WO2012049246A2 - Verfahren zum langzeitbetrieb einer heterogen katalysierten partiellen gasphasenoxidation von propen zu acrolein - Google Patents
Verfahren zum langzeitbetrieb einer heterogen katalysierten partiellen gasphasenoxidation von propen zu acrolein Download PDFInfo
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- WO2012049246A2 WO2012049246A2 PCT/EP2011/067887 EP2011067887W WO2012049246A2 WO 2012049246 A2 WO2012049246 A2 WO 2012049246A2 EP 2011067887 W EP2011067887 W EP 2011067887W WO 2012049246 A2 WO2012049246 A2 WO 2012049246A2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C47/22—Acryaldehyde; Methacryaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
Definitions
- the present invention relates to a process for the long-term operation of a heterogeneously catalyzed partial gas phase oxidation of propene to acrolein, in which a propylene, molecular oxygen and at least one inert gas-containing reaction gas input mixture containing the molecular oxygen and the propene in a molar ratio O2: C3H6> 1, with the proviso of a fixed catalyst bed whose active material is at least one multimetal oxide containing the elements Mo, Fe and Bi, results in the fixed catalyst bed being arranged in two spatially successive (and usually adjacent) temperature zones A, B (over two both the temperature T A of the temperature zone A and the temperature T B of the temperature zone B is a temperature in the temperature range from 280 to 420 ° C., the reaction gas input mixture the temperature zones A, B in the chronological order
- a diluent gas which is essentially inert under the conditions of the heterogeneously catalyzed gas phase partial oxidation of propene to acrolein (also termed "inert gas” in this document) is understood in this document to mean diluent gases whose constituents are under the conditions of the heterogeneously catalyzed gas phases - partial oxidation (or partial gas-phase oxidation) - each component considered separately tet - to more than 95 mol%, preferably more than 97 mol% and more preferably more than 99 mol% remain unchanged.
- reaction gas mixture eg reaction gas input mixture
- Normlitern Nl; the volume in liters, the corresponding reaction gas mixture amount under normal conditions, ie, at 0 ° C and 1 atm (1013 , 25 hPa)
- the load can also be related to only one component of the reaction gas mixture. Then it is the volume of Nl of this component which is fed to the fixed catalyst bed per hour, based on the volume of its bed.
- the reaction gas input mixture contains i.a. therefore, inert gas to keep the reaction gas mixture outside the explosion range.
- Acrylic acid is a significant monomer which can be used as such or in the form of its alkyl esters to produce e.g. as adhesives suitable or water-absorbing polymers is used.
- Acrolein is a significant intermediate.
- the fixed catalyst bed has the task of causing the desired particle oxidation of the propene, e.g. towards the complete oxidation of propene to carbon oxides and water, preferably expires.
- the chemical reaction takes place when the reaction gas mixture flows through the fixed catalyst bed, during the residence time of the reaction gas mixture in selbigem.
- the heterogeneously catalyzed partial gas-phase oxidation of propene to acrolein is highly exothermic.
- the sole measure of a catalyst addition is normally insufficient in view of the most selective conversion of the propene to acrolein.
- the temperature zones A, B are thereby usually realized by introducing the fixed catalyst bed into a reaction space (eg the interior of a (reaction) pipe), in two substantially separate from each other, in the flow direction of the reaction gas mixture
- a fluid (preferably liquid) heat transfer medium a heat exchange medium
- a heat exchange medium is guided or glided (in and out) in space-sequential (and usually contiguous) sections A, B Enclosure of the reaction space (the wall of the reaction space) along the respective section A or B touched (is in contact with the same).
- the guided in section A heat transfer medium is normally at the temperature T A and the guided in section B heat transfer medium is normally supplied at the temperature T B.
- the total heat capacity of the guided heat transfer stream is normally much larger than the total heat capacity of the reaction gas mixture stream.
- Heat transfer medium is implicitly described in EP-A 700714 and explicitly described in EP-A 1547994.
- the temperature of the part of the fixed catalyst bed (or part of the fixed bed catalyst bed) in the temperature zone is determined by the method of the invention, but in the fictive absence of the chemical heat of reaction Understood.
- This temperature usually corresponds essentially to the temperature with which the associated heat transfer medium of the respective temperature zone flows.
- the fixed catalyst bed (the fixed catalyst bed) can be in the contact tubes (reaction tubes) of a so-called two-zone tubular bundle reactor (heaped up), as described, for example, in DE-A's
- a preferred variant of a two-zone tube bundle reactor which can be used according to the invention is disclosed in DE-C 2830765.
- the two-zone tube bundle disclosed in DE-C 2513405, US-A 3,147,084, DE-A 2201528, EP-A 383224 and DE-A 2903218 are also disclosed.
- actuators are suitable for carrying out the relevant procedure.
- the fixed-bed catalyst bed (fixed catalyst bed) to be used according to the invention is located in the reaction tubes of a multi-contact fixed-bed reactor (tube bundle reactor) and around the reaction tubes are two substantially spatially separate tempering media (fluid heat exchangers, heat exchange means), e.g. ionic liquids, water (steam), molten salts or liquid metals (conducted, on and off).
- the pipe section, over which the respective salt bath or metal bath extends, represents a temperature zone.
- Corresponding temperature zones may also be used in thermal plate reactors, e.g. WO 2005/009608, or in heat exchanger plate reactors, e.g. EP-A 1577001 describes to be set up.
- the already mentioned inert diluent gases used in the reaction gas input mixture which are able to absorb the heat of reaction liberated with their heat capacity (internal measures of temperature control), contribute to the control of the reaction temperature course in the fixed catalyst bed.
- molecular nitrogen is automatically used whenever air is used as the source of oxygen for heterogeneously catalyzed gas phase partial oxidation.
- Another widely used inert diluent gas is water vapor due to its general availability and advantageous molar leaching capacity.
- inert diluent gases typically used are noble gases (eg He, Ar, Ne) or the carbon oxides CO2 and / or CO.
- Suitable inert gases with comparatively high molar heat capacity are, for example, saturated hydrocarbons such as, for example, n-propane and ethane, for the heterogeneously catalyzed partial gas-phase oxidation of propene to acrolein.
- recycle gas is also used as inert diluent gas (cf EP-A 1 180508).
- the residual gas is referred to, after a single-stage or multi-stage (the heterogeneously catalyzed partial oxidation of propene to acrolein can be used as only first reaction stage of a two-stage heterogeneously catalyzed partial oxidation of propene to acrylic acid) heterogeneously catalyzed gas phase partial oxidation of propene to acrolein or acrylic acid then remains, if one from the product gas mixture, the target product (acrolein or acrylic acid) more or less selectively (eg by absorption in a suitable solvent, or by fractional condensation, or by a superposition of absorption and condensation) has separated (see, eg, WO 2007/082827, page 6 ff).
- the inert diluent gases used for the partial oxidation consists predominantly of the inert diluent gases used for the partial oxidation and of water vapor which is usually formed by-product as a by-product or added as a diluent gas and carbon oxides formed as a side reaction by undesired complete oxidation. In some cases, it still contains small amounts of molecular oxygen not consumed in the partial oxidation (residual oxygen) and / or unreacted propene and / or unreacted intermediate acrolein.
- the effective temperature of the fixed catalyst bed is the actual temperature of the fixed catalyst bed, which includes both the influence of the guided outside the reaction space fluid heat carrier, and the heat of reaction of the partial oxidation (whereas the term "temperature of the temperature zone", as already said, the influence of the heat of reaction
- the temperature of a temperature zone is normally substantially constant in the flow direction along the same as the effective temperature of the fixed catalyst bed, and if the temperature of a temperature zone is not completely constant, the term "temperature of a temperature zone” means the (numerical) average the temperature over the temperature zone.
- the temperature of the individual temperature zones is essentially independent of each other. Normally, the effective temperature of the fixed catalyst bed at each bed height is greater than the temperature of the associated temperature zone.
- the temperature of the reaction gas mixture (and thus also the effective temperature of the fixed catalyst bed) during the transit
- the catalyst fixed bed in the direction of flow of the reaction gas mixture in the respective temperature zone passes through a maximum value or decreases from such a maximum value (the so-called hot spot value T maxA (in the temperature zone A) or j max B (j n of the temperature zone B)).
- T maxA in the temperature zone A
- j max B j n of the temperature zone B
- the difference between the hotspot value and the temperature of the associated temperature zone is referred to as the hotspot extent ⁇ ⁇ ⁇ (in the temperature zone A) or ⁇ ⁇ ⁇ (in the temperature zone B).
- the general process conditions are generally advantageously chosen so that T max A - T max B > 0 ° C. in the freshly charged fixed catalyst bed (compare WO 2004/085362, WO 2004/085370 and WO 2004/085363 ).
- the general process conditions are normally chosen so that both ⁇ ⁇ ⁇ and ⁇ ⁇ ⁇ do not generally exceed 90 ° C. Most of these temperature differences are> 3 ° C and ⁇ 80 ° C, or ⁇ 70 ° C, often> 5 ° C and ⁇ 60 ° C, or ⁇ 50 ° C. In terms of application, ⁇ ⁇ ⁇ is 40 to 90 ° C, or 40 to 80 ° C.
- the change of ⁇ ⁇ ⁇ or ⁇ ⁇ ⁇ normally increases when the temperature of the associated temperature zone increases by +1 ° C. (see the acknowledged prior art documents) ⁇ +9 ° C, preferably ⁇ + 7 ° C, or ⁇ + 5 ° C or ⁇ + 3 ° C, but> + 0 ° C (see for example EP-A 1 106598).
- T A and T B in the temperature range from 280 ° C to 420 ° C ensures economic propene conversions (typically> 90 mol%) in a single pass of the reaction gas mixture through the fixed catalyst bed (especially by the freshly charged fixed catalyst bed).
- the catalysts of the fixed catalyst bed for the heterogeneously catalyzed partial gas phase oxidation of propene to acrolein generally have as active composition at least one multimetal oxide containing the elements Mo, Fe and Bi (cf., for example, WO 2004/085362).
- the fixed catalyst bed normally loses quality with increasing operating time (see, for example, DE-A 102004025445).
- the volume-specific activity of the fixed catalyst bed generally deteriorates (under otherwise unchanged process conditions, the propene conversion related to the one-time passage of the reaction gas mixture through the fixed catalyst bed decreases with increasing operating time, which results in the intended space-time yield of acrolein production unit of acrolein or to acrolein and acrylic acid).
- the selectivity of the acrolein formation or of the overall target product formation on acrolein and acrylic acid also suffers.
- EP-A 1 106598 and DE-A 10351269 try to take into account the aforementioned development in the long-term operation of the heterogeneously catalyzed gas phase partial oxidation of the propene to acrolein by the temperature of the temperature zone in which the fixed catalyst bed is located, and with this Temperature of the fixed catalyst bed is gradually increased under otherwise largely constant operating conditions to substantially maintain the propene conversion with a single pass of the reaction gas mixture through the fixed catalyst bed (it can, as for example WO 2004/085369, the
- DE-A 10351269, DE-A 10350812 and EP-A 614872 recommend that the quality reduction of the fixed catalyst bed in long-term operation be counteracted in addition by the fact that the fixed catalyst bed is regenerated from time to time;
- the process of heterogeneously catalyzed fixed bed gas phase partial oxidation of propene to acrolein (or to acrolein and acrylic acid) is interrupted and, for. passing a hot mixture of molecular oxygen and inert gas through the fixed catalyst bed; In this way, it is possible to reverse a reversible part of the reduction in the quality (of the aging) of the fixed catalyst bed).
- Such regeneration can also according to DE-A
- EP-A 1 106598 and DE-A 10351269 suggest a synchronous increase in the temperature in the two temperature zones A, B. That is, T A and T B are each increased to the same extent (by as much ° C).
- WO 2007/082827 therefore recommends carrying out the long-term operation of a heterogeneously catalyzed partial gas phase oxidation of propene to acrolein as described above (this is always also a gas phase partial oxidation of propene to acrolein and acrylic acid) so as to counteract the reduction in the quality of the fixed catalyst bed ,
- the fixed catalyst bed must be at least partially replaced (see DE-A 10232748) or completely by a fresh fixed catalyst bed for the overall target product formation on acrolein and acrylic acid. This time is referred to as the endpoint of the service life of the fixed catalyst bed.
- the object of the present invention was therefore to provide an improved process for the long-term operation of a heterogeneously catalyzed partial gas phase oxidation of propene to acrolein carried out in two temperature zones as described at the beginning of this document To provide, which also ensures a satisfactory selectivity of the acrolein formation or the overall target product formation of acrolein and acrylic acid with an improved service life of the fixed catalyst bed over the operating time.
- a method for the long-term operation of a heterogeneously catalyzed partial gas phase oxidation of propene to acrolein (this is always a Gasphasenpartialoxida- tion of propene to acrolein and acrylic acid), which comprises a propene, molecular oxygen and at least one inert gas reaction gas input mixture containing the molecular Oxygen and the propene in a molar ratio O2: C 3 H6> 1, as determined by a fixed catalyst bed, the active material is at least one containing the elements Mo, Fe and Bi multimetal, that
- the fixed catalyst bed is arranged in two spatially successive temperature zones A, B,
- both the temperature T A of the temperature zone A and the temperature T B of the temperature zone B are a temperature in the temperature range from 280 to 420 ° C,
- the load of the fixed catalyst bed with the propene contained in the reaction gas input mixture is> 140 Nl propene / liter fixed catalyst bed h
- the difference ⁇ ⁇ for carrying out the process according to the invention on the freshly charged fixed catalyst bed is usually ⁇ 50 ° C. and preferably ⁇ 40 ° C.
- the setting of the above differences AT BA for carrying out the process according to the invention on the freshly charged fixed catalyst bed is accompanied by a difference T maxA -T maxB which is> 0 ° C. and ⁇ 80 ° C., or ⁇ 70 ° C.
- T maxA - T maxB in carrying out the process according to the invention on freshly charged fixed catalyst bed (ie, at the beginning of the inventive method) are therefore> 1 ° C and ⁇ 60 ° C, or ⁇ 50 ° C, preferably> 2 ° C and ⁇ 40 ° C, with advantage> 3 ° C and ⁇ 30 ° C, with particular advantage> 5 ° C or> 10 ° C and ⁇ 25 ° C and very particularly preferably> 5 ° C and ⁇ 20 ° C or ⁇ 15 ° C.
- T B undergoes a greater increase in long-term operation as T A.
- both T B and T A can be increased.
- the increase in T B is 1, 2 to 5 times the increase in T A , in each case based on the same operating time in the long-term operation of the method according to the invention. That is, favorable processes of the invention are those in which the increase in T B is 1.5 to 4 times, or 1.5 to 3 times (eg, 2 times) the increase in T A , respectively to the same operating time in the long-term operation of the method according to the invention.
- the procedure of the invention includes a "negative" is the difference T maxA - jmaxB n j C
- the temperatures of the temperature zones A and B in large-scale operation for various reasons certain fluctuations (usually within the interval ⁇ 20 ° C or ⁇ 10 ° C lying) may be subject (For example, if an intermediate regeneration according to DE-A 10351269 is made immediately after the intermediate regeneration (compared to the operation immediately before the intermediate regeneration) are generally lower temperatures (in individual cases, this temperature difference can also be up to 40 ° C or more amount) of the temperature zones is sufficient to ensure the same propene conversion, based on the single pass of the reaction gas mixture through the fixed catalyst bed, under otherwise unchanged conditions).
- the actual course of the temperature of the respective zone is plotted over time and a compensation curve is set by the measuring points according to the method of the least sum of the deviation squares developed by Legendre and Gauss. If the features according to the invention are fulfilled on the basis of these compensation curves, use is made of the method according to the invention.
- Propene charges of the fixed catalyst bed which are in an interval (X ⁇ 10) Nl / lh, are considered for the purposes of the invention as one and the same Propenbelastung.
- a procedure according to the invention is also present if the long-term operation is interrupted in the case of propene loadings of the fixed catalyst bed of> 140 Nl per liter / l fixed catalyst bed h by a low-load operation (propene loading of the fixed catalyst bed ⁇ 140 Nl / lh) and when the low-load operating phases are blanked out high load long-term operating pattern according to the invention results.
- the process according to the invention makes use of the process according to the invention only over a certain time range of the long-term operation and leaves the long-term mode of operation according to the invention in advance of the partial or complete replacement of the fixed catalyst bed by a fresh bed.
- ⁇ ⁇ does not exceed 70 ° C. in the long-term operation of the process according to the invention.
- ⁇ ⁇ will particularly advantageously not exceed 60 ° C., and very particularly advantageously not exceed 50 ° C.
- Particularly favorable methods according to the invention are those in which ⁇ ⁇ over the entire operating life of the long-term operation in the range 10 ° C to 50 ° C, preferably in the range 15 ° C to 45 ° C, and most preferably in the range 20 ° C to 40 ° C is.
- Processes according to the invention are, for example, those processes in which ⁇ ⁇ increases by at least 5 ° C, or at least 10 ° C, or at least 15 ° C, or at least 20 ° C, or at least 25 ° C, with increasing service life increased by at least 30 ° C.
- ⁇ ⁇ in the process according to the invention will increase by not more than 50 ° C, usually by not more than 30 ° C, often by not more than 20 ° C.
- the temperature T A will be in the range from 300 to 400 ° C, and preferably in the range from 310 ° C to 390 ° C or in the range from 320 ° C to 380 ° C over the entire operating time.
- the temperature T B over the entire service life often in the range of 305 ° C to 415 ° C, preferably in the range of 315 ° C to 410 ° C and more preferably in the range of 330 ° C to 410 ° C. move.
- the conversion of propylene resulting in the temperature zone A in the long-term operation according to the invention over the entire operating time is advantageously 50 to 80 mol% and particularly advantageously 55 to 75 mol%.
- the conversion of the propene based on a single pass of the reaction gas mixture over the entire operating time in the long-term operation according to the invention is advantageous according to the invention to a value of> 92 mol%, or> 94 mol%, preferably> 96 mol% and very particularly prefers
- the long-term operation of the method according to the invention will be at least 2 months of operation, or at least 4 operating months, or at least 6 months of operation, or at least 9 months of operation, or at least 1 year of operation, or at least 1, 5 years of operation, or at least 2 Operating years, or at least 2.5 years of operation, or at least 3 years of operation, and in some cases even for at least 5 years of operation, or at least 7 years of operation and in some cases even 10 years of service or more.
- the rate of change of T B averaged over an operating time of 1000 days in the method according to the invention can be eg + 0.04 ° C / day, while at the same time the rate of change of T A averaged over the same operating time only + 0.02 ° C / day is.
- the catalysts to be used for the process according to the invention and other process conditions will be suitably chosen so that the selectivity of acrolein formation, based on the propene reacted in the single pass of the reaction gas mixture through the fixed catalyst bed, is advantageously> 82 mol%, or
- acrylic acid is formed as a by-product (based on the molar amount of acrolein formed, as a rule in amounts of ⁇ 15 mol% and ⁇ 10 mol%, respectively).
- the latter is particularly welcome as a by-product, when the process according to the invention forms the first reaction stage of a two-stage process of heterogeneously catalyzed partial gas phase oxidation of propene to acrylic acid.
- the catalysts and other process conditions to be used for the process according to the invention will suitably be selected such that the selectivity of the overall target product formation, based on the propene conversion in a single pass of the reaction gas mixture through the fixed catalyst bed ,> 93 mol%, or> 95 mol%, or> 96 mol%, or> 97 mol%, or> 98 mol%.
- the method according to the invention is preferably carried out in the two-zone multi-contact tube reactors already mentioned.
- the radial temperature gradient of the heat carrier within a temperature zone is generally 0.01 to 5 ° C, often 0.1 to 2 ° C, and is advantageous according to the invention as low as possible.
- the current strength of the heat carrier is generally chosen following the teaching of EP-A 700714 such that the temperature of the heat carrier from entry into the temperature zone to the exit from the temperature zone (due to de exothermic reaction) by 0 to 15 ° C. increases.
- the aforesaid ⁇ will be 1 to 10 ° C, or 2 to 8 ° C, or 3 to 6 ° C in the present invention.
- Advantageously ⁇ is small.
- process according to the invention can also be carried out in other reactors of the type of an indirect heat exchanger having two temperature zones.
- the procedure according to the invention is particularly advantageous over the procedures recommended in the prior art if the propene loading of the fixed catalyst bed is> 150 Nl / lh, or> 160 Nl / lh, or> 170 Nl / lh, or> 180 Nl / lh, or> 190 Nl / lh, or> 200 Nl / lh.
- the propene loading of the fixed catalyst bed in the process according to the invention will be ⁇ 600 Nl / l-h, usually ⁇ 400 Nl / l-h, or ⁇ 300 Nl / l-h, or ⁇ 250 Nl / l-h.
- the catalyst quality is increasingly irreversibly reduced with increasing operating time, which, in addition, at the same time, upon further increase in the fixed catalyst bed temperature, causes a considerable increase in the proportion of undesired full combustion in the temperature zone A.
- An early indicator of the early onset of behavior as described above is often the time course of ⁇ ⁇ ⁇ . While ⁇ ⁇ ⁇ in the freshly charged catalyst fixed bed usually increases initially with increasing operating time and increase in T A , when using the procedure according to WO 2007/082827 in long-term operation, the time is often comparatively early, from the ⁇ ⁇ ⁇ on continuation of operation decreases. The onset of this decrease is usually a significant clue to already pronounced irreversible damage to the fixed catalyst bed.
- condition T maxA - T maxB > 0 alone is indeed a necessary, but not sufficient, condition for a successful long-term mode of operation .
- particularly advantageous results are obtained if, during long-term operation, the highest effective temperature of the fixed catalyst bed is maintained for as long as possible in temperature zone A and at comparatively low absolute values. The latter is the case with the long-term mode of operation according to the invention.
- the procedure according to the invention can also be used for propene loads of the fixed catalyst bed of ⁇ 140 Nl / lh, or ⁇ 130 Nl / lh, or ⁇ 120 Nl / lh, or ⁇ 1 10 Nl / lh, or ⁇ 100 Nl / lh, or ⁇ 90 Nl / lh, or ⁇ 80 Nl / lh (usually> 60 Nl / lh).
- the procedure according to WO 2007/082827 gains advantage over such a procedure.
- the procedure of the invention can be applied analogously to a heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid. Due to the comparatively lower exothermicity of this partial oxidation and a higher temperature sensitivity of the total oxidation (full combustion) of acrylic acid in comparison to acrolein, a procedure according to WO 2007/082827 is preferable in this case, even at high acrolein loadings of the fixed catalyst bed.
- the process according to the invention is normally not taken up directly at the high propene loading of the fixed catalyst bed intended for stationary operation, together with the associated target conversion of propene to a single pass of the reaction gas mixture through the fixed catalyst bed.
- T maxA in the process according to the invention will be> 350 ° C., usually> 360 ° C. and often> 370 ° C. or> 380 ° C.
- the operating phases of the heterogeneously catalyzed Gasphasenpartialoxidationsvons from startup or restart of the catalyst fixed bed to reach the conditions of steady-state operation are not attributed to the inventive method of long-term operation (usually they extend to ⁇ 72 h, often ⁇ 48 h or ⁇ 24 h).
- the aforementioned percentage for partial catalyst change is often not less than 5, or not less than 10, or not less than 20%.
- the molar ratio of O 2: C 3 H 6 in the reaction gas input mixture for a partial oxidation of propene to acrolein according to the invention is> 1. Usually, this ratio will be at values ⁇ 3. Frequently, the molar ratio of O 2: C 3 H 6 in the reaction gas input mixture in the process according to the invention is> 1, 2, or> 1, 5 and ⁇ 2.0.
- Catalysts which are advantageous according to the invention are those whose active composition is a multimetal oxide which contains at least the elements Mo, Fe and Bi, and additionally at least one of the two elements Ni and Co. It proves to be favorable if, of the abovementioned five elements (other than oxygen), based on their molar total amount G contained in the active composition, the largest molar fraction (in mol%, based on the total molar mass G), is the element Mo eliminated.
- Multielement oxide active compositions which are particularly suitable according to the invention are thus in particular those of general formula I of DE-A 19955176, the multielement oxide active compounds of general formula I of DE-A 19948523, the multielement oxide active compounds of general formula I, II and III of DE-A 10101695, the multielement oxide active compositions of the general For my I, II and I II of DE-A 19948248 and the Multielementoxidgenmassen the general formulas I, II and I II of DE-A 19955168 and in the specifications EP-A 700 714,
- DE-A 197 46 210 and DE-A 198 55 913 are particularly preferred. Particularly noteworthy in this context are a catalyst according to Example 1c of the
- the active composition has the composition Moi2Ni6,5Zn 2 Fe2Bii P 0 , oo65K 0 , o60x ⁇ 10 S1O2.
- the consecutive number 3 from DE-A 198 55 913 (stoichiometry: Moi 2 Co 7 Fe 3 Bio, 6K o, 8Sii, 60x) as hollow cylinder full catalyst of the geometry 5 mm ⁇ 3 mm ⁇ 2 mm or 5 mm ⁇ 2 mm x 2 mm (each outer diameter x height x inner diameter) and the Multimetalloxid II - full catalyst according to Example 1 of DE-A 197 46 210.
- multimetal oxide catalysts of US Pat. No. 4,438,217 should be mentioned.
- the latter applies in particular if this has a hollow cylinder geometry of the dimensions 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 x 3 mm, or 7 mm x 3 mm x 4 mm (each outer diameter x height x inner diameter).
- IVIultimetalloxidkatalysatoren and geometries of DE-A 101 01 695 and WO 02/062737 are suitable.
- the example 1 from DE-A 100 46 957 (stoichiometry: [B12W2O9 x 2W0 3 ] o, 5 ⁇ [Moi2Co5,6Fe2,94Sii, 59Ko, oeOx] i) as a hollow cylinder (ring) vollkatalysator the geometry 5 mm x 3 mm ⁇ 2 mm or 5 mm ⁇ 2 mm ⁇ 2 mm (in each case external diameter ⁇ length ⁇ internal diameter), as well as the coated catalysts 1, 2 and 3 from DE-A 100 63 162 (stoichiometry: Moi2Bii, 0 Fe 3 Co7Sii, 6K 0 , o8), but applied as annular shell catalysts corresponding Scha ⁇ lendicke and on carrier rings of geometry 5 mm x 3 mm x 1, 5 mm or 7 mm x 3 mm x 1, 5 mm (each outer diameter x length x inner diameter) , suitable.
- a large number of the multielement oxide active substances suitable for the process according to the invention can be classified under the general formula I
- 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,
- b 0.01 to 5, preferably 2 to 4,
- c 0.1 to 10, preferably 3 to 10,
- d 0 to 2, preferably 0.02 to 2
- e 0 to 8, preferably 0 to 5,
- n a number, which is determined by the valence and frequency of the elements other than oxygen in I, subsume.
- Coated catalysts ie preformed inert support bodies coated with the active composition. pern, used. Of course, they can also be used in powder form as catalysts.
- active compounds of the general formula I can be prepared in a simple manner by producing a very intimate, preferably finely divided, stoichiometrically composed, dry mixture of suitable sources of their elemental constituents and calcined this at temperatures of 350 to 650 ° C.
- the quenching may be carried out both under inert gas and under an oxidative atmosphere such as e.g. Air (mixture of inert gas and oxygen) as well as under reducing atmosphere (for example, mixture of inert gas, N H3, CO and / or H2) take place.
- the calcination time can be several minutes to a few hours and usually decreases with temperature.
- Suitable sources of the elemental constituents of the multimetal oxide active compounds I 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.
- such starting compounds are halides, nitrates, formates, oxalates, citrates, acetates, carbonates, amine complexes, ammonium salts and / or hydroxides (such compounds as N H4OH, (NH 4) 2 C0 3, N H4NO3 are N H4CHO2, CH 3 COOH, NH 4 CH 3 C02 and / or ammonium oxalate which decompose latest during the subsequent Kalcinieren to gaseous form escaping compounds and / or can be decomposed, can additionally be incorporated into the intimate dry mixture).
- the intimate mixing of the starting compounds for the preparation of multimetal oxide active compounds I can be carried out in dry or in wet form. If it is carried out in dry form, then the starting compounds are expediently used as finely divided powders and subjected to the Kaicination after mixing and optionally compacting. Preferably, however, the intimate mixing takes place in wet form.
- the starting compounds are mixed together in the form of an aqueous solution and / or suspension. Particularly intimate dry mixtures are obtained in the described mixing process when starting exclusively from sources of the elementary constituents present in dissolved form.
- the solvent used is preferably water.
- the resulting aqueous composition is dried, wherein the drying process is preferably carried out by spray-drying the aqueous mixture with outlet temperatures of 100 to 150 ° C.
- the multimetal oxide active compounds of the general formula I are used in the (fresh) fixed bed catalyst charge for a gas phase partial oxidation according to the invention to form acrolein not in powder form but to specific catalyst geometries, wherein the shaping can take place before or after the final quenching.
- the active composition or its uncalcined and / or partially calcined precursor composition can be obtained by compaction to the desired catalyst geometry (e.g.
- Suitable Vollkatalysatorgeometrien are eg 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.
- the full catalyst may also have spherical geometry, wherein the ball diameter may be 2 to 10 mm.
- a particularly favorable hollow cylinder geometry is 5 mm ⁇ 3 mm ⁇ 2 mm (outer diameter ⁇ length ⁇ inner diameter), in particular in the case of solid catalysts.
- the shaping of the pulverulent active composition or its pulverulent, not yet and / or partially calcined precursor composition can also be effected by application to preformed inert catalyst supports.
- the coating of the carrier bodies for the preparation of the coated catalysts is usually carried out in a suitable rotatable container, as e.g. from DE-A 29 09 671, EP-A 293 859 or from EP-A 714 700 is known.
- the powder to be applied is moistened to coat the carrier body and after application, e.g. by means of hot air, dried again.
- the layer thickness of the powder mass applied to the carrier body is expediently selected in the range from 10 to 1000 ⁇ m, preferably in the range from 50 to 500 ⁇ m, and more preferably in the range from 150 to 250 ⁇ m.
- 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. As a rule, they are essentially inert with respect to the target reaction according to the invention.
- the carrier bodies may be regularly or irregularly shaped, with regularly shaped carrier bodies having a marked surface roughness, e.g. Spheres or hollow cylinders are preferred.
- substantially nonporous, surface roughness, spherical supports of steatite for example steatite C 220 from CeramTec
- the diameter of which is 1 to 8 mm, preferably 4 to 5 mm, is suitable.
- cylinders as carrier bodies whose length is 2 to 10 mm and whose outer diameter is 4 to 10 mm.
- the wall thickness is usually from 1 to 4 mm.
- annular carrier 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.
- rings of the geometry 7 mm ⁇ 3 mm ⁇ 4 mm are also suitable according to the invention
- Y 2 molybdenum, or tungsten, or molybdenum and tungsten
- Y 3 an alkali metal, thallium and / or samarium
- Y 4 nickel and / or cobalt, and optionally one or more of the elements copper, manganese, zinc, tin, cadmium, mercury and the alkaline earth metals,
- 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,
- x ', y' numbers which are determined by the valence and frequency of the elements other than oxygen in II and
- p, q numbers whose ratio p / q is 0.1 to 10, comprising three-dimensionally extended regions of the chemical composition Y 1 a Y 2 b Cy whose local diameter is defined by their local environment due to their different compositions from their local environment ( longest passing through the center of gravity of the range connecting distance of two located on the surface (interface) of the area points) 1 nm to 100 ⁇ , often 10 nm to 500 nm or 1 ⁇ to 50 or to 25 ⁇ , is.
- Particularly advantageous multimetal II invention are those in which Y 1 is only bismuth.
- 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
- e 0.01 to 5, preferably 0.1 to 3,
- x ", y" numbers determined by the valence and frequency of the element different from oxygen in III
- multimetal oxide compositions II catalysts With regard to the shaping, with respect to multimetal oxide compositions II catalysts, what has been said for the multimetal oxide compositions I catalysts applies.
- the preparation of multimetal oxide compositions II active compounds is described, for example, in DE Application No. 102008054586.4, DE-A 102008040093, DE-A 102008040094, EP-A 575 897 and DE-A 198 55 913.
- the inert carrier materials recommended above are, inter alia, also suitable as inert materials for dilution and / or delimitation of the corresponding fixed catalyst bed, or as their protective bedding or as bedding.
- the volume-specific activity of the (fresh) fixed catalyst bed in the flow direction of the reaction gas mixture over the length of the flow path may be constant, or advantageously at least once (continuously, or abruptly or stepwise ) increase. It is advantageous if the active composition does not change over the length of the flow path of the reaction gas mixture (i.e., within the fresh fixed catalyst bed).
- the fixed-bed catalyst charge consists of at least two spatially successive fixed bed catalyst charge zones, wherein the volume-specific activity within a fixed bed catalyst charge zone is substantially constant and increases rapidly in the flow direction of the reaction gas mixture during the transition from one fixed bed catalyst charge zone to another fixed bed catalyst charge zone.
- volume-specific (ie normalized to the unit of the respective bulk volume) activity of a fixed bed catalyst bed zone can now be adjusted in a substantially constant manner over the fixed bed catalyst bed zone by starting from a basic quantity of uniformly prepared shaped catalyst bodies (their bed corresponds to the maximum) achievable volume-specific activity) and this in the respective fixed bed catalyst bed zone with respect to the heterogeneously catalyzed partial gas phase oxidation substantially inert behaving moldings (dilution molded article) homogeneously diluted.
- Suitable materials for such inert shaped diluents are, in principle, all those which are also suitable as support material for shell catalysts suitable in accordance with the invention.
- porous or non-porous aluminum oxides e.g. porous or non-porous aluminum oxides, silicon dioxide, thioxide, zirconium dioxide, silicon carbide, silicates such as magnesium silicate or aluminum silicate or the already mentioned steatite (for example steatite C 220 from CeramTec).
- silicates such as magnesium silicate or aluminum silicate or the already mentioned steatite (for example steatite C 220 from CeramTec).
- inert shaped diluent bodies can in principle be arbitrary. That is, it may be, for example, balls, polygons, solid cylinders or rings. According to the invention, preference is given to choosing those whose inertial geometry corresponds to that of the shaped catalyst bodies to be diluted with them as inert shaped diluents. According to the invention, it is favorable, as already stated, if the chemical composition of the active composition used does not change over the entire fixed bed catalyst charge. That is, although the active composition used for a single shaped catalyst body can be a mixture of different multimetal oxides containing, for example, the elements Mo, Fe and Bi, the same mixture must be used for all shaped catalyst bodies of the fixed catalyst bed.
- a volume-specific activity which increases zone-wise (is particularly advantageous) in the flow direction of the reaction gas mixture over the fixed-bed catalyst charge can thus be achieved in a simple manner, e.g. set by starting the bed in a first fixed bed catalyst bed zone with a high proportion of inert diluent with respect to a variety of shaped catalyst bodies, and then reduces this proportion of diluent bodies in the flow direction zone by zone.
- a zone-wise increase in volume-specific activity advantageous according to the invention is also e.g.
- volume-specific activity can be achieved by using different bulk density catalyst geometries (e.g., in full catalysts having identical active composition of the various geometries). Needless to say, the variants described can also be used in combination.
- mixtures of catalysts having a chemically different active-material composition and as a consequence of this different composition of different activity can in turn be varied zone by zone in their composition and / or diluted with different amounts of inert diluent molding so that the volume-specific activity in the flow direction of the reaction gas mixture increases in zones.
- inert material eg only shaped diluent bodies
- the shaped tablets used for the inert bed can have the same geometry as the shaped catalyst bodies used in the fixed-bed catalyst bed.
- the geometry of the shaped bodies used for the inert packing can also be different from the abovementioned geometry of the shaped catalyst bodies (for example spherical instead of annular).
- the temperature zones A and B may also extend to the Inert subjectungen in the inventive method.
- both the temperature zone A and the temperature zone B for a partial oxidation of propene to acrolein according to the invention advantageously do not detect more than three fixed bed catalyst bed zones (according to the invention, at least one fixed bed catalyst bed zone is advantageously detected by both temperature zones).
- the entire fixed bed catalyst bed particularly preferably does not comprise more than five, suitably not more than four or three fixed bed catalyst bed zones.
- the volume-specific active material ie, the weight of the unit in the bulk volume contained Multimetalloxiditmasse
- the volume-specific active material expediently by at least 5 wt. -%, preferably by at least 10 wt .-% increase (this is especially true for uniform shaped catalyst bodies over the entire fixed bed catalyst bed).
- this increase in the process according to the invention of a heterogeneously catalyzed partial oxidation of propene to acrolein will not be more than 50% by weight, usually not more than 40% by weight.
- the difference in the volume-specific active mass of the fixed-bed catalyst charge zone with the lowest volume-specific activity and that fixed-bed catalyst charge zone with the highest volume-specific activity should advantageously not exceed 50% by weight, preferably not more than 40% Wt .-% and usually not more than 30 wt .-% amount.
- the fixed bed catalyst charge will consist of only two fixed bed catalyst charge zones.
- the last fixed bed catalyst bed zone of the fixed bed catalyst bed which is the last in the flow direction of the reaction gas mixture is undiluted. That is, it preferably consists exclusively of shaped catalyst bodies. If necessary, it may also consist of a bed of shaped catalyst bodies whose volume-specific activity is lowered, for example by dilution with inert material, for example by 10%
- the fixed-bed catalyst bed for a heterogeneously catalyzed partial oxidation of propene to acrolein only consists of two fixed-bed catalyst bed zones, it is generally advantageous according to the invention if the fixed-bed catalyst bed zone having the highest volume-specific activity does not protrude into temperature zone A (especially if in the temperature zone) A and in the temperature zone B, the temperature control by means of a flowing heat carrier takes place, each of which flows in countercurrent (viewed over the reactor) to the reaction gas mixture).
- the fixed bed catalyst bed zone having the lower volume specific activity will protrude into temperature zone B and begin and end the fixed bed catalyst bed zone having the higher volume specific activity in temperature zone B (ie, past the transition from temperature zone A to temperature zone B) Have the beginning).
- the fixed bed catalyst bed only consists of three fixed bed catalyst bed zones, it is generally likewise advantageous if the fixed bed catalyst bed zone with the higher volume specific activity does not protrude into the temperature zone A but begins and ends in the temperature zone B, ie behind the transition from the Temperature zone A in the temperature zone B has its beginning (especially if in the temperature zone A and in the temperature zone B, the temperature control by means of a flowing heat carrier takes place, each of which flows in countercurrent to the reaction gas mixture). That is, normally, in this case, the fixed bed catalyst bed zone having the second highest volume specific activity will protrude into both the temperature zone A and the temperature zone B.
- the fixed-bed catalyst bed consists of four fixed-bed catalyst bed zones, it is generally advantageous according to the invention if the fixed-bed catalyst bed zone with the third highest volume-specific activity protrudes both into the temperature zone A and into the temperature zone B (in particular if in the temperature zone A and in the temperature zone B) Tempering by means of a flowing heat carrier takes place, which in each case flows in countercurrent to the reaction gas mixture).
- a flowing heat carrier takes place, which in each case flows in countercurrent to the reaction gas mixture.
- the volume-specific activity between two fixed bed catalyst charge zones of a fixed bed catalyst charge can be experimentally easily differentiated so that under identical boundary conditions (preferably the conditions of the envisaged process) over fixed bed catalyst beds of the same length but corresponding to the composition of the respective fixed bed catalyst charge zone, the same Propen containing reaction gas mixture is performed.
- the higher amount of propene reacted has the higher volume specific activity.
- the fixed-bed catalyst charge (without incorporation of mere inert precursors and / or replenishments) in the flow direction of the reaction gas mixture is structured as follows.
- both the shaped catalyst bodies and the shaped diluent bodies advantageously have inventive method substantially the ring geometry 5 mm x 3 mm x 2 mm (outer diameter x length x inner diameter) on.
- shell-shaped catalyst bodies are used whose active mass fraction is 2 to 15% by weight lower than the active material content of the shell catalyst molded body optionally used at the end of the fixed catalyst bed.
- a pure Inertmaterial sectionung whose length, based on the length of the Festbettkatalysa- tor thoroughlyung, expediently 5 to 20%, leads in the flow direction of the reaction gas mixture usually on the fixed catalyst bed. It is normally used as a heating zone for the reaction gas mixture.
- the fixed-bed catalyst bed zone with the lower volume-specific activity now extends to 5 to 20%, frequently to 5 to 15% of its length, into the temperature zone B in the abovementioned fixed-bed catalyst feeds.
- the temperature zone A expediently extends to a bed of inert material optionally applied to the packed catalyst bed.
- temperature zones A, B may be followed by further additional temperature zones.
- this is not preferred according to the invention.
- support bodies are suitable which have an increased surface roughness, since these generally result in an increased adhesive strength of the applied shell of active composition.
- the surface roughness Rz of the carrier body is in the range from 30 to 200 ⁇ m, preferably 30 to 100 ⁇ m (determined according to DIN 4768, sheet 1 with a "Hommel tester” for DIN-ISO surface measured variables from Hommelwerke.)
- the support materials can be porous or non-porous
- the process of the partial oxidation of propene to acrolein in a Zweizonenrohrbündel- reactor, as described for example in DE-A's 19910508, DE-C 2830765 discloses a preferred variant of a two-zone tube bundle reactor which can be used according to the invention 383224, WO 2007/082827, WO 2004/08362, the
- EP-A 1547994 and DE-A 2903218 disclosed two-zone tube bundle reactors are suitable for carrying out such a method. That is, in the simplest way to be used for such a process according to the invention Festbettkatalysator forung (possibly with upstream and / or downstream Inert- spills) in the metal tubes of a tube bundle reactor and the metal tube are two mutually substantially spatially separated tempering, in usually molten salt, led.
- the pipe section, over which the respective salt bath extends, represents according to the invention a temperature zone.
- a salt bath A flows around that section of the tubes (the temperature zone A) in which the oxidative conversion of the propene (in single pass) until a conversion U A in the range required according to the invention takes place and a salt bath B flows around the section of the tubes (the temperature zone B) in which the oxidative terminal reaction of the propene (in a single pass) until a conversion value U B of at least 90 mol% is reached (if necessary, the temperature zones A, B connect further temperature zones, which are kept at individual temperatures).
- a propene partial oxidation according to the invention to acrolein does not include any such further temperature zones. That is, the salt bath B expediently flows around the section of the tubes in which the oxidative terminal reaction of the propene (in single pass) to a conversion value> 90 mol%, or> 92 mol% or> 94 mol% or more ,
- the two salt baths A, B can be conducted in cocurrent or in countercurrent through the space surrounding the reaction tubes relative to the flow direction of the reaction gas mixture flowing through the reaction tubes.
- a direct flow and in the temperature zone B, a countercurrent are applied in the temperature zone A, a direct flow and in the temperature zone B, a countercurrent (or vice versa) are applied.
- the flow rate of the fluid heat carrier is advantageously dimensioned in accordance with the teaching of the aforementioned documents such that, in the case of a further increase in this flow rate, essentially no increase in the heat transfer from the inside of the reaction tube to the heat transfer medium is effected.
- typical heat transfer coefficients from the material envelope of the reaction space (for example from the outer wall of the reaction tube) to the fluid heat carrier (for example to the molten salt) are advantageously> 700 W / m 2 K in the process according to the invention advantageously> 1000 W / m 2 K, very particularly advantageously> 1500 or> 2000 W / m 2 K, but generally ⁇ 3000 W / m 2 K.
- a reaction gas input mixture of the fixed bed catalyst bed is fed to the temperature of the temperature zone A preheated.
- the contact tubes are made of ferritic steel and typically have a wall thickness of 1 to 3 mm. Their inner diameter is usually 20 to 30 mm, often 21 to 26 mm. Their length is suitably 2 to 4 m, preferably 2.5 to 3.5 m.
- the fixed bed catalyst bed occupies at least 60%, or at least 75%, or at least 90% of the length of the zone. The remaining, if any, remaining length is optionally occupied by an inert coating.
- the number of catalyst tubes accommodated in the tube bundle container is expediently at least 5,000, preferably at least 10,000. Frequently, the number of catalyst tubes accommodated in the reaction container is 15,000 to 30,000 or up to 40,000.
- Tube bundle reactors with a number of contact tubes above 50,000 tend to be the exception
- the contact tubes are normally distributed homogeneously (preferably 6 equidistant neighboring tubes per contact tube), wherein the distribution is expediently chosen such that the distance between the central inner axes of closest contact tubes (the so-called contact tube pitch) is 35 to 45 mm (cf., for example, EP-B 468290).
- fluid temperature control media are also suitable as heat exchangers for the two-zone process.
- melts of salts such as potassium nitrate, potassium nitrite, sodium nitrite and / or sodium nitrate, or of low-melting metals, such as sodium, mercury and alloys of various metals, is particularly favorable.
- the flow rate of the heat exchange medium within the two required heat exchange medium circuits is such that the temperature of the heat exchange medium from the point of entry into the temperature zone to the exit point from the temperature zone (due to the exothermicity of the reaction ) rises by 0 to 15 ° C. That is, the aforesaid ⁇ may be 1 to 10 ° C or 2 to 8 ° C or 3 to 6 ° C in the present invention. According to the invention, it is low.
- the inlet temperatures of the heat exchange means in the temperature zones A, B of the Zweizonenrohrbündelreaktoren are in a propene partial oxidation to acrolein according to the invention to be chosen so that they correspond to the required for this reaction in this document for the temperature zones A, B temperatures and temperature differences ⁇ ⁇ (or this require). In the long-term operation according to the invention they are to be changed according to the invention. It should be pointed out again at this point that for carrying out a propene partial oxidation according to the invention to acrolein, in particular also in the
- DE-AS 2201528 described two-zone tube bundle reactor type can be used, which includes the ability to dissipate a partial amount of the hot heat exchange agent of the temperature zone B to the temperature zone A to possibly cause warming of a cold reaction gas inlet mixture or a cold recycle gas.
- the tube bundle characteristic can be designed within an individual temperature zone as described in EP-A 382098.
- a second two-zone process stage for the heterogeneously catalyzed partial gas phase oxidation of the acrolein to the acrylic acid will be used in the process stage of the invention and operated as described in WO 2007/082827.
- the effective temperature of the fixed catalyst bed in a reaction tube of a tube reactor can have a centered through the reaction tube extending from top to bottom thermal sleeve in which determined by means guided in the thermowell thermocouples, the effective fixed catalyst bed temperature (the reaction temperature) over the entire reaction tube length can be.
- the reaction temperature the reaction temperature
- any reaction tube located in a tube bundle reactor and charged with the fixed catalyst bed could be equipped as described above.
- thermoreaction tubes for example, page 56 of WO 2007/082827, EP-A 873783, EP-A 1270065 and US 7,534,339 B2).
- thermo tubes still have to accommodate the thermal sleeve in addition to the fixed catalyst bed, they would have an identical heat exchange surface, but a smaller free cross-section, which can be absorbed by the fixed catalyst bed, than a mere "reaction tube.” This is taken into account by using them
- the reaction tube and the thermal tube have the same fixed catalyst bed structure over their tube length for the same tube length
- make sure that the profile of the pressure loss profile that is created in the flow of reaction tube or thermal tube with reaction gas mixture over the tube length is uniform in both tube types the filling of the tubes with the moldings and / or the concomitant use of crushed (split Moldings) can be influenced in a corresponding manner (cf., for example, EP-A 873783 and US 7,534,339 B2).
- thermotube is so representative of many reaction tubes to map the course of the effective fixed catalyst bed temperature in the reaction tube.
- the propene content in the product gas mixture of this partial oxidation is 10000 ppm by weight, preferably 6000 ppm by weight, and particularly preferably 4000 to
- the propene content in the reaction gas input mixture can be used in the process of the invention, e.g. at values of 2 to 25 vol.%, often 3 to 20 vol.%, or 4 to 15 vol.%, often 5 to 12 vol.% and 6 to 8 vol based on the total volume).
- Particularly suitable propene sources are "polymer grade propene” and "chemical grade propene” according to WO 2004/009525.
- the propene-> acrolein process according to the invention is frequently used for a propene: oxygen: inert gases (including water vapor) volume ratio in the starting reaction gas mixture of 1: (1.0 to 3.0) :( 5 to 25), preferably 1 : (1, 7 to 2,3): (10 to 15).
- the inert gas will consist of at least 20% of its volume of molecular nitrogen.
- molecular nitrogen can also be> 30 vol .-%, or> 40 vol .-%, or> 50 vol .-%, or> 60 vol .-%, or> 70 vol .-%, or > 80% by volume, or> 90% by volume, or> 95% by volume of molecular nitrogen (possible inert gases are, in addition to molecular nitrogen, for example gases such as propane, ethane, methane, pentane, butane, CO 2, CO, water vapor and / or noble gases).
- gases such as propane, ethane, methane, pentane, butane, CO 2, CO, water vapor and / or noble gases.
- the inert diluent gas can also consist of up to 50 mol%, or up to 75 mol% and more of propane (for example, all of the documents WO 2007/13504 are used for the process according to the invention , WO 2007/060036, WO 2007/042457, WO 2006/002713, WO 2006/002708 and WO 2006/002703 for the propene partial oxidation to acrolein disclosed reaction gas input mixtures into consideration).
- Part of the diluent gas can also be cycle gas, as it remains in the two-stage propene partial oxidation to acrylic acid after the separation of the acrylic acid from the product gas mixture.
- composition ranges also apply to such two-stage processes, both in cases of secondary gas supply (e.g., supply of air and / or inert gas between first and second reaction stages) and in cases where no secondary gas is supplied.
- Reaction gas input mixtures suitable according to the invention are e.g. those that are out
- reaction gas inlet mixture Particularly in the case of a two-stage heterogeneously catalyzed gas phase partial oxidation of propene to acrylic acid, in which the process according to the invention forms only the first reaction stage, the following properties of the reaction gas inlet mixture are also suitable.
- reaction gas input mixture > 0.01, or> 0.1, or> 0.5, or
- the reaction gas input mixture when air is used as the source of the molecular oxygen in the process according to the invention, the reaction gas input mixture will contain molecular nitrogen as further inert diluent gas.
- the reaction gas input mixture in the process according to the invention can be> 1% by volume, or> 5% by volume, or> 10% by volume, or> 20% by volume, or> 30% by volume, or> 40% by volume .-% of molecular nitrogen.
- the content of the reaction gas input mixture of molecular nitrogen will be values of ⁇ 80 mol%, or ⁇ 70 mol%, or ⁇ 60 mol%.
- the reaction gas input mixture (as already mentioned) contain propane as an inert diluent gas.
- This propane content of the reaction gas input mixture can be up to 70% by volume (eg 5 to 70% by volume), or up to 60% by volume, or up to 50% by volume, or up to 40% by volume, or to 30 vol.%, or to 20 vol.%, or up to 10 vol.%.
- this propane content is> 0.5 or> 1% by volume. But it can also be at values of> 0.01 vol .-%, or
- reaction gas input mixture contains ⁇ 10% by volume, in many cases ⁇ 5% by volume of propane.
- this propane can be deliberately added as an inert diluent gas to be fed separately to the reaction gas feed mixture.
- the propane can also be part of the reaction gas input mixture that acts as a propene source for the same, a partial dehydrogenation or O-xidehydrtechnik of propane (usually these are done heterogeneously catalyzed).
- the propene contained in the reaction gas input mixture can be fed to the reaction gas inlet mixture at least partially accompanied by unreacted propane from a partial dehydrogenation (for example homogeneously and / or heterogeneously catalyzed, in the presence and / or exclusion of molecular oxygen).
- the process according to the invention also encompasses those embodiments in which the reaction gas input mixture is> 0 to 35% by volume, frequently 1 to 25% by volume, or 5 to 15% by volume, or 10% by volume H 2 0 contains.
- Typical reaction gas input mixtures are e.g. those that contain:
- molecular oxygen being such that the molar ratio of molecular oxygen to propene contained is 1 to 3, and the remainder being up to 100 vol. % Total molecular nitrogen.
- Inventive reaction gas input mixtures may also contain
- reaction gas input mixtures according to the invention may also contain up to 20% by volume of H. That is, reaction gas input mixtures of the process according to the invention may also contain:
- the process according to the invention is also favorable if the starting reaction gas mixture contains 0.1 to 30% by volume of CO.sub.2.
- a second reaction stage of the heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid can be added to the process according to the invention.
- part of the reaction gas input mixture can be so-called recycle gas.
- This is gas, e.g. in a two-stage partial oxidation of propene to acrylic acid after product separation (acrylic acid separation) from the product mixture of the second stage remains and is usually recycled in a series connection of the two stages partly as an inert diluent gas for charging the first and / or second stage.
- Typical circulating gas contents are:
- the removal of acrylic acid may be e.g. as in EP-A 982 287, EP-A 982 289, DE-A 199 24 532, DE-A 101 15 277, DE-A 196 06 877, DE-A 197 40 252, the
- the present patent application comprises in particular the following embodiments according to the invention: Process for the long-term operation of a heterogeneously catalyzed partial gas-phase oxidation of propene to acrolein, in which a propylene, molecular oxygen and at least one inert gas-containing reaction gas input mixture containing the molecular acid erstoff and the propene in a molar ratio O2: C3H6> 1, with the proviso by a fixed catalyst bed whose active material is at least one Mo, Fe and Bi containing multimetal oxide, that the fixed catalyst bed in two spatially sequential temperature zones A, B is arranged, both the temperature T A of the temperature zone A, and the temperature T B of the temperature zone B is a temperature in the temperature range from 280 to 420 ° C, the reaction gas input mixture, the temperature zones A, B in the time sequence "A first and" then flows through B, wherein the temperature zone A extends to a conversion U A of propene contained in the reaction gas input mixture in the range
- Method characterized in that after fresh feed of the fixed catalyst bed , the difference between the maximum reaction temperature in the temperature zone A, T maxA , and the maximum reaction temperature in the temperature zone B, T maxB , formed as T maxA - T maxB ,> 0 ° C and ⁇ 80 ° C.
- T maxA - T maxB is > 0 ° C and ⁇ 70 ° C.
- T maxA - T maxB is > 2 ° C and ⁇ 40 ° C.
- T maxA - T maxB is > 5 ° C and ⁇ 25 ° C.
- T maxA - T maxB is > 10 ° C and ⁇ 25 ° C.
- T B and T A is increased.
- T A over the entire operating time in the range of 300 to 400 ° C. 30.
- T A is over the entire operating time in the range of 310 to 390 ° C. 31.
- Process according to one of embodiments 1 to 40 characterized in that the loading of the fixed catalyst bed with propene is> 150 Nl / lh.
- Process according to one of the embodiments 1 to 40 characterized in that the loading of the fixed catalyst bed with propene is> 160 Nl / lh.
- Process according to one of embodiments 1 to 40 characterized in that the loading of the fixed catalyst bed with propene is> 170 Nl / l-h. Process according to any one of embodiments 1 to 40, characterized in that the loading of the fixed catalyst bed with propene is> 180 Nl / l-h.
- Process characterized in that the long-term operation is interrupted and the fixed catalyst bed is regenerated by passing a hot gas mixture of molecular oxygen and inert gas through the fixed catalyst bed and subsequently continuing the long-term operation.
- Method according to one of the embodiments 1 to 49 characterized in that the reaction gas input mixture contains 2 to 25 vol .-% propene.
- Method according to one of the embodiments 1 to 49 characterized in that the reaction gas input mixture contains 4 to 15 vol .-% propene.
- Method according to one of the embodiments 1 to 49 characterized in that the reaction gas input mixture contains 5 to 12 vol .-% propene.
- Method according to one of the embodiments 1 to 52 characterized in that the at least one inert gas consists of at least 40% of its volume of molecular nitrogen. Method according to one of embodiments 1 to 52, characterized in that the at least one inert gas consists of up to 50% of its volume of n-propane. 55.
- reaction gas input mixture contains the molecular oxygen and the propene in a molar ratio O2: C3H6 ⁇ 3.
- the reaction gas input mixture contains the molecular oxygen and the propene in a molar ratio O2: C3H6> 1, 2 and ⁇ 3.
- the active material of the fixed catalyst bed is at least one of the elements Mo, Fe and Bi, and additionally at least one of the two elements Ni and Co containing multimetal oxide.
- the method according to embodiment 58 characterized in that of the five elements Mo, Fe, Bi, Ni and Co, based on their molar mass contained in the active composition, the element Mo, the largest molar fraction in mol% and based on the total molar amount G is omitted.
- the active composition at least one Multimetalloxiditmasse of the general formula I.
- 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,
- n a number determined by the valency and frequency of the elements other than oxygen in I.
- Method according to one of the embodiments 60 to 61 characterized in that the stoichiometric coefficient d is 0.02 to 2. 64.
- Method according to one of the embodiments 1 to 63 characterized in that AT BA increases by at least 10 ° C with increasing operating time.
- Method according to one of the embodiments 1 to 69 characterized in that the maximum reaction temperature in the reaction zone A, T maxA ,> 370 ° C.
- thermoreaction tube V2A steel, 33.7 mm outer diameter, 2 mm wall thickness, 29.7 mm inner diameter, length: 350 cm, and in the center of a thermal tube centered from top to bottom thermal protection tube (thermowell) for receiving a thermocouple, with the the total tube length, the reaction temperature (the effective catalyst fixed bed temperature) was loaded from top to bottom as follows:
- Section 1 50 cm in length
- Section 2 140 cm in length
- thermoreaction tube is the behavior of a bare reaction tube of the corresponding material and with identical tube length, the inner diameter of 2 mm wall thickness is 26 mm and which is charged in a similar manner as the thermal reaction tube, it is seen that in the case of the thermal reaction tube in the respective Section respectively split weight fraction of unsupported catalyst rings in the bare reaction tube, ie in ring form in the feed enters.
- thermoreaction tube From top to bottom, the first 175 cm of the thermoreaction tube were thermostated by means of a 175 cm to the reaction mixture in countercurrent pumped salt bath A, which was supplied at the temperature T A.
- the second 175 were thermostated by means of a correspondingly countercurrently pumped salt bath B, which was supplied at the temperature T B.
- the respective salt bath temperature was essentially constant over the respective temperature zone.
- the two salt baths A, B each consisted of 53% by weight of potassium nitrate, 40% by weight of sodium nitrite and 7% by weight of sodium nitrate.
- the flow of the reaction tube was carried out substantially vertically to the flow direction of the reaction gas.
- the flow rate of both salt melts was such that a further increase would have substantially no effect on improving the heat transfer from the inside of the thermal tube to the salt bath (cf EP-A1547994).
- the thermal tube fed as described above was charged in stationary operation with a reaction gas input mixture which had the following contents and was produced from air (as an oxygen source), chemical grade propene and cycle gas:
- the loading of the fixed catalyst bed with propene contained in the reaction gas input mixture was always in the interval 185 ⁇ 10 Nl / l-h during the stationary operating phases.
- the pressure at the entrance of the thermal reaction tube was substantially 2.0 atm.
- a stationary operating phase extended over 24 operating days. At the end of a stationary operating phase, the partial oxidation process was interrupted in each case and the fixed catalyst bed was regenerated as described in WO 2004/085369.
- the propene load of the fixed catalyst bed was lowered to 100 Nl / lh for recommissioning and for initial commissioning, and T A , T B were limited under the proviso ⁇ ⁇ > 0 such that the propene conversion based on a single pass of the reaction gas mixture through the thermal tube was 94 mol. % was limited.
- the operating conditions of steady-state operation were controlled such that T maxA was always> T maxB and always smaller than T maxA in the subsequent stationary operation.
- Table 1 shows the values for T maxA resulting from the respective propene loading PL of the fixed catalyst bed as a function of T A and T B and the overall selectivity S AC + AA of the formation of acrolein and acrylic acid (the selectivity of the overall target product formation referred to in one-time passage of the reaction gas mixture through the thermal tube (thermal reaction tube) reacted propene). Furthermore, Table 1 shows the values for ⁇ ⁇ and for ⁇ ⁇ ⁇ . All information relates to the 24th day of operation of the respective stationary operating phase.
- the fixed catalyst bed was replaced with a fresh fixed catalyst bed.
- the resulting propene conversion based on a single pass of the reaction gas mixture through the thermal tube was 95.1 ⁇ 0.3 mol%.
- the propene conversion in the temperature zone A was in the range of 60 to 72 mol% during the entire operating phases.
- the resulting propene conversion based on a single pass of the reaction gas mixture through the thermal tube was only 91.8 mol%.
- jmaxB was j n ai
- the difference TmaxB - TmaxA was 15 ° C and decreased to 1.5 ° C during long-term operation.
- the fixed catalyst bed was replaced with a fresh fixed catalyst bed.
- the resulting propene conversion based on a single pass of the reaction gas mixture through the thermal tube was 94.8 ⁇ 0.3 mol%.
- the propene conversion in the temperature zone A was in the range 65 to 77 mol% during the entire operating phase.
Abstract
Description
Claims
Priority Applications (6)
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BR112013009049-9A BR112013009049B1 (pt) | 2010-10-15 | 2011-10-13 | processo para operação a longo prazo de uma oxidação de fase de gás parcial catalisada heterogeneamente de propeno a acroleína |
CN201180060736.2A CN103270013B (zh) | 2010-10-15 | 2011-10-13 | 丙烯非均相催化部分气相氧化为丙烯醛的长期操作方法 |
EP11776727.7A EP2627622B1 (de) | 2010-10-15 | 2011-10-13 | Verfahren zum langzeitbetrieb einer heterogen katalysierten partiellen gasphasenoxidation von propen zu acrolein |
KR1020137012394A KR101856270B1 (ko) | 2010-10-15 | 2011-10-13 | 아크롤레인이 수득되는 프로펜의 불균질 촉매된 부분 기체 상 산화의 장기간 작업을 위한 방법 |
JP2013533214A JP5889313B2 (ja) | 2010-10-15 | 2011-10-13 | プロペンからアクロレインへの不均一系接触部分気相酸化の長期運転法 |
RU2013121973/04A RU2568636C2 (ru) | 2010-10-15 | 2011-10-13 | Способ продолжительного проведения гетерогенно-катализируемого частичного газофазного окисления пропилена в акролеин |
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DE102010048405A DE102010048405A1 (de) | 2010-10-15 | 2010-10-15 | Verfahren zum Langzeitbetrieb einer heterogen katalysierten partiellen Gasphasenoxidation von Proben zu Acrolein |
US61/393,370 | 2010-10-15 |
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KR (1) | KR101856270B1 (de) |
CN (1) | CN103270013B (de) |
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Citations (86)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3147084A (en) | 1962-03-08 | 1964-09-01 | Shell Oil Co | Tubular catalytic reactor with cooler |
DE2201528B1 (de) | 1972-01-13 | 1972-11-02 | Deggendorfer Werft Eisenbau | Reaktionsapparat zur durchfuehrung exo- und endothermer katalytischer prozesse mit radialstroemung des waermetauschmittels |
DE2903218A1 (de) | 1979-01-27 | 1980-08-07 | Basf Ag | Verfahren zur herstellung von papier mit hoher trockenfestigkeit und niedriger nassfestigkeit |
EP0015565A1 (de) | 1979-03-12 | 1980-09-17 | BASF Aktiengesellschaft | Verfahren zur Herstellung von 3 bis 4 C-Atome enthaltenden alpha,beta-olefinisch ungesättigten Aldehyden |
DE2909671A1 (de) | 1979-03-12 | 1980-10-02 | Basf Ag | Verfahren zur herstellung von schalenkatalysatoren |
DE2513405C2 (de) | 1975-03-26 | 1982-10-21 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von Acrylsäure durch Oxidation von Propylen mit Sauerstoff enthaltenden Gasen in zwei getrennten Katalysatorstufen, die in einem Röhrenreaktor hintereinander angeordnet sind |
DE3300044A1 (de) | 1982-01-06 | 1983-07-14 | Nippon Shokubai Kagaku Kogyo Co. Ltd., Osaka | Katalysator fuer die oxidation von propylen |
EP0279374A1 (de) | 1987-02-17 | 1988-08-24 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Katalysator zur Oxydation von Olefin oder tertiärem Alkohol und Verfahren zu seiner Herstellung |
DE3338380C2 (de) | 1982-10-22 | 1988-10-27 | Nippon Shokubai Kagaku Kogyo Co. Ltd., Osaka, Jp | |
EP0293224A1 (de) | 1987-05-27 | 1988-11-30 | Nippon Shokubai Co., Ltd. | Verfahren zur Herstellung von Acrylsäure |
EP0293859A1 (de) | 1987-06-05 | 1988-12-07 | Nippon Shokubai Co., Ltd. | Katalysator für die Oxydierung von Acrolein und Verfahren zu seiner Herstellung |
EP0382098A2 (de) | 1989-02-10 | 1990-08-16 | Mitsubishi Jukogyo Kabushiki Kaisha | Mehrrohrtypwärmetauscher |
EP0383224A2 (de) | 1989-02-17 | 1990-08-22 | Jgc Corporation | Rohrbündelapparat mit einer Zwischenrohrplatte |
JPH03294239A (ja) | 1990-04-11 | 1991-12-25 | Nippon Shokubai Co Ltd | アクロレインおよびアクリル酸の製造方法 |
DE4023239A1 (de) | 1990-07-21 | 1992-01-23 | Basf Ag | Verfahren zur katalytischen gasphasenoxidation von propen oder iso-buten zu acrolein oder methacrolein |
DE2830765C2 (de) | 1977-07-13 | 1992-06-25 | Nippon Shokubai Kagaku Kogyo Co., Ltd., Osaka, Jp | |
EP0575897A1 (de) | 1992-06-25 | 1993-12-29 | BASF Aktiengesellschaft | Multimetalloxidmassen |
EP0614872A1 (de) | 1993-03-12 | 1994-09-14 | Nippon Shokubai Co., Ltd. | Verfahren zur Entfernung von festen organischen Stoffen |
EP0700714A1 (de) | 1994-09-08 | 1996-03-13 | Basf Aktiengesellschaft | Verfahren zu katalytischen Gasphasenoxidation von Propen zu Acrolein |
EP0700893A1 (de) | 1994-09-08 | 1996-03-13 | Basf Aktiengesellschaft | Verfahren zur katalytischen Gasphasenoxidation von Acrolein zu Acrylsäure |
EP0714700A2 (de) | 1994-11-29 | 1996-06-05 | Basf Aktiengesellschaft | Verfahren zur Herstellung eines Katalysators, bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Oxidmasse |
DE19606877A1 (de) | 1996-02-23 | 1997-08-28 | Basf Ag | Verfahren zur Reinigung von Acrylsäure und Methacrylsäure |
EP0807465A1 (de) | 1996-05-14 | 1997-11-19 | Nippon Kayaku Co., Ltd. | Katalysator und Verfahren zur Herstellung ungesättigter Aldehyde und Säure |
DE19627847A1 (de) | 1996-07-10 | 1998-01-15 | Basf Ag | Verfahren zur Herstellung von Acrylsäure |
WO1998024746A1 (fr) | 1996-12-03 | 1998-06-11 | Nippon Kayaku Kabushiki Kaisha | Procede de preparation d'acroleine et d'acide acrylique |
EP0873783A1 (de) | 1997-04-23 | 1998-10-28 | Basf Aktiengesellschaft | Vorrichtung und Verfahren zur Temperaturmessung in Rohrreaktoren |
DE19740252A1 (de) | 1997-09-12 | 1999-03-18 | Basf Ag | Verfahren zur Herstellung von Acrylsäure und Methacrylsäure |
DE19746210A1 (de) | 1997-10-21 | 1999-04-22 | Basf Ag | Verfahren der heterogen katalysierten Gasphasenoxidation von Propan zu Acrolein und/oder Acrylsäure |
EP0982288A2 (de) | 1998-08-26 | 2000-03-01 | Basf Aktiengesellschaft | Verfahren zur kontinuierlichen Gewinnung von (Meth)acrylsäure |
EP0982287A1 (de) | 1998-08-26 | 2000-03-01 | Basf Aktiengesellschaft | Verfahren zur kontinuierlichen Gewinnung von (Meth)acrylsäure |
EP0982289A2 (de) | 1998-08-26 | 2000-03-01 | Basf Aktiengesellschaft | Verfahren zur kontinuerlichen Gewinnung von (Meth)acrylsäure |
DE19855913A1 (de) | 1998-12-03 | 2000-06-08 | Basf Ag | Multimetalloxidmasse zur gasphasenkatalytischen Oxidation organischer Verbindungen |
DE19902562A1 (de) | 1999-01-22 | 2000-07-27 | Basf Ag | Verfahren zur Herstellung von Acrolein durch heterogen katalysierte Gasphasen-Partialoxidation von Propen |
DE19910506A1 (de) | 1999-03-10 | 2000-09-14 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrolein |
DE19910508A1 (de) | 1999-03-10 | 2000-09-21 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Acrolein zu Acrylsäure |
DE19924532A1 (de) | 1999-05-28 | 2000-11-30 | Basf Ag | Verfahren der fraktionierten Kondensation eines Acrylsäure enthaltenden Produktgasgemisches einer heterogen katalysierten Gasphasen-Partialoxidation von C3-Vorläufern der Acrylsäure mit molekularem Sauerstoff |
DE19955176A1 (de) | 1999-11-16 | 2001-01-04 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrylsäure |
DE19948248A1 (de) | 1999-10-07 | 2001-04-12 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrylsäure |
DE19948523A1 (de) | 1999-10-08 | 2001-04-12 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrylsäure |
DE19948241A1 (de) | 1999-10-07 | 2001-04-12 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrolein |
DE19955168A1 (de) | 1999-11-16 | 2001-05-17 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrylsäure |
EP1106598A2 (de) | 1999-11-23 | 2001-06-13 | Rohm And Haas Company | Verfahren mit hoher Kohlenwasserstoffraumgeschwindigkeit zum Herstellen von ungesättigten Aldehyden und Karbonsäuren |
EP1159244A1 (de) | 1999-03-10 | 2001-12-05 | Basf Aktiengesellschaft | Verfahren der katalytischen gasphasenoxidation von propen zu acrolein |
EP1180508A1 (de) | 2000-08-07 | 2002-02-20 | Nippon Shokubai Co., Ltd. | Verfahren zum Anfahren eines Reaktors |
DE10046957A1 (de) | 2000-09-21 | 2002-04-11 | Basf Ag | Verfahren zur Herstellung eines Multimetalloxid-Katalysators, Verfahren zur Herstellung ungesättigter Aldehyde und/oder Carbonsäuren und Bandcalziniervorrichtung |
DE10115277A1 (de) | 2001-03-28 | 2002-06-13 | Basf Ag | Verfahren zur kontinuierlichen Gewinnung von(Meth)acrylsäure |
DE10063162A1 (de) | 2000-12-18 | 2002-06-20 | Basf Ag | Verfahren zur Herstellung einer Mo, Bi, Fe sowie Ni und/oder Co enthaltenden Multimetalloxidativmasse |
DE10101695A1 (de) | 2001-01-15 | 2002-07-18 | Basf Ag | Verfahren zur heterogen katalysierten Gasphasenpartialoxidation von Vorläuferverbindungen der (Meth)acrylsäure |
EP1270065A1 (de) | 2001-06-26 | 2003-01-02 | Nippon Shokubai Co., Ltd. | Vorrichtung zur Druck- und Temperaturmessungen in Rohrreaktoren |
WO2004008362A1 (ja) | 2002-07-15 | 2004-01-22 | Sony Corporation | ビデオプログラム制作システム、構成表提供装置、端末装置、端末処理方法、プログラム、記録媒体 |
WO2004007064A1 (en) | 2002-07-10 | 2004-01-22 | Lg Chem, Ltd. | Catalytic oxidation reactor with enhanced heat exchanging system |
WO2004009525A1 (de) | 2002-07-18 | 2004-01-29 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten gasphasen-partialoxidation wenigstens einer organischen verbindung |
WO2004085362A1 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von propen zu acrolein |
WO2004085367A1 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von propen zu acrylsäure |
WO2004085363A1 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von propen zu acrolein |
WO2004085369A1 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von propen zu acrylsäure |
WO2004085365A2 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von acrolein zu acrylsäure |
WO2004085370A1 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von acrolein zu acrylsäure |
WO2005009608A1 (de) | 2003-07-24 | 2005-02-03 | Basf Aktiengesellschaft | Reaktor für partialoxidationen mit thermoblechplattenmodulen |
DE102004025445A1 (de) | 2004-05-19 | 2005-02-10 | Basf Ag | Verfahren zum Langzeitbetrieb einer heterogen katalysierten Gasphasenpartialoxidation wenigstens einer organischen Verbindung |
WO2005042459A1 (de) | 2003-10-31 | 2005-05-12 | Basf Aktiengesellschaft | Verfahren zum langzeitbetrieb einer heterogen katalysierten gasphasenpartialoxidation von propen zu acrylsäure |
DE10350812A1 (de) | 2003-10-29 | 2005-06-02 | Basf Ag | Verfahren zum Langzeitbetrieb einer heterogen katalysierten Gasphasenpartialoxidation von Propen zu Acrolein |
DE10351269A1 (de) | 2003-10-31 | 2005-06-02 | Basf Ag | Verfahren zum Langzeitbetrieb einer heterogen katalysierten Gasphasenpartialoxidation von Propen zu Acrylsäure |
EP1547994A1 (de) | 2002-08-23 | 2005-06-29 | Mitsubishi Chemical Corporation | Verfahren zur katalytischen dampfphasenoxidation unter einsatz eines rohrb ndelreaktors |
EP1547944A1 (de) | 2003-12-17 | 2005-06-29 | MARCHETTI, Antonio | Antriebssystem für Förderbänder |
DE102004008573A1 (de) | 2004-02-19 | 2005-09-08 | Stockhausen Gmbh | Ein Verfahren zur Entfernung kohlenstoffhaltiger Rückstände in einem Reaktor |
EP1577001A1 (de) | 2002-12-26 | 2005-09-21 | Mitsubishi Chemical Corporation | Plattenofen für katalytische reaktionen |
WO2006002703A1 (de) | 2004-07-01 | 2006-01-12 | Basf Aktiengesellschaft | Verfahren zur herstellung von acrylsäure durch heterogen katalysierte partielle gasphasen oxidation von propylen |
WO2006002713A1 (de) | 2004-07-01 | 2006-01-12 | Basf Aktiengesellschaft | Verfahren zur herstellung von acrolein, oder acrylsäure oder deren gemisch aus propan |
WO2006002708A1 (de) | 2004-07-01 | 2006-01-12 | Basf Aktiengesellschaft | Verfahren zur herstellung von acrolein oder acrylsäure oder deren gemisch durch heterogen katalysierte partielle gasphasenoxidation von propylen |
WO2007013504A1 (ja) | 2005-07-29 | 2007-02-01 | Rohm Co., Ltd. | フラットパネルディスプレイ |
WO2007017431A1 (de) | 2005-08-05 | 2007-02-15 | Basf Aktiengesellschaft | Verfahren zur herstellung von katalysatorformkörpern, deren aktivmasse ein multielementoxid ist |
WO2007042457A1 (de) | 2005-10-14 | 2007-04-19 | Basf Se | Verfahren zur herstellung von acrolein, oder acrylsäure oder deren gemisch aus propan |
WO2007060036A1 (de) | 2005-11-24 | 2007-05-31 | Basf Se | Verfahren zur herstellung von acrolein, oder acrylsäure, oder deren gemisch aus propan |
WO2007082827A1 (de) | 2006-01-18 | 2007-07-26 | Basf Se | Verfahren zum langzeitbetrieb einer heterogen katalysierten partiellen gasphasenoxidation einer organischen ausgangsverbindung |
DE102007005606A1 (de) | 2007-01-31 | 2008-04-03 | Basf Ag | Verfahren zur Herstellung von Katalysatorformkörpern, deren Aktivmasse ein Multielementoxid ist |
WO2008087115A2 (de) | 2007-01-16 | 2008-07-24 | Basf Se | Verfahren zur herstellung einer das element eisen in oxidischer form enthaltenden multielementoxidmasse |
WO2008087116A1 (de) | 2007-01-19 | 2008-07-24 | Basf Se | Verfahren zur herstellung von katalysatorformkörpern, deren aktivmasse ein multielementoxid ist |
DE102007004961A1 (de) | 2007-01-26 | 2008-07-31 | Basf Se | Verfahren zur Herstellung von Katalysatorformkörpern, deren Aktivmasse ein Multielementoxid ist |
DE102008040093A1 (de) | 2008-07-02 | 2008-12-18 | Basf Se | Verfahren zur Herstellung eines ringähnlichen oxidischen Formkörpers |
DE102008040094A1 (de) | 2008-07-02 | 2009-01-29 | Basf Se | Verfahren zur Herstellung eines oxidischen geometrischen Formkörpers |
DE102008042060A1 (de) | 2008-09-12 | 2009-06-18 | Basf Se | Verfahren zur Herstellung von geometrischen Katalysatorformkörpern |
DE102008042064A1 (de) | 2008-09-12 | 2010-03-18 | Basf Se | Verfahren zur Herstellung von geometrischen Katalysatorformkörpern |
DE102008042061A1 (de) | 2008-09-12 | 2010-03-18 | Basf Se | Verfahren zur Herstellung von geometrischen Katalysatorformkörpern |
DE102008054586A1 (de) | 2008-12-12 | 2010-06-17 | Basf Se | Verfahren zur kontinuierlichen Herstellung von geometrischen Katalysatorformkörpern K |
DE102009047291A1 (de) | 2009-11-30 | 2010-09-23 | Basf Se | Verfahren zur Herstellung von (Meth)acrolein durch heterogen katalysierte Gasphasen-Partialoxidation |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1086506A (en) * | 1964-10-26 | 1967-10-11 | Ici Ltd | Catalytic oxidation of propene |
JPH0293224A (ja) | 1988-09-30 | 1990-04-04 | Matsushita Electric Ind Co Ltd | 除湿機 |
DE10235847A1 (de) | 2002-08-05 | 2003-08-28 | Basf Ag | Verfahren zur Herstellung von Acrylsäure |
DE10313209A1 (de) | 2003-03-25 | 2004-03-04 | Basf Ag | Verfahren der heterogen katalysierten partiellen Gasphasenoxidation von Propen zu Acrylsäure |
DE10313212A1 (de) * | 2003-03-25 | 2004-10-07 | Basf Ag | Verfahren der heterogen katalysierten partiellen Gasphasenoxidation von Propen zu Acrolein |
KR100553825B1 (ko) * | 2003-09-01 | 2006-02-21 | 주식회사 엘지화학 | 고정층 촉매 부분 산화 반응기에서 개선된 제열 시스템을통한 불포화알데히드 및 불포화산의 제조 방법 |
WO2005047224A1 (de) * | 2003-10-29 | 2005-05-26 | Basf Aktiengesellschaft | Verfahren zum langzeitbetrieb einer heterogen katalysierten gasphasenpartialoxidation von propen zu acrolein |
JP2005314314A (ja) * | 2004-04-30 | 2005-11-10 | Mitsubishi Chemicals Corp | (メタ)アクリル酸または(メタ)アクロレインの製造方法 |
DE102006058129A1 (de) * | 2006-12-09 | 2008-06-19 | Evonik Degussa Gmbh | Keramisches Formteil zur Steuerung der Edukt-Dichten |
DE102010048405A1 (de) | 2010-10-15 | 2011-05-19 | Basf Se | Verfahren zum Langzeitbetrieb einer heterogen katalysierten partiellen Gasphasenoxidation von Proben zu Acrolein |
-
2010
- 2010-10-15 DE DE102010048405A patent/DE102010048405A1/de not_active Withdrawn
-
2011
- 2011-10-12 US US13/271,448 patent/US8618336B2/en active Active
- 2011-10-13 RU RU2013121973/04A patent/RU2568636C2/ru not_active IP Right Cessation
- 2011-10-13 WO PCT/EP2011/067887 patent/WO2012049246A2/de active Application Filing
- 2011-10-13 JP JP2013533214A patent/JP5889313B2/ja active Active
- 2011-10-13 KR KR1020137012394A patent/KR101856270B1/ko active IP Right Grant
- 2011-10-13 BR BR112013009049-9A patent/BR112013009049B1/pt active IP Right Grant
- 2011-10-13 CN CN201180060736.2A patent/CN103270013B/zh active Active
- 2011-10-13 EP EP11776727.7A patent/EP2627622B1/de not_active Not-in-force
Patent Citations (93)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3147084A (en) | 1962-03-08 | 1964-09-01 | Shell Oil Co | Tubular catalytic reactor with cooler |
DE2201528B1 (de) | 1972-01-13 | 1972-11-02 | Deggendorfer Werft Eisenbau | Reaktionsapparat zur durchfuehrung exo- und endothermer katalytischer prozesse mit radialstroemung des waermetauschmittels |
DE2513405C2 (de) | 1975-03-26 | 1982-10-21 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von Acrylsäure durch Oxidation von Propylen mit Sauerstoff enthaltenden Gasen in zwei getrennten Katalysatorstufen, die in einem Röhrenreaktor hintereinander angeordnet sind |
DE2830765C2 (de) | 1977-07-13 | 1992-06-25 | Nippon Shokubai Kagaku Kogyo Co., Ltd., Osaka, Jp | |
DE2903218A1 (de) | 1979-01-27 | 1980-08-07 | Basf Ag | Verfahren zur herstellung von papier mit hoher trockenfestigkeit und niedriger nassfestigkeit |
EP0015565A1 (de) | 1979-03-12 | 1980-09-17 | BASF Aktiengesellschaft | Verfahren zur Herstellung von 3 bis 4 C-Atome enthaltenden alpha,beta-olefinisch ungesättigten Aldehyden |
DE2909671A1 (de) | 1979-03-12 | 1980-10-02 | Basf Ag | Verfahren zur herstellung von schalenkatalysatoren |
US4438217B1 (de) | 1982-01-06 | 1990-01-09 | Nippon Shokubai Kagak Kogyo Co | |
DE3300044A1 (de) | 1982-01-06 | 1983-07-14 | Nippon Shokubai Kagaku Kogyo Co. Ltd., Osaka | Katalysator fuer die oxidation von propylen |
US4438217A (en) | 1982-01-06 | 1984-03-20 | Nippin Shokubai Kagako Kogyo Co., Ltd. | Catalyst for oxidation of propylene |
DE3338380C2 (de) | 1982-10-22 | 1988-10-27 | Nippon Shokubai Kagaku Kogyo Co. Ltd., Osaka, Jp | |
EP0279374A1 (de) | 1987-02-17 | 1988-08-24 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Katalysator zur Oxydation von Olefin oder tertiärem Alkohol und Verfahren zu seiner Herstellung |
EP0293224A1 (de) | 1987-05-27 | 1988-11-30 | Nippon Shokubai Co., Ltd. | Verfahren zur Herstellung von Acrylsäure |
EP0293859A1 (de) | 1987-06-05 | 1988-12-07 | Nippon Shokubai Co., Ltd. | Katalysator für die Oxydierung von Acrolein und Verfahren zu seiner Herstellung |
EP0382098A2 (de) | 1989-02-10 | 1990-08-16 | Mitsubishi Jukogyo Kabushiki Kaisha | Mehrrohrtypwärmetauscher |
EP0383224A2 (de) | 1989-02-17 | 1990-08-22 | Jgc Corporation | Rohrbündelapparat mit einer Zwischenrohrplatte |
JPH03294239A (ja) | 1990-04-11 | 1991-12-25 | Nippon Shokubai Co Ltd | アクロレインおよびアクリル酸の製造方法 |
DE4023239A1 (de) | 1990-07-21 | 1992-01-23 | Basf Ag | Verfahren zur katalytischen gasphasenoxidation von propen oder iso-buten zu acrolein oder methacrolein |
EP0468290B1 (de) | 1990-07-21 | 1994-03-02 | BASF Aktiengesellschaft | Verfahren zur katalytischen Gasphasenoxidation von Propen oder iso-Buten zu Acrolein oder Methacrolein |
EP0575897A1 (de) | 1992-06-25 | 1993-12-29 | BASF Aktiengesellschaft | Multimetalloxidmassen |
EP0614872A1 (de) | 1993-03-12 | 1994-09-14 | Nippon Shokubai Co., Ltd. | Verfahren zur Entfernung von festen organischen Stoffen |
EP0700893A1 (de) | 1994-09-08 | 1996-03-13 | Basf Aktiengesellschaft | Verfahren zur katalytischen Gasphasenoxidation von Acrolein zu Acrylsäure |
EP0700714A1 (de) | 1994-09-08 | 1996-03-13 | Basf Aktiengesellschaft | Verfahren zu katalytischen Gasphasenoxidation von Propen zu Acrolein |
EP0714700A2 (de) | 1994-11-29 | 1996-06-05 | Basf Aktiengesellschaft | Verfahren zur Herstellung eines Katalysators, bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Oxidmasse |
DE19606877A1 (de) | 1996-02-23 | 1997-08-28 | Basf Ag | Verfahren zur Reinigung von Acrylsäure und Methacrylsäure |
EP0807465A1 (de) | 1996-05-14 | 1997-11-19 | Nippon Kayaku Co., Ltd. | Katalysator und Verfahren zur Herstellung ungesättigter Aldehyde und Säure |
DE19627847A1 (de) | 1996-07-10 | 1998-01-15 | Basf Ag | Verfahren zur Herstellung von Acrylsäure |
WO1998024746A1 (fr) | 1996-12-03 | 1998-06-11 | Nippon Kayaku Kabushiki Kaisha | Procede de preparation d'acroleine et d'acide acrylique |
EP0873783A1 (de) | 1997-04-23 | 1998-10-28 | Basf Aktiengesellschaft | Vorrichtung und Verfahren zur Temperaturmessung in Rohrreaktoren |
DE19740252A1 (de) | 1997-09-12 | 1999-03-18 | Basf Ag | Verfahren zur Herstellung von Acrylsäure und Methacrylsäure |
DE19746210A1 (de) | 1997-10-21 | 1999-04-22 | Basf Ag | Verfahren der heterogen katalysierten Gasphasenoxidation von Propan zu Acrolein und/oder Acrylsäure |
EP0982288A2 (de) | 1998-08-26 | 2000-03-01 | Basf Aktiengesellschaft | Verfahren zur kontinuierlichen Gewinnung von (Meth)acrylsäure |
EP0982287A1 (de) | 1998-08-26 | 2000-03-01 | Basf Aktiengesellschaft | Verfahren zur kontinuierlichen Gewinnung von (Meth)acrylsäure |
EP0982289A2 (de) | 1998-08-26 | 2000-03-01 | Basf Aktiengesellschaft | Verfahren zur kontinuerlichen Gewinnung von (Meth)acrylsäure |
DE19855913A1 (de) | 1998-12-03 | 2000-06-08 | Basf Ag | Multimetalloxidmasse zur gasphasenkatalytischen Oxidation organischer Verbindungen |
DE19902562A1 (de) | 1999-01-22 | 2000-07-27 | Basf Ag | Verfahren zur Herstellung von Acrolein durch heterogen katalysierte Gasphasen-Partialoxidation von Propen |
DE19910506A1 (de) | 1999-03-10 | 2000-09-14 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrolein |
DE19910508A1 (de) | 1999-03-10 | 2000-09-21 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Acrolein zu Acrylsäure |
EP1159244A1 (de) | 1999-03-10 | 2001-12-05 | Basf Aktiengesellschaft | Verfahren der katalytischen gasphasenoxidation von propen zu acrolein |
DE19924532A1 (de) | 1999-05-28 | 2000-11-30 | Basf Ag | Verfahren der fraktionierten Kondensation eines Acrylsäure enthaltenden Produktgasgemisches einer heterogen katalysierten Gasphasen-Partialoxidation von C3-Vorläufern der Acrylsäure mit molekularem Sauerstoff |
DE19948248A1 (de) | 1999-10-07 | 2001-04-12 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrylsäure |
DE19948241A1 (de) | 1999-10-07 | 2001-04-12 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrolein |
DE19948523A1 (de) | 1999-10-08 | 2001-04-12 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrylsäure |
DE19955176A1 (de) | 1999-11-16 | 2001-01-04 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrylsäure |
DE19955168A1 (de) | 1999-11-16 | 2001-05-17 | Basf Ag | Verfahren der katalytischen Gasphasenoxidation von Propen zu Acrylsäure |
WO2001036364A1 (de) | 1999-11-16 | 2001-05-25 | Basf Aktiengesellschaft | Verfahren der katalytischen gasphasenoxidation von propen zu acrylsäure |
EP1106598A2 (de) | 1999-11-23 | 2001-06-13 | Rohm And Haas Company | Verfahren mit hoher Kohlenwasserstoffraumgeschwindigkeit zum Herstellen von ungesättigten Aldehyden und Karbonsäuren |
EP1180508A1 (de) | 2000-08-07 | 2002-02-20 | Nippon Shokubai Co., Ltd. | Verfahren zum Anfahren eines Reaktors |
DE10046957A1 (de) | 2000-09-21 | 2002-04-11 | Basf Ag | Verfahren zur Herstellung eines Multimetalloxid-Katalysators, Verfahren zur Herstellung ungesättigter Aldehyde und/oder Carbonsäuren und Bandcalziniervorrichtung |
DE10063162A1 (de) | 2000-12-18 | 2002-06-20 | Basf Ag | Verfahren zur Herstellung einer Mo, Bi, Fe sowie Ni und/oder Co enthaltenden Multimetalloxidativmasse |
DE10101695A1 (de) | 2001-01-15 | 2002-07-18 | Basf Ag | Verfahren zur heterogen katalysierten Gasphasenpartialoxidation von Vorläuferverbindungen der (Meth)acrylsäure |
WO2002062737A2 (de) | 2001-01-15 | 2002-08-15 | Basf Aktiengesellschaft | Heterogene katalysierte gasphasenpartialoxidation von vorläuferverbindungen der (meth)acrylsäure |
DE10115277A1 (de) | 2001-03-28 | 2002-06-13 | Basf Ag | Verfahren zur kontinuierlichen Gewinnung von(Meth)acrylsäure |
EP1270065A1 (de) | 2001-06-26 | 2003-01-02 | Nippon Shokubai Co., Ltd. | Vorrichtung zur Druck- und Temperaturmessungen in Rohrreaktoren |
US7534339B2 (en) | 2001-06-26 | 2009-05-19 | Nippon Shokubai Co., Ltd | Reactor filled with solid particle and gas-phase catalytic oxidation with the reactor |
WO2004007064A1 (en) | 2002-07-10 | 2004-01-22 | Lg Chem, Ltd. | Catalytic oxidation reactor with enhanced heat exchanging system |
WO2004008362A1 (ja) | 2002-07-15 | 2004-01-22 | Sony Corporation | ビデオプログラム制作システム、構成表提供装置、端末装置、端末処理方法、プログラム、記録媒体 |
WO2004009525A1 (de) | 2002-07-18 | 2004-01-29 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten gasphasen-partialoxidation wenigstens einer organischen verbindung |
EP1547994A1 (de) | 2002-08-23 | 2005-06-29 | Mitsubishi Chemical Corporation | Verfahren zur katalytischen dampfphasenoxidation unter einsatz eines rohrb ndelreaktors |
EP1577001A1 (de) | 2002-12-26 | 2005-09-21 | Mitsubishi Chemical Corporation | Plattenofen für katalytische reaktionen |
WO2004085362A1 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von propen zu acrolein |
WO2004085365A2 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von acrolein zu acrylsäure |
WO2004085370A1 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von acrolein zu acrylsäure |
WO2004085369A1 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von propen zu acrylsäure |
WO2004085363A1 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von propen zu acrolein |
WO2004085367A1 (de) | 2003-03-25 | 2004-10-07 | Basf Aktiengesellschaft | Verfahren der heterogen katalysierten partiellen gasphasenoxidation von propen zu acrylsäure |
WO2005009608A1 (de) | 2003-07-24 | 2005-02-03 | Basf Aktiengesellschaft | Reaktor für partialoxidationen mit thermoblechplattenmodulen |
DE10350812A1 (de) | 2003-10-29 | 2005-06-02 | Basf Ag | Verfahren zum Langzeitbetrieb einer heterogen katalysierten Gasphasenpartialoxidation von Propen zu Acrolein |
WO2005042459A1 (de) | 2003-10-31 | 2005-05-12 | Basf Aktiengesellschaft | Verfahren zum langzeitbetrieb einer heterogen katalysierten gasphasenpartialoxidation von propen zu acrylsäure |
DE10351269A1 (de) | 2003-10-31 | 2005-06-02 | Basf Ag | Verfahren zum Langzeitbetrieb einer heterogen katalysierten Gasphasenpartialoxidation von Propen zu Acrylsäure |
EP1547944A1 (de) | 2003-12-17 | 2005-06-29 | MARCHETTI, Antonio | Antriebssystem für Förderbänder |
WO2005082517A1 (de) | 2004-02-19 | 2005-09-09 | Stockhausen Gmbh | Ein verfahren zur entfernung kohlenstoffhaltiger rückstände in einem reaktor |
DE102004008573A1 (de) | 2004-02-19 | 2005-09-08 | Stockhausen Gmbh | Ein Verfahren zur Entfernung kohlenstoffhaltiger Rückstände in einem Reaktor |
DE102004025445A1 (de) | 2004-05-19 | 2005-02-10 | Basf Ag | Verfahren zum Langzeitbetrieb einer heterogen katalysierten Gasphasenpartialoxidation wenigstens einer organischen Verbindung |
WO2006002703A1 (de) | 2004-07-01 | 2006-01-12 | Basf Aktiengesellschaft | Verfahren zur herstellung von acrylsäure durch heterogen katalysierte partielle gasphasen oxidation von propylen |
WO2006002713A1 (de) | 2004-07-01 | 2006-01-12 | Basf Aktiengesellschaft | Verfahren zur herstellung von acrolein, oder acrylsäure oder deren gemisch aus propan |
WO2006002708A1 (de) | 2004-07-01 | 2006-01-12 | Basf Aktiengesellschaft | Verfahren zur herstellung von acrolein oder acrylsäure oder deren gemisch durch heterogen katalysierte partielle gasphasenoxidation von propylen |
WO2007013504A1 (ja) | 2005-07-29 | 2007-02-01 | Rohm Co., Ltd. | フラットパネルディスプレイ |
WO2007017431A1 (de) | 2005-08-05 | 2007-02-15 | Basf Aktiengesellschaft | Verfahren zur herstellung von katalysatorformkörpern, deren aktivmasse ein multielementoxid ist |
WO2007042457A1 (de) | 2005-10-14 | 2007-04-19 | Basf Se | Verfahren zur herstellung von acrolein, oder acrylsäure oder deren gemisch aus propan |
WO2007060036A1 (de) | 2005-11-24 | 2007-05-31 | Basf Se | Verfahren zur herstellung von acrolein, oder acrylsäure, oder deren gemisch aus propan |
WO2007082827A1 (de) | 2006-01-18 | 2007-07-26 | Basf Se | Verfahren zum langzeitbetrieb einer heterogen katalysierten partiellen gasphasenoxidation einer organischen ausgangsverbindung |
WO2008087115A2 (de) | 2007-01-16 | 2008-07-24 | Basf Se | Verfahren zur herstellung einer das element eisen in oxidischer form enthaltenden multielementoxidmasse |
WO2008087116A1 (de) | 2007-01-19 | 2008-07-24 | Basf Se | Verfahren zur herstellung von katalysatorformkörpern, deren aktivmasse ein multielementoxid ist |
DE102007004961A1 (de) | 2007-01-26 | 2008-07-31 | Basf Se | Verfahren zur Herstellung von Katalysatorformkörpern, deren Aktivmasse ein Multielementoxid ist |
DE102007005606A1 (de) | 2007-01-31 | 2008-04-03 | Basf Ag | Verfahren zur Herstellung von Katalysatorformkörpern, deren Aktivmasse ein Multielementoxid ist |
DE102008040094A1 (de) | 2008-07-02 | 2009-01-29 | Basf Se | Verfahren zur Herstellung eines oxidischen geometrischen Formkörpers |
DE102008040093A1 (de) | 2008-07-02 | 2008-12-18 | Basf Se | Verfahren zur Herstellung eines ringähnlichen oxidischen Formkörpers |
DE102008042060A1 (de) | 2008-09-12 | 2009-06-18 | Basf Se | Verfahren zur Herstellung von geometrischen Katalysatorformkörpern |
DE102008042064A1 (de) | 2008-09-12 | 2010-03-18 | Basf Se | Verfahren zur Herstellung von geometrischen Katalysatorformkörpern |
DE102008042061A1 (de) | 2008-09-12 | 2010-03-18 | Basf Se | Verfahren zur Herstellung von geometrischen Katalysatorformkörpern |
DE102008054586A1 (de) | 2008-12-12 | 2010-06-17 | Basf Se | Verfahren zur kontinuierlichen Herstellung von geometrischen Katalysatorformkörpern K |
DE102009047291A1 (de) | 2009-11-30 | 2010-09-23 | Basf Se | Verfahren zur Herstellung von (Meth)acrolein durch heterogen katalysierte Gasphasen-Partialoxidation |
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WO2019141534A1 (de) | 2018-01-19 | 2019-07-25 | Basf Se | Mo, bi, fe und cu enthaltende multimetalloxidmassen |
DE102018200841A1 (de) | 2018-01-19 | 2019-07-25 | Basf Se | Mo, Bi, Fe und Cu enthaltende Multimetalloxidmassen |
US10682631B2 (en) | 2018-01-19 | 2020-06-16 | Basf Se | Multimetal oxide compositions comprising Mo, Bi, Fe and Cu |
EP3770145A1 (de) | 2019-07-24 | 2021-01-27 | Basf Se | Verfahren zur kontinuierlichen herstellung von acrolein oder acrylsäure als zielprodukt aus propen |
WO2021013640A1 (en) | 2019-07-24 | 2021-01-28 | Basf Se | A process for the continuous production of either acrolein or acrylic acid as the target product from propene |
WO2024037905A1 (de) | 2022-08-16 | 2024-02-22 | Basf Se | Verfahren zur herstellung von vollkatalysatorformkörpern zur gasphasenoxidation eines alkens und/oder eines alkohols zu einem α,β-ungesättigtem aldehyd und/oder einer α,β-ungesättigten carbonsäure |
Also Published As
Publication number | Publication date |
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RU2568636C2 (ru) | 2015-11-20 |
US20120095267A1 (en) | 2012-04-19 |
KR101856270B1 (ko) | 2018-06-25 |
CN103270013A (zh) | 2013-08-28 |
JP5889313B2 (ja) | 2016-03-22 |
DE102010048405A1 (de) | 2011-05-19 |
EP2627622A2 (de) | 2013-08-21 |
RU2013121973A (ru) | 2014-11-20 |
KR20140001899A (ko) | 2014-01-07 |
WO2012049246A3 (de) | 2012-06-14 |
BR112013009049A2 (pt) | 2016-07-26 |
EP2627622B1 (de) | 2015-03-04 |
JP2014500855A (ja) | 2014-01-16 |
US8618336B2 (en) | 2013-12-31 |
BR112013009049B1 (pt) | 2018-12-18 |
CN103270013B (zh) | 2014-10-29 |
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