ITMI20121610A1 - CATALYTIC SYSTEM FOR THE AMMOSSIDATION OF PROPYLENE TO ACRILONITRILE. - Google Patents
CATALYTIC SYSTEM FOR THE AMMOSSIDATION OF PROPYLENE TO ACRILONITRILE. Download PDFInfo
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- ITMI20121610A1 ITMI20121610A1 IT001610A ITMI20121610A ITMI20121610A1 IT MI20121610 A1 ITMI20121610 A1 IT MI20121610A1 IT 001610 A IT001610 A IT 001610A IT MI20121610 A ITMI20121610 A IT MI20121610A IT MI20121610 A1 ITMI20121610 A1 IT MI20121610A1
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- Prior art keywords
- catalytic system
- molybdate
- propylene
- promoter
- weight
- Prior art date
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- 230000003197 catalytic effect Effects 0.000 title claims description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 25
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000411 antimony tetroxide Inorganic materials 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 3
- 235000012239 silicon dioxide Nutrition 0.000 claims 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 239000002002 slurry Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
- B01J27/192—Molybdenum with bismuth
Description
SISTEMA CATALITICO PER L'AMMOS S IDAZIONE DEL PROPILENE AD ACR ILONITRILE CATALYTIC SYSTEM FOR AMMOS S IDATION OF PROPYLENE TO ACR ILONITRILE
DESCRIZIONE DESCRIPTION
La presente invenzione riguarda un sistema catalitico, in particolare per l 'ammossidazione del propilene ad acrilonitrile, e un processo per l'ammossidazione del propilene ad acrilonitrile che impiega tale sistema catalitico. The present invention relates to a catalytic system, in particular for the amoxidation of propylene to acrylonitrile, and a process for the amoxidation of propylene to acrylonitrile which uses this catalytic system.
Sono noti vari tipi di catalizzatori per la suddetta ammossidazione: i più diffusi sono del tipo molibdato multi metallico che comprende come elementi fondamentali Mo, Bi, Fe, Co e/o Ni, Ce e metalli alcalini, in particolare K e Cs. Various types of catalysts for the aforementioned amoxidation are known: the most common are of the multi-metal molybdate type which includes Mo, Bi, Fe, Co and / or Ni, Ce and alkali metals, in particular K and Cs, as basic elements.
Nel corso degli anni questi catalizzatori sono stati sviluppati dando luogo a formulazioni sempre più complesse, e a sistemi in cui il molibdato multi metallico viene impiegato insieme a promotori tra cui uno dei più rappresentativi à ̈ costituito da antimoniato di ferro (US 5.513.269). Over the years these catalysts have been developed giving rise to increasingly complex formulations, and to systems in which the multi-metal molybdate is used together with promoters, one of the most representative of which is iron antimonate (US 5,513,269).
Il brevetto italiano 1320123 descrive un sistema catalitico comprendente un molibdato multi metallico e come promotore antimoniato di cromo. The Italian patent 1320123 describes a catalytic system comprising a multi metallic molybdate and chromium antimoniate promoter.
La preparazione del promotore viene effettuata aggiungendo ossido di antimonio Sb2O3a nitrato di cromo sciolto in acqua e portando poi a secco la sospensione ottenuta su piastra riscaldata. The preparation of the promoter is carried out by adding antimony oxide Sb2O3a chromium nitrate dissolved in water and then drying the suspension obtained on a heated plate.
Il solido così ottenuto viene calcinato a 700°C. The solid thus obtained is calcined at 700 ° C.
Il molibdato multi metallico viene preparato utilizzando come sale di molibdeno di partenza ep tamol ibdato di ammonio (NH4)6MO7O24*4H2O) . The multi-metal molybdate is prepared using ep ammonium tamol ibdate (NH4) (NH4) 6MO7O24 * 4H2O) as starting molybdenum salt.
Uno scopo della presente invenzione à ̈ quello di fornire un sistema catalitico che permetta l'ottenimento di rese elevate di prodotto. In particolare, uno scopo della presente invenzione à ̈ quello di fornire un sistema catalitico per la preparazione di acrilonitrile per ammossidazione del propilene, che permetta di ottenere prestazioni migliori di quelle conseguite con il sistema noto. An object of the present invention is to provide a catalytic system which allows to obtain high product yields. In particular, an object of the present invention is to provide a catalytic system for the preparation of acrylonitrile by amoxidation of propylene, which allows to obtain better performances than those achieved with the known system.
La presente invenzione fornisce un sistema catalitico che raggiunge questi scopi, che comprende : The present invention provides a catalytic system which achieves these purposes, which comprises:
A) Un molibdato multi metallico di formula: Mo12Bi 0,1-2Fe1 -3Co2-8Mg0 ,5-2Mn0,1-1Cr0 ,1-1Ce0,1 -1K0, 01-1Cs0,01-10x A) A multi metallic molybdate of formula: Mo12Bi 0,1-2Fe1 -3Co2-8Mg0, 5-2Mn0,1-1Cr0, 1-1Ce0,1 -1K0, 01-1Cs0,01-10x
in cui x à ̈ il numero di atomi di ossigeno necessari a soddisfare la valenza degli altri elementi, e opzionalmente contenente anche almeno un altro elemento rispetto alla formula indicata sopra, scelto tra Ni, Zn, Li, Na, Rb, e Te, where x is the number of oxygen atoms necessary to satisfy the valence of the other elements, and optionally also containing at least one other element with respect to the formula indicated above, chosen from Ni, Zn, Li, Na, Rb, and Te,
detto molibdato essendo ottenibile utilizzando un composto di Mo che à ̈ prodotto mediante reazione di MoO3con H2O2al 35 %, diluita con un volume di acqua pari alla metà del volume di H2O2, ed impiegata in eccesso molare rispetto a Mo03, in cui la reazione à ̈ condotta mantenendo una temperatura inferiore a 50 °C fino a completa dissoluzione; e B) Un promotore costituito da una miscela formata per il 7 0-85% in peso da un composto di formula CrxSbyO4in (cui x+y =2; con x,y ≠0) e per il 30-15% da un ossido Sb204, detto promotore essendo presente in quantità di 5-25 % in peso rispetto alla somma delle quantità di molibdato multi metallico e promotore . said molybdate being obtainable using a Mo compound which is produced by reaction of MoO3 with 35% H2O2, diluted with a volume of water equal to half the volume of H2O2, and used in molar excess with respect to Mo03, in which the reaction is conducted maintaining a temperature below 50 ° C until complete dissolution; and B) A promoter consisting of a mixture consisting of 7 0-85% by weight of a compound of the formula CrxSbyO4in (where x + y = 2; with x, y â ‰ 0) and 30-15% of a Sb204 oxide, said promoter being present in quantities of 5-25% by weight with respect to the sum of the quantities of multi-metal molybdate and promoter.
Il molibdato multi metallico del sistema catalìtico della presente invenzione opzionalmente comprende anche almeno un altro elemento rispetto alla formula indicata sopra, scelto tra Ni, Zn, Li, Na, Rb, e Te. Questi elementi, quando presenti, possono essere in un rapporto atomico rispetto al molibdeno di (0-3)/12 per Ni e Zn, di (0.01-1)/12 per Li, Na e Rb, e (0-2)/12 per Te. The multi-metallic molybdate of the catalytic system of the present invention optionally also comprises at least one other element with respect to the formula indicated above, selected from Ni, Zn, Li, Na, Rb, and Te. These elements, when present, can be in an atomic ratio with respect to molybdenum of (0-3) / 12 for Ni and Zn, of (0.01-1) / 12 for Li, Na and Rb, and (0-2) / 12 for you.
La presente invenzione fornisce inoltre un processo per la preparazione di acrilonitrile per ammos sidazione del propilene realizzato in un reattore a letto fluido utilizzando un sistema catalitico secondo la presente invenzione e una miscela gassosa di reagenti comprendente ossigeno, propilene e ammoniaca, con un rapporto molare ossigeno/propilene di 1-2, un rapporto molare ammoniaca/propilene di 1- 1,5, una velocità spaziale (espressa come grammi di propilene per ora per grammo di catalizzatore) , della miscela dei reagenti di 0,045 - 0,1 h<-1>una pressione di 1 - 1,8 bar assolute ed una temperatura compresa tra 380 °C e 500 °C. The present invention also provides a process for the preparation of acrylonitrile by amoxidation of propylene carried out in a fluidized bed reactor using a catalytic system according to the present invention and a gaseous mixture of reactants comprising oxygen, propylene and ammonia, with a molar oxygen ratio. / propylene of 1-2, an ammonia / propylene molar ratio of 1- 1.5, a space velocity (expressed as grams of propylene per hour per gram of catalyst), of the reagent mixture of 0.045 - 0.1 h <- 1> a pressure of 1 - 1.8 absolute bar and a temperature between 380 ° C and 500 ° C.
Si à ̈ ora inaspettatamente trovato che se al posto dell 'eptamolibdato di ammonio sopra menzionato si impiega il prodotto della reazione di triossido di molibdeno (MoO3) con acqua ossigenata al 35% in peso condotta come di seguito precisato si ottiene un sistema catalitico dotato di prestazioni significativamente maggiori di quelle conseguibili impiegando l'eptamolibdato di ammonio. La reazione tra MoO3e H2O2à ̈ condotta diluendo l'acqua ossigenata al 35% di cui sopra con un volume di acqua pari alla metà del volume della stessa ed impiegando quantitativi molari di H2O2in eccesso rispetto a MoO3, controllando che la temperatura non superi 50°C e mantenendo in agitazione la miscela fino a completa dissoluzione del solido. It has now been unexpectedly found that if instead of the ammonium heptamolybdate mentioned above, the reaction product of molybdenum trioxide (MoO3) with hydrogen peroxide at 35% by weight is obtained, carried out as specified below, a catalytic system equipped with significantly higher performance than those achievable using ammonium heptamolybdate. The reaction between MoO3 and H2O2 is carried out by diluting the hydrogen peroxide to 35% above with a volume of water equal to half its volume and using molar quantities of H2O2 in excess of MoO3, checking that the temperature does not exceed 50 ° C and stirring the mixture until complete dissolution of the solid.
Il molibdato multi metallico comprende i seguenti elementi fondamentali: The multi metallic molybdate includes the following fundamental elements:
MO12Bi0,1-2Fe1-3CO2-8Mg0,5-2Mn0,1-Cr0,1-1Ce0,1-1K0,01-1CS0 , 01 - 1OxMO12Bi0,1-2Fe1-3CO2-8Mg0,5-2Mn0,1-Cr0,1-1Ce0,1-1K0,01-1CS0.01 - 1Ox
in cui x à ̈ il numero di atomi di ossigeno necessari a soddisfare la valenza degli altri elementi . where x is the number of oxygen atoms needed to satisfy the valence of the other elements.
Il molibdato multi metallico di preferenza ha la seguente composizione: The multi-metal molybdate preferably has the following composition:
MOi2Bi0,2f<1>eI, eCo5, 2Mg2# iMno,5Cro , 2Ce0,4Ko ,07CS0,OÃŒOZMOi2Bi0,2f <1> eI, eCo5, 2Mg2 # iMno, 5Cro, 2Ce0,4Ko, 07CS0, OÃŒOZ
in cui z à ̈ il numero di atomi di ossigeno necessari a soddisfare la valenza degli altri elementi . where z is the number of oxygen atoms needed to satisfy the valence of the other elements.
Può comprendere almeno uno dei seguenti elementi facoltativi: (Ni e Zn), (Li, Na e Rb), (Te) in rapporto atomico rispetto al Mo rispettivamente di (0-3)/12; (0,01-1)/12; (0~2)/12. It can include at least one of the following optional elements: (Ni and Zn), (Li, Na and Rb), (Te) in atomic ratio with respect to Mo respectively of (0-3) / 12; (0.01-1) / 12; (0 ~ 2) / 12.
Il sistema catalitico viene supportato su Si02, Al2O3, Zr02o Ce02;preferibilmente viene impiegato Si02in quantità di 30 -80% in peso sul peso totale del molibdato mul t imetallico , promotore e supporto, in particolare 30-60% in peso e più in particolare 40-60% in peso. The catalytic system is supported on Si02, Al2O3, Zr02 or Ce02; Si02 is preferably used in an amount of 30 -80% by weight of the total weight of the multi-metal molybdate, promoter and support, in particular 30-60% by weight and more particularly 40-60% by weight.
Il molibdato utilizzato nel sistema catalitico della presente invenzione può essere ottenuto da un composto di Mo che à ̈ prodotto mediante reazione di MoO3 con H2O2 al 35 diluita con un volume di acqua pari alla metà del volume di H2O2, ed impiegata in eccesso molare rispetto a MoO3, in cui la reazione à ̈ condotta mantenendo una temperatura inferiore a 50 °C fino a completa dissoluzione, e sali degli altri elementi metallici presenti nella formula . The molybdate used in the catalytic system of the present invention can be obtained from a Mo compound which is produced by reaction of MoO3 with H2O2 at 35 diluted with a volume of water equal to half the volume of H2O2, and used in molar excess with respect to MoO3, in which the reaction is carried out maintaining a temperature below 50 ° C until complete dissolution, and salts of the other metal elements present in the formula.
La preparazione del molibdato multi metallico viene effettuata secondo i metodi convenzionali sciogliendo ad esempio i nitrati dei vari elementi in acqua acida per acido nitrico ad eccezione del composto di molibdeno la cui preparazione viene realizzata a parte secondo la modalità in precedenza descritta. The preparation of the multi-metallic molybdate is carried out according to conventional methods by dissolving, for example, the nitrates of the various elements in acid water for nitric acid with the exception of the molybdenum compound, the preparation of which is carried out separately according to the previously described method.
La soluzione dei nitrati e quella del prodotto di reazione di MoO3con acqua ossigenata vengono miscelate con silice colloidale a sua volta miscelata con acqua sotto agitazione. The solution of nitrates and that of the reaction product of MoO3 with hydrogen peroxide are mixed with colloidal silica which is in turn mixed with water under stirring.
Si aggiunge quindi il promotore, preparato miscelando ad esempio una soluzione di nitrato di cromo con ossido di antimonio trivalente portando a secco e calcinando a 700°C, sospeso in acqua. La torbida finale cosi ottenuta viene macinata con mulino a sfere. The promoter is then added, prepared by mixing, for example, a solution of chromium nitrate with trivalent antimony oxide, drying and calcining at 700 ° C, suspended in water. The final slurry thus obtained is ground with a ball mill.
Segue un trattamento di essiccamento in cui la torbida viene portata a secco mediante spraydrying ottenendo così una polvere microsferoidale che viene poi calcinata in un forno in flusso di aria in cui la temperatura del letto viene, ad esempio, portata da temperatura ambiente a 400°C in circa 6 ore, con salita della temperatura lineare, mantenuta a 400°C per 2 ore, quindi portata linearmente a 590°C in un'ora e mantenuta a 590°C per due ore. A drying treatment follows in which the slurry is brought to dryness by spraydrying, thus obtaining a microspheroidal powder which is then calcined in an oven in an air flow in which the temperature of the bed is, for example, brought from room temperature to 400 ° C in about 6 hours, with linear temperature rise, maintained at 400 ° C for 2 hours, then brought linearly to 590 ° C in one hour and maintained at 590 ° C for two hours.
Il processo di ammossidazione del propilene, utilizzando il sistema catalitico secondo l'invenzione, viene realizzato nelle seguenti condizioni: temperatura tra 380 °C e 500 °C , preferibilmente tra 420°C e 460 °C, rapporti molari ossigeno/propilene di 1-2, ammoniaca/propilene di 1-1,5, preferibilmente 1, velocità spaziale della miscela gassosa dei reagenti di 0,045-1 (g propilene/h) /g cat., preferibilmente 0,07h<-1>e pressioni di 1 - 1,8 bar assolute. The amoxidation process of propylene, using the catalytic system according to the invention, is carried out under the following conditions: temperature between 380 ° C and 500 ° C, preferably between 420 ° C and 460 ° C, oxygen / propylene molar ratios of 1- 2, ammonia / propylene of 1-1.5, preferably 1, space velocity of the gaseous mixture of the reactants of 0.045-1 (g propylene / h) / g cat., Preferably 0.07h <-1> and pressures of 1 - 1.8 absolute bar.
I seguenti esempi vengono forniti a titolo illustrativo ma non limitativo dell'invenzione. The following examples are provided for illustrative but not limitative purposes of the invention.
Esempi Examples
Si prepara il sistema catalitico eseguendo le seguenti operazioni: The catalytic system is prepared by carrying out the following operations:
a) Preparazione della soluzione dei nitrati In un bicchiere contenente 250 ml di acqua deionizzata e 86 g di acido nitrico al 70 si sciolgono nell'ordine 16,98 g di Bi(NO3)3* 5 H2O ; 30,47 g di Ce (NO3)3*6H2O ; 127,57 di Fe (N03)3*9H20 ; 14,04 di Cr (N03)3*9H20 ; 94,19 g di Mg (N03)2*6H20 , 2 67,2 6 g di Co (N03)2*6H20 ; 20,74g di Mn (N03)2*4H20 ; 1,24 g di KN03e 1,37 g di C sNO3. a) Preparation of the nitrate solution In a beaker containing 250 ml of deionized water and 86 g of 70 nitric acid dissolve in the order 16.98 g of Bi (NO3) 3 * 5 H2O; 30.47 g of Ce (NO3) 3 * 6H2O; 127.57 of Fe (N03) 3 * 9H20; 14.04 of Cr (N03) 3 * 9H20; 94.19 g of Mg (N03) 2 * 6H20, 2 67.2 6 g of Co (N03) 2 * 6H20; 20.74g of Mn (N03) 2 * 4H20; 1.24 g of KN03 and 1.37 g of C sNO3.
b) Preparazione della soluzione del prodotto della reazione tra MoO3e H2O2b) Preparation of the solution of the product of the reaction between MoO3 and H2O2
In un bicchiere di circa 1000 ml si versano 302,9 g di MoO3ed una miscela costituita da 500 ml di H2O2al 35 % e da 250 ml di acqua deionizzata. Si pone in agitazione e si controlla che la temperatura non superi i 50 eventualmente raffreddando con un bagno di acqua e ghiaccio. Si lascia in agitazione fino a completa dissoluzione, Pour 302.9 g of MoO3 and a mixture of 500 ml of 35% H2O2 and 250 ml of deionized water into a glass of about 1000 ml. It is stirred and checked that the temperature does not exceed 50, possibly by cooling with a water and ice bath. It is left to stir until completely dissolved,
c) Preparazione del promotore Cr/Sb c) Preparation of the Cr / Sb promoter
Ad una soluzione di 63,54 g di Cr ( NO3)3* 9H2O sono aggiunti 46,29g di Sb2O3. 46.29g of Sb2O3 are added to a solution of 63.54 g of Cr (NO3) 3 * 9H2O.
La sospensione à ̈ tirata a secco su piastra riscaldata. Il solido à ̈ essiccato a 120 °C e calcinato a 700 °C. Il solido così ottenuto à ̈ disperso in acqua. Il prodotto calcinato ha la seguente composizione in percentuale in peso determinata dallo spettro di diffrazione dei raggi X col metodo di Rietveld: composto CrxSbYO477,1%, Sb2O422,9 % d) Preparazione della torbida e trattamenti termici The suspension is dried on a heated plate. The solid is dried at 120 ° C and calcined at 700 ° C. The solid thus obtained is dispersed in water. The calcined product has the following composition in percentage by weight determined by the X-ray diffraction spectrum with the Rietveld method: compound CrxSbYO477.1%, Sb2O422.9% d) Preparation of the slurry and heat treatments
In un reattore munito di agitazione meccanica si versano 1250 g di silice colloidale Ludox AS40 e 420 ml di acqua deionizzata. Si aggiungono nell'ordine la soluzione nitrica dei sali e la soluzione del composto di molibdeno. Si ottiene una soluzione. La soluzione à ̈ successivamente trattata a 50 °C per Ih sotto agitazione. Si ottiene una torbida alla quale si aggiungono 62,2 g del promotore Sb/Cr mescolati a 150 ml di acqua deionizzata. La torbida à ̈ successivamente omogeneizzata mediante macinazione a umido in un mulino a sfere ad ottenere un diametro medio delle particelle sospese al di sotto di 3 micron. La torbida à ̈ poi lasciata in agitazione per 24 h e quindi essiccata mediante atomizzazione. Il prodotto finale à ̈ attivato in forno ventilato con la procedura seguente: si porta la temperatura da quella ambiente a 400°C in circa 6 ore, con salita lineare, si mantiene la temperatura a 400°C per 2 ore, quindi la si porta linearmente a 590°C in un'ora e la si mantiene a 590°C per due ore. Si raffredda poi naturalmente. 1250 g of Ludox AS40 colloidal silica and 420 ml of deionized water are poured into a reactor equipped with mechanical stirring. The nitric solution of the salts and the solution of the molybdenum compound are added in order. A solution is obtained. The solution is subsequently treated at 50 ° C for 1 hour under stirring. A slurry is obtained to which 62.2 g of the Sb / Cr promoter are added mixed with 150 ml of deionized water. The slurry is subsequently homogenized by wet grinding in a ball mill to obtain an average diameter of the suspended particles below 3 microns. The slurry is then left to stir for 24 hours and then dried by atomization. The final product is activated in a ventilated oven with the following procedure: the temperature is brought from the room temperature to 400 ° C in about 6 hours, with a linear rise, the temperature is kept at 400 ° C for 2 hours, then it is brought linearly at 590 ° C in one hour and kept at 590 ° C for two hours. It then cools naturally.
Test catalitici Catalytic tests
Il processo di ammossidazione del propilene ad acrilonitrile, utilizzando il sistema catalitico di cui all'esempio 1, viene realizzato nelle seguenti condizioni: tra 440°C e 460°C, rapporti molari ossigeno/propilene di 2 e ammoniaca/propilene di 1,00 velocità spaziale della miscela dei reagenti gassosi di 0,07 (g prop./h)/g cat e pressioni di 1,6-1,8 bar assoluti. The amoxidation process of propylene to acrylonitrile, using the catalytic system referred to in example 1, is carried out under the following conditions: between 440 ° C and 460 ° C, oxygen / propylene molar ratios of 2 and ammonia / propylene of 1.00 spatial velocity of the mixture of gaseous reactants of 0.07 (g prop./h)/g cat and pressures of 1.6-1.8 absolute bar.
Esempio 1 Example 1
Il sistema catalitico viene preparato secondo le indicazioni riportate ai punti a) d) precedenti. The catalytic system is prepared according to the indications given in points a) d) above.
Il molibdato multi metallico ha la seguente composizione The multi metal molybdate has the following composition
Mo12Bi0 , 2Fe1, 8CO5 , 2Mg2 , iMn0, sCro, 2Ceo, 4Ko; 07CS0, o4Οχ Mo12Bi0, 2Fe1, 8CO5, 2Mg2, iMn0, sCro, 2Ceo, 4Ko; 07CS0, o4ÎŸÏ ‡
in cui x à ̈ il numero di atomi di ossigeno necessari a soddisfare la valenza degli altri elementi where x is the number of oxygen atoms needed to satisfy the valence of the other elements
Il sistema catalitico comprendente il molibdato multi metallico ed il promotore ha la composizione espressa in peso % di molibdato e di promotore: Molibdato 87,56%, promotore12 ,44%. The catalytic system comprising the multi-metallic molybdate and the promoter has the composition expressed by weight% of molybdate and promoter: Molybdate 87.56%, promoter 12, 44%.
Il test catalitico à ̈ stato condotto nelle condizioni precedentemente indicate. The catalytic test was conducted under the conditions indicated above.
La conversione molare del propilene à ̈ stata del 95,8%; la resa molare in acrilonitrile del 77,5%. Esempio comparativo 1 The molar conversion of propylene was 95.8%; the molar yield in acrylonitrile of 77.5%. Comparative example 1
La preparazione del sistema catalitico viene effettuata secondo le indicazioni riportate ai punti a)-d) con la sola differenza che nella preparazione del molibdato di cui al punto b) Ã ̈ stato impiegato eptamolibdato di ammonio nel quantitativo di 371,65g disciolto in acqua The preparation of the catalytic system is carried out according to the indications given in points a) -d) with the only difference that in the preparation of the molybdate referred to in point b) ammonium heptamolybdate was used in the quantity of 371.65g dissolved in water
Il test catalitico à ̈ stato condotto nelle condizioni dell'esempio 1. The catalytic test was carried out under the conditions of Example 1.
La conversione molare del propilene à ̈ stata del 96,6% la resa molare in acrilonitrile del 74,9%. The molar conversion of propylene was 96.6% and the molar yield in acrylonitrile was 74.9%.
Claims (6)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5834394A (en) * | 1996-08-06 | 1998-11-10 | China-Petro-Chemical Corporation | Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile |
| ITMI20002603A1 (en) * | 2000-12-01 | 2002-06-01 | Snam Progetti | CATALYTIC SYSTEM FOR THE PRODUCTION OF ACRYLONITRILE FROM PROPYLENE |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5834394A (en) * | 1996-08-06 | 1998-11-10 | China-Petro-Chemical Corporation | Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile |
| ITMI20002603A1 (en) * | 2000-12-01 | 2002-06-01 | Snam Progetti | CATALYTIC SYSTEM FOR THE PRODUCTION OF ACRYLONITRILE FROM PROPYLENE |
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