DE19736105A1 - Multi-metal oxide catalyst for gas-phase oxidation of acrolein - Google Patents

Multi-metal oxide catalyst for gas-phase oxidation of acrolein

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Publication number
DE19736105A1
DE19736105A1 DE1997136105 DE19736105A DE19736105A1 DE 19736105 A1 DE19736105 A1 DE 19736105A1 DE 1997136105 DE1997136105 DE 1997136105 DE 19736105 A DE19736105 A DE 19736105A DE 19736105 A1 DE19736105 A1 DE 19736105A1
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aqueous solution
mass
temperature
starting mass
aqueous
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Hartmut Prof Dr Hibst
Signe Dr Unverricht
Andreas Dr Tenten
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BASF SE
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BASF SE
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Priority claimed from BR9811310-0A external-priority patent/BR9811310A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00Compounds of tungsten
    • C01G41/006Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/28Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/885Molybdenum and copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/888Tungsten
    • B01J23/8885Tungsten containing also molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/0006Catalysts containing parts with different compositions
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252Preparation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/50Solid solutions
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    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
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    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/60Optical properties, e.g. expressed in CIELAB-values

Abstract

Improved multi-metal oxide catalysts are obtained by mixing a finely divided mixed oxide of copper (Cu) and other elements at \} 70 deg C with an aqueous solution containing sources of molybdenum (Mo), vanadium (V) and other elements. A process for the production of multi-metal oxide materials of formula: ApBq (I); (where: A = Mo12Va(X<1>)b(X<2>)c(X<3>)d(X<4>)e(X<5>)f(X<6>)gOx; B = (X<7>)12CuhHiOy; X<1> = tungsten, niobium, tantalum, chromium and/or cerium; X<2> = copper, nickel, cobalt, iron, manganese and/or zinc; X<3> = antimony and/or bismuth; X<4> = lithium, sodium, potassium, rubidium, caesium and/or hydrogen; X<5> = magnesium, calcium, strontium and/or barium; X<6> = silicon, aluminium, titanium and/or zirconium; X<7> = molybdenum, tungsten, vanadium, niobium and/or tantalum; a = 1-8; b = 0.2-5; c = 0-23; d = 0-50; e = 0-2; f = 0-5; g = 0-50; h = 4-30; i = 0-20; x, y are determined by the valency and frequency of the elements other than oxygen;) involves preparing the mixed oxide (B) in finely-divided form (starting material 1), mixing in required weight ratio (p : q) (where: p, q are numbers other than zero, such that p:q = (160:1)-(1:1); with an aqueous solution containing sources of elements of component (A) in given stoichiometry ratios (without oxygen; material 2), then drying the mixture and calcining at 250-600 deg C before or after shaping to the required catalyst geometry. Independent claims are also included for: (a) multi-metal oxide materials obtained by the process; (b) an aqueous solution of (A), obtained by dissolving the various sources in water at a temperature (TL) of \- 60 deg C and then cooling to a lower temperature (TE); (c) the solid obtained by drying the solution.

Description

The present invention relates to a process for the preparation of multimetal oxide compositions of the general formula I.

[A] p [B] q (I),

in which the variables have the following meaning:
A: Mo 12 V a X 1 b X 2 c X 3 d X 4 e X 5 f X 6 g O x ,
B: X 7 12 Cu h H i O y ,
X 1 : W, Nb, Ta, Cr and / or Ce, preferably W, Nb and / or Cr,
X 2 : Cu, Ni, Co, Fe, Mn and / or Zn, preferably Cu, Ni, Co and / or Fe,
X 3 : Sb and / or Bi, preferably Sb,
X 4 : Li, Na, K, Rb, Cs and / or H, preferably Na and / or K,
X 5 : Mg, Ca, Sr and / or Ba, preferably Ca, Sr and / or Ba,
X 6 : Si, Al, Ti and / or Zr, preferably Si, Al and / or Ti,
X 7 : Mo, W, V, Nb and / or Ta, preferably Mo and / or W,
a: 1 to 8, preferably 2 to 6,
b: 0.2 to 5, preferably 0.5 to 2.5,
c: 0 to 23, preferably 0 to 4,
d: 0 to 50, preferably 0 to 3,
e: 0 to 2, preferably 0 to 0.3,
f: 0 to 5, preferably 0 to 2,
g: 0 to 50, preferably 0 to 20,
h: 4 to 30, preferably 6 to 24, particularly preferably 8 to 18,
i: 0 to 20, preferably 0 to 10,
x, y: numbers which are determined by the valency and frequency of the elements in I other than oxygen and
p, q: numbers other than zero, the ratio p / q of which is 160: 1 to 1: 1, preferably 20: 1 to 1: 1 and particularly preferably 15: 1 to 3: 1,
in which a multimetal oxide mass B

X 7 12 Cu h H i O y (B),

separately in finely divided form (starting mass 1) and then the preformed solid starting mass 1 in an aqueous solution of sources of the elements Mo, V, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , which contain the aforementioned elements in stoichiometry A

Mo 12 V a X 1 b X 2 c X 3 d X 4 e X 5 f X 6 g (A),

contains (starting mass 2), in the desired quantitative ratio p: q incorporated, the resulting aqueous mixture dries and the resulting precursor mass before or after it Forming to the desired catalyst geometry at temperatures of 250 to 600 ° C, preferably at temperatures of 300 to 450 ° C, calcined.

Multimetal oxide compositions of the general formula I are, for. B. from the DE-A 195 28 646 known and find z. B. in gas phase catalytic Oxidations of organic compounds such as preferably 3 to 6 carbon atoms me containing alkanes, alkanols, alkanals, alkenes and alkene nols (e.g. propylene, acrolein, methacrolein, tert-butanol, Methyl ether of tert-butanol, isobutene, isobutane or isobu tyraldehyde) to olefinically unsaturated aldehydes and / or carbon acids, as well as the corresponding nitriles (ammoxidation) everything from propene to acrylonitrile and from isobutene or tert-Bu tanol to methacrylonitrile) as catalysts.

DE-A 195 28 646 recommends the production of the multimetal oxide to produce masses as described at the beginning, in the case of playful embodiments incorporating the fixed off initial mass 1 in the aqueous starting mass 2 in all cases at a temperature of ≧ 80 ° C. Additional information on the DE-A 195 28 646 does not contain the incorporation temperature.

A disadvantage of the aforementioned production method of DE-A 195 28 646 is that when using the resulting multimetal oxide mass I as catalysts for gas-phase catalytic oxides tion of acrolein to acrylic acid the selectivity of acrylic acid cannot fully satisfy education.

The production of multimetal oxide compositions of the general formula I is also known from EP-A 668 104.

The method of manufacture in EP-A 668 104 is the same as in US Pat DE-A 195 28 646. Information about the incorporation temperature makes the solid starting mass 1 into the aqueous starting mass 2 EP-A 668 104 essentially does not.  

The object of the present invention was therefore a improved process for the production of multimetal oxide materials I provide that does not have the aforementioned disadvantage has more.

Accordingly, there has been a process for producing multimetal oxide mass I found as described in the introduction, characterized by it is that the incorporation of the solid starting mass 1 in the aqueous starting mass 2 takes place at a temperature ≦ 70 ° C. The incorporation temperature is preferably ≦ 60 ° C., and particularly preferred ≦ 40 ° C. As a rule, the familiarization with Room temperature take place so that the incorporation temperature in general ≧ 0 ° C.

According to the invention, the finely divided starting mass 1 consists, in part, of particles whose size diameter d B (longest connecting path through the center of gravity of the particles of two points located on the surface of the particles) <0 to 300 μm, preferably 0.1 to 200 μm, particularly preferably 0.5 to 50 microns and most preferably 1 to 30 microns. Of course, the particle diameter d B can also be 10 to 80 µm or 75 to 125 µm.

It is also advantageous if the starting material 1 to be used according to the invention has a specific surface O B (determined according to DIN 66 131 by gas adsorption (N 2 ) according to Brunauer-Emmet-Tel ler (BET)) ≦ 20 m 2 / g, preferably ≦ 5 m 2 / g and especially before gt 1 m 2 / g. As a rule, O B will be <0.1 m 2 / g.

In principle, the starting mass 1 can both Amorphous and / or crystalline are used here.

It is favorable if the starting mass 1 consists of crystallites of oxometalates or contains those oxometal crystallites which have the X-ray diffraction pattern and thus the crystal structure type of at least one of the subsequent copper molybdates (the expression in brackets represents the source for the associated X-ray diffraction fingerprint) or if the starting mass 1 consists of crystallites of these copper molybdates or contains such copper molybdate crystallites:
Cu 4 Mo 6 O 20 [A. Moini et al., Inorg. Chem. 25 (21) (1986) 3782-3785],
Cu 4 Mo 5 O 17 [index card 39-181 of the JCPDS-ICDD index (1991)],
α-CuMoO 4 [index card 22-242 of the JCPDS-ICDD index (1991)],
Cu 6 Mo 5 O 18 [index card 40-865 of the JCPCS-ICDD index (1991)],
Cu 4-x Mo 3 O 12 with x = 0 to 0.25 [index cards 24-56 and 26-547 of the JCPCS-ICDD index (1991)],
Cu 6 Mo 4 O 15 [index card 35-17 of the JCPDS-ICDD index (1991)],
Cu 3 (MoO 4 ) 2 (OH) 2 [index card 36-405 of the JCPDS-ICDD index (1991)],
Cu 3 Mo 2 O 9 [index cards 24-55 and 34-637 of the JCPDS-ICDD index (1991)],
Cu 2 MoO 5 [index card 22-607 of the JCPDS-ICDD index (1991)].

Advantageous according to the invention are multimetal oxide compositions B which contain or consist of oxometalates, which have the X-ray diffraction pattern and thus the crystal structure type of the subsequent copper molybdate or which contain this copper molybdate itself or consist of it:
CuMoO 4 -III with a tungsten structure according to Russian Journal of Inorganic Chemistry 36 (7) (1991) 927-928, Table 1.

Among these are those with the following stoichiometry II

CuMo A W B V C Nb D Ta E O y . (H 2 O) F (II),

With
1 / (A + B + C + D + E): 0.7 to 1.3, preferably 0.85 to 1.15, particularly preferably 0.95 to 1.05 and very particularly preferably 1,
F: 0 to 1,
B + C + D + E: 0 to 1, preferably 0 to 0.7, and
y is a number that is determined by the valency and frequency of the elements other than oxygen,
prefers.

Particularly preferred among these are those of the stoichiomas III, IV or V:

CuMo A W B V C O y (III),

With
1 / (A + B + C): 0.7 to 1.3, preferably 0.85 to 1.15, particularly preferably 0.95 to 1.05 and very particularly preferably 1,
B + C: 0 to 1, preferably 0 to 0.7, and
y is a number determined by the valency and frequency of elements other than oxygen;

CuMo A W B O y (IV),

With
1 / (A + B): 0.7 to 1.3, preferably 0.85 to 1.15, particularly preferably 0.95 to 1.05 and very particularly preferably 1,
A, B: 0 to 1 and
y is a number determined by the valency and frequency of elements other than oxygen;

CuMo A V C O y (V),

With
1 / (A + C): 0.7 to 1.3, preferably 0.85 to 1.15, particularly preferably 0.95 to 1.05 and very particularly preferably 1,
A, C: 0 to 1 and
y: a number determined by the valency and frequency of elements other than oxygen.

The preparation of such oxometalates or starting materials B is open for example, EP-A 668 104.  

Suitable multimetal oxide compositions B are also those which contain oxometal late of the stoichiometry VI below

CuMo A W B V C Nb D Ta E O y (VI),

With
1 / (A + B + C + D + E): 0.7 to 1.3, preferably 0.85 to 1.15, particularly preferably 0.95 to 1.05 and very particularly preferably 1,
(B + C + D + E) / A: 0.01 to 1, preferably 0.05 to 0.3, particularly preferably 0.075 to 0.15 and very particularly preferably 0.11 and
y: a number determined by the valency and frequency of the elements other than oxygen,
of a structure type, which is referred to as HT copper molybdate structure and is subsequently defined by its X-ray diffraction pattern (fingerprint), represented by its most characteristic and most intense diffraction lines in the form of network plane spacings d [Å] which are independent of the wavelength of the X-ray radiation used:
6.79 ± 0.3
3.56 ± 0.3
3.54 ± 0.3
3.40 ± 0.3
3.04 ± 0.3
2.96 ± 0.3
2.67 ± 0.2
2.66 ± 0.2
2.56 ± 0.2
2.36 ± 0.2
2.35 ± 0.2
2.27 ± 0.2
2.00 ± 0.2
1.87 ± 0.2
1.70 ± 0.2
1.64 ± 0.2
1.59 ± 0.2
1.57 ± 0.2
1.57 ± 0.2
1.55 ± 0.2
1.51 ± 0.2
1.44 ± 0.2.

In the event that the multimetal oxide mass B is a mixture of contains or from various oxometalates there is a mixture of oxometalates with tungsten and HT copper molybdate structure preferred. The weight ratio of Crystallites with HT copper molybdate structure to crystallites with Tungsten structure can be 0.01 to 100, 0.1 to 10, 0.25 to 4 and 0.5 to 2.

The production of oxometalates VI or Aus containing them Gang B reveals z. B. DE-A 195 28 646.

In principle, suitable multimetalloxidmas sen B according to the invention can be prepared in a simple manner by generating an intimate, preferably finely divided, stoichiometric composition of suitable sources from suitable sources of their elemental constituents, and this at temperatures of 200 to 1000 ° C, preferably 250 to 800 ° C, several hours calcined under inert gas or preferably in air, the calcination time being from a few minutes to a few hours. The calcination atmosphere can additionally contain water vapor. As sources for the elementary constituents of the multimetal oxide mass B, those compounds are considered which are already oxides and / or those compounds which can be converted into oxides by heating, at least in the presence of oxygen. In addition to the oxides, such starting compounds are, above all, halides, nitrates, formates, oxalates, citrates, acetates, carbonates, amine complex salts, ammonium salts and / or hydroxides (compounds such as NH 4 OH, (NH 4 ) 2 CO 3 , NH 4 NO 3 , NH 4 CHO 2 , CH 3 COOH, NH 4 CH 3 CO 2 or ammonium oxalate, which can be broken down and / or decomposed at the latest during later calcination to completely gaseous compounds and / or can be decomposed). The intimate mixing of the starting compounds for the production of multimetal oxide compositions B 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 compressing, 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 dry process described if only the sources of the elementary constituents in dissolved form are assumed. Water is preferably used as the solvent. The aqueous composition 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 dried mass is then calcined as described above.

In another production variant of the multimetal oxide compositions B the mixture is used for thermal treatment Output connections in a pressure vessel (autoclave) in counter were from water vapor at superatmospheric pressure Temperatures in the range of <100 to 600 ° C. The print area typically extends up to 500 atm, preferably point up to 250 atm. This is particularly advantageous hydrothermal treatment in the temperature range from <100 to 374.15 ° C (critical temperature of water) in the water vapor and liquid water under the resulting pressures coexist.

The multimetal oxide materials B available as described in the same the oxometalates of a single structure type or a mixture of oxometalates of different structure types can contain or exclusively from oxometalates of a single structure typs or from a mixture of oxometalates of various Structural types can now exist, if necessary after grinding and / or classification to desired sizes, e.g. B. for itself as solid starting mass 1 can be used.

For the preparation of the aqueous starting mass 2 required according to the invention, sources of elemental constituents are also those compounds which are already oxides and / or those compounds which are formed by heating, at least in the presence of oxygen, in oxides are transferable. In addition to the oxides, such starting compounds are, above all, halides, nitrates, formates, oxalates, citrates, acetates, carbonates and / or hydroxides (compounds such as NH 4 OH, (NH 4 ) 2 CO 3 , NH 4 HCO 3 , NH 4 NO 3 , NH 4 CHO 2 , CH 3 COOH or NH 4 CH 3 CO 2 , which can decompose and / or decompose to form completely gaseous compounds at the latest during the later calcination, can also be incorporated). Particularly suitable starting compounds of Mo, V, W and Nb are also their oxo compounds (molybdates, vanadates, tungstates and niobates) or the acids derived therefrom. This applies in particular to the corresponding ammonium compounds (ammonium molybdate, ammonium vanadate, ammonium wolf mat).

To produce an aqueous solution required according to the invention as starting material 2, starting from the aforementioned sources of the elemental constituents, the use of elevated temperatures is generally required. Usually temperatures ≧ 60 ° C, mostly ≧ 70 ° C, but normally ≦ 100 ° C are used. The latter and the following applies in particular when the ammonium heptamolybdate tetrahydrate [AHM = (NH 4 ) 6 Mo 7 O 24 .4 H 2 O] and / or the vanadium source ammonium metavanadate [AMV = NH 4 VO 3 ] is used as the Mo element source . The situation is particularly difficult when the element W is part of the aqueous starting mass 2 and ammonium paratungstate heptahydrate [APW = (NH 4 ) 10 W 12 O 41 .7 H 2 O] in addition to at least one of the two aforementioned element sources as the starting compound of the relevant one aqueous solution is used.

It has now surprisingly been found that at elevated temperatures aqueous solutions produced as starting mass 2 with and after the subsequent cooling below the dissolving temperature, even at Content of the element Mo of ≧ 10% by weight and cooling temperatures of up to 20 ° C or below (usually not <0 ° C), based on the aqueous solution, are usually stable. That is, at or after no solid precipitates on cooling the aqueous solution. Featured the stated statement usually also applies to the corresponding bezo Mo contents of up to 20% by weight.

The Mo content of such is usually at temperatures cooled down to 20 ° C or below (usually not below 0 ° C), as starting mass 2 suitable, aqueous solutions on the solution related, not more than 35 wt .-%.

The above finding, the method according to the invention for the first time possible, is attributed to the fact that when loosening at elevated temperatures obviously compounds of relevan ten elements arise that have an increased water solubility point. This idea is supported by the fact that also from such an aqueous solution can be obtained by drying back stood (e.g. spray drying) a correspondingly increased (even at the corresponding low temperatures) Solubility in Has water.

Furthermore, it was surprisingly found that using Invention as the starting mass 2 prepared aqueous solutions multimetal oxide masses I produced (for their production the incorporation of the finely divided starting mass 1 at deeper Temperature takes place), especially in the partial gas phases  oxidation of acrolein to acrylic acid to higher acrylic acid selec lead activities.

According to the invention, it is therefore expedient to proceed as follows. At a temperature T L ≧ 60 ° C (for example up to 65 ° C, or up to 75 ° C, or up to 85 ° C, or at up to 95 ° C or at ≦ 100 ° C) an aqueous solution suitable as starting mass 2 is produced. After cooling to a temperature T E <T L, the finely divided solid starting material 1 is then incorporated into this aqueous solution. Often T L will be <70 ° C and T E ≦ 70 ° C. When accepting somewhat lower dissolving speeds and lower solids contents, however, T L ≧ 60 ° C is also possible.

Incorporation of the prepared solid starting mass 1 in the aqueous starting mass 2 usually takes place by addition the starting mass 1 into that, as already stated, cooled aqueous starting mass 2 and subsequent mechanical Vermi z. B. using stirring or dispersing aid over a period of a few hours to several days, preferably in a period of several hours. As before executed, it is particularly advantageous according to the invention if the Incorporation of the solid starting material 1 into the aqueous starting material mass 2 at temperatures ≦ 70 ° C, preferably at temperatures ≦ 60 ° C and particularly preferably at temperatures ≦ 40 ° C. In the As a rule, the incorporation temperature will be ≧ 0 ° C.

Furthermore, it is particularly advantageous according to the invention if the one working the solid starting mass 1 in an aqueous starting mass se 2 takes place, the pH of which is 4 to 7, preferably 5, at 25 ° C. is up to 6.5. The latter can e.g. B. can be achieved in that one of the aqueous starting mass 2 one or more pH buffers systems adds. An additive, for example, is suitable as such of ammonia and acetic acid and / or formic acid or an additive of ammonium acetate and / or ammonium formate. Of course can also ammonium with respect to the aforementioned purpose carbonate can be used with.

The drying of the in the incorporation of the starting mass 1 in the aqueous starting mass 2 obtained aqueous mixture usually by spray drying. This will be more appropriate outlet temperatures of 100 to 150 ° C. It can spray dried both in cocurrent and in countercurrent the.

When using in the context of the aforementioned spray drying falling precursor masses for the production of catalysts for the gas phase catalytic oxidation of acrolein to acrylic acid  the desired catalyst geometry is shaped preferably by application to preformed inert catalyst carrier, applying before or after the final Calcination can be done. As a rule, the relevant Precursor mass calcined before the carrier coating. The Coating of the carrier body for the production of the shell catalyst sators is usually in a suitable rotatable container executed how he z. B. from DE-A 29 09 671 or from EP-A 293 859 is known. Expediently, for coating the Carrier body moistens the powder mass to be applied and after the application, e.g. B. by means of hot air, who dried again the. The layer thickness of the pul applied to the carrier body dimensions are advantageously in the range of 50 to 500 microns before ranges from 150 to 250 µm.

Usual porous or non-porous can be used as carrier materials Aluminum oxides, silicon dioxide, thorium dioxide, zirconium dioxide, Silicon carbide or silicates such as magnesium or aluminum silicate be used. The carrier bodies can be regular or irregular be shaped like a gel, with regularly shaped carrier bodies with clearly formed surface roughness, e.g. B. balls or Hollow cylinders are preferred. Again, there are balls among them particularly advantageous. The use is particularly advantageous of essentially non-porous, rough-surface, spherical Carriers made of steatite, the diameter of which is 1 to 8 mm, preferably 4 is up to 5 mm.

Of course, the Ver precursors resulting from spray drying also for Manufacture of full catalysts can be used. In this regard the precursor mass is gained before or after the calcination Catalyst geometry is compressed (e.g. by tableting, Extrude or extrude), where appropriate the per se usual tools, such as. B. graphite or stearic acid as Lubricants and / or molding aids and reinforcing agents such as Microfibers made of glass, asbestos, silicon carbide or potassium titanate can be added. Preferred all-catalyst geometries are hollow cylinders with an outer diameter and a length of 2 to 10 mm and a wall thickness of 1 to 3 mm.

The calcination of the precursor compositions produced according to the invention in the context of the aforementioned spray drying to form the actual catalytically active multimetal oxide compositions is carried out, regardless of whether before or after shaping, at temperatures of 250 to 600 ° C., preferably at temperatures of 300 to 450 ° C. The Calcina tion can under inert gas (e.g. N 2 ), a mixture of inert gas and oxygen (e.g. air), reducing gases such as hydrocarbons (e.g. methane), aldehydes (e.g. acrolein ) or ammonia, but also under a mixture of O 2 and reducing the gases (z. B. all of the above), as described for example in DE-A 43 35 973. When calcining under reducing conditions, it should be noted, however, that the metallic constituents are not reduced to the element. The calcination is therefore expediently carried out under an oxidizing atmosphere. The calcination time usually extends over a few hours and decreases in the usual way with increasing calcination temperature.

The multimetal oxide compositions I obtainable according to the invention are particularly suitable as catalysts with increased selectivity (for a given conversion) for the gas-phase catalytic oxidation of acrolein to acrylic acid. Acrolein is normally used in the process, which was generated by the catalytic gas phase oxidation of propene. As a rule, the acrolein-containing reaction gases from this propene oxidation are used without intermediate cleaning. The gas-phase catalytic oxidation of acrolein in tube bundle reactors is usually carried out as a heterogeneous fixed bed oxidation. Oxygen is used as the oxidizing agent in a manner known per se, expediently diluted with inert gases (for example in the form of air). Suitable dilution gases are e.g. B. N 2 , CO 2 , hydrocarbon, recycled reaction gases and / or water vapor. In acrolein oxidation, an acrolein: oxygen: water vapor: inert gas volume ratio of 1: (1 to 3): (0 to 20): (3 to 30), preferably 1: (1 to 3): (0.5 to 10): (7 to 18) set. The reaction pressure is generally 1 to 3 bar and the total space load is preferably 1000 to 3500 Nl / (1.h). Typical multi-tube fixed bed reactors are e.g. B. in the documents DE-A 28 30 765, DE-A 22 01 528 or US-A 3 147 084. The reaction temperature is usually chosen so that the acrolein conversion in a single pass is above 90%, preferably above 98%. In this case, reaction temperatures of 230 to 330 ° C are normally required.

In addition to the gas phase catalytic oxidation of acrolein to acrylic The process products according to the invention are also capable of acid the gas-phase catalytic oxidation of other organic compounds such as in particular other, preferably 3 to 6, carbon atoms containing alkanes, alkanols, alkanals, alkenes and alkenols (e.g. propylene, methacrolein, tert-butanol, methyl ether of tert-butanol, isobutene, isobutane or isobutyraldehyde) olefinically unsaturated aldehydes and / or carboxylic acids, and the corresponding nitriles (ammoxidation, especially of propene  to acrylonitrile and from isobutene or tert-butanol to methacrylic nitrile) to catalyze. The production is mentioned as an example of acrolein, methacrolein and methacrylic acid. They are suitable but also for the oxidative dehydrogenation of olefinic compounds.

Incidentally, turnover, selectivity and residence time are defined as follows in this document, unless stated otherwise:

Examples Comparative Example 1

In 5430 g of water, 732.7 g of ammonium heptamolybdate tetrahydrate (82.5% by weight of MoO 3 ) and 146.5 g of ammonium metavanadate (75.2% by weight of V 2 O 5 ) were added with stirring at 50 ° C. within solved in a few minutes. Subsequently, 126.3 g of ammonium paratungstate heptahydrate (89.0% by weight of WO 3 ) were added and the suspension was stirred at 50 ° C. for 3 days. A complete solution could not be achieved even after the 3 days.

example 1

In 5,430 g of water, 732.7 g of ammonium heptamolybdate tetrahydrate (82.5% by weight of MoO 3 ), 146.5 g of ammonium metavanadate (75.2% by weight of V 2 O 5 ) and 126, 3 g of ammonium para tungstate heptahydrate (89.0% by weight WO 3 ) dissolved. A complete solution could be achieved after just 1 hour. The clear, orange solution obtained was stirred at 95 ° C. for a further 24 h and remained unchanged. The clear, orange solution obtained was then cooled to 25 ° C. The orange solution remained clear and clear at 25 ° C. for 24 h.

Example 2

126.3 g ammonium paratungstate heptahydrate (89.0% by weight WO 3 ), 146.5 g ammonium metavanadate (75.2% by weight V 2 O 5 ) and 732. 7 g of ammonium hepta molybdate tetrahydrate (82.5% by weight MoO 3 ) dissolved. A complete solution could be achieved after only 0.5 h.

The temperature of the solution was then reduced to 40 ° C. The solution remained clear and rainless.

Example 3 Initial mass 1

219.8 g of ammonium heptamolybdate tetrahydrate (82.5% by weight of MoO 3 ) and 328.25 g of ammonium paratungstate heptahydrate (89.0% by weight of WO 3 ) were dissolved in 5 l of water at 95 ° C. with stirring (solution A). 482.34 g of copper acetate hydrate (41.6% by weight of CuO) were mixed with 3 l of water and 445.0 g of a 25% by weight aqueous ammonia solution and stirred at 25 ° C. for 15 minutes, a deep blue solution being obtained (Solution B). Solution B was then stirred into solution A pointing to 95 ° C., the temperature of solution A not falling below 80 ° C. The resulting suspension C was stirred at 80 ° C. for 1 h and had a pH (glass electrode) of 8.5. The suspension C was spray-dried at an inlet temperature of 310 ° C. and an outlet temperature of 110 ° C. The resulting light green spray powder was kneaded with water (200 g of water per 1 kg of spray powder) and shaped into 6 mm thick strands (approx. 1 cm long) on an extruder with 50 bar. These strands were dried in air at 110 ° C for 16 hours. The strands were then calcined in air. The calcined material was placed in an oven at 300 ° C., left at this temperature for 30 minutes, heated to 750 ° C. within 1 hour and left at this temperature of 750 ° C. for 1 hour. The resulting product had a red-brown color and, after grinding in a centrifugal mill from Retsch, DE, a specific surface area according to DIN 66 131 of 0.8 m 2 / g and the composition Cu 12 Mo 6 W 6 O 48 . Using Cu-Kα radiation (Siemens diffractometer D-5000, 40 kV, 30 mA, with automatic divergence-scattered beam and counter tube diaphragm and Peltier detector), the crystalline powder obtained had the composition Cu 12 Mo 6 W 6 O 48 a powder X-ray diffractogram showing a superposition of the tungsten fingerprint with the HT-copper fermolybdate fingerprint, that is, it had a two-phase structure. According to the line intensities, the two structure types were approximately 90 (tungsten structure): 10 (HT copper molybdate structure).

Initial mass 2

732.7 g of ammonium heptamolybdate tetrahydrate (82.5% by weight of MoO 3 ), 146.5 g of ammonium meta vanadate (75.2% by weight of V 2 O 5 ) and 126, 3 g of ammonium paratungstate hydrate (89.0% by weight WO 3 ) dissolved. The aqueous solution (starting mass 2) was therefore based on the following element stoichiometry:

Mo 12 V 3.46 W 1.39 .

Active mass

The clear, orange-colored solution obtained (starting mass 2) was then cooled to 25 ° C. 172.7 g of the starting mass 1 were stirred into the starting mass 2 cooled to 25 ° C., so that the molar ratio of the aforementioned stoichiometric units was 1.6 (starting mass 1) to 1 (starting mass 2). Subsequently, 150.0 g of ammonium acetate were stirred into the aqueous suspension, the resulting suspension was stirred at 25 ° C. for 1 h and then the aqueous mixture was spray-dried. The spray powder was then kneaded with a mixture of 70% by weight of water and 30% by weight of acetic acid (0.35 kg of liquid per 1 kg of spray powder). The kneaded material obtained was dried in air at 110 ° C. for 16 hours. The comminuted kneaded material was calcined in a rotary tube charged with an oxygen / nitrogen mixture. 700 g of calcined material were introduced into the cylindrical calcining chamber (length: 51 cm, inside diameter: 12.5 cm) of the rotary tube. During the entire calcination process, a mixture of 10 Nl / h air and 200 Nl / h nitrogen preheated to the calcination temperature was passed through the calcining chamber of the rotary tube. In the course of the calcination, the modeling clay was first heated to 210 ° C. in 20 minutes, then heated to 400 ° C. in the course of 5 hours and then held at this temperature for 3 hours. The resulting catalytically active material had the following gross stoichiometry:

[Mo 12 V 3.46 W 1.39 O x ] 6.5 [Cu 12 Mo 6 W 6 O 48 ].

The X-ray diffractogram of the active composition obtained contained as before the superposition of the tungsten structure type and HT-Kup fermolybdate structure type. After grinding the calcined active mass became non-porous and upper in a rotating drum rough surface steatite balls with a diameter of 4 to 5 mm in  a quantity of 50 g active powder per 200 g steatite balls simultaneous addition of 18 g of water coated. Subsequently was the shell catalyst obtained with 110 ° C hot air dried.

Example 4 Initial mass 1

Starting mass 1 was starting mass 1 from Example 3 used.

Initial mass 2

732.7 g of ammonium heptamolybdate tetrahydrate (82.5% by weight of MoO 3 ), 146.5 g of ammonium meta vanadate (75.2% by weight of V 2 O 5 ) and 126, 3 g of ammonium paratungstate hydrate (89.0% by weight WO 3 ) dissolved. The aqueous solution (starting mass 2) was therefore based on the following element stoichiometry:

Mo 12 V 3.46 W 1.39 .

Active mass

Then the clear orange solution obtained (Initial mass 2) cooled to 25 ° C and successively in this 116.9 g acetic acid and 132.3 g ammonia solution (25 wt% ammonia in water). From the starting mass 1 172.7 g were in the Cooled to 25 ° C and buffered starting mass 2 stirred, see above that the molar ratio of the aforementioned stoichiometric one units was 1.6 (starting mass 1) to 1 (starting mass 2). The suspension obtained was stirred at 25 ° C. for 1 h. The resulting aqueous mixture was then spray dried and processed as in Example 3.

Comparative Example 2

The procedure was as in Example 3. Deviating from that however, starting mass 1 at 95 ° C. into aqueous starting mass 2 stirred and the resulting suspension after the Ammo nium acetate addition stirred at 95 ° C for 1 h.

Example 5

The multimetal oxide catalysts prepared in Examples 3, 4 and Comparative Example 2 were placed in a tubular reactor (V2A steel, 25 mm inside diameter, 2000 g catalyst bed, salt bath temperature control) and at reaction temperatures in the range from 250 to 270 ° C. using a residence time of 2.0 sec with a gaseous mixture of the composition
5 vol.% Acrolein,
7 vol.% Oxygen,
10 vol .-% water vapor and
78 vol% nitrogen
loaded. The salt bath temperature was set in all cases in such a way that, after the formation had ended, a single pass resulted in a uniform acrolein conversion U of 99%. The product gas mixture flowing out of the reactor was analyzed by gas chromatography. The results for the selectivity of acrylic acid formation using the various catalysts are shown in the table below.
Catalyst: S%
Example 3: 96.3
Example 4: 96.4
Comparative Example 2: 96.0.

Claims (9)

1. Process for the preparation of multimetal oxide compositions of the general formula I
[A] p [B] q (I),
in which the variables have the following meaning:
A: Mo 12 V a X 1 b X 2 c X 3 d X 4 e X 5 f X 6 g O x ,
B: X 7 12 Cu h H i O y ,
X 1 : W, Nb, Ta, Cr and / or Ce,
X 2 : Cu, Ni, Co, Fe, Mn and / or Zn,
X 3 : Sb and / or Bi,
X 4 : Li, Na, K, Rb, Cs and / or H,
X 5 : Mg, Ca, Sr and / or Ba,
X 6 : Si, Al, Ti and / or Zr,
X 7 : Mo, W, V, Nb and / or Ta,
a: 1 to 8,
b: 0.2 to 5,
c: 0 to 23,
d: 0 to 50,
e: 0 to 2,
f: 0 to 5,
g: 0 to 50,
h: 4 to 30,
i: 0 to 20,
x, y: numbers which are determined by the valency and frequency of the elements in I other than oxygen and
p, q: non-zero numbers whose ratio p / q is 160: 1 to 1: 1,
in which a multimetal oxide mass B
X 7 12 Cu h H i O y (B),
separately in finely divided form (starting mass 1) and then the preformed solid starting mass 1 in an aqueous solution of sources of the elements Mo, V, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , which contain the aforementioned elements in stoichiometry A
Mo 12 V a X 1 b X 2 c X 3 d X 4 e X 5 f X 6 g (A),
contains (starting mass 2), incorporated in the desired quantitative ratio p: q, the resulting aqueous mixture dries and the resulting precursor mass is calcined before or after its formation to the desired catalyst geometry at temperatures of 250 to 600 ° C, characterized in that the incorporation the preformed solid starting mass 1 into the aqueous starting mass 2 at a temperature ≦ 70 ° C.
2. The method according to claim 1, characterized in that the Incorporation of the preformed solid starting mass 1 into the aqueous starting mass 2 takes place at a temperature ≦ 60 ° C.
3. The method according to claim 1, characterized in that the Incorporation of the preformed solid starting mass 1 into the aqueous starting mass 2 at a temperature ≦ 40 ° C.
4. Multimetal oxide materials, obtainable by a process according to one of claims 1 to 3.
5.Aqueous solution containing the elements Mo, V, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 in the stoichiometry Mo 12 V a X 1 b X 2 c X 3 d X 4 e X 5 f X 6 g contains dissolved, the variables having the meaning according to claim 1, obtainable by dissolving sources of the aforementioned elements at a temperature T L ≧ 60 ° C in water and then the aqueous solution to a temperature T E <T L cools down.
6. Aqueous solution according to claim 5, characterized in that T L <70 ° C and T E ≦ 70 ° C.
7. Aqueous solution according to claim 5, characterized in that T L <80 ° C and T E ≦ 80 ° C.
8. Aqueous solution according to one of claims 5 to 7, characterized ge indicates that their Mo content, based on the aqueous Solution, 10 to 35 wt .-% is.
9. Solid, obtainable by making an aqueous solution dries according to one of claims 5 to 8.
DE1997136105 1997-08-20 1997-08-20 Multi-metal oxide catalyst for gas-phase oxidation of acrolein Withdrawn DE19736105A1 (en)

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DE1997136105 DE19736105A1 (en) 1997-08-20 1997-08-20 Multi-metal oxide catalyst for gas-phase oxidation of acrolein
BR9811310-0A BR9811310A (en) 1997-08-20 1998-07-25 Process for the preparation of multimetal oxide materials, multimetal oxide material, aqueous solution, solid, and, process for the preparation of acrylic acid by catalytically oxidizing the gas phase of acrolein
EP19980939640 EP1005394A1 (en) 1997-08-20 1998-07-25 Method for producing multi-metal oxide masses containing mo, v and cu
AU88077/98A AU8807798A (en) 1997-08-20 1998-07-25 Method for producing multi-metal oxide masses containing mo, v and cu
PCT/EP1998/004665 WO1999008788A1 (en) 1997-08-20 1998-07-25 Method for producing multi-metal oxide masses containing mo, v and cu
KR1020007001700A KR20010023081A (en) 1997-08-20 1998-07-25 Method for Producing Multi-Metal Oxide Masses Containing Mo, V and Cu
CN 98808266 CN1267236A (en) 1997-08-20 1998-07-25 Method for producing multi-metal oxide masses contg. Mo, V and Cu
JP2000509519A JP2001515004A (en) 1997-08-20 1998-07-25 Method for producing composite metal oxide material containing Mo, V and Cu
CA 2301704 CA2301704A1 (en) 1997-08-20 1998-07-25 Method for producing multi-metal oxide masses containing mo, v and cu

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004009525A1 (en) 2002-07-18 2004-01-29 Basf Aktiengesellschaft Method for the heterogeneously-catalysed gas phase partial oxidation of at least one organic compound
EP1579910A2 (en) * 2004-03-25 2005-09-28 Nippon Shokubai Co., Ltd. Catalyst for production of acrylic acid and process for production of acrylic acid using the catalyst
US7015354B2 (en) 2003-08-14 2006-03-21 Basf Aktiengesellschaft Preparation of (meth)acrolein and/or (meth)acrylic acid
CN100345631C (en) * 2004-03-25 2007-10-31 株式会社日本触媒 Catalyst for production of acrylic acid and process for production of acrylic acid using this catalyst
WO2011067363A2 (en) 2009-12-04 2011-06-09 Basf Se Producing acetaldehyde and/or acetic acid from bioethanol
WO2012035019A1 (en) 2010-09-16 2012-03-22 Basf Se Method for producing acrylic acid from ethanol and formaldehyde
WO2012163931A1 (en) 2011-06-03 2012-12-06 Basf Se Aqueous solution comprising acrylic acid and the conjugate base thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004009525A1 (en) 2002-07-18 2004-01-29 Basf Aktiengesellschaft Method for the heterogeneously-catalysed gas phase partial oxidation of at least one organic compound
US7015354B2 (en) 2003-08-14 2006-03-21 Basf Aktiengesellschaft Preparation of (meth)acrolein and/or (meth)acrylic acid
EP1579910A2 (en) * 2004-03-25 2005-09-28 Nippon Shokubai Co., Ltd. Catalyst for production of acrylic acid and process for production of acrylic acid using the catalyst
EP1579910A3 (en) * 2004-03-25 2006-06-07 Nippon Shokubai Co., Ltd. Catalyst for production of acrylic acid and process for production of acrylic acid using the catalyst
CN100345631C (en) * 2004-03-25 2007-10-31 株式会社日本触媒 Catalyst for production of acrylic acid and process for production of acrylic acid using this catalyst
US7378367B2 (en) 2004-03-25 2008-05-27 Nippon Shokubai Co., Ltd. Catalyst for production of acrylic acid and process for production of acrylic acid using the catalyst
WO2011067363A2 (en) 2009-12-04 2011-06-09 Basf Se Producing acetaldehyde and/or acetic acid from bioethanol
WO2012035019A1 (en) 2010-09-16 2012-03-22 Basf Se Method for producing acrylic acid from ethanol and formaldehyde
DE102010040923A1 (en) 2010-09-16 2012-03-22 Basf Se Process for the preparation of acrylic acid from ethanol and formaldehyde
US8507721B2 (en) 2010-09-16 2013-08-13 Basf Se Process for preparing acrylic acid from ethanol and formaldehyde
WO2012163931A1 (en) 2011-06-03 2012-12-06 Basf Se Aqueous solution comprising acrylic acid and the conjugate base thereof
US9150483B2 (en) 2011-06-03 2015-10-06 Basf Se Aqueous solution comprising acrylic acid and the conjugate base thereof

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