ITMI20130043A1 - CATALYTIC SYSTEM FOR THE AMMOSSIDATION OF PROPYLENE TO ACRILONITRILE. - Google Patents
CATALYTIC SYSTEM FOR THE AMMOSSIDATION OF PROPYLENE TO ACRILONITRILE.Info
- Publication number
- ITMI20130043A1 ITMI20130043A1 IT000043A ITMI20130043A ITMI20130043A1 IT MI20130043 A1 ITMI20130043 A1 IT MI20130043A1 IT 000043 A IT000043 A IT 000043A IT MI20130043 A ITMI20130043 A IT MI20130043A IT MI20130043 A1 ITMI20130043 A1 IT MI20130043A1
- Authority
- IT
- Italy
- Prior art keywords
- promoter
- catalytic system
- weight
- chromium
- respect
- Prior art date
Links
- 230000003197 catalytic effect Effects 0.000 title claims description 38
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 26
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims description 14
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000011651 chromium Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 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 claims description 12
- 238000001228 spectrum Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 10
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite 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
- 239000000376 reactant Substances 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 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
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 238000001238 wet grinding Methods 0.000 claims description 2
- KECAIQNCFZTEBM-UHFFFAOYSA-N antimony;chromium Chemical compound [Sb]#[Cr] KECAIQNCFZTEBM-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 229910000410 antimony oxide Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 3
- 230000002051 biphasic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000003991 Rietveld refinement Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002751 molybdenum 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
SISTEMA CATALITICO PER L'AMMOSSIDAZIONE DEL PROPILENE AD ACRILONITRILE CATALYTIC SYSTEM FOR AMOXIDATION OF PROPYLENE TO ACRYLONITRILE
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 utilizzabili per 1'ammossidazione del propilene ad acrilonitrile. I più diffusi comprendono un molibdato multi-metallico i cui elementi fondamentali sono Mo, Bi, Fe, Co e/o Ni, Ce e metalli alcalini, in particolare K e Cs. Nel corso degli anni i catalizzatori sono stati modificati dando luogo a formulazioni sempre più complesse comprendenti anche sistemi in cui il molibdato multi-metallico viene impiegato insieme a promotori di vario tipo di cui uno dei più rappresentativi à ̈ l'antimoniato di ferro. (US 5.513.269). Various types of catalysts are known which can be used for the ammoxidation of propylene to acrylonitrile. The most common include a multi-metallic molybdate whose basic elements are Mo, Bi, Fe, Co and / or Ni, Ce and alkali metals, in particular K and Cs. Over the years, the catalysts have been modified giving rise to increasingly complex formulations also including systems in which the multi-metallic molybdate is used together with various types of promoters, one of the most representative of which is iron antimonate. (US 5,513,269).
Una domanda di brevetto italiano MI2012A001610 descrive un sistema catalitico che contiene un promotore costituito da antimoniato di cromo, preparato a partire da ossido di antimonio e da un sale di cromo solubile in acqua, portando a secco la sospensione che ne deriva su piastra riscaldata, e calcinando a 700°C il solido essiccato, ad ottenere il promotore. An Italian patent application MI2012A001610 describes a catalytic system that contains a promoter consisting of chromium antimoniate, prepared starting from antimony oxide and a water-soluble chromium salt, drying the resulting suspension on a heated plate, and calcining the dried solid at 700 ° C, to obtain the promoter.
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 rese in acrilonitrile elevate. 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 high acrylonitrile yields.
La presente invenzione fornisce un sistema catalitico che ragqiunge questi scopi, comprendente The present invention provides a catalytic system which achieves these objects, comprising
A) n molibdato multi-metallico di formula A) n multi-metallic molybdate of formula
MO12Bi0,1 -2Fe1_3Co2-8Mg0,5-3Îœn0, 1-2Cr0, 1-2Ce0, 1-1K0,01-1Cs0, 01-1Ox in cui x indica il numero di atomi di ossigeno necessari a soddisfare la valenza degli altri elementi; e MO12Bi0,1 -2Fe1_3Co2-8Mg0,5-3Îœn0, 1-2Cr0, 1-2Ce0, 1-1K0,01-1Cs0, 01-1Ox where x indicates the number of oxygen atoms necessary to satisfy the valence of the other elements; And
B) un promotore comprendente almeno 85% in peso, rispetto al peso totale del promotore, di antimoniato di cromo di composizione CrxSbyO2 (x+y), in cui x+y=2 e y/x à ̈ compreso nell'intervallo da 2 a 3, detto promotore essendo impiegato in quantità in peso % di 5-25 rispetto al peso totale del molibdato multi-metallico e del promotore. B) a promoter comprising at least 85% by weight, with respect to the total weight of the promoter, of chromium antimoniate of composition CrxSbyO2 (x + y), in which x + y = 2 and y / x is in the range from 2 to 3, said promoter being used in an amount by weight of 5-25% with respect to the total weight of the multi-metal molybdate and of the promoter.
Nel sistema catalitico secondo la presente invenzione il promotore à ̈ detto monofasico e comprende ad esempio 86% o 90% o 95% o 99% o 100% in peso, rispetto al peso totale del promotore, di antimoniato di cromo di composizione CrxSbyO2(x+y), in cui x+y=2 e y/x à ̈ superiore a uno e inferiore o uguale a tre. In the catalytic system according to the present invention, the promoter is called monophasic and comprises for example 86% or 90% or 95% or 99% or 100% by weight, with respect to the total weight of the promoter, of chromium antimoniate of composition CrxSbyO2 (x + y), where x + y = 2 and y / x is greater than one and less than or equal to three.
Preferibilmente, nel sistema catalitico secondo la presente invenzione 1' antimoniato di cromo ha la composizione Cr0, 666Sb1;O2. Preferably, in the catalytic system according to the present invention the chromium antimoniate has the composition Cr0, 666Sb1; O2.
Il promotore detto "monofasico" costituito da antimoniato di cromo di composizione Cr0, 666Sb1, O ha uno spettro di diffrazione dei raggi X riferito alla figura 1 e alla tabella 1 e à ̈ iso-strutturale al composto CrSbO4(vedi tabella 3) detto promotore essendo impiegato in quantità in peso% di 5-25 rispetto alla somma molibdato multimetallico più promotore. The so-called "monophasic" promoter consisting of chromium antimoniate of composition Cr0, 666Sb1, O has an X-ray diffraction spectrum referred to in figure 1 and in table 1 and is iso-structural to the compound CrSbO4 (see table 3) said promoter being used in an amount by weight of 5-25% with respect to the sum of multimetallic molybdate plus promoter.
Il molibdato multi-metallico del sistema catalitico della presente invenzione opzionalmente comprende 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 (0-1)/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 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 (0-1) / 12 for Li Na and Rb, and (0⠀ "2) / 12 for you.
In questo caso, il molibdato multi-metallico può avere la formula In this case, the multi-metal molybdate can have the formula
MO12B ÃŒ0,1-2Fei-3Co2-8Mgo, s-sMno, 1-2CG0, 1-lKo, 01<_>lC S 0 , 01-1 Ni0-3Zn0-3Lio-i Na 0-1RÃ’ 0-1 Te 0-2 Οχ MO12B ÃŒ0,1-2Fei-3Co2-8Mgo, s-sMno, 1-2CG0, 1-lKo, 01 <_> lC S 0, 01-1 Ni0-3Zn0-3Lio-i Na 0-1Rà '0-1 Te 0-2 ÎŸÏ ‡
in cui x indica il numero di atomi di ossigeno necessari a soddisfare la valenza degli altri elementi e almeno un elemento tra Ni, Zn, Li, Na, Rb, Te à ̈ presente. where x indicates the number of oxygen atoms necessary to satisfy the valence of the other elements and at least one element among Ni, Zn, Li, Na, Rb, Te is present.
La presente invenzione fornisce inoltre un processo per la preparazione di un sistema catalitico secondo la presente invenzione, comprendente le fasi di: The present invention also provides a process for the preparation of a catalytic system according to the present invention, comprising the steps of:
A) fornire un molibdato multi-metallico di formula A) provide a multi-metal molybdate of formula
ΜΠ̧χ2Î’ Î ̄Î ̧, l-2FSi-3C02-8Mgo, 5-3Mn0, l-2Cr0,l~2Ce0,1-1^0, 01-ΠΟχ in cui x indica il numero di atomi di ossigeno necessari a soddisfare la valenza degli altri elementi ; ΜΠ̧Ï ‡ 2Î 'Î ̄Î ̧, l-2FSi-3C02-8Mgo, 5-3Mn0, l-2Cr0, l ~ 2Ce0,1-1 ^ 0, 01-Î ÎŸÏ ‡ where x indicates the number of oxygen atoms necessary to satisfy the value of the other elements;
B) preparare un promotore comprendente almeno 85% in peso, rispetto al peso totale del promotore, di antimoniato di cromo di composizione CrxSbyO2 (X+y), in cui x+y=2 e y/x à ̈ compreso nell'intervallo da 2 a 3, detto promotore essendo impiegato in quantità in peso % di 5-25 rispetto al peso totale del molibdato multimetallico e del promotore, portando a secco una sospensione di acetato di antimonio e di nitrato di cromo mediante evaporazione sotto vuoto e in agitazione, ad una temperatura tra quella ambiente e 90°C, e calcinando ad una temperatura compresa tra 600 e 800°C; B) prepare a promoter comprising at least 85% by weight, with respect to the total weight of the promoter, of chromium antimoniate of composition CrxSbyO2 (X + y), in which x + y = 2 and y / x is in the range from 2 to 3, said promoter being used in a quantity by weight of 5-25% with respect to the total weight of the multimetallic molybdate and of the promoter, drying a suspension of antimony acetate and chromium nitrate by evaporation under vacuum and under stirring, to a temperature between ambient and 90 ° C, and calcining at a temperature between 600 and 800 ° C;
C) aggiungere il promotore suddetto al molibdato multi-metallico in quantità di 5-25% in peso riferito al peso totale del molibdato multimetallico e del promotore; C) adding the above promoter to the multi-metallic molybdate in an amount of 5-25% by weight referred to the total weight of the multimetallic molybdate and of the promoter;
D) macinare in un mulino a sfere la sospensione per ottenere un diametro medio delle particelle in sospensione inferiore a 3 Î1⁄4m e D) grind the suspension in a ball mill to obtain an average diameter of the suspended particles of less than 3 Î1⁄4m and
E) opzionalmente ottenere una polvere microsferoidale mediante atomizzazione ed essiccamento della sospensione. E) optionally obtaining a microspheroidal powder by atomization and drying of the suspension.
La presente invenzione fornisce inoltre un processo per la preparazione di acrilonitrile per ammossidazione 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, in cui il rapporto molare ossigeno/propilene à ̈ 1-2 e il rapporto molare ammoniaca/propilene à ̈ 1-1,5, la velocità spaziale della miscela gassosa dei reagenti (espressa come grammi di propilene per ora per grammo di catalizzatore) à ̈ 0,045-0,120 hr<-1>, la pressione à ̈ di 1-1,8 bar assolute e la temperatura à ̈ 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, in which the molar ratio of oxygen / propylene is 1-2 and the ammonia / propylene molar ratio is 1-1.5, the space velocity of the gaseous mixture of the reactants (expressed as grams of propylene per hour per gram of catalyst) is 0.045-0.120 hr < -1>, the pressure is 1-1.8 absolute bar and the temperature is between 380 ° C and 500 ° C.
Per promotore "monofasico" si intende qui anche un materiale costituito da un composto isostrutturale con il composto CrSbO4(vedi tabella 3) e contenente meno del 15% di un qualsivoglia ossido di antimonio. By "monophasic" promoter is also meant here a material consisting of an isostructural compound with the CrSbO4 compound (see table 3) and containing less than 15% of any antimony oxide.
Infatti, l'antimoniato di cromo stechiometrico CrSbO4(con rapporto Sb/Cr=1) à ̈ un prodotto che appartiene a una famiglia di composti i cui cationi, per la loro affinità di dimensioni ed elettronica, sono in grado di inter-scambiarsi le posizioni occupate nel reticolo cristallino, ciò fa si che i siti del cromo possano essere eventualmente occupati parzialmente dall'antimonio. In questi composti la somma dei cationi à ̈ sempre 2, mentre il loro rapporto può variare entro limiti non ben definiti a priori. Il promotore utilizzato nell'invenzione ha una composizione nominale di Cr0,666Sb1.334O4, con un rapporto Sb/Cr di circa 2. In fact, the stoichiometric chromium antimoniate CrSbO4 (with ratio Sb / Cr = 1) is a product that belongs to a family of compounds whose cations, due to their size and electronic affinity, are able to interchange positions occupied in the crystal lattice, this means that the chromium sites may eventually be partially occupied by the antimony. In these compounds the sum of the cations is always 2, while their ratio can vary within limits that are not well defined a priori. The promoter used in the invention has a nominal composition of Cr0,666Sb1.334O4, with an Sb / Cr ratio of about 2.
Si à ̈ ora inaspettatamente trovato che se la preparazione dell' antimoniato di cromo viene effettuata, per reazione con nitrato di cromo, a partire da acetato di antimonio [Sb (CH3COO)3] anziché dall'ossido Sb2O3, il materiale finale risulta costituito in pratica da una sola fase cristallina CraSbbO4da b/a maggiore di uno fino a b/a di circa tre; mentre se si parte dall'ossido Sb2O3il materiale finale, a parità di composizione nominale e preparazione, à ̈ costituito da due fasi cristalline, cioà ̈ da una miscela di CrxSbyO4,in cui x+y=2 (con x,y≠0) e da un ossido di antimonio (ad esempio SbO2), in cui il componente CrxSbyO4, isostrutturale con l'antimoniato di cromo CrSbO4, può essere presente tra circa il 70 e l'85% in peso. Il rapporto esatto tra Sb e Cr in questo antimoniato CrxSbyO4non à ̈ noto, ma à ̈ comunque inferiore a quello del caso precedente preparato da acetato di antimonio. It has now been unexpectedly found that if the preparation of chromium antimoniate is carried out, by reaction with chromium nitrate, starting from antimony acetate [Sb (CH3COO) 3] instead of Sb2O3 oxide, the final material is constituted in practice from a single crystalline phase CraSbbO4da b / a greater than one up to b / a of about three; while if we start from Sb2O3 oxide, the final material, with the same nominal composition and preparation, is made up of two crystalline phases, i.e. a mixture of CrxSbyO4, in which x + y = 2 (with x, yâ ‰ 0) and from an antimony oxide (for example SbO2), in which the component CrxSbyO4, isostructural with the chromium antimoniate CrSbO4, can be present between about 70 and 85% by weight. The exact ratio of Sb to Cr in this CrxSbyO4 antimonate is not known, but it is still lower than in the previous case prepared from antimony acetate.
In figura 1 Ã ̈ riportato lo spettro di diffrazione dei raggi X del promotore sostanzialmente monofasico, mentre in tabella 1 Ã ̈ riportata l'indicizzazione dello stesso spettro. Figure 1 shows the X-ray diffraction spectrum of the substantially monophasic promoter, while table 1 shows the indexing of the same spectrum.
Tabella 1 Dati cristallografici relativi Table 1 Relative crystallographic data
allo spettro di figura 1 to the spectrum of figure 1
Fase - 1 calcolato secondo il metodo Pawley Phase - 1 calculated according to the Pawley method
Nome della fase: Cr0,Sb1,O Phase name: Cr0, Sb1, O
h k 1 d(A) Th2 h k 1 d (A) Th2
1 1 0 3.26608 27.28320 1 1 0 3.26608 27.28320
0 1 1 2.53900 35.32227 0 1 1 2.53900 35.32227
0 2 0 2.30947 38 .96745 0 2 0 2.30947 38 .96745
1 1 1 2.22500 40.51033 1 1 1 2.22500 40.51033
2 1 0 2.06565 43.79015 2 1 0 2.06565 43.79015
2 1 1 1.70844 53.60018 2 1 1 1.70844 53.60018
2 2 0 1.63304 56.28882 2 2 0 1.63304 56.28882
0 0 2 1.51969 60.91225 0 0 2 1.51969 60.91225
3 1 0 1.46064 63.65607 3 1 0 1.46064 63.65607
2 2 1 1.43855 64.75157 2 2 1 1.43855 64.75157
1 1 2 1.37784 67.98185 1 1 2 1.37784 67.98185
0 3 1 1.37347 68.22765 0 3 1 1.37347 68.22765
3 1 1 1.31650 71.62134 3 1 1 1.31650 71.62134
3 2 0 1.28106 73.92556 3 2 0 1.28106 73.92556
0 2 2 1.26950 74 .71313 0 2 2 1.26950 74 .71313
2 1 2 1.22411 77 .99320 2 1 2 1.22411 77 .99320
3 2 1 1.18049 81.46445 3 2 1 1.18049 81.46445
0 4 0 1.15473 83 .68391 0 4 0 1.15473 83 .68391
4 1 0 1.12026 86.88218 4 1 0 1.12026 86.88218
2 2 2 1.11250 87.64130 2 2 2 1.11250 87.64130
In figura 2 Ã ̈ mostrato lo spettro di Figure 2 shows the spectrum of
diffrazione dei raggi X del materiale ottenuto a partire da ossido di antimonio Sb2O3, mentre la X-ray diffraction of the material obtained starting from antimony oxide Sb2O3, while the
tabella 2 mostra l'indicizzazione dello stesso table 2 shows the indexing of the same
spettro . spectrum.
Tabella 2 Dati cristallografici relative allo Table 2 Crystallographic data relating to
spettro di figura 2 spectrum of figure 2
Fase - 1 calcolato secondo il metodo Pawley Phase - 1 calculated according to the Pawley method
Nome della fase CrxSbyO4Phase name CrxSbyO4
h k_ 1_ d(A) Th2 h k_ 1_ d (A) Th2
1 1 0 3.24690 27.44756 1 1 0 3.24690 27.44756
0 1 1 2.54023 35.30458 0 1 1 2.54023 35.30458
0 2 0 2.29590 39.20710 0 2 0 2.29590 39.20710
1 1 1 2.22277 40.55273 1 1 1 2.22277 40.55273
2 1 0 2.05352 44 .06241 2 1 0 2.05352 44 .06241
2 1 1 1.70329 53.77501 2 1 1 1.70329 53.77501
2 2 0 1.62345 56.65135 2 2 0 1.62345 56.65135
0 0 2 1.52467 60.69231 0 0 2 1.52467 60.69231
3 1 0 1.45206 64.07684 3 1 0 1.45206 64.07684
2 2 1 1.43301 65.03231 2 2 1 1.43301 65.03231
1 1 2 1.38009 67.85619 1 1 2 1.38009 67.85619
0 3 1 1.36795 68.54172 0 3 1 1.36795 68.54172
3 1 1 1.31101 71.96848 3 1 1 1.31101 71.96848
3 2 0 1.27354 74.43597 3 2 0 1.27354 74.43597
0 2 2 1.27011 74 .67074 0 2 2 1.27011 74 .67074
2 1 2 1.22415 77 .99001 2 1 2 1.22415 77 .99001
3 2 1 1.17516 81.91223 3 2 1 1.17516 81.91223
0 4 0 1.14795 84.29166 0 4 0 1.14795 84.29166
4 1 0 1.11368 87.52513 4 1 0 1.11368 87.52513
2 2 2 1.11138 87.75161 2 2 2 1.11138 87.75161
fase - 2 calcolato secondo il metodo Pawley phase - 2 calculated according to the Pawley method
nome della fase SbO2phase name SbO2
h k 1 d Th2 h k 1 d Th2
0 0 2 5.88675 15 .03775 0 0 2 5.88675 15 .03775
0 1 1 4.45201 19.92722 0 1 1 4.45201 19.92722
1 1 0 3.60548 24 .67229 1 1 0 3.60548 24 .67229
1 1 1 3.44745 25 .82235 1 1 1 3.44745 25.82235
1 1 2 3.07462 29.01825 1 1 2 3.07462 29.01825
0 1 3 3.04056 29.35063 0 1 3 3.04056 29.35063
0 0 4 2.94338 30.34258 0 0 4 2.94338 30.34258
2 0 0 2.72419 32.85032 2 0 0 2.72419 32.85032
1 1 3 2.65509 33.73045 1 1 3 2.65509 33.73045
2 0 1 2.65407 33.74384 2 0 1 2.65407 33.74384
2 0 2 2.47229 36.30799 2 0 2 2.47229 36.30799
0 2 0 2.40454 37 .36835 0 2 0 2.40454 37 .36835
2 1 0 2.37031 37.92853 2 1 0 2.37031 37.92853
2 1 1 2.32368 38.71957 2 1 1 2.32368 38.71957
1 1 4 2.28008 39.49045 1 1 4 2.28008 39.49045
2 0 3 2.23787 40.26711 2 0 3 2.23787 40.26711
0 2 2 2.22600 40.49125 0 2 2 2.22600 40.49125
1 2 0 2.19983 40.99449 1 2 0 2.19983 40.99449
2 1 2 2.19876 41.01540 2 1 2 2.19876 41.01540
1 2 1 2.16241 41.73674 1 2 1 2.16241 41.73674
0 1 5 2.11480 42.72177 0 1 5 2.11480 42.72177
1 2 2 2.06065 43.90193 1 2 2 2.06065 43.90193
2 1 3 2.02895 44.62439 2 1 3 2.02895 44.62439
2 0 4 1.99929 45.32286 2 0 4 1.99929 45.32286
1 1 5 1.97150 45.99831 1 1 5 1.97150 45.99831
0 0 6 1.96225 46.22756 0 0 6 1.96225 46.22756
2 3 1.91893 47.33414 2 4 1.86215 48.86994 1 4 1.84611 49.32266 2 0 1.80274 50.59184 2 1 1.78197 51.22385 0 5 1.78145 51.23997 2 4 1.76208 51.84484 2 2 1.72372 53.08743 1 6 1.72353 53.09385 1 0 1.69901 53.92163 1 1 1.68159 54.52624 1 5 1.67051 54.91805 2 3 1.63817 56.09693 1 2 1.63238 56.31364 2 5 1.60748 57.26583 0 6 1.59220 57.86699 3 1 1.58837 58.01978 1 7 1.58763 58.04942 1 3 1.55917 59.21351 3 0 1.53785 60.11834 2 4 1.53731 60.14141 3 1 1.52489 60.68248 1 7 1.52424 60.71132 2 6 1.52028 60.88619 1 6 1.51151 61.27710 3 2 1.48791 62.35672 3 3 1.48400 62.53952 0 8 1.47169 63.12268 1 4 1.47146 63.13360 2 6 1.46434 63.47626 2 0 1.44921 64.21764 2 1 1.43836 64 .76115 3 3 1.43184 65 .09220 2 5 1.43141 65 . 11427 0 7 1.43114 65.12812 2 2 1.40720 66.37749 3 0 1.38158 67.77293 1 5 1.37780 67 . 98430 3 1 1.37216 68.30183 1 7 1.37169 68.32890 3 4 1.36302 68 . 82420 1 8 1.36255 68 .85117 0 0 1.36209 68 . 87756 2 3 1.35948 69.02854 0 1 1.35307 69.40249 3 2 1.34503 69 . 87720 2 7 1.33614 70 . 41087 2 6 1.32754 70 . 93524 0 2 1.32703 70 . 96671 3 5 1.32511 71.08549 1 0 1.31054 71 . 99802 3 3 1.30318 72.46867 1 1 1.30250 72.51305 2 4 1.30016 72 . 66402 0 8 1.29482 73.01195 3 5 1.28757 73.49018 0 3 1.28679 73.54207 1 6 1.28444 73 . 69878 1 2 1.27922 74 .04961 1 9 1.26230 75.21288 2 8 1.25524 75 .70989 3 4 1.25066 76 . 03680 1 8 1.25030 76 .06271 1 3 1.24306 76 . 58522 0 4 1.23615 77 .09221 2 5 1.23419 77 . 23673 2 7 1.22980 77 .56448 1 9 1.22973 77 .56975 2 8 1 . 22320 78 . 06193 3 6 1.21041 79 . 04685 4 0 1.20227 79 . 68847 3 0 1.20183 79 . 72392 1 4 1 .19723 80 . 09180 3 1 1 .19561 80 .22205 1 7 1 .19530 80 . 24757 3 5 1 .19161 80 . 54647 2 0 1 . 18515 81 . 07669 0 9 1 . 17925 81 .56824 2 1 1 . 17919 81 . 57289 0 5 1 . 17904 81 .58560 4 2 1 . 17795 81 . 67689 3 2 1 . 17754 81 .71214 0 10 1 . 17735 81 . 72771 4 0 1 . 17403 82 . 00869 4 1 1 .16823 82 .50373 2 6 1 .16575 82 .71819 2 2 1 .16184 83 .05783 3 7 1 .16040 83 . 18363 4 2 1 . 15135 83 . 98563 3 3 1 . 14915 84 .18364 2 1 9 1.14532 84.53032 2 3 1.91893 47.33414 2 4 1.86215 48.86994 1 4 1.84611 49.32266 2 0 1.80274 50.59184 2 1 1.78197 51.22385 0 5 1.78145 51.23997 2 4 1.76208 51.84484 2 2 1.72372 53.08743 1 6 1.72353 53.09381 1.80274 50.59184 2 1 1.78197 51.22385 0 5 1.78145 51.23997 2 4 1.76208 51.84484 2 2 1.72372 53.08743 1 6 1.72353 53.09381 54.91 54.91 1.615 1 1.63817 56.09693 1 2 1.63238 56.31364 2 5 1.60748 57.26583 0 6 1.59220 57.86699 3 1 1.58837 58.01978 1 7 1.58763 58.04942 1 3 1.55917 59.21351 3 0 1.53785 60.11834 2 4 1.53731 60.14141 3 1 1.52489 60.6824811 1 7 1.524.26 61.21 601.511 6011 6011 2 3 2 1.48791 62.35672 3 3 1.48400 62.53952 0 8 1.47169 63.12268 1 4 1.47146 63.13360 2 6 1.46434 63.47626 2 0 1.44921 64.21764 2 1 1.43836 64 .76115 3 3 1.43184 65 .09220 2 5 1.43141 65. 11427 0 7 1.43114 65.12812 2 2 1.40720 66.37749 3 0 1.38158 67.77293 1 5 1.37780 67. 98430 3 1 1.37216 68.30183 1 7 1.37169 68.32890 3 4 1.36302 68. 82420 1 8 1.36255 68 .85117 0 0 1.36209 68. 87756 2 3 1.35948 69.02854 0 1 1.35307 69.40249 3 2 1.34503 69. 87720 2 7 1.33614 70. 41087 2 6 1.32754 70. 93524 0 2 1.32703 70. 96671 3 5 1.32511 71.08549 1 0 1.31054 71. 99802 3 3 1.30318 72.46867 1 1 1.30250 72.51305 2 4 1.30016 72. 66402 0 8 1.29482 73.01195 3 5 1.28757 73.49018 0 3 1.28679 73.54207 1 6 1.28444 73. 69878 1 2 1.27922 74 .04961 1 9 1.26230 75.21288 2 8 1.25524 75 .70989 3 4 1.25066 76. 03680 1 8 1.25030 76 .06271 1 3 1.24306 76. 58522 0 4 1.23615 77 .09221 2 5 1.23419 77. 23673 2 7 1.22980 77 .56448 1 9 1.22973 77 .56975 2 8 1. 22 320 78. 06193 3 6 1.21041 79. 04685 4 0 1.20227 79. 68847 3 0 1.20183 79. 72392 1 4 1 .19723 80. 09180 3 1 1 .19561 80 .22205 1 7 1 .19530 80. 24757 3 5 1 .19161 80. 54647 2 0 1. 18515 81. 07669 0 9 1. 17925 81 .56824 2 1 1. 17919 81. 57289 0 5 1. 17904 81 .58560 4 2 1. 17795 81. 67689 3 2 1. 17754 81 .71214 0 10 1. 17735 81. 72771 4 0 1. 17403 82. 00869 4 1 1 .16823 82 .50373 2 6 1 .16575 82 .71819 2 2 1 .16184 83 .05783 3 7 1 .16040 83. 18363 4 2 1. 15 135 83. 98563 3 3 1. 14915 84 .18364 2 1 9 1.14532 84.53032
4 1 5 1.14513 84.54758 4 1 5 1.14513 84.54758
2 2 8 1.14004 85.01343 2 2 8 1.14004 85.01343
1 3 7 1.13495 85.48557 1 3 7 1.13495 85.48557
4 2 3 1.13455 85.52287 4 2 3 1.13455 85.52287
2 3 6 1.12966 85.98176 2 3 6 1.12966 85.98176
1 4 3 1.12478 86.44700 1 4 3 1.12478 86.44700
1 2 9 1.12438 86.48479 1 2 9 1.12438 86.48479
1 1 10 1.11919 86.98555 1 1 10 1.11919 86.98555
4 0 6 1.11894 87.01020 4 0 6 1.11894 87.01020
0 4 4 1.11300 87.59168 0 4 4 1.11300 87.59168
3 3 4 1.11265 87 .62660 3 3 4 1.11265 87 .62660
3 1 8 1.11239 87 .65176 3 1 8 1.11239 87 .65176
2 4 0 1.09992 88.90611 2 4 0 1.09992 88.90611
4 2 4 1.09938 88.96101 4 2 4 1.09938 88.96101
3 2 7 1.09788 89.11452 3 2 7 1.09788 89.11452
2 4 1 1.09515 89.39669 2 4 1 1.09515 89.39669
1 4 4 1.09048 89.88293 1 4 4 1.09048 89.88293
4 1 6 1.08983 89.95155 4 1 6 1.08983 89.95155
La tabella 3 riporta l'indicizzazione del Table 3 shows the indexing of the
composto di riferimento CrSbO4. Nelle prime tre CrSbO4 reference compound. In the first three
colonne delle tabelle 1-3 sono riportati gli columns of tables 1-3 show the
indici di Miller dei piani cristallografici, nella Miller indices of the crystallographic planes, in
terza colonna sono riportate le distanze dei piani third column shows the distances of the floors
cristallografici (in A) mentre nella quarta crystallographic (in A) while in the fourth
colonna sono mostrati gli angoli di diffrazione in column shows the diffraction angles in
2 theta. 2 theta.
Tabella 3: dati cristallografici del composto di Table 3: crystallographic data of the compound of
riferimento CrSbO4cartellino JCPDS 00-035-1288 reference CrSbO4 JCPDS tag 00-035-1288
Nome fase CrSbO4 Phase name CrSbO4
h k 1 d(A) Th2 h k 1 d (A) Th2
1 1 0 3.244000 27.4719 1 1 0 3.244000 27.4719
1 0 1 2.542000 35.2783 1 0 1 2.542000 35.2783
2 0 0 2.294000 39.2400 2 0 0 2.294000 39.2400
1 1 1 2.224000 40.5283 1 1 1 2.224000 40.5283
2 1 0 2 .052000 44.0956 2 1 0 2 .052000 44.0956
2 1 1 1.703000 53.7837 2 1 1 1.703000 53.7837
2 2 0 1.623000 56.6670 2 2 0 1.623000 56.6670
0 0 2 1.526000 60.6323 0 0 2 1.526000 60.6323
3 1 0 1.451000 64.1274 3 1 0 1.451000 64.1274
1 1 2 1.381000 67.8034 1 1 2 1.381000 67.8034
3 0 1 1.367700 68.5539 3 0 1 1.367700 68.5539
2 0 2 1.270900 74.6147 2 0 2 1.270900 74.6147
2 1 2 1.224800 77.9384 2 1 2 1.224800 77.9384
3 2 1 1.174900 81.9323 3 2 1 1.174900 81.9323
4 0 0 1.147500 84.3300 4 0 0 1.147500 84.3300
2 2 2 1.111900 87.6980 2 2 2 1.111900 87.6980
3 3 0 1.081900 90.7908 3 3 0 1.081900 90.7908
La differenza di composizione porta a The difference in composition leads to
differenti prestazioni del sistema catalitico che different performances of the catalytic system which
ne deriva utilizzando questa miscela come it derives from using this mixture as
promotore . promoter.
Il sistema in cui si impiega l'antimoniato di The system in which the antimoniate of
cromo "monofasico" permette di ottenere rese in acrilonitrile inaspettatamente molto più elevate di quelle ottenibili con il sistema che usa il componente bifasico. "monophasic" chromium allows to obtain unexpectedly much higher acrylonitrile yields than those obtainable with the system that uses the biphasic component.
Si à ̈ trovato inoltre che se la fase di essiccamento della sospensione che contiene l'acetato di antimonio ed il nitrato di cromo viene realizzata mediante evaporazione condotta sotto vuoto e agitazione a temperatura tra quella ambiente e 90°C si ottiene un materiale monofasico, mentre se l'essiccamento viene effettuato mediante spray-drying il materiale à ̈ bifasico con composizione simile a quella che si ottiene partendo da ossido di antimonio. Il sistema catalitico preparato con il materiale ottenuto da acetato di antimonio per atomizzazione fornisce prestazioni simili a quello del sistema in cui si impiega l'antimoniato di cromo ottenuto con l'utilizzo di Sb2O3. It has also been found that if the drying step of the suspension containing antimony acetate and chromium nitrate is carried out by evaporation carried out under vacuum and stirring at a temperature between room temperature and 90 ° C, a monophasic material is obtained, while if the drying is carried out by spray-drying, the material is biphasic with a composition similar to that obtained starting from antimony oxide. The catalytic system prepared with the material obtained from antimony acetate by atomization provides performance similar to that of the system in which the chromium antimoniate obtained with the use of Sb2O3 is used.
In entrambi i casi, il materiale ottenuto portando a secco sotto vuoto o per spray-drying e previo ulteriore essiccamento in stufa a 120°C può essere calcinato a temperature tra 450°C e 750°C, 700°C essendo la temperatura preferita. In both cases, the material obtained by drying under vacuum or by spray-drying and after further drying in an oven at 120 ° C can be calcined at temperatures between 450 ° C and 750 ° C, 700 ° C being the preferred temperature.
Il riscaldamento, nel caso della calcinazione a 700°C, può prevedere la salita della temperatura da quella ambiente a 700°C in modo lineare in un tempo di circa 11 ore; si mantiene poi la temperatura a 700°C per 6 ore. The heating, in the case of calcination at 700 ° C, can foresee the increase of the temperature from the ambient one to 700 ° C in a linear way in a time of about 11 hours; the temperature is then maintained at 700 ° C for 6 hours.
Il raffreddamento può essere naturale. Cooling can be natural.
Il promotore viene aggiunto al molibdato multi-metallico in quantità di 5-25% in peso riferito al peso totale molibdato multimetallico+promotore, preferibilmente 10-16%. The promoter is added to the multi-metal molybdate in an amount of 5-25% by weight referred to the total weight of the multimetallic molybdate + promoter, preferably 10-16%.
Il molibdato multi-metallico comprende i seguenti elementi fondamentali: Multi-metallic molybdate includes the following basic elements:
ΜΠ̧ι2Î’Î ̄ο, i-iFso-3C02-aMgo, 5-3Mn0, i-iCro, i_iCeo, i-iKoroi-iCso, oi-10xin cui x à ̈ il numero di atomi di ossigeno necessari a soddisfare la valenza degli altri elementi . ΜΠ̧ι2Î'Î ̄ο, i-iFso-3C02-aMgo, 5-3Mn0, i-iCro, i_iCeo, i-iKoroi-iCso, oi-10x in which x is the number of oxygen atoms needed to satisfy the valence of other elements.
Il molibdato preferito ha la seguente formula: Moi2Bior2Fei, gCo5f 2Mg2,ìMno, sCro^Ceo,4K0,07CS0, O-JOZin cui z à ̈ il numero di atomi di ossigeno necessari a soddisfare la valenza degli altri elementi . The preferred molybdate has the following formula: Moi2Bior2Fei, gCo5f 2Mg2, ìMno, sCro ^ Ceo, 4K0,07CS0, O-JOZin which z is the number of oxygen atoms necessary to satisfy the valence of the other elements.
Il molibdato multi-metallico 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)/1 2; (0-2)/12. The multi-metallic molybdate can comprise 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) / 1 2; (0-2) / 12.
Il sistema catalitico comprendente il molibdato multi-metallico e il promotore può essere diluito con un ossido quale SiO2, Al2O3, ZrO2, CeO2in quantità di 30-80% in peso sul totale, preferibilmente 30-60% in peso sul peso totale del molibdato multi- metallico, promotore e supporto, più preferibilmente 40-60% in peso sul totale . The catalytic system comprising the multi-metallic molybdate and the promoter can be diluted with an oxide such as SiO2, Al2O3, ZrO2, CeO2 in an amount of 30-80% by weight of the total, preferably 30-60% by weight of the total weight of the multi-molybdate. - metal, promoter and support, more preferably 40-60% by weight of the total.
SiO2à ̈ il supporto preferito e può essere ad esempio utilizzato in quantità di 30-80% in peso sul totale del molibdato multi-metallico, promotore e supporto, preferibilmente 30-60%, più preferibilmente 40-60%. SiO2 is the preferred support and can be used for example in quantities of 30-80% by weight of the total of the multi-metal molybdate, promoter and support, preferably 30-60%, more preferably 40-60%.
La preparazione del molibdato multi-metallico viene effettuata secondo i metodi convenzionali, come mediante reazione di nitrati dei metalli che devono essere compresi nel molibdato multi metallico con molibdato di ammonio, opzionalmente in presenza di silice. The preparation of the multi-metal molybdate is carried out according to conventional methods, such as by reaction of nitrates of the metals that are to be included in the multi-metal molybdate with ammonium molybdate, optionally in the presence of silica.
Ad esempio, si sciolgono i nitrati dei vari metalli , ad eccezione di Mo il cui sale viene sciolto a parte, in acqua, acida per acido nitrico (al 65%). For example, the nitrates of the various metals are dissolved, with the exception of Mo whose salt is dissolved separately, in water, acidic to nitric acid (65%).
Il molibdato di ammonio [(NH4) 6MO7O24*4H2O] viene sciolto a parte in acqua a circa 30°C. The ammonium molybdate [(NH4) 6MO7O24 * 4H2O] is dissolved separately in water at about 30 ° C.
La soluzione dei nitrati à ̈ miscelata sotto agitazione con la silice colloidale, quindi si aggiunge la soluzione del molibdato di ammonio sempre sotto agitazione. In alternativa la soluzione dei nitrati può essere aggiunta dopo aver miscelato le soluzioni di molibdato di ammonio e silice colloidale. The nitrate solution is mixed under stirring with the colloidal silica, then the ammonium molybdate solution is added while stirring. Alternatively, the nitrate solution can be added after mixing the ammonium molybdate and colloidal silica solutions.
Si aggiunge quindi il promotore in sospensione in acqua. The promoter in suspension in water is then added.
La torbida finale così ottenuta viene macinata ad umido in mulino a sfere, fino ad ottenere un diametro medio delle particelle in sospensione inferiore a 3 micron, e successivamente portata a secco mediante atomizzazione. Si ottiene una polvere micro sferoidale che viene calcinata in muffola ventilata con aria. La temperatura del letto viene aumentata a 400°C con velocità di 100°C/h, la temperatura viene mantenuta a 400°C per 2 ore, successivamente viene portata a 590°C in 1 ora e mantenuta a 590°C per 2 ore. The final slurry thus obtained is wet ground in a ball mill, to obtain an average diameter of the suspended particles of less than 3 microns, and subsequently dried by atomization. A micro spheroidal powder is obtained which is calcined in a muffle ventilated with air. The bed temperature is increased to 400 ° C with a speed of 100 ° C / h, the temperature is maintained at 400 ° C for 2 hours, then it is brought to 590 ° C in 1 hour and maintained at 590 ° C for 2 hours .
Il processo di ammossidazione del propilene ad acrilonitrile, 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 e ammoniaca/propilene di 1-1,5, preferibilmente 1, velocità spaziale della miscela dei reagenti gassosi (cioà ̈ grammi di miscela gassosa per ora per grammo di catalizzatore) di 0,045-0,120 hr<-1>, preferibilmente 0,07 hr<-1>e pressioni di 1-1,8 bar assoluti . The amoxidation process of propylene to acrylonitrile, 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 and ammonia / propylene of 1-1.5, preferably 1, space velocity of the mixture of gaseous reactants (i.e. grams of gas mixture per hour per gram of catalyst) of 0.045-0.120 hr <-1>, preferably 0 , 07 hr <-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 nitrica a) Preparation of the nitric solution
In un bicchiere contenente 250 mi di acqua deionizzata e 86 g di acido nitrico al 70% si sciolgono nell'<'>ordine 16,98 g di Bi (NO3)3*5H2O, 30,47 g di Ce (NO3)3*6H20, 127,57 g di Fe (N03)3*9H20, 14,04 g di Cr (N03)3*93⁄40, 94,19 g di Mg (N03)2*63⁄40, 267,26 g di Co (N03)2*63⁄40, 20,74 g di Mn (N03)2*4H20, 1,24 g di KN03, 1,37 g di CsN03. In a glass containing 250 ml of deionized water and 86 g of 70% nitric acid dissolve in the order 16.98 g of Bi (NO3) 3 * 5H2O, 30.47 g of Ce (NO3) 3 * 6H20, 127.57 g of Fe (N03) 3 * 9H20, 14.04 g of Cr (N03) 3 * 93⁄40, 94.19 g of Mg (N03) 2 * 63⁄40, 267.26 g of Co (N03) 2 * 63⁄40, 20.74 g of Mn (N03) 2 * 4H20, 1.24 g of KN03, 1.37 g of CsN03.
b) Preparazione della soluzione del sale di molibdeno b) Preparation of the molybdenum salt solution
In un bicchiere contenente 750 mi di acqua deionizzata si sciolgono 371,65 g di [ (NH4)6ΜΠ̧7Î ̧24*4Η20] alla temperatura di circa 30°C. In a beaker containing 750 ml of deionized water, 371.65 g of [(NH4) 6ΜΠ̧7Î ̧24 * 4Î — 20] are dissolved at a temperature of about 30 ° C.
c) Preparazione _ del _ promotore _ Cr/Sb monofasico c) Preparation of the monophasic Cr / Sb promoter
In un pallone per rotavapor munito di lobi, del volume di 2 litri si sciolgono 254,16 g di nitrato di cromo idrato [Cr (N03)3*9H20] in 200 mi di acqua deionizzata. Si aggiungono 379,68 g di acetato di antimonio [Sb (CH3COO)3] e si utilizzano 100 mi di acqua per eventuali altri lavaggi e per diluire la sospensione. In a rotavapor flask equipped with lobes, with a volume of 2 liters, 254.16 g of hydrated chromium nitrate [Cr (N03) 3 * 9H20] are dissolved in 200 ml of deionized water. 379.68 g of antimony acetate [Sb (CH3COO) 3] are added and 100 ml of water are used for any other washings and to dilute the suspension.
Si monta il pallone su di un evaporatore rotante e si porta a secchezza lentamente scaldando sotto vuoto. The flask is mounted on a rotating evaporator and slowly brought to dryness by heating under vacuum.
La massa secca ottenuta à ̈ messa in stufa a 120°C con tutto il pallone per una notte. Il prodotto secco à ̈ recuperato, omogeneizzato mediante macinazione in mulino a secco e quindi calcinato in muffola ventilata con la seguente procedura: da temperatura ambiente fino a 700 °C salita lineare in 11,5 ore, stazionamento a 700°C per 6 ore. The dry mass obtained is put in an oven at 120 ° C with the whole flask for one night. The dry product is recovered, homogenized by grinding in a dry mill and then calcined in a ventilated muffle with the following procedure: from room temperature up to 700 ° C linear rise in 11.5 hours, stationary at 700 ° C for 6 hours.
Raffreddamento naturale. Natural cooling.
Il materiale ottenuto ha la seguente composizione determinata dallo spettro di diffrazione dei raggi x col metodo di Rietveld. Composto Cr0rSbi, 34O (vedi figura 1 e tabella 1) L'analisi à ̈ stata condotta per mezzo di un diffrattometro automatico per polveri Phillips X' Pert 9/29 con geometria Bragg - Brentano, utilizzando radiazione Cu Kα con λ= 1,5406 A e potenza 1,5kw. L'intervallo angolare utilizzato à ̈ da 5 a 90 (2Î ̃) con passi di 0,02° (2Î ̃) e tempo di acquisizione pari a 3 secondi per passo. The material obtained has the following composition determined by the X-ray diffraction spectrum with the Rietveld method. Compound Cr0rSbi, 34O (see figure 1 and table 1) The analysis was carried out by means of a Phillips X 'Pert 9/29 automatic powder diffractometer with Bragg - Brentano geometry, using Cu KÎ ± radiation with Î »= 1 , 5406 A and power 1,5kw. The angular interval used is from 5 to 90 (2Î ̃) with steps of 0.02 ° (2Î ̃) and acquisition time equal to 3 seconds per step.
l' affinamento strutturale e l'analisi quantitativa sono stati condotti utilizzando il metodo di Rietveld implementato nel pacchetto software GSAS (Generalized System Analysis System) , avendo come riferimento la struttura isomorfa del composto CrSbO4: cartellino JCPDS 00-035-1288 (vedi tabella 3). the structural refinement and quantitative analysis were carried out using the Rietveld method implemented in the GSAS (Generalized System Analysis System) software package, having as reference the isomorphic structure of the CrSbO4 compound: JCPDS 00-035-1288 tag (see table 3 ).
d) Preparazione della torbida e trattamenti termici d) Preparation of the slurry and heat treatments
In un reattore munito di agitazione meccanica si versano 1250 g di silice Ludox AS40 (SiO240% in peso) e 420 mi di acqua deionizzata. Si aggiungono nell'ordine la soluzione nitrica dei sali e la soluzione del sale di molibdeno. Si ottiene una torbida, che à ̈ mantenuta in agitazione per circa 30 minuti, alla quale si aggiungono 62,2 g del promotore Cr/Sb monofasico (vedi spettro di figura 1 e tabella 1) mescolato a 150 mi 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 Î1⁄4m. La torbida à ̈ poi lasciata in agitazione per 24 ore quindi portata a secco mediante atomizzazione (spray drying) . Si ottiene una polvere micro-sferoidale. Il prodotto à ̈ attivato in forno ventilato con la procedura seguente: da RT a 400°C a 100°C/h; permanenza 400°C 2 ore; da 400°C a 590°C salita lineare in 1 ora, permanenza a 590°C 2 ore. 1250 g of Ludox AS40 silica (SiO240% by weight) 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 salt are added in order. A slurry is obtained, which is kept stirred for about 30 minutes, to which 62.2 g of the monophasic Cr / Sb promoter are added (see spectrum in figure 1 and table 1) 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 Î1⁄4m. The slurry is then left to stir for 24 hours and then dried by spray drying. A micro-spheroidal powder is obtained. The product is activated in a ventilated oven with the following procedure: from RT to 400 ° C at 100 ° C / h; permanence 400 ° C 2 hours; from 400 ° C to 590 ° C linear rise in 1 hour, permanence at 590 ° C 2 hours.
Test catalitici Catalytic tests
I test catalitici sono stati eseguiti in un reattore a letto fluido utilizzando una velocità spaziale di 0,045 hr<-1>, le temperature del test sono comprese tra 440°C e 460°C. il rapporto tra ammoniaca e propilene utilizzato per i test à ̈ compreso tra 1,00 e 1,15, il rapporto tra ossigeno e propilene à ̈ invece pari a 2,00. The catalytic tests were performed in a fluidized bed reactor using a space velocity of 0.045 hr <-1>, the test temperatures are between 440 ° C and 460 ° C. the ratio between ammonia and propylene used for the tests is between 1.00 and 1.15, the ratio between oxygen and propylene is instead equal to 2.00.
Esempio 1 Example 1
II 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 : Multi-metal molybdate has the following composition:
Moi2Bio,2Fei,8Co5,2Mg2,iMnQ,5Cr0,2Ceor 4K0ro7Csoro40z Moi2Bio, 2Fei, 8Co5,2Mg2, iMnQ, 5Cr0,2Ceor 4K0ro7Csoro40z
Il sistema catalitico comprendente il molibdato multi-metallico ed il promotore ha la seguente composizione espressa in peso % di molibdato e di promotore: Molibdato 87,56%, promotore 12,44%. The catalytic system comprising the multi-metallic molybdate and the promoter has the following 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 97,8%, la resa massima in acrilonitrile del 77,5%. The molar conversion of propylene was 97.8%, the maximum yield in acrylonitrile was 77.5%.
Esempio comparativo 1 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 promotore Cr/Sb di cui al punto c) à ̈ stato impiegato ossido dì antimonio (Sb2O3) nel quantitativo di 185,16 g (vedi spettro di figura 2 e tabella 2) . Il test catalitico à ̈ stato condotto nelle condizioni dell' esempio 1. 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 Cr / Sb promoter referred to in point c) antimony oxide (Sb2O3) was used in the quantity of 185.16 g (see spectrum in figure 2 and table 2). 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%.
Esempio comparativo 2 Comparative example 2
Il sistema catalitico viene preparato secondo le indicazioni riportate ai punti a)-d) con la sola differenza che la sospensione di cui al punto c) contenente l'acetato di antimonio e il sale di cromo à ̈ stata portata a secco mediante spraydrying a 120°C. The catalytic system is prepared according to the indications given in points a) -d) with the only difference that the suspension referred to in point c) containing the antimony acetate and the chromium salt was brought to dryness by spraydrying at 120 ° C.
Il promotore ottenuto à ̈ bifasico con composizione simile a quella ottenuta impiegando Sb2O3come composto di partenza (spettro di figura 2 e tabella 2). The promoter obtained is biphasic with a composition similar to that obtained using Sb2O3 as starting compound (spectrum of figure 2 and table 2).
Il test catalitico à ̈ stato condotto nelle condizioni dell'esempio 1. La prestazione del sistema catalitico à ̈ simile a quella ottenuta nell'esempio comparativo 1, i valori indicativi del test essendo: conversione molare del propilene 96,3%, resa molare in acrilonitrile 74,5%. The catalytic test was carried out under the conditions of example 1. The performance of the catalytic system is similar to that obtained in comparative example 1, the indicative values of the test being: molar conversion of propylene 96.3%, molar yield in 74.5% acrylonitrile.
Claims (16)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960921A (en) * | 1986-09-08 | 1990-10-02 | The Standard Oil Company | Multiply promoted MN-SB oxide catalysts |
| 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 |
| US20030109381A1 (en) * | 1999-09-17 | 2003-06-12 | Junzo Ohishi | Catalyst |
| EP1452231A1 (en) * | 2001-10-11 | 2004-09-01 | Dia-Nitrix Co., Ltd. | Method for producing ammoxidation catalyst |
| WO2010066386A1 (en) * | 2008-12-08 | 2010-06-17 | Sasol Technology (Pty.) Limited | Olefin selective ft catalyst composition and preparation thereof |
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2013
- 2013-01-15 IT IT000043A patent/ITMI20130043A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960921A (en) * | 1986-09-08 | 1990-10-02 | The Standard Oil Company | Multiply promoted MN-SB oxide catalysts |
| US5834394A (en) * | 1996-08-06 | 1998-11-10 | China-Petro-Chemical Corporation | Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile |
| US20030109381A1 (en) * | 1999-09-17 | 2003-06-12 | Junzo Ohishi | Catalyst |
| ITMI20002603A1 (en) * | 2000-12-01 | 2002-06-01 | Snam Progetti | CATALYTIC SYSTEM FOR THE PRODUCTION OF ACRYLONITRILE FROM PROPYLENE |
| EP1452231A1 (en) * | 2001-10-11 | 2004-09-01 | Dia-Nitrix Co., Ltd. | Method for producing ammoxidation catalyst |
| WO2010066386A1 (en) * | 2008-12-08 | 2010-06-17 | Sasol Technology (Pty.) Limited | Olefin selective ft catalyst composition and preparation thereof |
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