2004 032 129 and the residual gas as gaseous output stream 2 returned to the heterogeneously catalyzed dehydrogenation.

The Procedure may also be as described, but with the difference carried out be that in the reaction zone A each catalyst horde only with the same amount of dehydrogenation catalyst is charged, d. h., without Use of inert material for dilution purposes.

IV. Modification of the procedure according to III. With increasing operating time

With increasing operating time of the pilot plant decreases the propylene content in the product gas mixture stream A, even if the dehydrogenation catalyst regenerated or replaced by a freshly produced batch.

simultaneously is a decrease in the maximum temperature in the first fixed catalyst bed (in flow direction) the Horden reactor detectable.

With Generation of motive jet mixture stream in the sequence residual gas, fresh propane, Water vapor (then indirect heat exchange) and then only molecular hydrogen can be the original Restore results on new operation.

Claims (7)

A process for the preparation of acrolein, or acrylic acid or their mixture of propane, comprising: A) feeding a reaction gas mixture input stream A to the inlet into a first reaction zone A by combining at least four different gaseous starting streams 1 . 2 . 3 and 4 was generated with the proviso that the three gaseous output currents 1 . 2 and 3 Containing propane th, the gaseous output current 4 molecular hydrogen and the gaseous output stream 3 Fresh propane is the reaction gas mixture input stream A in the reaction zone A by at least one catalyst bed leads to which, optionally with the supply of additional gas streams, by partial heterogeneously catalyzed dehydrogenation of propane, a propane and propylene containing product gas mixture stream A, the product gas mixture stream A through the outlet of the first reaction zone A leads out of selbiger and thereby in two product gas mixture A partial streams 1 and 2 divided with identical composition and the product gas mixture A partial stream 1 in the first cycle gas mode as gaseous output current 1 returns to the first reaction zone A, the product gas mixture A partial stream 2 optionally in a first separation zone A, to separate a subset or more of the same contained in it, other than propane and propylene components, and thereby to produce a remaining propane and propylene, product gas mixture stream A ', B) the product gas mixture stream A- partial flow 2 or the product gas mixture stream A 'used in a second reaction zone B to feed at least one oxidation reactor and in the at least one oxidation reactor that in the product gas mixture A partial stream 2 or Propylene contained in the product gas mixture stream A 'a selective heterogeneously catalyzed partial gas phase oxidation with molecular oxygen to an acrolein, or acrylic acid, or their mixture as the target product, unreacted propane and optionally unreacted propylene and excess molecular oxygen containing product gas mixture stream B, the product gas mixture stream B from the reaction zone B and in a second separation zone B in product gas mixture stream B contained target product and separated from the remaining, unreacted propane, molecular oxygen and optionally unreacted propylene containing residual gas at least one unreacted propane, molecular oxygen and optionally unreacted propylene containing subset in second cycle gas mode as gaseous output current 2 with the proviso in the reaction zone A that leads to the gaseous output streams 2 . 3 and 4 and optionally additional from the gaseous output stream 1 combines different gaseous output streams to a gaseous propellant jet mixed stream and then with the gaseous propellant jet stream as propulsion jet a jet pump, which comprises a motive nozzle, a mixing section, a diffuser and an inlet, operates, wherein the conveying direction of the relaxed by the motive nozzle via the mixing section and the diffuser propellant jet in the inlet of the first reaction zone A and the suction of the suction nozzle in the direction of the product gas mixture stream A leading outlet of the first reaction zone A and thereby by the negative pressure generated in the suction under distribution of the product gas mixture stream A in the two partial streams 1 and 2 the product gas mixture A partial stream 1 sucks, transported with simultaneous mixing with the propulsion jet through the mixing section via the diffuser and the resulting reaction gas mixture input stream A discharges into the inlet of the first reaction zone A, characterized in that initially the gaseous output streams 2 and 3 and optionally additional, from the gaseous output streams 1 and 4 different gaseous output streams combined in any sequence to form a gaseous starting mixture stream and only the gaseous starting mixture stream to form the gaseous propellant jet mixture stream, the gaseous output stream 4 adds. A method according to claim 1, characterized in that the reaction gas mixture input stream A by merging five different gaseous output streams 1 . 2 . 3 . 4 and 5 was generated and the gaseous output current 5 Steam is. A method according to claim 2, characterized in that the union of the gaseous output streams 1 and 4 various gaseous output streams to the gaseous output mixed stream in the sequence gas-shaped output stream 2 , gaseous output current 5 and then gaseous output stream 3 he follows. Method according to one of claims 1 to 3, characterized that from the time of formation of the motive jet mixture stream until at the time when the reaction gas mixture input stream A is the in the flow direction first catalyst bed reaches the reaction zone A, not more than 30 seconds pass. Method according to one of claims 1 to 3, characterized that from the time of formation of the motive jet mixture stream until at the time when the reaction gas mixture input stream A is the in the flow direction first catalyst bed reaches the reaction zone A, not more than 10 seconds pass. Method according to one of claims 1 to 5, characterized the reaction zone A is a tray reactor. Method according to one of claims 1 to 6, characterized that the partial heterogeneously catalyzed dehydrogenation of propane occurs autothermally in the reaction zone A.