EP1656335A1 - Procede pour produire de l'aldehyde (meth)acrylique et/ou de l'acide (meth)acrylique - Google Patents

Procede pour produire de l'aldehyde (meth)acrylique et/ou de l'acide (meth)acrylique

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Publication number
EP1656335A1
EP1656335A1 EP04741050A EP04741050A EP1656335A1 EP 1656335 A1 EP1656335 A1 EP 1656335A1 EP 04741050 A EP04741050 A EP 04741050A EP 04741050 A EP04741050 A EP 04741050A EP 1656335 A1 EP1656335 A1 EP 1656335A1
Authority
EP
European Patent Office
Prior art keywords
gas mixture
meth
acrolein
feed gas
partial oxidation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04741050A
Other languages
German (de)
English (en)
Inventor
Jochen Petzoldt
Signe Unverricht
Heiko Arnold
Klaus Joachim MÜLLER-ENGEL
Martin Dieterle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2003137788 external-priority patent/DE10337788A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1656335A1 publication Critical patent/EP1656335A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein

Definitions

  • the present invention relates to a process for the preparation of (meth) acrolein and / or (eth) acrylic acid by heterogeneously catalyzed gas phase partial oxidation, in which a fresh fixed catalyst bed in a reactor is charged at elevated temperature with a feed gas mixture which, in addition to at least one, is partially added oxidizing organic precursor compound and molecular oxygen as the oxidizing agent comprises at least one diluent gas which is essentially inert under the conditions of the heterogeneously catalyzed gas phase partial oxidation.
  • the notation (meth) acrolein stands for methacrolein or acrolein.
  • (meth) acrylic acid stands for methacrylic acid or acrylic acid.
  • (eth) acrolein and (meth) acrylic acid form reactive monomers which e.g. for the production of polymers that include can be used as adhesives are suitable.
  • (meth) acrolein and (meth) acrylic acid mainly by heterogeneously catalyzed gas-phase partial oxidation of suitable C 3 - / C -Vorstoryr- compounds, in particular of propene and propane in the case of acrolein and acrylic acid or of iso-butene and iso-butane in the case of methacrylic acid and methacrolein.
  • suitable C 3 - / C -Vorstoryr- compounds in particular of propene and propane in the case of acrolein and acrylic acid or of iso-butene and iso-butane in the case of methacrylic acid and methacrolein.
  • propane, isobutene and isobutane other compounds containing 3 or 4 carbon atoms, such as isobutanol, n-propanol or the methyl ether (as a precursor of a C 4 precursor) from iso, are also suitable as starting materials butanol.
  • the catalysts to be used for such gas phase partial oxidations are normally multi-element oxides in the solid state.
  • the heterogeneously catalyzed gas-phase partial oxidation of C / C precursors to (meth) acrolein and / or (meth) acrylic acid is therefore usually carried out by charging a fixed catalyst bed at elevated temperature with a Feed mixture which, in addition to the at least one organic precursor compound to be partially oxidized, contains molecular oxygen as the oxidizing agent.
  • the fixed catalyst bed is usually surrounded by an envelope (e.g. it can be in the contact tubes of a tube bundle reactor).
  • an envelope e.g. it can be in the contact tubes of a tube bundle reactor.
  • the exothermic partial oxidation takes place during the dwell time on the catalyst surface, and on the other side of the envelope a heat transfer medium (e.g. a salt bath) is conducted to absorb and remove the heat of reaction.
  • a heat transfer medium e.g. a salt bath
  • the reactants are generally diluted with a gas which is essentially inert under the conditions of the gas phase partial oxidation and which, with its heat capacity, is able to absorb additionally released heat of reaction and, in most cases, can at the same time have a favorable influence on the explosion behavior of the feed gas mixture. In addition, it usually has an advantageous influence on the reaction rate.
  • Non-combustible gases are typically used as the inert diluent gases.
  • molecular nitrogen is automatically used whenever air is used as the oxygen source for the heterogeneously catalyzed gas phase partial oxidation.
  • Circular gas is the residual gas that remains in the heterogeneously catalyzed gas phase partial oxidation of the at least one organic precursor compound when the target product ((meth) acrolein and / or (meth) acrylic acid) is more or less selectively (e.g. through Absorption in a suitable solvent) has separated.
  • the inert diluent gases used for the heterogeneously catalyzed gas phase partial oxidation as well as of water vapor usually formed as a by-product in the gas phase partial oxidation and of carbon oxides formed by undesired complete secondary oxidation.
  • it contains small amounts of oxygen (residual oxygen) not consumed in the gas phase partial oxidation and / or of unreacted organic starting compounds.
  • residual oxygen residual oxygen
  • the gas phase partial oxidation of the precursor compound can predominantly to (meth) acrolein, or lead to a mixture of (meth) acrolein and (meth) acrylic acid, or predominantly to (meth) acrylic acid.
  • the two steps are carried out on catalyst feeds which are different from one another and are arranged spatially one behind the other, the individual catalyst feed being tailor-made for the respective reaction step to be catalyzed.
  • the product gas mixture leaving the first stage is then passed directly into the second stage, where appropriate after intermediate cooling and / or supplementation with molecular oxygen (for example in the form of air), where the (meth) acrolein formed in the first stage leads to (meth ) acrylic acid is further oxidized.
  • the temperature in the respective reaction stage is usually also adapted in an optimizing manner to the respective reaction step.
  • Reactor e.g. in a tube bundle reactor
  • EP-A 700 893 e.g. EP-A 700 893
  • both reaction stages can also be carried out in a single reactor, which then generally has more than one temperature zone (cf. e.g.
  • multielement oxide active materials are also known which can catalyze more than just one step (cf., for example, EP-A 962 253, EP-A 1 260 495, DE-A 10 122 027, EP-A 1 192 987 and EP-A 962 253).
  • a single reaction step can also be carried out in a reactor which more than one to improve the target product selectivity Has temperature zone, as is recommended, for example, in EP-A 1 106598, in WO 00/53556, in WO 00/53559, in WO 00/53557 and in WO 00/53558.
  • Reaction gas starting mixture comprising the partial oxidation of essentially inert diluent gas (the feed gas mixture) is passed through a fixed catalyst bed feed at elevated temperature (generally a few hundred ° C., usually 100 to 600 ° C.).
  • elevated temperature generally a few hundred ° C., usually 100 to 600 ° C.
  • a disadvantage of such a heterogeneously catalyzed gas phase partial oxidation is that the heat of reaction has to be dissipated at a sufficient rate on the one hand in order to avoid overheating of the system. On the other hand, the heat must not be dissipated too quickly, otherwise the reaction may fall asleep. Conversely, especially at the beginning, the reaction must develop sufficient heat to start. This balance is made more difficult by the fact that the reactant concentration during passage through the catalyst feed is not constant, but rather decreases.
  • WO 02/098827 recommends changing the composition of the feed gas mixture over time such that a feed gas mixture with a very low content of the partially oxidized organic substances is initially used for at least one hour Compound (typically 0 to ⁇ 0.5 vol .-%) is used. The content of the reactants is then Gaseous gas mixture increased in stages. As the reactant concentration in the feed gas mixture increases, the reactant ratio is also varied. Finally, an essentially stationary feed gas mixture is passed over the fixed catalyst bed.
  • the loading of the catalyst feed with the feed gas mixture is kept constant.
  • the object of the present invention was therefore to largely remedy the disadvantages of the procedure according to the recognized prior art.
  • a process for the production of (meth) acrolein and / or (meth) acrylic acid by heterogeneously catalyzed gas phase partial oxidation in which a fresh fixed catalyst bed in a reactor is charged at elevated temperature with a feed gas mixture, the In addition to at least one organic precursor compound to be partially oxidized and molecular oxygen as the oxidizing agent, at least one diluent gas which is essentially inert under the conditions of the heterogeneously catalyzed gas phase partial oxidation is found, which is characterized in that the process after adjusting the composition of the feed gas mixture at im substantially constant conversion of the organic precursor compound and with essentially unchanged composition of the feed gas mixture initially over a running-in period of 3 days to 10 days at a low load and then carried out at a higher load on the catalyst feed with feed gas mixture.
  • the advantage of the process according to the invention over the process of the prior art lies in the fact that it trims excessive heat development not by reducing the reactant content of the feed gas mixture but, in the case of full reactant content, by reducing the load on the fixed catalyst bed with feed gas mixture.
  • the conversion of the organic precursor compound (based on the single passage of the feed gas mixture through the fixed catalyst bed) is adjusted essentially constant to the target conversion.
  • Essentially constant means that the maximum deviation from the sales arithmetically averaged over time is not more than ⁇ 10%, preferably not more than ⁇ 5% (reference basis is the sales arithmetically averaged over time).
  • composition of the feed gas mixture remaining essentially the same means that the maximum deviation of the volume fraction of one of the components molecular oxygen, organic precursor compound and inert diluent gas in the feed gas mixture from the respective volume fraction, arithmetically averaged over time, of the respective component in the feed gas mixture does not exceed ⁇ 10%, preferably not more than ⁇ 5% (reference base is the respective volume fraction of the respective component in the feed gas mixture, arithmetically averaged over time).
  • the setting of the composition of the feed gas mixture and the temperature of the fixed catalyst bed for the process according to the invention can in principle be carried out according to the procedure described in WO 02/098827.
  • the time frame required for this, however, is usually well under an hour.
  • it can also be carried out in such a way that in a line leading via a static mixer, the reactor containing the fixed bed of catalyst initially only (optionally with a content of 2 to 4% by volume oxygen) inert gas (including water vapor), then the at least one organic one Vor meetingrverbin- and finally the oxygen source (normally air).
  • the fixed catalyst bed is already brought to the temperature required by the heat transfer medium during the inert gas supply, which is required at low loads in order to achieve the target conversion in a single pass through the catalyst feed.
  • Lower loading of the fixed catalyst bed with feed gas mixture in the process according to the invention means that the lower loading is typically 40 to 80%, preferably 50 to 70% of the higher target (end) loading for which the reactor, including its catalyst loading, is designed.
  • the reactor and fixed catalyst bed are designed for end loading with e.g. 150 NI propene / l fixed catalyst bed • h designed (the propene content in the feed gas mixture of a propene partial oxidation to acrolein and / or acrylic acid is typically 4 to 12 vol .-%), the 3 to 10 days run-in according to the invention is typically under a load of 100 Nl propene / l • h carried out. The above run-in could then also be carried out with appropriate loads of 80 to 120 Nl propene / l • h.
  • the 3 to 10 day run-in according to the invention is typically carried out with a load of 120 Nl propene / l • h etc.
  • the above run-in could then also with appropriate loads of 100 to 140 Nl propene / l • h.
  • the desired final load with an organic precursor compound is values ⁇ 80 Nl / I • h, mostly values ⁇ 100 Nl / I • h or ⁇ 120 Nl / I • h.
  • Final loads of 600 Nl / I • h or often 300 Nl / I • h are usually not exceeded.
  • the load can be increased suddenly, continuously or step by step to the desired final load.
  • the advantage of the procedure according to the invention is that after the running-in phase of 3 to 10 days, often 4 to 9 or 5 to 8 days, the process can be continued under higher loads with a comparatively increased target product selectivity and at the same time a comparatively lower heat transfer medium temperature.
  • Suitable fixed bed catalysts for the process according to the invention for the production of (meth) acrolein, in particular for the production of acrolein from propene are all those whose active composition is at least one multimetal oxide containing Mo, Bi and Fe. They are to be referred to here as fixed bed catalysts 1.
  • Example 1 c from EP-A 15565 and a catalyst to be produced in a corresponding manner, the active composition of which, however, has the composition Mo 12 i 6 5 5 Zn 2 Fe 2 Bi ⁇ Po, oo65 o, o 6 ⁇ x • 10SiO 2 having. Also to be emphasized is the example with the current No.
  • these hollow cylinders have a geometry of 5 mm x 2 mm x 2 mm, or 5 mm x 3 mm x 2 mm, or 6 mm x 3 mm x 3 mm, or 7 mm x 3 mm x 4 mm (each Outside diameter x height x inside diameter).
  • X 1 nickel and / or cobalt
  • X 2 thallium, an alkali metal and / or an alkaline earth metal
  • X 3 zinc, phosphorus, arsenic, boron, antimony, tin, cerium, lead and / or tungsten,
  • X 4 silicon, aluminum, titanium and / or zirconium
  • n a number which is determined by the valency and frequency of the elements in I other than oxygen.
  • suitable active compositions for the fixed bed catalysts 1, in particular those of the general formula I can be prepared in a simple manner by generating an intimate, preferably finely divided, dry mixture of suitable stoichiometry from suitable sources of their elemental constituents and this at temperatures of Caicinated at 350 to 650 ° C.
  • the calcination can take place both under inert gas and under an oxidative atmosphere such as air (mixture of inert gas and oxygen) and also under a reducing atmosphere (eg mixture of inert gas, NH 3 , CO and / or H 2 ).
  • the duration of the calculation can range from a few minutes to a few hours and usually decreases with temperature.
  • Suitable sources for the elementary constituents of the multimetal oxide active materials 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 in particular halides, nitrates, formates, oxalates, citrates, acetates, carbonates, amine complexes, ammonium salts and / or hydroxides (compounds such as NH 4 OH, (NH) 2 CO 3 , NH 4 NO 3 , NH 4 CHO 2 , CH 3 COOH, NH 4 CH 3 CO 2 and / or ammonium oxalate, which can decompose and / or decompose into fully gaseous compounds at the latest during later calcination, can also be incorporated into the intimate dry mixture) ,
  • the intimate mixing of the starting compounds for the production of multimetal oxide masses I can take place in dry or in wet form. If it is carried out in dry form, the starting compounds are expediently used as finely divided powders and, after mixing and optionally compacting, are subjected to the calcination. However, the intimate mixing is preferably carried out in wet form. Usually, the starting compounds are mixed together in the form of an aqueous solution and / or suspension. Particularly intimate dry mixtures are obtained in the mixing process described if only sources of the elementary constituents present in dissolved form are used. Water is preferably used as the solvent. The aqueous mass obtained is then dried, the drying process preferably being carried out by spray drying the aqueous mixture at exit temperatures of 100 to 150 ° C.
  • the multimetal oxide compositions suitable as fixed bed catalysts 1 according to the invention can be used for the process according to the invention both in powder form and in the form of certain catalyst geometries, it being possible for the shaping to take place before or after the final calculation.
  • full catalysts can be produced from the powder form of the active composition or its uncalcined and / or partially caicinated precursor composition by compressing it to the desired catalyst geometry (e.g. by tableting, extruding or extruding), where appropriate auxiliaries such as e.g.
  • Graphite or stearic acid can be added as a lubricant and / or molding aid and reinforcing agent such as microfibers made of glass, asbestos, silicon carbide or potassium titanate.
  • Suitable unsupported catalyst geometries are e.g. Solid cylinder or hollow cylinder with an outer diameter and a length of 2 to 10 mm. In the case of the hollow cylinders, a wall thickness of 1 to 3 mm is appropriate.
  • the full catalyst can also have a spherical geometry, the spherical diameter being 2 to 10 mm.
  • the shape of the powdery active composition or its powdery, not yet and / or partially caicinated, precursor composition can also be achieved by Applied to preformed inert catalyst supports.
  • the coating of the support bodies for producing the coated catalysts is generally carried out in a suitable rotatable container, as is known, for example, from DE-A 2909671, EP-A 293859 or from EP-A 714700.
  • the powder mass to be applied is expediently moistened and dried again after application, for example by means of hot air.
  • the layer thickness of the powder composition applied to the carrier body is expediently selected in the range from 10 to 1000 mm, preferably in the range from 50 to 500 mm and particularly preferably in the range from 150 to 250 mm.
  • carrier bodies can have a regular or irregular shape, with regularly shaped carrier bodies with a clearly formed surface roughness, e.g. Balls or hollow cylinders are preferred. It is suitable to use essentially non-porous, rough-surface, spherical supports made of steatite, the diameter of which is 1 to 8 mm, preferably 4 to 5 mm. However, it is also suitable to use cylinders as carrier bodies, the length of which is 2 to 10 mm and the outside diameter is 4 to 10 mm.
  • the wall thickness is moreover usually 1 to 4 mm.
  • Annular support bodies to be used preferably according to the invention have a length of 3 to 6 mm, an outer diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm.
  • rings of geometry 7 mm x 3 mm x 4 mm are particularly suitable as carrier bodies.
  • the fineness of the catalytically active oxide compositions to be applied to the surface of the carrier body is of course adapted to the desired shell thickness (cf. EP-A 714700).
  • compositions to be used according to the invention as fixed bed catalysts 1 are furthermore compositions of the general formula II
  • Y 1 bismuth, tellurium, antimony, tin and / or copper
  • Y 2 molybdenum and / or tungsten
  • Y 3 an alkali metal, thallium and / or samarium
  • Y 4 an alkaline earth metal, nickel, cobalt, copper, manganese, zinc, tin, cadmium and / or mercury
  • Y 5 iron, chromium, cerium and / or vanadium
  • Y 6 phosphorus, arsenic, boron and / or antimony
  • Y 7 a rare earth metal, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and / or uranium,
  • a ' 0.01 to 8
  • b' 0.1 to 30,
  • c ' 0 to 4
  • d' 0 to 20
  • e ' 0 to 20
  • f 0 to 6
  • x', y ' numbers determined by the valency and frequency of the elements in II other than oxygen
  • p, q numbers whose ratio p / q is 0.1 to 10 .
  • compositions II according to the invention are those in which Y 1 is bismuth.
  • Z 2 molybdenum and / or tungsten
  • Z 4 thallium, an alkali metal and / or an alkaline earth metal
  • Z 5 phosphorus, arsenic, boron, antimony, tin, cerium and / or lead,
  • Z 6 silicon, aluminum, titanium and / or zirconium
  • Z 7 copper, silver and / or gold
  • a " 0.1 to 1
  • b" 0.2 to 2
  • c " 3 to 10
  • d" 0.02 to 2
  • e 0.01 to 5, preferably 0.1 to 3
  • f " 0 to 5
  • g" 0 to 10
  • h 0 to 1
  • x y
  • q " Numbers whose ratio p "/ q" is 0.1 to 5, preferably 0.5 to 2
  • multimetal oxide materials II active materials is e.g. described in EP-A 575897 and in DE-A 19855913.
  • the heterogeneously catalyzed gas-phase partial oxidation of an organic precursor compound to (meth) acrolein according to the invention is carried out in a tube bundle reactor charged with fixed-bed catalysts 1, as described e.g. is described in EP-A 700714.
  • the fixed-bed catalyst 1 to be used is in the simplest way in the metal tubes of a tube bundle reactor and a temperature medium (single-zone mode of operation), usually a molten salt, is passed around the metal tubes.
  • a temperature medium usually a molten salt
  • the molten salt can also be passed through the reactor, viewed in a meandering manner, around the tube bundle, so that, viewed across the entire reactor, there is only a cocurrent or countercurrent to the direction of flow of the reaction gas mixture.
  • the flow rate of the temperature control medium is usually dimensioned such that the temperature rise (due to the exothermic nature of the reaction) of the heat exchange medium from the point of entry into the reactor to the point of exit from the reactor is ⁇ 0 to 10 ° C, often ⁇ 2 to 8 ° C, often ⁇ 3 to 6 ° C.
  • the entry temperature of the heat exchange medium into the tube bundle reactor in particular in the case of the conversion of propene to acrolein, is generally 310 to 360 ° C., frequently 320 to 340 ° C.
  • Fluid heat transfer media are particularly suitable as heat exchange medium.
  • 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 feed gas mixture of the feed with fixed bed catalyst 1 is expediently preheated to the desired reaction temperature.
  • DE-C 2830765 discloses a preferred variant of a two-zone tube bundle reactor which can be used according to the invention.
  • the two-zone tube bundle reactors disclosed in DE-C 2513405, US-A 3147084, DE-A 2201528, EP-A 383224 and DE-A 2903218 are also suitable.
  • the fixed bed catalyst 1 to be used is located in the metal tubes of a tube bundle reactor, and two temperature-regulating media, generally salt melts, which are essentially spatially separated from one another, are guided around the metal tubes.
  • the pipe section over which the respective salt bath extends represents a reaction zone.
  • a salt bath A flows around that section of the tubes (reaction zone A) in which, for example, the oxidative conversion of the propene (in a single pass) takes place until conversion in the range from 40 to 80 mol% is achieved
  • a salt bath B flows around, for example, the section of the tubes (reaction zone B), in which, for example, the oxidative subsequent conversion of the propene (in a single pass) until a Sales value of at least 90 mol .-% is usually carried out (if necessary, reaction zones A, B can be followed by further reaction zones which are kept at individual temperatures).
  • the salt bath can be conducted within the respective temperature zone as with the single-zone procedure.
  • the temperature of salt bath B is normally at least 5 ° C above the temperature of salt bath A.
  • the two-zone high-load mode e.g. as in DE-A 19948523 or as described in DE-A 19948248.
  • the process according to the invention is suitable for propene loads on the fixed bed catalyst bed 1 of> 70 Nl / I • h, ⁇ 130 Nl / I • h, ⁇ 180 Nl / I • h, ⁇ 240 Nl / I • h, ⁇ 300 Nl / I • h, but usually ⁇ 600 Nl / l • h.
  • the inert gas to be used for the feed gas mixture can be added
  • inert gases should generally be those used here for the single passage through the respective fixed bed catalyst bed to less than 5%, preferably less, for the process according to the invention convert as 2%) Diluent gases such as propane, ethane, methane, pentane, butane, CO 2 , CO, steam and / or noble gases are recommended for the feed gas mixture.
  • the working pressure in the process according to the invention in the propene partial oxidation can be both below normal pressure (for example up to 0.5 bar) and above normal pressure. Typically, the working pressure will be between 1 and 5 bar, often between 1.5 and 3.5 bar.
  • the reaction pressure during the propene partial oxidation will normally not exceed 100 bar.
  • the molar ratio of O 2 : C 3 H 6 in the feed gas mixture is normally ⁇ 1. Usually this ratio will be values ⁇ 3. Often the molar ratio of O 2 : C 3 H 6 in the feed gas mixture is ⁇ 1, 5 and ⁇ 2.0.
  • the propene content in the feed gas mixture can e.g. at values from 4 to
  • the process according to the invention is often used in the case of a propene: oxygen: indifferent gases (including water vapor) volume ratio in the reaction gas starting mixture (feed gas mixture) of 1: (1.0 to 3.0) :( 5 to 25), preferably 1: (1st , 5 to 2.3) :( 10 to 15).
  • feed gas mixture 1: (1.0 to 3.0) :( 5 to 25), preferably 1: (1st , 5 to 2.3) :( 10 to 15).
  • the feed gas mixture compositions of DE-A 10313209 can also be used according to the invention.
  • X 2 Cu, Ni, Co, Fe, Mn and / or Zn,
  • X 3 Sb and / or Bi
  • X 4 one or more alkali metals
  • X 5 one or more alkaline earth metals
  • X 1 W, Nb, and / or Cr
  • X 2 Cu, Ni, Co, and / or Fe
  • X 5 Ca, Sr and / or Ba
  • multimetal oxides IV are those of the general formula V Mo 12 V a .Y 1 b .Y 2 c .Y 5 f Y 6 g .O n (V),
  • Y 5 Ca and / or Sr
  • multimetal oxide active compositions (IV) which are suitable according to the invention are known per se, e.g. available in DE-A 4335973 or in EP-A 714700.
  • suitable multimetal oxide active compositions in particular those of the general formula IV, can be prepared as fixed bed catalysts 2 in a simple manner by generating an intimate, preferably finely divided, dry mixture of stoichiometry in accordance with their stoichiometry from suitable sources of their elemental constituents and this Temperatures from 350 to 600 ° C caicinated.
  • the caicination can be carried out both under inert gas and under an oxidative atmosphere such as air (mixture of inert gas and oxygen) and under a reducing atmosphere (eg mixtures of inert gas and reducing gases such as H 2 , NH 3 , CO, methane and / or acrolein or the reducing gases mentioned are carried out by themselves).
  • the caicination time can last from a few minutes to a few hours and usually decreases with temperature.
  • Suitable sources for the elementary constituents of the multimetal oxide active compositions IV are those compounds which are already oxides and / or those compounds which can be converted into oxides by heating, at least in the presence of oxygen.
  • the intimate mixing of the starting compounds for the production of multimetal oxide compositions IV can take place in dry or in wet form. If it is carried out in dry form, the starting compounds are expediently in the form of finely divided powders used and subjected to calcination after mixing and optionally compressing. However, the intimate mixing is preferably carried out in wet form.
  • the starting compounds are mixed with one another in the form of an aqueous solution and / or suspension.
  • Particularly intimate dry mixtures are obtained in the mixing process described if only sources of the elementary constituents present in dissolved form are used. Water is preferably used as the solvent.
  • the aqueous mass obtained is then dried, the drying process preferably being carried out by spray drying the aqueous mixture at exit temperatures of 100 to 150 ° C.
  • the multimetal oxide compositions suitable according to the invention as fixed bed catalysts 2, in particular those of the general formula IV, can be used for the process according to the invention both in powder form and in the form of certain catalyst geometries, it being possible for the shaping to take place before or after the final caicination.
  • full catalysts can be produced from the powder form of the active composition or its uncalcined precursor composition by compression to the desired catalyst geometry (e.g. by tableting, extrusion or extrusion), where appropriate auxiliaries such as e.g. Graphite or stearic acid can be added as a lubricant and / or molding aid and reinforcing agent such as microfibers made of glass, asbestos, silicon carbide or potassium titanate.
  • Suitable unsupported catalyst geometries are e.g. Solid cylinder or hollow cylinder with an outer diameter and a length of 2 to 10 mm. In the case of the hollow cylinders, a wall thickness of 1 to 3 mm is appropriate.
  • the full catalyst can also have a spherical geometry, the spherical diameter being 2 to 10 mm.
  • the powdery active composition or its powdery, not yet caicinated, precursor composition can also be shaped by application to preformed inert catalyst supports.
  • the coating of the support bodies for the production of the coated catalysts is usually carried out in a suitable rotatable container, as is e.g. is known from DE-A 2909671, EP-A 293859 or from EP-A 714700.
  • the powder mass to be applied is expediently moistened and dried again after application, for example by means of hot air.
  • the layer thickness of the powder composition 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 particularly preferably in the range from 150 to 250 ⁇ m.
  • Conventional porous or non-porous aluminum oxides, silicon dioxide, thorium dioxide, zirconium dioxide, silicon carbide or silicates such as magnesium or aluminum silicate can be used as carrier materials.
  • the carrier bodies can have a regular or irregular shape, preference being given to regularly shaped carrier bodies with a clearly formed surface roughness, for example balls or hollow cylinders.
  • annular support bodies to be used preferably according to the invention have a length of 3 to 6 mm, an outer diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm.
  • Particularly suitable according to the invention are rings of geometry 7 mm x 3 mm x 4 mm (outer diameter x length x inner diameter) as the carrier body.
  • the fineness of the catalytically active oxide materials to be applied to the surface of the carrier body is of course adapted to the desired shell thickness (cf. EP-A 714700).
  • compositions to be used according to the invention as fixed bed catalysts 2 are furthermore compositions of the general formula VI,
  • Z 1 W, Nb, Ta, Cr and / or Ce
  • Z 2 Cu, Ni, Co, Fe, Mn and / or Zn
  • z 3 Sb and / or Bi
  • z 4 Li, Na, K, Rb, Cs and / or H
  • z 5 Mg, Ca, Sr and / or Ba
  • z 6 Si, Al, Ti and / or Zr
  • z 7 Mo, W, V, Nb and / or Ta
  • starting mass 1 separately formed in f one-piece form (starting mass 1) and then the pre-formed solid starting mass 1 in an aqueous solution, an aqueous suspension or in a finely divided dry mixture of sources of the elements Mo, V, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , which the aforementioned elements in the stoichiometry D
  • the multimetal oxide compositions VI are preferred, in which the preformed solid starting composition 1 is incorporated into an aqueous starting composition 2 at a temperature ⁇ 70 ° C.
  • a detailed description of the production of multimetal oxide materials VI catalysts contain e.g. EP-A 668104, DE-A 19736105 and DE-A 19528646.
  • the heterogeneously catalyzed gas phase partial oxidation of acrolein to acrylic acid according to the invention will be carried out in a tube bundle reactor charged with the fixed bed catalysts 2, as described, for example, in EP-A 700893. That is, in the simplest way, the fixed bed catalyst 2 to be used is located in the metal tubes of a tube bundle reactor and a temperature control medium (single-zone mode), usually a molten salt, is passed around the metal tubes. The molten salt and reaction gas mixture can be carried out in simple cocurrent or countercurrent.
  • the temperature control medium (the molten salt) can, however, also be viewed through the reactor in a meandering manner around the tube bundle, so that viewed only across the entire reactor, there is a cocurrent or countercurrent to the direction of flow of the reaction gas mixture.
  • the volume flow of the temperature control medium (heat exchange medium) is usually dimensioned such that the temperature rise (due to the exothermic nature of the reaction) of the heat exchange medium from the entry point into the reactor to the exit point from the reactor 0 to 10 ° C., frequently w 2 to 8 ° C, often 3 to 6 ° C.
  • the inlet temperature of the heat exchange medium in the tube bundle reactor is usually 230 to 300 ° C, often 245 to 285 ° C or 245 to 265 ° C.
  • Suitable heat exchangers are the same fluid tempering media as have already been described for the heterogeneously catalyzed gas-phase partial oxidation according to the invention of an organic precursor compound to (meth) acrolein.
  • the feed gas mixture is expediently fed to the feed with fixed bed catalyst 2 preheated to the desired reaction temperature.
  • the process according to the invention is expediently carried out in a two-zone tube bundle reactor.
  • a preferred variant of a two-zone tube bundle reactor which can be used according to the invention for this purpose is disclosed in DE-C 2830765. But also those in DE-C 2513405, US-A 3147084, DE-A 2201528, EP-A 383224 and DE-A 2903582 disclosed two-zone tube bundle reactors are suitable.
  • the fixed bed catalyst 2 to be used according to the invention is in a simple manner in the metal tubes of a tube bundle reactor, and two tempering media which are essentially spatially separated from one another, usually molten salts, are passed around the metal tubes.
  • the pipe section over which the respective salt bath extends represents a reaction zone.
  • a salt bath C preferably flows around those sections of the tubes (reaction zone C) in which the oxidative conversion of acrolein (in a single pass) takes place until a conversion value in the range of 55 to 85 mol% is reached and a salt bath D flows around the Section of pipes (the recession zone D), in which the oxidative subsequent conversion of acrolein (in a single pass) takes place until a conversion value of generally at least 90 mol% is reached (if necessary, further reaction zones can follow the reaction zones C, D to be used according to the invention, which are kept at individual temperatures).
  • the salt bath can be conducted within the respective temperature zone as with the single-zone procedure.
  • the temperature of the salt bath D is normally at least 5 to 10 ° C above the temperature of the salt bath C.
  • the two-zone high-load mode can e.g. as in DE-A 19948523 or as described in DE-A 19948248.
  • the process according to the invention is suitable for acrolein loads in the fixed bed catalyst bed 2 of ⁇ 70 Nl / I • h,> 130 Nl / I • h, ⁇ 180 Nl / I • h, ⁇ 240 Nl / I • h,> 300 Nl / I • h, but usually ⁇ 600 Nl / l • h.
  • the inert gas to be used for the feed gas mixture can be ⁇ 20 vol.%, Or> 30 vol.%, Or ⁇ 40 vol.%, Or ⁇ 50 vol.%, Or> 60 vol. -%, or> 70 vol .-%, or ⁇ 80 vol .-%, or ⁇ 90 vol .-%, or ⁇ 95 vol .-% of molecular nitrogen.
  • the inert diluent gas is often 5 to 20% by weight H 2 O (formed in the first reaction stage) and 70 up to 90 vol .-% consist of N 2 .
  • inert diluent gases such as propane, ethane, methane, butane, pentane, CO, CO, water vapor and / or noble gases is recommended for the process according to the invention.
  • these gases can also be used at lower acrolein loads.
  • the working pressure in the gas phase partial oxidation of acrolein can be both below normal pressure (e.g. up to 0.5 bar) and above normal pressure.
  • the working pressure in the gas phase partial oxidation of acrolein will be from 1 to 5 bar, often 1 to 3 bar.
  • the reaction pressure in the partial oxidation of acrolein will normally not exceed 100 bar.
  • the molar ratio of O: acrolein in the feed gas mixture of the fixed bed catalyst bed 2 will normally be ⁇ 1. This ratio will usually be at values ⁇ 3.
  • the molar ratio of O: acrolein in the above-mentioned feed gas mixture will frequently be 1 to 2 or 1 to 1.5 according to the invention.
  • the process according to the invention is often used with an acrolein: oxygen.
  • the acrolein content in the feed gas mixture can e.g. at values of 3 to 15% by volume, often 4 to 10% by volume or 5 to 8% by volume (in each case based on the total volume).
  • the heterogeneously catalyzed gas phase partial oxidation of methacrolein to methacrylic acid can be carried out analogously to that of acrolein to acrylic acid.
  • those of EP-A 668103 are preferably used as catalysts.
  • the other reaction conditions are also advantageously determined in accordance with EP-A 668103.
  • the multimetal oxide catalysts such as those used e.g. the documents DE-A 10248584, DE-A 10029338, DE-A 10033121, DE-A 10261186, DE-A 10254278, DE-A 10034825, EP-A 962253, EP-A 1260495, DE-A 10122027, EP-A 192987 and DE-A 10254279 recommend.
  • reaction conditions can also be selected in accordance with these documents.
  • a single-zone reactor will usually be used as the reactor.
  • a reaction tube (V2A steel; 30 mm outside diameter, 2 mm wall thickness, 26 mm inside diameter, length: 350 cm) as well as a thermotube centered in the middle of the reaction tube (4 mm outside diameter) for receiving a thermocouple with which the temperature in the reaction tube is determined over its entire length was freshly loaded from top to bottom as follows:
  • Section 1 80 cm length steatite rings of geometry 7 mm x 7 mm x 4 mm (outer diameter x length x inner diameter) as a pre-fill.
  • Section 2 100 cm length of catalyst feed with a homogeneous mixture of 30% by weight of steatite rings of geometry 5 mm x 3 mm x 2 mm (outside diameter x length x inside diameter) and 70% by weight of full catalyst from section 3.
  • test arrangement was in each case continuously with a feed gas mixture (mixture of air, polymer grade propylene and cycle gas) of the composition
  • a comparison of the example and the comparative example shows that an immediate start-up of the fresh catalyst feed under the desired final load results in a catalyst feed that requires significantly higher salt bath temperatures for the same conversion. The higher maximum temperatures also cause the catalyst feed to age prematurely.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé servant à produire de l'aldéhyde (méth)acrylique et/ou de l'acide (méth)acrylique par oxydation partielle en phase gazeuse, à catalyse hétérogène, d'un composé précurseur organique sur un lit fixe de catalyseur frais. Selon l'invention, on démarre le procédé avec une sollicitation diminuée du lit fixe de catalyseur à l'aide d'un mélange gazeux de chargement.
EP04741050A 2003-08-14 2004-07-15 Procede pour produire de l'aldehyde (meth)acrylique et/ou de l'acide (meth)acrylique Withdrawn EP1656335A1 (fr)

Applications Claiming Priority (3)

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US49481403P 2003-08-14 2003-08-14
DE2003137788 DE10337788A1 (de) 2003-08-14 2003-08-14 Verfahren zur Herstellung von (Meth)acrolein und/oder (Meth)acrylsäure
PCT/EP2004/007871 WO2005016861A1 (fr) 2003-08-14 2004-07-15 Procede pour produire de l'aldehyde (meth)acrylique et/ou de l'acide (meth)acrylique

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EP1656335A1 true EP1656335A1 (fr) 2006-05-17

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US (1) US7015354B2 (fr)
EP (1) EP1656335A1 (fr)
JP (1) JP2007502254A (fr)
KR (1) KR20060061357A (fr)
BR (1) BRPI0413440A (fr)
MY (1) MY138925A (fr)
RU (1) RU2361853C2 (fr)
TW (1) TW200523245A (fr)
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DE102007004960A1 (de) 2007-01-26 2008-07-31 Basf Se Verfahren zur Herstellung von Acrylsäure
DE102007055086A1 (de) 2007-11-16 2009-05-20 Basf Se Verfahren zur Herstellung von Acrylsäure
WO2023006503A1 (fr) 2021-07-28 2023-02-02 Basf Se Procédé de production d'acide acrylique
WO2025172146A1 (fr) 2024-02-15 2025-08-21 Basf Se Procédé de production d'acide acrylique
WO2025219136A1 (fr) 2024-04-17 2025-10-23 Basf Se Procédé d'utilisation de flux de déchets de production d'acide acrylique
WO2025219137A1 (fr) 2024-04-17 2025-10-23 Basf Se Procédé d'utilisation de flux de déchets de production d'acide acrylique par gazéification et fermentation
WO2025219135A1 (fr) 2024-04-17 2025-10-23 Basf Se Procédé d'utilisation de flux de déchets de production d'acide acrylique à pouvoir calorifique élevé

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WO2015067659A1 (fr) 2013-11-11 2015-05-14 Basf Se Corps moulé de catalyseur cylindrique creux mécaniquement stable pour l'oxydation en phase gazeuse d'un alcène pour donner un aldéhyde insaturé et/ou un acide carboxylique insaturé
KR20230002897A (ko) 2020-04-21 2023-01-05 바스프 에스이 원소 Mo, W, V 및 Cu를 함유하는 촉매 활성 다원소 산화물의 제조 방법
CN116490275A (zh) 2020-10-29 2023-07-25 巴斯夫欧洲公司 制备核壳催化剂的方法
JP2025541831A (ja) 2022-12-07 2025-12-23 ベーアーエスエフ・エスエー 元素Ｍｏ、Ｗ、Ｖ、Ｃｕ、およびＳｂを含有する触媒活性多元素酸化物を製造するための方法
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DE102007055086A1 (de) 2007-11-16 2009-05-20 Basf Se Verfahren zur Herstellung von Acrylsäure
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WO2025172146A1 (fr) 2024-02-15 2025-08-21 Basf Se Procédé de production d'acide acrylique
WO2025219136A1 (fr) 2024-04-17 2025-10-23 Basf Se Procédé d'utilisation de flux de déchets de production d'acide acrylique
WO2025219137A1 (fr) 2024-04-17 2025-10-23 Basf Se Procédé d'utilisation de flux de déchets de production d'acide acrylique par gazéification et fermentation
WO2025219135A1 (fr) 2024-04-17 2025-10-23 Basf Se Procédé d'utilisation de flux de déchets de production d'acide acrylique à pouvoir calorifique élevé

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RU2006107501A (ru) 2006-07-27
MY138925A (en) 2009-08-28
WO2005016861A1 (fr) 2005-02-24
US7015354B2 (en) 2006-03-21
TW200523245A (en) 2005-07-16
RU2361853C2 (ru) 2009-07-20
BRPI0413440A (pt) 2006-10-17
JP2007502254A (ja) 2007-02-08
KR20060061357A (ko) 2006-06-07

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