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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
• • 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
  • 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
  • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
  • B01J27/198—Vanadium
  • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
• • 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
  • B01J35/19—Catalysts containing parts with different compositions
• • 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
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
• • 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
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0027—Powdering
  • B01J37/0036—Grinding
• • 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
  • B01J37/04—Mixing
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
  • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
  • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
  • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
• • 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
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • 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
• • 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
• • 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

Definitions

• the present invention relates to a compound comprising a combination of two crystalline phases, a crystalline phase being of the phosphomolybdic type, and a process for its manufacture and several uses of this compound.
• the compound according to the invention is more particularly intended to catalyze certain reactions of oxidation of alkanes, and in particular the oxidation of isobutane to methacrylic acid and methacrolein, which leads to the formation of methyl methacrylate.
• catalysts comprising two phases, in which one of the two phases is of the phosphomolybdic type.
• the compound used as a catalyst consists of a phospho (arsenio) molybdic acid phase and a phase based on ferrous iron orthophosphate. In both phases, some of the phosphorus must be substituted with arsenic. This catalyst therefore contains a large amount of arsenic, the toxicity of which limits the industrial use of the catalyst.
• the object of the invention is to provide a compound which can be used as a catalyst which does not have the abovementioned disadvantages, that is to say a compound which does not contain toxic elements and exhibits stable catalytic properties over time.
• the subject of the invention is a compound comprising the combination of two crystalline phases.
• the first crystal phase is phosphomolybdic type and has the formula (1): A a E b V c P d Mo e O f M g (1) wherein:
• - A is an alkali metal
• E is selected from the elements Te, Sb or Bi, preferably Te or Bi;
• the indices a, b, c, d, e, g are such that: 0 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 3, 0 ⁇ c ⁇ 3, 0 ⁇ d ⁇ 13, 0 ⁇ e ⁇ 2, 0 ⁇ g ⁇ 3, and f represents the number of oxygen atoms needed to satisfy the valence and relative atomic proportions of the elements present.
• the alkali metal A is cesium.
• Element E is preferably tellurium.
• the second crystalline phase corresponds to formula (2):
• Z is chosen from trivalent rare earths
• X is selected from the elements V, Ga, Fe, Bi, Ce, Ti, Sb, Mn, Zn, Te, preferably V, Ga, Fe, Bi, Ce, Ti, Mn, Zn, Te;
• the indices g, h, and i are such that: 0 ⁇ g ⁇ 3, 0 ⁇ h ⁇ 3, 0 ⁇ i ⁇ 1 and j represents the number of oxygen atoms necessary to satisfy the valence and the atomic proportions relating to the elements present.
• the first and second crystalline phases are free of Sb atom which has a high toxicity, thus allowing an easier use of the compound on an industrial scale.
• the element Z represents lanthanum.
• the element X is vanadium.
• the proportion of the second crystalline phase is less than or equal to 50% by weight relative to the total weight of the compound.
• the first crystalline phase can meet the formula Cs 2 Teo, 3Vo, - ⁇ Ho, 4 PMo-i 2 ⁇ 4 o.
• the second crystalline phase can meet the formula La 2 Mo 2 Og or the formula
• the process for preparing a compound according to the invention comprises the following steps:
• the synthesis of the first crystalline phase can comprise the following successive steps:
• the acids of element E such as telluric acid, chlorides or alkoxides of element E.
• the salts of element A mention may be made of carbonates or nitrates. Cesium carbonate is particularly preferred.
• vanadium compounds mention may be made of vanadium oxide or vanadium acetylacetonate.
• the synthesis of the second crystalline phase may comprise the following successive steps: - grinding mixture of molybdenum oxide MoO 3 in the solid state and an oxide of element Z in the solid state;
• the annealing temperature is between about 850 ° C. and 960 ° C.
• the oxide used is then La 2 O 3 .
• the molybdenum oxide is partially replaced by a compound of the element X. If X represents vanadium, the compound used may be vanadium oxide or ammonium vanadate.
• a compound according to the invention is advantageously used as a catalyst for the oxidation of alkanes, in particular isobutane, propane and pentane. It can also be advantageously used as a catalyst for the oxidation of isobutene and methacrolein to methacrylic acid.
• the compound according to the invention is particularly effective as a catalyst for the oxidation of isobutane to methacrylic acid and methacrolein, as the examples hereinafter describe.
• the preparation of methacrylic acid and methacrolein from isobutane comprises passing a gaseous mixture containing isobutane and water, and optionally an inert gas and / or molecular oxygen, on a compound according to the invention.
• the tests carried out have shown that a synergistic effect between the two phases of the compound according to the invention took place, the observed activity does not correspond to the simple sum of the activities of the pure phases.
• the cesium was determined by atomic emission in air-acetylene flame (on a spectrometer marketed by Perkin-Elmer) and the other elements were determined by atomic emission in a plasma ICP (Inductively Coupled Plasma), on a spectrometer marketed by Spectro.
• the wavelengths used for the analysis are shown in Table 1.
• the infra-red spectra were recorded in transmission between 4000 and 400 cm -1 on a Fourier transform apparatus, marketed by BRUCKER under the reference VECTOR 22.
• the samples were prepared in the form of pellets after a dilution of about 1 mg of solid in 300 mg of KBr.
• the gases used are distributed respectively by the valves 1a, 1b, 1c and 1d, by means of mass flowmeters 2a, 2b, 2c and 2d of BROOKFIELD type allowing precise regulation of the respective flow rates.
• the hot box 4 is maintained at 169 ° C by a temperature control system 3 associated with an oven 5, to avoid condensation in the pipes.
• the water is synthesized in the hot box 4 from oxygen and hydrogen on a platinum catalyst supported on Al 2 O 3 .
• the box 4 is equipped with a four-way valve 9.
• a fixed-bed reactor Pyrex 6 fixed with a condensation system 7 is used.
• the catalyst is placed on a frit and a thermowell (not shown) allows the measurement of the temperature directly in the catalytic bed. It is this temperature that is reported in all the tables of results.
• the masses of the tested catalysts are 2.0 g.
• the condensation system 7 is installed at the outlet of the reactor 6 in order to trap the condensable organic compounds.
• the trap containing an aqueous hydroquinone solution is kept at 0 ° C. in ice.
• the non-condensable gases (CO, CO 2 , C 4 H 10 , C 4 H 8 , N 2 and O 2 ) are analyzed online by chromatography after the trapping system.
• the analysis system consists of two gas chromatographs and a liquid chromatograph.
• the first two mounted in line, allow gas analysis.
• the first 10 chromatograph equipped with a molecular sieve 11 (CP-I MOLS ® 5 ⁇ EVE), a packed column 13 (Porapak Q ®) and a six-way valve 12, permits the separation and quantitation of CO , CO 2 , N 2 and O 2 .
• the device is equipped with a detector 14 which is a katharometer, and the carrier gas is helium. This system allows the detection of isobutane and isobutene, but not their separation.
• a second chromatograph (not shown for reasons of simplification) equipped with a filled column (Silica-PIot ® ) is used to effect this separation. Four analyzes are performed for each temperature, which represents a condensation time of about 120 minutes.
• the condensable products are analyzed on a chromatograph CHROMPACK 9001 equipped with a FID detector comprising a filled column 16 (Silica-PIOT ® ) and a column 17 (CP-Sil ® ), and a CPWAX58 / FF ® column.
• the measurement system is shown schematically under the reference 18, and the reference system is shown schematically under reference 19.
• the carrier gas used is nitrogen.
• the injection is carried out using a CHROMPACK automatic sample changer type CP9005.
• the volume injected is 0.5 mL and 5 injections per sample are made. Uncertainties on measurements are less than 2%.
• the chromatogram obtained shows the characteristic peaks of methacrylic acid, acrylic acid, acetic acid and methacrolein.
• the activities and selectivities were calculated by considering the following reaction products: methacrylic acid (AMA), methacrolein (MA), acetic acid (AAc), acrylic acid (Acr), acetone ( Ace), CO and CO 2 .
• N (R) O -N (R) F C (R) N (R) 0 wherein N (R) 0 is the number of moles of reactants R in the initial reaction mixture, and N (R) is the number of moles of reagent R at time t during the test.
• the selectivity (S) of the various products is defined by the following equation: c (r) - N (P) * n (P) ⁇ N (P) * n (P) wherein N (P) is the number of moles of product P at time t during the test, nc (P) is the carbon (or oxygen) number in the product molecule P.
• the product yield P (R (P)) is defined by the equation:
• R (P) C (RfS (P)
• the first solution is prepared by solubilizing 8.16 g of phosphomolybdic acid (marketed by Fluka under the reference 79560) and 0.18 g of telluric acid (marketed by Interchim under the reference 014197) in 140 ml of water.
• the second solution is prepared by solubilizing 1, 3 g of cesium carbonate
• the second solution is added to the first with stirring.
• the solid precipitate is recovered in a rotary evaporator at 80 ° C, dried in an oven at 120 ° C and calcined at 360 ° C for 6 hours (up to 5 °. Min '1, air flow of 50 ml. Min " 1 )
• the solid obtained (6.5 g) is reacted with vanadium acetylacetone (V [CsO 2 H 7 ] S )
• the progress of the reaction is followed by the color change of the solution which is initially colored, and loses its color when the vanadium has reacted with the solid which is not soluble.
• the reaction is complete after 10 to 12 hours under argon.
• the stoichiometries calculated correspond to those desired.
• the solid was also characterized by infra-red spectroscopy after annealing under nitrogen at 36 ° C. The allocation of the bands is presented in Table 3.
• the observed lines are characteristic of the Keggin structure anion of formula [PM ⁇ i2 ⁇ 4o, 4 ].
• the indices a, b, c and d correspond to the oxygen atoms located at different positions in this anion.
• a central tetrahedron (PO 4 ) surrounded by 12 MoO ⁇ octahedra in four groups of 3.
• the trimers, in which the octahedra share edges, are connected to each other and to the central tetrahedron by vertices.
• oxygen atoms are equivalent, while those of oxygen atoms are not, there are four types of oxygen atoms: 4 oxygen atoms (O 3 ) common to the tetrahedron (PO 4 ) and three Mo oc ⁇ octahedra sharing edges, 12 oxygen atoms (O b ) common to two octahedrons sharing a vertex, 12 oxygen atoms (O c ) common to two octahedra sharing one edge, and 12 oxygen atoms (O d ) bound to one bond double to a single metal atom.
• Catalytic properties of the first crystalline phase a) Evolution of the catalytic properties as a function of the reaction time
• FIG. 2 shows the evolution of the conversion (C 1 %) with time (t, in hours) during the catalytic test under the standard conditions defined above, at the reaction temperature of 35 ° C. deactivation of the sample at the beginning of the reaction, for about 5 hours, then stabilization. Measurements of the specific surface before and after catalytic test show that it has decreased from 28 to 11.8 m 2 .g -1 .
• FIG. 3 shows the evolution of the selectivities (S,% ) to methacrolein (4), meth acrylic acid (A), acetic acid (•), CO (o) and CO 2 (D), and the conversion (C,%) of isobutane (m) depending on the contact time (t, in seconds). It is observed that the increase in the contact time leads to an increase in the conversion of isobutane, selectivities in CO, CO 2 and acetic acid, and a decrease in the selectivity to methacrolein and methacrylic acid. d) Evolution of the catalytic properties according to the molar ratio isobutane / oxygen
• the composition of the filler plays a very important role in the oxidation reaction of isobutane to methacrylic acid
• the molar ratio of isobutane / oxygen (iBu / O 2 ) was also chosen as a study parameter.
• the contact time was set at 4.8 seconds, the percentage of nitrogen and water respectively at 49.5 and 10% and the reaction temperature at 34 ° C. The results obtained are shown in the table. 5.
• the first phase was characterized after catalytic test by X-ray diffraction and infrared spectroscopy.
• the diffractogram after test is comparable to that before testing, showing that no profound change has occurred.
• Infrared spectroscopy characterization results are shown in Table 7.
• This phase is prepared by reaction in the solid state between M0O 3 (marketed by Chernpiir under the reference 005565) and La 2 ⁇ 3 (marketed by Alfa Aesar under the reference 011264).
• the reagents are weighed in stoichiometric proportions and ground in an agate mortar.
• La 2 O 3 compound was preheated to 1000 0 C to prevent its hydration in time and the formation of La (OH) 3 .
• the mixture is then transferred to an alumina boat. It undergoes a preheating at 500 0 C and two successive annealing with a duration of 15 hours at a temperature of 96O 0 C, between which the mixture is ground in acetone to homogenize and ensure a good dispersion of the grains, and this until the pure product.
• the purity of the product, in terms of phase composition, is controlled by X-ray diffraction.
• the second phase was characterized by X-ray diffraction.
• the final compound is prepared by mixing the first and second phases by simple mechanical grinding.
• FIGS. 5a and 5b represent the evolution of the conversion C (in%) of isobutane (m), the selectivities S (in%) of AMA (A) and MA (4) and the yield of AMA and MA (0) at 345 ° C. (FIG. 5a) and 369 ° C. (FIG. 5b) as a function of the content by weight of lanthanum molybdate (denoted LM, in%).
• LM lanthanum molybdate
• X-ray diffractograms of compound 1c before catalytic test (diffractogram a) and after catalytic test (diffractogram b) are shown in FIG. 6 (the intensity is given in counts per second (CPS)).
• the signs (T) represent the peaks corresponding to the second crystalline phase La 2 M ⁇ 2 ⁇ g. These diffractograms do not show any phase transformation.
• This compound consists of a first phase identical to that of Example 1, and a different second phase.
• the first crystalline phase was prepared using the same experimental conditions as for the first phase of Example 1.
• the second crystalline phase was synthesized under experimental conditions similar to those described for the second phase of Example 1, with the exception that the compound V 2 O 5 (marketed by Alfa Aesar under the reference 81110) was added to MOO 3 and La 2 Os in stoichiometric proportions and that, after preheating, the mixture has undergone 7 successive annealings of a duration of 15 hours at a temperature of 925 ° C.
• V 2 O 5 marketed by Alfa Aesar under the reference 81110
• the second phase was characterized by X-ray diffraction.
• the diffractogram of the second phase (FIG. 7, in which intensity I is indicated in counts per second) corresponds to that of the cubic phase of lanthanum molybdate.
• the catalytic performances of the second crystalline phase are indicated in Table 12 below, the tests having been conducted at the temperature of 360 ° C., with a contact time of 6 seconds, and by varying the feed conditions (defined by the ratios C 4 H 0/0 2 / H 2 0 / N 2 ).
• the final compound is prepared by mixing the first and second phases by simple mechanical grinding.
• FIG. 8 represents the evolution of the productivity in (AMA + MA) ( ⁇ ), the selectivity in (AMA + MA) (m) and the conversion of isobutane (A) as a function of the amount of CO 2 in the reaction mixture.

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