WO2015067659A1 - Mechanisch stabiler hohlzylindrischer katalysatorformkörper zur gasphasenoxidation eines alkens zu einem ungesättigten aldehyd und/oder einer ungesättigten carbonsäure - Google Patents
Mechanisch stabiler hohlzylindrischer katalysatorformkörper zur gasphasenoxidation eines alkens zu einem ungesättigten aldehyd und/oder einer ungesättigten carbonsäure Download PDFInfo
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- WO2015067659A1 WO2015067659A1 PCT/EP2014/073820 EP2014073820W WO2015067659A1 WO 2015067659 A1 WO2015067659 A1 WO 2015067659A1 EP 2014073820 W EP2014073820 W EP 2014073820W WO 2015067659 A1 WO2015067659 A1 WO 2015067659A1
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- hollow cylindrical
- range
- shaped catalyst
- cylindrical shaped
- catalyst body
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Classifications
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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Definitions
- the present invention relates to hollow cylindrical shaped catalyst bodies for the gas phase oxidation of an alkene to an ⁇ , ⁇ -unsaturated aldehyde and / or an ⁇ , ⁇ -unsaturated carboxylic acid, comprising a compacted multimetal with an outside diameter AD, an internal diameter ID and a height H.
- the present invention Process for the preparation of hollow cylindrical shaped catalyst bodies, and their use as catalysts for the heterogeneously catalyzed partial gas phase oxidation of organic compounds, in particular those of propene to acrolein as Hauptproduckt and acrylic acid as a byproduct.
- Hollow cylinders are known as suitable geometry for shaped catalyst bodies.
- US Pat. No. 4,366,093 describes hollow-cylindrical shaped catalyst bodies having an outer diameter of from 3 to 6 mm, an inner diameter of at least 1.0 mm, a wall thickness of at most 1.5 mm and a height of from 3 to 6 mm. Specifically disclosed is also a hollow cylindrical shaped catalyst having an outer diameter of 4 mm, an inner diameter of 1, 8 mm and a height of 3 mm.
- the disclosed hollow cylindrical shaped catalysts comprise sintered aluminum oxide, from which impregnated catalyst bodies were obtained containing 18% by weight of copper chloride and 1.5% by weight of potassium chloride. These shaped catalyst bodies were used for the oxychlorination of ethene.
- US Pat. No. 4,438,217 discloses the use of hollow cylindrical shaped catalyst bodies comprising a multimetal oxide for the gas phase oxidation of propene to acrolein. known. Specifically disclosed is a catalyst having an outer diameter of 4 mm, an inner diameter of 1, 0 mm, a height of 4.4 mm and a wall thickness of 2 mm.
- hollow cylindrical shaped catalyst bodies By using hollow cylindrical shaped catalyst bodies increased selectivity and activity, a low pressure drop and improved heat transfer could be achieved compared to full cylindrical shaped catalyst bodies with the same outer diameter and height.
- DE 101 01 695 A1 describes a process of the heterogeneously catalyzed gas-phase partial oxidation of a precursor compound of (meth) acrylic acid in a catalyst test bed which contains a mixed oxide active material shaped into a geometric body, wherein at least one cavity is incorporated into the surface of the geometric body and the ratio of the volume of the geometric body to the volume of the underlying geometric base is at most 0.63 and the ratio of the surface of the body to the volume of the body is at least 22 cm -1 .
- hollow cylindrical shaped catalyst bodies which comprise a multimetal oxide, in particular those with an outer diameter x height x inner diameter of 5.5 ⁇ 3 ⁇ 3.5 mm (wall thickness 1 mm), 6 ⁇ 3 ⁇ 4 mm (wall thickness 1 mm) , 7 x 3 x 4.5 mm (wall thickness 1, 25 mm), 7 x 3 x 5 mm (wall thickness 1 mm), is shown as preferred.
- the catalyst moldings corresponding to the teachings of DE 101 01 695 A1, when used in a process for the heterogeneously catalyzed oxidation of propene, resulted in an improved selectivity of the formation of desired product, ie. the formation of acrolein and acrylic acid.
- the ratio of the surface to the volume of a hollow cylindrical shaped catalyst body can be reduced inter alia by reducing the wall thickness. It is all the more conspicuous that, for processes for the gas-phase oxidation of an alkene to an ⁇ , ⁇ -unsaturated aldehyde and / or an ⁇ , ⁇ -unsaturated carboxylic acid, there is disclosed no hollow carbonaceous catalyst mold comprising a multimetal oxide catalyst similarly dimensioned to the supported catalysts described in US 4,366,093 for the oxychlorination of ethylene were. Only geometries with thicker wall thickness, larger outer diameter or greater height were described.
- the advantageousness of a high ratio of the surface of the body to the volume of the body 22 cm -1 ) is known from DE 101 01 695 A1.
- the wall thickness of the hollow cylindrical shaped catalyst bodies of DE 101 01 695 A1 is in the range of 1 to 1, 25 mm.
- a disadvantage of the hollow cylindrical shaped catalyst bodies of DE 101 01 695 A1 is their low mechanical stability and the low catalyst mass density of the catalyst bed due to the low ratio of the volume of the geometric body to the volume of the underlying geometric base body (20, 63).
- the low mechanical stability leads to high material losses in large-scale catalyst production and due to excessive breakage when filling the reaction tubes to yield losses due to uneven flow through the individual reaction tubes of the tube bundle reactor.
- the low catalyst mass density of the catalyst bed is disadvantageous because the resulting higher reaction temperatures lead to an accelerated catalyst deactivation.
- the object of the present invention is to provide a mechanically stable shaped catalyst body which catalyzes the partial oxidation of an alkene to the value products of ⁇ , ⁇ -unsaturated aldehyde and ⁇ , ⁇ -unsaturated carboxylic acid with high selectivity. It is also an object to provide shaped catalyst bodies which ensure good long-term stability and acceptable pressure drop due to a sufficiently high catalyst mass density of the catalyst charge.
- a hollow cylindrical shaped catalyst body for the gas phase oxidation of an alkene to an ⁇ , ⁇ -unsaturated aldehyde and / or an ⁇ , ⁇ -unsaturated carboxylic acid comprising a compacted multimetal with an outer diameter AD, an inner diameter ID and a height H, where
- the ratio p according to the following equation is selected in the range of 0.5 to 1.
- the hollow cylindrical shaped catalyst bodies have a sufficient mechanical resistance (breaking stability) during the reactor filling.
- a measure of the mechanical stability of the catalyst particles provided is the following drop test: 50 g of catalyst are dropped through a 3 m long 23 mm diameter clear tube. The catalyst falls into a shell of porcelain immediately below the tube and is separated from the dust and breakage resulting from the impact. The separated intact catalyst bodies are weighed. The proportion of intact shaped catalyst bodies is determined by comparing the mass determined in this case with the mass of the shaped catalyst body used for the drop test. The proportion of intact shaped catalyst bodies is a measure of the resistance of the shaped catalyst body to mechanical stresses.
- the fraction of intact shaped catalyst bodies thus determined in the falling test is preferably at least 70%, preferably at least 75%, more preferably at least 80%.
- the lateral compressive strength of the hollow cylindrical shaped catalyst bodies is generally at least 4 N, preferably at least 6 N, more preferably at least 7 N.
- the lateral compressive strength of the hollow cylindrical catalyst bodies is less than 23 N, usually less than 20 N, usually less than 14 N. Die Side pressure resistance is particularly preferably 7 to 14 N.
- the experimental determination of the lateral compressive strength is thereby as in the documents WO
- the hollow cylindrical geometry of the present shaped catalyst bodies can be described by two cylinders of equal height whose axes coincide. One of the cylinders has a diameter ID. The other cylinder has a diameter AD. The lateral surface of the inner cylinder coincides with the inner surface of the hollow cylindrical shaped catalyst body. The outer surface of the outer cylinder coincides with the outer surface of the hollow cylindrical shaped catalyst body.
- the outer diameter AD is preferably selected in the range of 3.6 to 4.4 mm, preferably in the range of 3.7 to 4.3 mm, particularly preferably in the range of 3.8 to 4.2 mm.
- the quotient q corresponds to the ratio of the inside diameter of the hollow cylindrical shaped catalyst body to the outside diameter of the hollow cylindrical shaped catalyst body, q is preferably selected in the range of 0.45 to 0.55.
- the quotient p corresponds to the ratio of the height of the hollow cylindrical shaped catalyst body to the outer diameter of the hollow cylindrical shaped catalyst body, p is preferably selected in the range of 0.60 to 0.95, particularly preferably in the range of 0.65 to 0.90.
- the geometric volume of the hollow cylindrical shaped catalyst body is preferably 22 to 34 mm 3 .
- the geometric volume can be calculated based on the height H of the hollow cylinder, the outer diameter AD and the inner diameter ID.
- the ratio of the geometric volume of the shaped catalyst body to the volume of the underlying geometric base body is preferably 0.7 to 0.85.
- the underlying geometric basic body of a hollow cylinder is a solid cylinder with the same AD and the same H.
- the ratio of the geometric surface of the shaped catalyst body to the geometric volume of the shaped catalyst body, hereinafter also referred to as the effective surface is preferably 22 to 32 cm -1 idealized size and does not take into account the surface enlargement due to the porosity or surface roughness of the molded article
- the geometric surface of the hollow cylindrical shaped catalyst article is calculated by the following formula:
- the density of the hollow cylindrical shaped catalyst body is preferably 1.2 to 2.0 g / cm 3 . It is calculated by dividing the mass of the shaped catalyst body by its geometric volume.
- a low wall thickness WS of the hollow cylindrical shaped catalyst body is favorable because it merges with a large effective surface area of the catalyst body, which leads to a reduction of the characteristic diffusion length and therefore to an increased value product selectivity and increased rate of target product formation.
- the wall thickness can not be reduced arbitrarily, since the mechanical resistance of the catalyst mold body otherwise drops too much. Therefore, the value WS is according to the following equation
- An inventively preferred hollow cylindrical shaped catalyst body has an outer diameter in the range of 3.7 to 4.3 mm, a height in the range of 2.3 to 3.2 mm and an inner diameter in the range of 1, 8 to 2.2 mm.
- An inventively particularly preferred hollow cylindrical shaped catalyst body has an outer diameter in the range of 3.9 to 4.1 mm, a height in the range of 2.9 to 3.1 mm and an inner diameter in the range of 1, 9 to 2.1 mm.
- a very particularly preferred hollow cylindrical shaped catalyst body according to the invention has an outer diameter of 4 mm, a height of 3 mm and an inner diameter of 2 mm.
- the faces of the hollow cylindrical shaped catalyst bodies can also either either or only one as described in EP-A 184790 or US 4,656,157 be curved and z. B. such that the radius of curvature is preferably 0.4 to 5 times the outer diameter A. According to the invention, none of the end faces is curved.
- the hollow cylindrical shaped catalyst body comprises a compacted multimetal oxide.
- the hollow cylindrical shaped catalyst bodies preferably consist predominantly, in particular from 80 to 100% by weight, more preferably from 85 to 100% by weight, particularly preferably from 90 to 100% by weight, of the compacted multimetal oxide (so-called unsupported catalyst molding).
- the hollow cylindrical shaped catalyst body in particular shaping aids such.
- B. reinforcing agents Particularly suitable reinforcing agents are microfibers.
- the microfibers can be made of glass, asbestos, silicon carbide or potassium titanate, for example. They have a beneficial effect on the cohesion of the molding.
- the hollow cylindrical shaped catalyst body lubricant such as graphite include.
- Preferred lubricants are graphite, carbon black, polyethylene glycol, stearic acid, starch, polyacrylic acid, mineral or vegetable oil, water, glycerol, cellulose ethers, boron trifluoride and / or boron nitride.
- Particularly preferred lubricant is graphite.
- the aforementioned additional amount ä 0.5 wt .-% usually> 2.5 wt .-%.
- Preferably added graphites according to the invention are Timcal T44, Asbury 3160 and Asbury 4012.
- the lubricants escape, in particular during the calcination, completely or partially in the form of gaseous compounds (for example CO, CO2).
- Multimetal oxides for the gas phase oxidation of alkenes to ⁇ , ⁇ -unsaturated aldehydes and / or ⁇ , ⁇ -unsaturated carboxylic acids are known per se. It is therefore possible to use any multimetal oxide capable of catalyzing this gas phase oxidation.
- the multimetal oxide preferably comprises at least the elements iron, bismuth and at least one of the elements molybdenum and tungsten, for example at least the elements molybdenum, iron and bismuth.
- the multimetal oxide may correspond, for example, to the formula (I),
- X 2 represents thallium, an alkali metal and / or an alkaline earth metal
- X 3 represents zinc, phosphorus, arsenic, boron, antimony, tin, cerium, lead, vanadium, chromium and / or tungsten,
- X 4 represents silicon, aluminum, titanium and / or zirconium
- a is a number in the range of 0.2 to 5
- b is a number in the range of 0.01 to 10,
- c is a number in the range of 0 to 10,
- d is a number in the range of 0 to 2
- e is a number in the range of 0 to 8
- f stands for a number in the range of 0 to 10
- n is a number determined by the valency and frequency of the elements other than oxygen in (I); or of formula (II),
- Y 1 for bismuth or for bismuth and at least one of the elements tellurium, antimony,
- Y 2 is molybdenum or tungsten, or molybdenum and tungsten
- Y 3 is an alkali metal, thallium and / or samarium
- Y 4 for an alkaline earth metal, nickel, cobalt, manganese, zinc, tin, cadmium and / or
- Y 5 is iron or iron and at least one of vanadium, chromium and cerium is
- Y 6 is phosphorus, arsenic, boron, antimony and / or bismuth
- Y 7 is a rare earth metal, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, copper, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and / or uranium;
- Y 8 stands for molybdenum or tungsten, or stands for molybdenum and tungsten,
- a ' is a number in the range of 0.01 to 8
- b ' is a number in the range of 0.1 to 30,
- c ' is a number in the range of 0 to 4,
- d ' is a number in the range of 0 to 20,
- e ' is a number greater than 0 in the range of 0 to 20,
- f is a number in the range of 0 to 6
- g ' is a number in the range of 0 to 15,
- h ' is a number in the range of 8 to 16
- x 'and y' are numbers determined by the valency and frequency of the elements other than oxygen in (II)
- p and q are numbers whose ratio p / q is 0.1 to 10.
- the stoichiometric coefficient b is preferably 2 to 4, the stoichiometric coefficient c is preferably 3 to 10, the stoichiometric coefficient d is preferably 0.02 to 2, the stoichiometric coefficient e is preferably 0 to 5, and the stoichiometric coefficient a is preferably 0.4 to 2.
- the stoichiometric coefficient f is advantageously 0.5 or 1 to 10. Particularly preferably, the abovementioned stoichiometric coefficients are simultaneously in the preferred ranges mentioned.
- X 1 is preferably cobalt
- X 2 is preferably K, Cs and / or Sr, particularly preferably K
- X 3 is preferably tungsten, zinc and / or phosphorus
- X 4 is preferably Si.
- Particularly preferred are the variables X 1 to X 4 simultaneously have the meanings given above.
- all stoichiometric coefficients a to f and all variables X 1 to X 4 have at the same time their aforementioned advantageous meanings.
- X 1 is Co and / or Ni
- X 2 is alkali
- X 4 represents Si and / or Al
- a is a number in the range of 0.3 to 1
- b is a number in the range of 0.5 to 10,
- c is a number in the range of 2 to 10,
- d is a number in the range of 0 to 0.5
- f stands for a number in the range of 0 to 10
- n is a number determined by the valency and frequency of the elements other than oxygen in (Ia).
- n is a number determined by the valency and frequency of the elements other than oxygen in (Ia).
- n is a number determined by the valency and frequency of the elements other than oxygen in (Ia).
- ⁇ -X 1 Mo04 as the main component Fe2 (Mo04) 3 as a minor component and no
- the multimetal oxide corresponds to the formula (Ia), wherein X 1 is Co, X 2 is K, X 4 is Si, a is a number in the range of 0.5 to 1, b stands for a number in the range of 1, 5 to 3, c stands for a number in the range of 7 to 8.5, d stands for a number in the range of 0 to 0.15, f for a number in the range of 0 to 2.5 stands.
- composition of the multimetal oxide according to (la) is preferably
- the multimetal oxide of the formula (Ia) satisfies the following conditions 1, 2 and 3:
- Condition 2 the quotient a / A stands for a number in the range of 0.2 to 1.3;
- ranges of the chemical composition [Y 1 a Y 2 b'Ox] and ranges of the chemical composition [Y 3 C Y 4 d Y 5 e'Y 6 fY 7 g'Y 8 hOy] are relative to one another as in a mixture of finely divided [Y 1 a 'Y 2 b'Ox] and finely divided [Y 3 cY 4 dY 5 eY 6 fY 7 gY 8 h'0 /] distributed.
- multimetal oxides of the formula (II) which contain three-dimensionally expanded regions of the chemical composition Y 1 a'Y 2 b Ox ', whose maximum diameter (longest through the center of gravity) is defined by their local environment based on their different composition from their local environment of the area going 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 25 ⁇ , is.
- the multimetal oxides of the stoichiometry (II) in the multimetal oxides of stoichiometry (II) are in the form of three-dimensionally extended regions of the chemical composition Y 1 a 'Y 2 bO x' which are differentiated from their local environment because of their chemical composition different from their local environment, whose maximum diameter is in the range 1 nm to .mu.m 100 ⁇ lies.
- Advantageous multimetal oxides of stoichiometry (II) are those in which Y 1 is only bismuth. Within the multimetal oxides of the formula (II), those corresponding to the formula (IIa) are preferred
- Y 3 is an alkali metal and / or thallium, preferably K, Cs,
- Y 4 is an alkaline earth metal, nickel, cobalt and / or tin,
- Y 6 is phosphorus, arsenic, boron, antimony, and / or bismuth
- Y 7 is titanium, zirconium, aluminum, silicon, copper, silver and / or gold, preferably Si,
- Y 8 stands for molybdenum or tungsten, or stands for molybdenum and tungsten
- a ' is a number in the range of 0.1 to 2
- b ' is a number in the range of 0.2 to 4,
- c ' is a number in the range of 0.02 to 2
- d ' is a number in the range of 3 to 10,
- e ' is a number in the range of 0.01 to 5, preferably 0.1 to 4, f is a number in the range of 0 to 5,
- g ' is a number in the range of 0 to 10, preferably for a number greater than 0 in the range of 0 to 10, more preferably for a number in the range of 0.2 to 10, and most preferably for a number in the range of 0, 4 to 3,
- x 'and y' represent numbers which are determined by the valence and frequency of the elements other than oxygen in (IIa), and
- p and q are numbers whose ratio p / q is 0.1 to 5, preferably 0.4 to 2.
- multimetal oxides of stoichiometry (IIa) are preferred, which contain three-dimensionally extended areas of the chemical composition Bi a Y 2 b'Oy defined by their local environment due to their composition different from their local environment, the largest diameter (longest of which)
- composition of the multimetal according to (IIa) [B12W2O9 ⁇ 2 W0 3 ] o, 5o [Moi2Co5,4Fe3, iSii, 5 Ko, o80y '], [BiiW20x'] o, 5 [Ko, o8Co 5 , 5Fe 3 Sii , 6Moi20y '] or
- WO3 0.50 [MOl2CO 5, 4Fe3, LSIL, 5 K0,08Oy '].
- the multimetal oxide is characterized by having substantially no local centers of elemental oxides (eg, iron oxide). Rather, these elements are largely part of complex, mixed Oxomolybdate. This reduces the undesirable full combustion of organic reaction gas constituents.
- elemental oxides eg, iron oxide
- the multimetal oxide can be prepared by producing from suitable sources of their (in particular non-oxygen) elemental constituents a preferably finely divided, intimately stoichiometric mixture of intimate dry mixture and this, optionally after compression (shaping) to form hollow cylindrical moldings , which optionally takes place with the concomitant use of shaping aids, calcined at temperatures in the range of 350 to 650 ° C.
- the calcination can be carried out both under inert gas and under an oxidative atmosphere such.
- the calcination time can be a few minutes to several hours and usually decreases with the calcination temperature. Normally, the calcination of the hollow cylindrical catalyst precursor body takes several hours (usually more than 5 h) to complete. Often, the total duration of the calcination extends to more than 10 hours. Preferably, a total duration of the calcination of 45 h or 25 h is not exceeded.
- the hollow cylindrical shaped catalyst body is obtained directly after Kalcination.
- the present invention is thus also a hollow cylindrical shaped catalyst body, obtainable by (i) producing an intimate dry mixture of sources of elemental constituents of the multimetal oxide,
- the intimate dry mixture is compressed by tabletting to form the hollow cylindrical precursor shaped body.
- the term source in this document denotes a starting material for the preparation of the multimetal oxide.
- Suitable sources are those compounds which are already oxides of metals contained in the metal oxide and / or those compounds which can be converted into oxides by heating, at least in the presence of oxygen.
- suitable sources are in particular halides, nitrates, formates, oxalates, citrates, acetates, carbonates, amine complexes, ammonium salts and / or hydroxides of metals contained in the metal oxide and hydrates of the abovementioned salts.
- Compounds such as NH 4 OH, (NH 4) C0 3, NH 4 N0 3, NH 4 CH0 2, CH 3 COOH, NH 4 CHsC02 and / or ammonium oxalate which decompose latest during the subsequent Kalcinieren to gaseous compounds which escape and / or be decomposed can be incorporated into the intimate dry mixture in addition.
- calcining decomposing substances and organic materials such.
- the intimate mixing of the sources for the preparation of the multimetal oxide can be carried out in dry or wet form. If it takes place in dry form, the sources are expediently used as finely divided powders. Preferably, however, the intimate mixing takes place in wet form.
- the sources are mixed together in the form of solutions and / or suspensions and the resulting wet mixture is subsequently dried to give the intimate dry mixture.
- the solvent and / or suspending agent used is preferably water or an aqueous solution. Particularly intimate dry mixtures are obtained in the above-described mixing process when starting exclusively from sources present in dissolved form and / or from colloidally dissolved sources of the elemental constituents.
- a parent compound may be a source for only one or more than one elemental constituent. Accordingly, a solute or colloidal source listed above may have only one or more than one elemental constituent.
- the drying of the resulting wet mixtures is preferably carried out by spray drying.
- the element silicon may for example be introduced in the form of a silica sol for the preparation of the wet mixture.
- Silica sols are colloidal solutions of amorphous silica in water. They are water-soluble and contain no sedimentable components. Their SiO 2 content can be up to 50% by weight and more, often lasting for years (without sedimentation).
- a source may also be partially dissolved and partially colloidal.
- a convenient Mo source is ammonium heptamolybdate tetrahydrate. Further possible Mo sources are ammonium orthomolybdate ((NH 4 ) 2MoO 4 ), ammonium dimolybdate (( ⁇ 4 ) 2 ⁇ 2 ⁇ 7), ammonium tetramolybdate dihydrate ((NH 4 ) 2Mo 4 Oi 3 ⁇ 5H 2 O) and ammonium decamolybdate dihydrate ((NH 4 ) 4 Moio032 x 2 H2O). Basically, but also z. B. molybdenum trioxide used.
- K source is KOH (potassium hydroxide).
- KNO3 potassium hydroxide
- KNO3 or its hydrate can also be used as K source.
- Bi sources have the Bi as Bi 3+ .
- Bi-sources come z.
- the W source used is preferably tungstic acid or its ammonium salts.
- Preferred Fe sources are salts of Fe 3+ , of which iron (III) nitrate hydrates are particularly preferred (cf., for example, DE-A 102007003076). Particularly preferred Fe source is iron (III) nitrate nonahydrate. Of course, salts of Fe 2+ can also be used as the Fe source. For the preparation of the multimetal, based on the total molar amount of Fe contained in them, at least 50 mol%, more preferably at least 75 mol% and preferably at least 95 mol% is introduced in the form of an Fe source which contains Fe as Fe 3 + has. Also Fe sources can be used which have both Fe 2+ and Fe 3+ .
- Suitable co-sources are its salts, which have the Co as Co 2+ and / or Co 3+ .
- Cobalt (II) nitrate hexahydrate is preferred.
- the production of the wet mixture is preferably carried out in air (advantageously, the wet mixture is saturated in air).
- the wet mixture is saturated in air.
- salts of Co 2+ and salts of Fe 2+ are used as the co-source and Fe source.
- these salts are the nitrates and / or their hydrates.
- the intimate mixing of the sources for producing the multimetal oxide is preferably carried out in wet form, particularly preferably in aqueous form.
- an aqueous solution A can be prepared from at least one source of the elements Co, Fe and Bi.
- the aqueous solution A is preferably an aqueous solution of the nitrates or nitrate hydrates of Co, Bi and Fe.
- the aqueous solution A is particularly preferably an aqueous solution of the nitrates or nitrate hydrates in aqueous nitric acid.
- Such a solution can also be obtained by dissolving the corresponding metals in aqueous nitric acid.
- an aqueous solution B can be prepared.
- Preferred Mo source for preparing an aqueous solution B is ammonium heptamolybdate tetrahydrate (( ⁇ 4 ) 6 ⁇ 7 ⁇ 2 4 x 4H 2 O). If the aqueous solution contains BK, KOH is advantageously used as its source for the preparation of the aqueous solution B.
- the total content of the aqueous solution A of Co, Fe and Bi is advantageously, based on the amount of water contained in the aqueous solution A, 10 to 25 wt .-%, advantageously 15 to 20 wt .-%.
- the total content of the aqueous solution B to Mo is expedient, based on the amount of water contained in the aqueous solution B, 3 to 25 wt .-%, preferably 5 to 15 wt .-%.
- the aqueous solution A and the aqueous solution B are mixed together.
- the procedure is such that the aqueous solution A is continuously stirred into the aqueous solution B, wherein the initially introduced aqueous solution B is preferably intensively stirred.
- the total content of the resulting wet mixture of aqueous solution A and aqueous solution B of Mo, Co, Fe and Bi is advantageously, based on the amount of water contained in the wet mixture, 5 to 25 wt .-%, preferably 8 to 20 wt .-%.
- the mixed oxide Y 1 a'Y 2 b'Oy or Bi a Y 2 b'O x is preferably formed by intimately mixing at least one Bi source and at least one W source in aqueous medium, the aqueous mixture Dries, eg spray-dried.
- the resulting dry matter is calcined at temperatures in the range from 400 to 900.degree. C. (preferably 600 to 900.degree. C. and particularly preferably 700 to 900.degree. C.).
- the resulting calcine is divided into a finely divided starting material. That is, as shown above, the hollow cylindrical shaped catalyst body can be obtained through the grooves (i), (ii) and (iii), but also the formation of the composite oxide preceding the step (i) may include a calcination step.
- the calcination temperature is preferably set such that, on the one hand, a certain phase composition of the calcination product is achieved, but on the other hand, the calcined material has a BET surface area> 0.2 m 2 / g.
- the phases WO3 (monoclinic) and B12W2O9 (orthorhombic) are desired, the presence of Y-B12WO6 (Russellite) is undesirable.
- the preparation is preferably repeated and the calcination temperature or the residence time is increased while maintaining the quenching temperature until the limit of 5% of intensity is reached or exceeded.
- the sources of the remaining constituents of the multimetal oxide are preferably premixed together in the form of solutions and / or suspensions.
- the solvent and / or suspending agent used is preferably water or an aqueous solution.
- the resulting mixture is converted by drying, preferably spray drying, in a dry premix.
- the mixed oxide with the sources of the remaining constituents of the multimetal preferably with the premix of the other constituents, particularly preferably with the dry premix of the other constituents, combined and optionally after drying, preferably spray drying, the intimate dry mixture of the sources of elemental Constituents of the multime- talloxids received.
- the mixed oxide comes into contact with solvent, in particular with water, during the preparation of the intimate dry mixture, it is preferably ensured that the mixed oxide Y 1 a 'Y 2 bO x' or Bi a Y 2 bO x 'is not appreciably dissolved in solution. solution works.
- a method of preparation as described above is described in DE-A 4407020, EP-A 835, EP-A 575897 and DE-C 3338380.
- aqueous silica sol (cf., for example, DE-A 102006044520) is used as the source thereof and this is stirred into the wet mixture in an expedient manner, water being able to be added in advance to the wet mixture.
- Aqueous silica sol and water are preferably added simultaneously.
- Spray drying steps done.
- the mixture to be dried in the respective processing stage is first divided into finely divided droplets and the finely divided droplets are then dried.
- the finely divided droplets are then dried.
- Spray drying in a hot air stream in principle, however, other hot gases can also be used for spray drying (for example nitrogen or air diluted with nitrogen and other inert gases).
- the spray drying can be done both in cocurrent and in countercurrent of the droplets to the hot gas.
- Typical gas inlet temperatures are in the range of 250 to 450 ° C, preferably 270 to 370 ° C.
- Typical gas outlet Temperatures are in the range of 100 to 160 ° C.
- the spray drying can be done both in cocurrent and in countercurrent of the droplets to the hot gas.
- the mixture to be dried in the respective processing stage can also be dried by conventional evaporation (preferably at reduced pressure, the drying temperature will generally not exceed 150 ° C.).
- the drying can also be carried out by freeze-drying.
- the intimate dry mixture can be calcined as such. Frequently, however, the intimate dry mix is too finely divided for immediate calcination.
- the intimate dry mixture can be coarsened by subsequent compacting (usually to a particle size of 100 ⁇ m to 1 mm). Subsequently, with the coarsened powder, the shaping of the hollow cylindrical precursor shaped body can be carried out, wherein, if necessary, once again finely divided lubricant can be added beforehand. Such compaction for the purpose of grain coarsening can be carried out, for example, by means of a compactor from Hosokawa Bepex GmbH (D-7421 1 Leingart), type Kompaktor K 200/100.
- the compaction is controlled such that the coarsened powder particles obtained have a bulk density which clearly exceeds the desired density of the shaped uncalcined hollow cylindrical precursor body. That in the shaping, e.g. by tabletting, a further compression of the coarsened powder particles.
- the compacting dry z.
- finely divided graphite and / or other shaping aids for example, lubricants and / or reinforcing agents mentioned in this document can be mixed under the intimate dry mixture (for example with a Röhnrad mixer).
- the compaction can be performed with a calender having two counter-rotating steel rolls.
- the compactate can be purposefully comminuted to the particle size appropriate for the intended re-use to a finely divided precursor material. This can be z. B. be done by pressing the compact material through a sieve with a defined mesh size.
- the compacting can basically be done wet.
- the intimate dry mixture can be kneaded with the addition of water.
- the kneaded mass can be comminuted to the desired fineness in accordance with subsequent use (see, for example, DE-A 10049873) and dried to give a finely divided precursor material.
- the finely divided precursor materials obtainable as described may now be calcined as such or first formed into hollow-cylindrical precursor shaped bodies and subsequently calcined.
- a hollow cylindrical shaped catalyst body can be produced by compacting into a hollow cylindrical shape (for example by tableting, extruding or extrusion molding).
- graphite or stearic acid as lubricants and / or shaping aids and reinforcing agents such as microfibers of glass, asbestos, silicon carbide or potassium titanate can be added.
- the intimate dry mixture is formed by compression into hollow cylindrical precursor moldings and transferred the hollow cylindrical precursor moldings by Kalcination in the hollow cylindrical shaped catalyst body.
- This procedure is particularly preferred when the intimate mixing of the sources of the elemental constituents of the multimetal oxide to the finely divided intimate dry mixture takes place in dry form (cf., for example, WO 2008/0871 16 and DE-A 102008042060).
- shaping aids can, for example, lubricants such.
- graphite, carbon black, polyethylene glycol, polyacrylic acid, stearic acid, starch, mineral oil, vegetable oil, water, glycerol, cellulose ethers, boron trifluoride and / or boron nitride are added.
- shaping aids are reinforcing agents such as microfibers made of glass, asbestos, silicon carbide or potassium titanate, which have a beneficial effect on the cohesion of the resulting precursor shaped body after completion of the compacting.
- reinforcing agents such as microfibers made of glass, asbestos, silicon carbide or potassium titanate, which have a beneficial effect on the cohesion of the resulting precursor shaped body after completion of the compacting.
- a co-use of lubricants in the context of a corresponding compression can be found z.
- Suitable finely divided graphites to be used are in particular those which are recommended in the publications WO 2005/030393, US-A 2005/0131253, WO 2008/0871 16 and DE-A 102007005606. This applies in particular to those graphites which are sen fonts in the examples and comparative examples are used.
- Especially preferred graphites are Asbury 3160 and Asbury 4012 from Asbury Graphite Mills, Inc., New Jersey 08802, USA and Timrex® T44 from Timcal Ltd., 6743 Bodio, Switzerland.
- Based on the mass to be formed into the unsupported catalyst precursor body generally 15% by weight, in most cases ⁇ 9% by weight, often ⁇ 5% by weight, often ⁇ 4% by weight, of graphite to be used according to the invention added.
- this z. B up to 15 wt .-% of finely divided lubricant (eg., Graphite) included.
- finely divided lubricant eg., Graphite
- the lubricant content is not more than 9% by weight, in many cases not more than 5% by weight, often not more than 4% by weight. this is especially true when the finely divided lubricant is graphite.
- the aforementioned additional amount is at least 0.5 wt .-%, usually at least 2.5 wt .-%.
- the compression to the hollow cylindrical precursor shaped body takes place by the action of external forces (pressure) on the dry mixture.
- the forming apparatus to be used or the forming method to be used are subject to no restriction.
- the compaction can be done by extrusion, tabletting or extrusion.
- the intimate dry mixture is preferably used dry to the touch. It can, however, z. B. contain up to 10% of its total weight of substances that are liquid under normal conditions (25 ° C, 1 atm (1, 01 bar)).
- the intimate dry mixture may also contain solid solvates (eg hydrates) which have such liquid substances in chemically and / or physically bound form.
- the intimate dry mixture can also be completely free of such substances.
- Preferred shaping method is tableting.
- the basic features of the tablet animal are z. B. in "The Tablet", Handbook of Development, Production and Quality Control, WA Ritschel and A. Bauer-Brandl, 2nd edition, Edition Verlag Aulendorf, 2002 described and transferable to the tableting of the intimate dry mix.
- a Kilian rotary machine from Kilian in D-50735 Cologne
- a tablet press Fa. Korsch (D-13509 Berlin) type PH 800-65 can be used.
- the temperature surrounding the tabletting machine is normally 25 ° C.
- the particle diameters of the intimate dry mixture are in the range 100 to 2000 ⁇ m, preferably 150 to 1500 ⁇ m, more preferably 400 to 1250 ⁇ m, or 400 to 1000 ⁇ m, or 400 to 800 ⁇ m (in advance
- the molding aid mixed in the compression is not taken into account here).
- the molding pressures are advantageously 50 to 5000 kg / cm 2 , preferably 200 to 3500 kg / cm 2 , particularly preferably 600 to 2500 kg / cm 2 .
- the hollow cylindrical precursor moldings have the lowest possible residual moisture.
- the residual moisture content of the hollow cylindrical precursor moldings is at most 10 wt .-%, more preferably at most 8 wt .-%, more preferably at most 6 wt .-%, and most preferably at most 4 wt .-% or at most 2 wt .-% (the Residue moisture determination can be carried out as described in "The Library of Technology", Volume 229, "Thermogravimetric Material Moisture Determination", Fundamentals and Practical Applications, Horst Nagel, Verlag Moderne Industrie (eg with the aid of a Computrac MAX 5000 XL from Arizona Instruments)).
- Hollow-cylindrical precursor shaped bodies should, if possible, be stored under exclusion of ambient air (which has air humidity) (storage is preferably carried out until calcination under anhydrous inert gas or under previously dried air).
- ambient air which has air humidity
- the compression of the intimate dry mixture is already carried out with the exclusion of ambient air having (atmospheric humidity) (for example under an IM 2 atmosphere).
- the calcination of the hollow-cylindrical precursor shaped bodies is normally carried out at temperatures which reach or generally exceed at least 350 ° C. Normally, however, the temperature of 650 ° C is not exceeded in the course of calcination (the term "calcination temperature” in this document means the temperature present in the calcation material).
- the temperature of 600 ° C preferably the temperature of 550 ° C and often the temperature of 500 ° C is not exceeded in the Kalcination.
- the temperature of 380 ° C. advantageously the temperature of 400 ° C., with particular advantage the temperature of 420 ° C. and very particularly preferably the temperature of 440 ° C., is preferably exceeded within the scope of the above calcination.
- the calcination can also be subdivided into several sections in their time sequence.
- Preferred temperature windows for the final calcination temperature are in the temperature range from 400.degree. C. to 600.degree. C., preferably 420 to 550.degree. C., particularly preferably 440 to 500.degree.
- the duration of the calcination is usually more than 10 h. Usually the duration is 45 h, or 25 h not exceeded. Often the duration is less than 20 hours. Basically, at higher calcination temperatures, a shorter calcination usually occurs than at lower calcination temperatures.
- the Kalcinationsdauer extends in the temperature range of 430 ° C to 500 ° C for 10 to 20 h.
- a thermal pretreatment is carried out at temperatures in the range of 120 ° C to 350 ° C, preferably 150 ° C to 320 ° C, more preferably 220 ° C to 290 ° C.
- Such a thermal pretreatment is expediently carried out until the constituents which decompose to gaseous compounds under the conditions of the thermal pretreatment have been largely (preferably completely) decomposed to form gaseous compounds (the time required in this respect can be, for example, 3 hours) 10 hours, often 4 hours to 8 hours).
- the thermal pretreatment is preferably carried out under conditions in which the maximum relative decrease in mass of the catalyst precursor shaped body (ie the mass change related to the mass of the catalyst precursor body) does not exceed 1% per minute.
- the conditions of the thermal pretreatment include, in particular, the temperature, the rate of increase in temperature, the composition of the surrounding gas atmosphere and the convection of the surrounding gas atmosphere.
- Both the calcination and the pre-calcination thermal pretreatment can be carried out both under inert gas and under an oxidative atmosphere such as e.g. As air (or a mixture of inert gas and molecular oxygen) and under reducing atmosphere (eg., A mixture of inert gas, NH3, CO and / or H2 or methane, acrolein, methacrolein) take place.
- the calcination and / or the thermal pretreatment can also be carried out under vacuum.
- the atmosphere can be varied over the course of calcination and / or thermal pretreatment.
- the calcination, and optionally also the pre-calcination thermal pretreatment takes place in an oxidizing atmosphere. Expediently, this consists predominantly of stationary or (preferably) agitated air (particularly preferably the calcined material flows through an air stream).
- the oxidizing atmosphere may also consist of a standing or moving mixture of z. B.
- the Kalcination and optionally also before the Kalcination thermal pretreatment in a variety of furnace types such.
- shaping aids can be retained or gaseous compounds to be escaped (for example CO, CO.sub.2) can be reacted.
- the hollow cylindrical shaped catalyst bodies may contain finely divided inert diluent materials. Suitable finely divided inert diluent materials include, among others, elemental oxides which are calcined at high temperatures and therefore relatively poor in pores, such as aluminum oxide, silicon dioxide, thorium dioxide and zirconium dioxide. But even finely divided silicon carbide or finely divided silicates such as magnesium and aluminum silicate or steatite can be included as inert diluent materials in the catalyst bodies. You can the calcined multimetal to Grind a finely divided powder, mix this with finely divided diluent material and form the resulting mixed powder using a forming method presented in this document (preferably by tabletting) to form a hollow cylindrical shaped body. By subsequently recalculating this shaped body, the hollow cylindrical shaped catalyst body is then obtained.
- a forming method presented in this document preferably by tabletting
- the finely divided inert diluent material can alternatively also be incorporated into the wet mixture before it is dried. Furthermore, incorporation of finely divided inert diluent material into a finely divided dry mixture of sources of the elemental constituents of the multimetal oxide can be carried out. However, such approaches are less preferred.
- the specific surface area of the hollow cylindrical shaped catalyst bodies is advantageously 2 to 20 or 15 m 2 / g, preferably 3 to 10 m 2 / g and particularly preferably 4 to 8 m 2 / g.
- the total pore volume is advantageously in the range from 0.1 to 1 cm 3 / g or to 0.8 cm 3 / g, preferably in the range 0.1 to 0.5 cm 3 / g and particularly preferably in the range from 0.2 to 0.4 cm 3 / g.
- pores having a pore radius of at most 0.1 ⁇ m contribute to the total pore volume of at most 0.05 cm 3 / g. If the contribution of such comparatively narrow pores to the total pore volume is more than 0.05 cm 3 / g, an increase in the calcination time and / or the calcination temperature can advantageously bring about a reduction in this contribution.
- Pores having a pore radius in the range from 0.2 to 0.4 ⁇ m preferably contribute to the total pore volume, based on the total pore volume, at least 70% by volume, advantageously at least 75% by volume, particularly preferably at least 85% by volume.
- the volume-related particle diameter distribution is then determined in accordance with ISO 13320 using the Malvern Mastersizer S laser diffraction spectrometer (Malvern Instruments, Worcestshire WR 14 1AT, United Kingdom).
- the particle diameter d x indicated as the measurement result is defined such that X% of the total particle volume consists of particles with this or a smaller diameter. This means that (100 - X)% of the total particle volume consists of particles with a diameter> d x .
- particle diameter determinations and d x taken from them refer to a dispersion pressure of 2 bar absolute used for the determination (determining the extent of dispersion of the dry powder during the measurement).
- the storage of the calcined shaped catalyst bodies is preferably carried out in 120 l metal drums, which are lined in the interior with a flat bag of loupoles and a material thickness of 0.1 mm.
- the invention also provides a process for the preparation of an ⁇ , ⁇ -unsaturated aldehyde and / or an ⁇ , ⁇ -unsaturated carboxylic acid, wherein an alkene with molecular oxygen over a fixed catalyst bed, which comprises a bed of inventive hollow cylindrical shaped catalyst body passes.
- the alkene is preferably selected from alkenes of 3 to 6, d. H. 3, 4, 5 or 6 carbon atoms; preferably selected from propene and isobutene. Propene is particularly preferred. There are in particular polymer grade propene and chemical grade propene into consideration, as z. B. DE-A 102 32 748 describes.
- the fixed catalyst bed comprises a bed having multiple reaction zones.
- the bed may contain inert diluent bodies in at least one reaction zone.
- the proportion of inert shaped diluent bodies can be different in at least two reaction zones.
- the bed in the reaction zone which contains no inert diluent shaped bodies or the smallest proportion of inert diluent shaped bodies, contains inventive hollow cylindrical catalyst bodies.
- the bed in the reaction zone in which the highest local temperature of the fixed catalyst bed occurs, according to the invention hollow-cylinder contain lindhari catalyst moldings.
- the bed comprises a hollow cylindrical catalyst mold according to the invention and not shaped bodies according to the invention.
- the process is particularly suitable for the preparation of ⁇ , ⁇ -unsaturated aldehydes, in particular for the production of acrolein by gas-phase oxidation of propene and methacrolein by gas-phase oxidation of isobutene.
- it is a process for the production of acrolein by gas phase oxidation of propene.
- the molecular oxygen and alkene are contacted with the fixed catalyst bed by passing the molecular oxygen and alkene over the fixed catalyst bed.
- a reaction gas containing the molecular oxygen and the alkene is passed over the fixed catalyst bed, thus converting it into a product gas.
- the molecular oxygen is preferably supplied to the process in the form of air.
- the proportion of the alkene contained in the reaction gas is generally 4 to 20% by volume, preferably 5 to 15% by volume, preferably 5 to 12% by volume, particularly preferably 5 to 8% by volume, in each case based on the reaction gas.
- the reaction gas also contains at least one inert diluent gas.
- Inert diluent gases are understood to mean those gases which remain chemically unchanged at least 95 mol%, preferably at least 98 mol%, in the course of the gas phase oxidation.
- Examples of inert diluent gases are N2, CO2, H2O and noble gases such as Ar and mixtures of the aforementioned gases.
- the inert diluent gas used is preferably molecular nitrogen.
- the inert diluent gas may, for. B.
- recycle gas is co-used as a reactant gas component.
- Cycle gas is understood as meaning the residual gas which remains when one selectively removes ⁇ , ⁇ -unsaturated aldehyde and / or ⁇ , ⁇ -unsaturated carboxylic acid substantially from the product gas of the gas phase oxidation.
- the process according to the invention optionally only the first stage of a two-stage gas phase oxidation to ⁇ , ⁇ -unsaturated carboxylic acid may be as the actual target compound, so that the recycle gas is then usually only after the second stage.
- the product gas of the first stage if appropriate after cooling and / or secondary oxygen addition (as a rule in the form of air), is supplied to the second gas phase oxidation.
- the reaction gas may also contain at least one additional gas component.
- the further gas constituent is preferably selected from CO, methane, ethane, propane, butane, pentane and h.
- the reaction gas preferably contains alkene: molecular oxygen: inert diluent gas in a volume ratio of 1: (1, 0 to 3.0): (5 to 25), preferably 1: (1, 5 to 2.3): (10 to 20 ).
- the load is at least 0.05 Nl alkene / (g catalyst h).
- the load is preferably at least 0.08 Nl alkene / (g catalyst h), preferably at least 0.08 Nl alkene / (g catalyst h) at a tempering zone, preferably at least 0.12 Nl alkene / (g catalyst h) at two tempering zones ,
- the load is at most 0.6, preferably at most 0.5, further preferably at most 0.4, particularly preferably at most 0.35, Nl alkene / (g catalyst h).
- Loads in the range of 0.08 to 0.35 Nl alkene / (g catalyst h), preferably 0.14 to 0.35 Nl alkene / (g catalyst h) at several tempering zones, or preferably 0.08 to 0.18 Nl alkene / (g catalyst h) in a tempering zone are particularly useful.
- the load expressed in "Nl alkene / (gcatalyst h)" corresponds to the alkene volume flow (in liters of alkene / hr) fed to the reactor based on the mass of catalyst in the reactor (in grams) "Nl alkene” the volume of alkene in liters, which would take the supplied alkene at normal conditions, ie, at 0 ° C and 1 atm (1, 01 bar).
- the bed only hollow cylindrical shaped catalyst bodies according to the invention or else substantially homogeneous mixtures of hollow cylindrical shaped catalyst bodies according to the invention and shaped diluents can be present.
- Dilution molded articles behave substantially inertly with respect to the heterogeneously catalyzed partial gas phase oxidation.
- materials for the dilution body come z.
- the geometry of the shaped diluent bodies can in principle be arbitrary. D. h., It may be, for example, balls, polygons, solid cylinder or hollow cylinder. It is possible to use hollow cylindrical shaped diluents. In particular, it is possible to use hollow cylindrical shaped diluent bodies whose dimensions substantially coincide with the hollow cylindrical shaped catalyst bodies in the same part of the bed (or reaction zone).
- the bed may have one or more reaction zones.
- a reaction zone is understood as meaning a contiguous section of the bed which comprises shaped catalyst bodies and in which the composition of the bed is substantially homogeneous. Even within a reaction zone, the bed is only approximately homogeneous, since the hollow cylindrical shaped catalyst body and, if necessary, diluent bodies in the reaction zone are usually randomly oriented and statistically distributed.
- the individual reaction zones differ from one another in at least one property selected from the content of inert diluent bodies, the form of the catalysts, the degree of space filling of the catalysts, the active mass fraction of the catalysts and the chemical composition of the active composition.
- At least one reaction zone contains hollow cylindrical shaped catalyst bodies according to the invention.
- the packed catalyst bed often comprises a bed having a plurality of reaction zones, wherein the bed contains inert diluent bodies in at least one reaction zone, and the proportion of inert shaped diluent bodies is different in at least two reaction zones. It is favorable to use hollow cylindrical shaped catalyst bodies according to the invention in at least the reaction zone which contains no or at least the smallest proportion of inert shaped diluent bodies.
- inventive hollow cylindrical shaped catalyst bodies in the reaction zone, which has the highest local temperature of the fixed catalyst bed.
- the fixed catalyst bed comprises two consecutive reaction zones wherein (i) the first reaction zone comprises from 25% to 50% of the volume of the catalyst solid. bedtowards.
- Hollow-cylindrical shaped catalyst bodies according to the invention are used at least in the first reaction zone or in both reaction zones.
- catalyst mold body having an outer diameter of 4 mm, a height of 3 mm and an inner diameter of 2 mm and in the second reaction zone with an outer diameter of 5 mm, a height of 3 mm and an inner diameter of 2 mm used become.
- the second reaction zone according to the invention hollow cylindrical shaped catalyst body, for example, with an outer diameter of 4 mm, a height of 3 mm and an inner diameter of 2 mm.
- the fixed catalyst bed comprises three consecutive reaction zones wherein (i) the first reaction zone is 2 to 5% of the fixed catalyst bed volume, (ii) the second reaction zone is 25 to 45% of the fixed catalyst bed volume, and (iii) the third reaction zone 50 to 73% of the volume of the fixed catalyst bed.
- preference may be given to shaped catalyst bodies according to the invention, e.g. with an outer diameter of 4 mm, a height of 3 mm and an inner diameter of 2 mm.
- the third reaction zone according to the invention hollow cylindrical shaped catalyst body, for example, with an outer diameter of 4 mm, a height of 3 mm and an inner diameter of 2 mm.
- the method may, for. B. in a tempering zone having Dahlnessrohr- fixed bed reactor, as described in DE-A 44 31 957, EP-A 700 714 and EP-A 700 893, performed.
- a tempering zone having Dahlnessrohr- fixed bed reactor as described in DE-A 44 31 957, EP-A 700 714 and EP-A 700 893, performed.
- the catalyst 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.
- a typical contact tube length amounts to z. B. at 3.20 m.
- the number of contact tubes accommodated in the tube bundle container preferably amounts to at least 1000, preferably to at least 5000. Frequently, the number of contact tubes accommodated in the reaction container is 15,000 to 35,000.
- Tube bundle reactors with a number of contact tubes above 40,000 tend to be the exception.
- the contact tubes are normally distributed homogeneously, the distribution suitably chosen is that the distance between the central inner axes of closest contact tubes (the so-called contact tube pitch) is 35 to 45 mm (see EP-B 468 290).
- the process can also be carried out in a multi-contact-tube fixed-bed reactor having a plurality of tempering zones, as described in DE-A 199 10 506, DE-A 103 13 213, DE-A 103 13 208 and EP-A 1 106 598 recommend.
- a typical contact tube length in the case of a multi-contact fixed-bed reactor having two temperature-control zones is 3.50 m. Everything else is essentially as described in the case of a multi-contact fixed-bed reactor having a temperature control zone.
- thermohull centered through the reaction tube from top to bottom, in which the temperature can be determined over the entire length of the reaction tube by means of thermocouples guided in the thermowell.
- any reaction tube located in a tube bundle reactor and charged with the fixed catalyst bed could be equipped as described above.
- a tube bundle reactor has only a limited number of such thermoreaction tubes or, for short, only "thermotubes" (cf., for example, page 56 of WO 2007/082827, EP-A 873783, EP-A 1270065 and US 7,534,339 B2).
- thermal tubes in addition to the fixed catalyst bed still have to take up the thermal sleeve, they would have an otherwise identical tube design, although an equal heat exchange surface, but a smaller free, impregnable from the catalyst fixed bed, cross-section as a mere "reaction tube”. This is taken into account by designing them (the thermal tubes) in such a way that the ratio of free cross-sectional area in the tube to the circumference of the tube in the thermotube and reaction tube is the same.
- the reaction tube and the thermal tube each have the same fixed catalyst bed structure over their tube length with identical tube length.
- thermo tube is so representative of many reaction tubes to map the course of the temperature in the reaction tube.
- a heat exchange medium is guided in each tempering zone.
- Preferred heat exchange agents are 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.
- the inlet temperature of the heat exchange medium is preferably set at 280 ° C to 420 ° C, preferably at 300 ° C to 400 ° C, more preferably at 320 ° C to 380 ° C.
- the heat exchange medium can be viewed via the respective temperature control zone, conducted in cocurrent or in countercurrent to the reaction gas mixture.
- the flow rate of the heat exchange medium within the respective tempering zone is usually selected so that the temperature of the heat exchange medium from the point of entry into the tempering zone to the exit point from the tempering zone at 0 to 15 ° C, often 1 to 10 ° C, or 2 to 8 ° C, or 3 to 6 ° C increases.
- the heat exchange medium is preferably guided in meandering fashion.
- the commissioning of the method can, for. B. as described in DE-A 103 37 788 or as described in DE-A 102009047291.
- An ⁇ , ⁇ -unsaturated aldehyde produced by the process according to the invention can be further reacted in a second stage to form the ⁇ , ⁇ -unsaturated carboxylic acid.
- a by-product formation of ⁇ , ⁇ -unsaturated carboxylic acid (acrylic acid, methacrylic acid) associated with the gas-phase oxidation of alkene (propene, isobutene) to ⁇ , ⁇ -unsaturated aldehyde (acrolein, methacrolein) is generally not unreasonable. wishes.
- the desired products (aldehyde and carboxylic acid) can be separated in a later process step.
- the resulting aqueous mixture was then stirred for 3 h at 25 ° C and then spray-dried.
- the spray drying was carried out in a rotary disk spray tower of the type FS 15 from Niro in hot air direct current at a gas inlet temperature of 300 ⁇ 10 ° C, a gas outlet temperature of 100 ⁇ 10 ° C, a disk speed of 18000 U / min, a throughput of 200 l / h and an air volume of 1800 Nm 3 / h.
- the spray powder obtained was then pasted with 16.7 wt .-% (based on the powder) of 25 ° C water in a Auspresskneter for 30 min and kneaded at a speed of 20 U / min and by means of an extruder into strands of the diameter Extruded 6 mm.
- the preformed calcined mixed oxide obtained in this way was ground at 2500 rpm with a Biplex cross-flow type sight mill Type 500 BQ from Hosokawa Alpine AG, Augsburg, so that the -W value of the finely divided starting material was 1.2 ⁇ (at a dispersing pressure of 2, 0 bar absolute measured), the BET surface area was 0.6 m 2 / g (measured by nitrogen adsorption after activation in vacuum for 4 h at 200 ° C) and the Y-Bi 2 W0 6 content was 2% by intensity.
- the finely divided starting material 1 in portions of 20 kg in a tilt mixer with mixing and cutting blade (speed mixing blade: 60 rev / min, blade speed: 3000 rev / min) within 5 min homogeneous particulate with 0.5 wt .-% (based on the respective finely divided starting material 1) hydrophobized S1O2 from Degussa type Sipernat ® D17 (bulk density 150 g / l;.
- a solution A was prepared by stirring in a water-tempered 1.75 m 3 - jacketed stainless steel vessel with a bar stirrer at 60 ° C with stirring (70 rev / min) to 660 I a temperature of 60 ° C water within one minute 1.075 kg of an aqueous potassium hydroxide solution having a temperature of 60 ° C. (47.5% by weight of KOH) and then, via a differential metering balance with a metering rate of 600 kg / h, 237.1 kg of ammonium heptamolybdate tetrahydrate at a temperature of 25 ° C.
- a solution B was prepared by mixing in a water-tempered 1.75 m 3 stainless steel jacketed vessel with a bar stirrer at 60 ° C. in 282.0 kg of an aqueous cobalt (III) nitrate solution having a temperature of 60 ° C.
- the solution B was discharged into the initially charged solution A and stirred at 70 U / min at 60 ° C for a further 15 minutes. 19.9 kg of a 25 ° C silica sol from Grace of the Ludox TM 50 type (50.1% by weight of SiO 2 , density: 1.29 g / ml, pH 8.5 to.) Were then added to the resulting aqueous mixture 9.5, alkali content max 0.5 wt .-%) was added and then stirred for a further 15 minutes at 70 U / min at 60 ° C.
- the Kompaktat in a turbulent mixer Drais company within 2 min further 2.5 wt .-% of graphite TIMREX T44 from Timcal AG were added.
- the rotation rate of the rotary was 35 to 45 rpm.
- the tableting was carried out so that the density of the hollow cylindrical shaped bodies (ratio of tablet mass and tablet volume) was identical and was 2.5 grams per milliliter.
- This temperature was maintained for 72 minutes and then increased to 190 ° C over 36 minutes.
- the 190 ° C was held for 72 minutes before the temperature was further increased to 220 ° C within 36 minutes.
- the 220 ° C was held for 72 min before the temperature was further increased to 265 ° C within 36 min.
- the 265 ° C was held for 72 min before the temperature was further increased to 380 ° C within 93 min.
- the 380 ° C was held for 187 min before the temperature was further increased to 430 ° C within 93 min.
- the 430 ° C was held for 187 min before the temperature was further increased within 93 min to the final calcination temperature of 464 ° C. de.
- the final calcination temperature was maintained for 467 minutes. It was then cooled to room temperature over 12 h. For this purpose, the shutdown of the heating of the furnace and the additional and above-described Gutstromvormakersung while retaining the air flow of 4500 Nl / h.
- a reaction tube (V2A steel, 21 mm outer diameter, 3 mm wall thickness, 15 mm inner diameter, length 120 cm) was charged from top to bottom in the flow direction as follows:
- Section 1 about 30 cm in length
- Section 2 about 70 cm in length
- the temperature of the reaction tube was carried out in each case by means of a bubbled with molecular nitrogen, the salt bath temperature T SB of 380 ° C having salt bath (53 wt .-% potassium nitrate, 40 wt .-% sodium nitrite and 7 wt .-% sodium nitrate).
- the salt bath was in a cylindrical envelope.
- the cylindrical envelope had the same length as the reaction tube. The latter was guided from top to bottom in the cylindrical envelope so that the two axes of symmetry coincided.
- the stream of nitrogen bubbled from below into the salt bath was 40 l / h.
- the heat losses of the salt bath to the environment were greater than the heat of reaction produced by the reactor during the partial oxidation.
- the salt bath was therefore kept at its temperature T SB (° C) by means of electric heating. In this way it was ensured that the outer wall of the reaction tube always had the corresponding temperature T SB (° C).
- the reactor was continuously charged with a feed gas mixture (mixture of air, polymer grade propylene and nitrogen) of the composition:
- the mixed gas flow rate was controlled so that the propene conversion U (in terms of a single pass of the reaction gas mixture through the reaction tube, in mol%), defined as,
- the load corresponds to the propene volume flow supplied to the reactor (in Nl / h) based on the mass of catalyst present in the reactor (in grams).
- a higher load corresponds to a higher activity.
- the shaped catalyst bodies according to the invention are stable (more than 85% intact shaped catalyst bodies in the drop test) and ensure a high value product selectivity of more than 95.3 mol%. In Comparative Example 3, the value product selectivity remains well behind that of Inventive Examples 1 and 2 (94.9 mol%).
- the activity of the catalysts according to the invention is higher (greater than or equal to 0.08 Nl propene / (g catalyst and hour)) than that of the noninventive catalyst of Example 3 (0.06 Nl propene / (g catalyst and hour)).
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Priority Applications (4)
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MYPI2016000810A MY173267A (en) | 2013-11-11 | 2014-11-05 | Mechanically stable hollow-cylindrical moulded catalyst body for the gas phase oxidation of an alkene in order to obtain an unsaturated aldehyde and/or an unsaturated carboxylic acid |
JP2016529945A JP6407278B2 (ja) | 2013-11-11 | 2014-11-05 | アルケンを気相酸化して不飽和アルデヒド及び/又は不飽和カルボン酸にするための、機械的に安定な中空円筒形触媒成形体 |
EP14793187.7A EP3068753A1 (de) | 2013-11-11 | 2014-11-05 | Mechanisch stabiler hohlzylindrischer katalysatorformkörper zur gasphasenoxidation eines alkens zu einem ungesättigten aldehyd und/oder einer ungesättigten carbonsäure |
CN201480072795.5A CN105899480B (zh) | 2013-11-11 | 2014-11-05 | 用于烯烃气相氧化以获得不饱和醛和/或不饱和羧酸的机械上稳定的中空圆柱形模制催化剂体 |
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EP3805194A1 (de) | 2020-09-25 | 2021-04-14 | Basf Se | Verfahren zur herstellung eines multimetalloxid-katalysators unter gasdichten bedingungen |
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 |
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WO2017072084A1 (en) * | 2015-10-26 | 2017-05-04 | Shell Internationale Research Maatschappij B.V. | Mechanically strong catalyst and catalyst carrier, its preparation, and its use |
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EP3068753A1 (de) | 2016-09-21 |
US20150133686A1 (en) | 2015-05-14 |
JP6407278B2 (ja) | 2018-10-17 |
CN105899480A (zh) | 2016-08-24 |
MY173267A (en) | 2020-01-09 |
US9700876B2 (en) | 2017-07-11 |
CN105899480B (zh) | 2018-11-13 |
JP2016538120A (ja) | 2016-12-08 |
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