SA06260446B1 - Catalytic oxidation methods of propane to acrylic acid - Google Patents

Abstract

Abstract: A catalytic system of oxide mixture of metals Mo - V - Ga - Pd - Nb -x ( such that w, In , Si, Zn, Ge = X), Te, La ) shows high selectivity for acrylic acid in the reaction Partial oxidation of propane with gas containing molecular oxygen at a low temperature.

Description

Y propane from propane catalytic oxidation methods of catalytic oxidation of acrylic acid to acrylic acid Full description: Background of the invention 11/4/1470 Partial of application No. 4470077130 filed on calla of this application; 999/97/14 1 at the Saudi Patent Office in the name of the Saudi Basic Industries Corporation (0 SABIC) (for the production of an ideal metal oxide mixture of catalytic system ° through catalytic partial oxidation in the medium Gaseous propane acrylic acid and acrolein acrylic acid and its use in the selective one-step production of acrolein at low temperatures Several publications have been included in this application for reference describing these. The field to which this invention relates and is therefore included by reference Als References 0 acrylic acid to propylene acrylic acid The two-step oxidation of propylene in a gaseous medium is known in this field. The production of acrylic acid from propane . related to production. propylene Vo

OA YANO from Propane US Patent No. acrylic acid sacrylic acid, which declared a method for partial oxidation of propylene to produce acrylic acid, acetic acid dioxide, acrolein, and propylene A mixture with a gas containing propylene Jeli by means of carbon dioxide contains molecular oxygen in the reaction range with a catalyst containing ©

Bi, Mo. V, A, :1 and 0 O,

v Whereas 1 is one or more of Tl Cs, Li, Na, K One or more of A such that is one or more of E , Ha while Ce, Zn, Co, Ni, Fe 01 is from zero to 6,1,8, af. Sr,Ca,Mg,B,Pb,Cu,P,Sn,Sb,Nb, W 1? To : 1 to 10 and 0 from 11 and 7 from 71 to 1.1 and © from 01 to 1.1 while 5 from 18:10 to 1 : 7.:0 and 7:06 from K * 0 15.4 acrylic acid was produced using a catalyst of the type of bismuth oxides in a psi ratio at a temperature of 400 and then .01 in a ratio of 719 at a pressure of propane at the conversion of propane European Patent 838.608.0 2 of Takashi et al.) declares a method for the manufacture of unsaturated; Mostly in an explosive system of a mixture of carboxylic acids (C) in the presence of a catalyst containing VAL, air and water at a temperature of propane Propane is at least one of the elements selected from X such that MOVTeXO is a mixture Metal oxide tantalum A558 indium, indium, cerium, bismuth, manganese, chromium, chromium, zirconium, zirconium, titanium, tungsten rhodium, rhodium, cobalt, and ruthenium And ruthenium, iron, manganese iron, so that platinum and antimony, platinum or antimony, palladium, palladium, nickel, and nickel 10. The ratio of the basic elements follows the total weight of the basic elements with the exception of oxygen, and the following formula is achieved: Where VX > Qap F > Wal > Tar Qurra > Vimo >

X,Te,V,Mo are molar fractions of VX, Vie, Vv, Vmo and so that - 4545147 (00467647) recently announced by Takashi and his colleagues in another Japanese patent No. in the presence of acrolein and acrolein acrylic acid on the preparation of acrylic acid) February 1994 P.Moy, V, WNA XO, dst < zero 0 and 18 - 1 # 5 and in the case of 1 82 and 580,2, Ti . © 4 by acroloin Yo by 717 Reference catalysts The metals reported in this release achieve a low yield of propane dake propylene acrylic acid at a fairly high temperature as propylene is produced

¢ High cost, especially in recycled processes. Thus, none of the previous fields presented or suggested catalysts for the selective production of acrylic acid and acrolein at low temperatures through the partial oxidation reaction of propane in the gaseous medium. Therefore, it is preferable to provide a catalyst designed in such a way that the catalyst works to produce acrylic acid and acrolein from propane in a transitional manner without clear production of intermediate compounds such as propylene. General description of the invention One of the objectives of the invention is to overcome the deficiencies previously identified . 01 Another objective of the invention is to present an improved catalytic system used in the catalytic oxidation of propane to acrylic acid. Another object of the invention is to present an improved catalytic system used in the one-step oxidation of propane to acrylic acid. The aim of the last invention remains to provide a method for preparing and using the improved catalytic system. The previous objectives and other objectives and advantages of the invention will be explained or clarified in the following description. The present invention relates to an improved catalytic system for the selective oxidation of propane to acrylic acid and methods for its preparation and use. According to one of the distinct applications of the invention. Propane is selectively oxidized to 0-acrylic acid and acrolein in a gaseous reaction at a temperature between 400 Jon "m and a pressure of 1-00 bar. This is achieved using a catalyst of the composition Mo , VyGa.Pd.N.E, roasted such that X is at least one of the elements selected from Zn, Ge, Te, La 18.8 , 17 . 0 : Ye « is from 1,1 to 1 .

°© is greater than 0 to 0.7 and is 0000085001 to 0.1 © is greater than 0 to 0.7 © is greater than 0 to #0 > The numerical values fue, 8, 0, 5, a represent the specific atomic ratios in grams for the elements X, Nb, Pd, Go, V, and Mo, respectively, in the catalyst, preferably because the elements are present in a different way with oxygen in the form of oxides various oxides. Preferably, the improved catalytic system should be prepared by the steps in the examples. The invention also relates to the low-temperature selective catalytic method for the production of 0 acrylic acid or acrolein or both by oxidation of propane in gaseous media preferably in a non-reductive system. 0 Other objectives, features, features, and advantages of the present invention will be clarified from the study of the current characteristics, which include protection elements. Specific examples. A brief explanation of the drawings. the shape ? : is the XRD model of a comparative catalyst 0. Detailed description A feature of the invention relates to the improved catalytic system for the selective oxidation of propane The catalytic system includes the acidified composition. 0 and obtain GaPds of :110.17 for which X is at least one of the elements selected from W,In, Si, Zn, Ge, Te, La 8 is ¢ n is from 1n to 0:1 . 11

: © is greater than 0 to 0.7 ad 06060696000 to DY © is greater than 0 to 0.7 F is greater than 0 to 0.5 Las > One of the applications of the invention includes the equivalence requirements for other elements present in the catalytic Aus. The catalyst of the present invention may be used with or without a substrate. Suitable catalyst supports include alumina (corundum), silica, titanium (titanium oxide), zirconia, zeolites, and silicon carbide; molybdenum carbide; 60 to 2705 m 00 m 17,08. Mo, Molecular Sieves and Other Microporous/Non-Porous Materials The catalyst supported is usually present in a ratio of 70 to 756 by weight. The catalytic composition, while the rest represents the support material. Another direction of the invention is related to the methods of preparing the improved catalysts. It affects the testing of the compounds used and the special way to prepare the catalyst. The effect of one of them is on the performance of the catalyst. It is preferable that the elements of the catalytic composition be mixed with oxygen in the form of 5 oxides. Metal 0 (salts, complexes or other compounds) It is preferable that the solution be in the form of an aqueous solution with a logarithm pH of 17 M between 1 to 01 and preferably between 1 to 7 . at a temperature between 0 and 100 degrees Celsius. In general, the mixture of compounds containing the elements is prepared by removing suitable amounts of the soluble compound and dispersing (suspension) the insoluble compounds to achieve the required atomic ratios of 0 elements in grams within the catalytic composition. Then prepare the catalytic composition by removing water and/or other solvent from the mixture of compounds in solution. The dry catalyst is acidified by heating it at a temperature between 7900 to 1040 C in air or oxygen for a period of time ranging from about 1 hour to 7 hours to produce the required catalytic composition. It is preferable to include molybdenum in the solution in the form of ammoniacal salts such as YO ammonium paramolybdate or organic acid salts of molybdenum such as acetates and oxalates y It is possible to use molybdenum compounds ‎ . glycolates, glycols mandelates, and water-soluble mandelates .molybdenum in the form of molybdenum AY! molybdenum in the solution in the form of ammoniacal salts such as vanadium it is preferable to include vanadium and ammonium decavanadate ammmonium metavanadate organic acids salts or ammonium decavanadate 0 such as vanadium organic vanadium oxalates Acetates and oxalates such as vanadium acetate can be used as compounds. Tartartes, tartrates, oxalates, acetates, acetates for partial water solubility, such as ALE vanadium vanadium oxides. vanadium sulfates and vanadium oxides tartaric acid or tartaric acid oxalic acid A specified amount of oxalic acid 0 in the form of gallium salts catalyst in its catalyst culture gallium and it is preferable to include gallium. And the like, nitrate, nitrate, chloride, and chloride oxide, such as gallium oxide, in a batch (slurry) catalyst in the form of 18 over palladium, and it is preferable to include palladium

Ja palladium or in the form of a solution of palladium salts, alumina, activated charcoal or alumina. And the like, nitrates, nitrates, chlorides, chlorides, acetates, acetates, Ve. It is preferable to include other metals in the catalyst slurry in the form of salts such as oxides. And the like nitrates, nitrates, chlorides, chloride acetates, acetates, oxides or oxalates in the form of niobium oxalates, and it is preferable to use the element niobium. Other sources of this metal in the dissolved form include compounds. hydrate oxides are aqueous diketones - Gad _ in which the metal is covalently bonded or complexed to a Y- or alcohol amine, a carboxylic acid alcohol amine, and a beta-diketonate carboxylic acid (alkanolamine is an amino alcohol). ) Alkanolamines For one of the distinct applications of the invention, the catalyst is prepared by the general method bes no on molybdenum “molybdenum vanadium” following. Aqueous solutions of vanadium are prepared at the molybdenum degree with the molybdenum vanadium solution separately; The Yo vanadium solution is mixed specifically, the remaining required ingredients are slowly added to the pH temperature of the logarithm of pH 1 Se The resulting colloidal solution After mixing, the resulting colloid is dried to a degree of wetness starting with

A

An hour and 16 degrees Celsius for 2 VY eB) ga after drying the resulting colloidal mixture at a temperature of ? degree (C / min) and it is acidified VON by heating the resulting catalyst to a temperature at the same temperature in the air for hours to produce the required oxide composition. Another direction of the invention relates to the method of using the innovative catalytic system in the selective oxidation of propane.acrylic acid to acrylic acid © propane The starting material used as a source for propane can be a gaseous stream which contains at least 1 percent by volume of propane or a mixture of propylene / propane The gaseous stream may also contain some amounts of Location: © , © or alkyl gas The gaseous stream may contain an apie of volume per BLY preferably less than .contain large quantities and greater than 0% by volume of diluted substances in vapor form 0 To carry out the reaction the reaction mixture must generally contain one mole of either in the form of 0001600187 oxygen to 1 mole of molecular oxygen propane 00 moles of oxygen or in the form of substances and zero to 1 mole of water at The form of steam hydrocarbons and oxygen-rich air depending on the cost of separation and conversion of hydrocarbons 1/1 to 1/8 required and catalyst selectivity, but in general this ratio ranges between 0

Fou to 1.1 The concentration of oxygen in the gaseous feed mixture varies widely from or to in the gaseous mixture by applying appropriate measurements in order to avoid explosive problems. Air is preferred as a source of oxygen in the feed mixture. The existing quantity of . hydrocarbons Oxygen is a standard amount according to the elemental union or less for hydrocarbons. In the ys argon feed mixture the reaction can be particularly affected by the presence of diluents such as argon or steam (so the ratio of propane to aqueous substances ranges between nitrogen and nitrogen.) 1/1 to 0/1 Water vapor or steam may be used as diluents in the reaction and as a release of the reaction temperature. It can also act as an accelerator for the aggregation of the reaction products in the oxidation reaction in the vapor media Yo. Other gases can be used as diluents in the reaction or as heat releases such as 7 carbon dioxide. 0 nitrogen and nitrogen helium helium

The liquid compounds resulting from the reaction can be separated from the unreacted hydrocarbons by equivalence or scrubbing, usually with water or dilute acids. Thanks to the fact that the gaseous components of the reaction mixture include propane and oxygen or oxygen with the diluents, it is preferable that these components be mixed in an orderly manner before adding them to the scope of the reaction. The components can be heated individually or after mixing them before adding them to the reaction range, which must have a temperature between 151 to 490 °C. The pressure of the reaction zone is generally between 1 to 5 + 0 bar. Celsius temperature, preferably between 100 to 7700 C. The contact time between the reaction mixture and the catalyst is between 1.00 seconds to 100 seconds, preferably between 1 second and 10 seconds. 1 The vacuum speed per hour is between 80 to 80,0086 hours, preferably from 001 to es hours, and in more detail between 0000 to 0000 hours. The contact time is defined as the ratio between the apparent volume of the catalyst bed and the volume of the gaseous reaction mixture feeding the bed and the catalyst under the given reaction conditions per unit time. The vacuum velocity is calculated by specifying the amount of gas outside the reactor in liters of the total amount 0 emitted during one hour divided by the number of liters of catalyst inside the reactor. The volume at room temperature is converted to the volume at zero degrees Celsius at bar. The pressure required for the reaction is dehydrated by feeding the gaseous reactants and dilute gas, but after the start of the reaction, the pressure can be maintained by using a pressure regulator placed at the outlet of the reactor. Y. While the required reaction temperature is achieved by placing the catalyst layer inside a tubular transformer with walls placed inside an oven heated to the required reaction temperature. The high yield of acrylic acid achieved is considered one of the advantages of the catalytic system of the invention. It is preferable that oxidation achieve the results of acrylic acid at least by CT Yo. Oxidation in the present invention achieves selectivity of acrylic acid at least by 7560 per Good passage through the reaction range, preferably at least 710. 11 Y.A

Yo.

Using the catalytic system of the invention, propylene is produced at a rate less than 71%, and it is preferable not to produce any propylene as side products of the reaction. In general, the method is done in one step using all the oxygen and the reactants fed as one atom with the reuse of the unreacted primitive reactants. Although oxygen or a hydrocarbon may be added

hydrocarbon© to the reactor in several steps and / or sale) the use of unreacted gases with the possibility of applying the purge pattern (cleaning) to improve productivity in general and / or improve the results of the desired products. SY List the methods used for the catalyst of the invention in propane oxidation to acrylic acid and acrolein. However, the catalyst 0 can be used for normal Cy oxidizing / ISO 180 © in the vapor medium (gaseous) using molecular oxygen to produce the corresponding unsaturated carboxylic acids in the alpha-beta Z position. aay The following examples are illustrative examples of some products and their preparation methods that are in line with V0 within the scope of the present invention. These proverbs are not in any way specific to the invention, but many changes and modifications can be made by referring to the invention. The catalyst samples prepared in the examples can be evaluated (tested) by the (AY) method. Catalyst test: The catalyst is evaluated inside a fixed-bed tubular reactor made of stainless steel, Ye, under standard reaction conditions. The composition of the feed gas used in catalyst evaluation contains propane, oxygen and nitrogen. The reactions were carried out at a temperature of 0 °C and a pressure of 10 °C with a sub-hour of approximately 009 hours. The reaction results are analyzed by direct gas chromatography from the reactor. Oxygen, argon, and carbon monoxide, Yo, are analyzed by a 7-meter column “¥ mm with a partial sieve X 0,” while carbon dioxide, propane, and propylene are analyzed using a column? Xia “mm Lins in

1 | It is sold under the name HAYESEPRQ. Liquid products (acrylic acid 0, acrolein, acetic acid, and water) are analyzed for a certain period of time inside a cold trap, and they are analyzed using a 1-meter VX column. MM is filled with a substance sold under the name PORPAKQR. In all cases, the conversion and selectivity calculations follow the standard measurements oo of the reactants. Manal 1 3 0001225 with 20 MO: Vo,398 Gaig-os 1 gm of ammonium meta-benefits 106127206 ammonium (Aldrich Chemicals and Calibration 744) is added to 80 ml of distilled water and then heated to 0 0°C with stirring. VE g of niobium oxide (NbOs/Z A+), YA g of oxalic acid and YALA g of ammonium paramolybdate are added to the vanadate solution vanadate to form the colloidal mixture. The required amount of palladium, then telluric acid, and gallium oxide are added slowly to the colloidal mixture. The colloidal mixture is stirred vigorously. To obtain a homogeneous slimy mixture that is dried to the desired dryness with continuous stirring. The resulting solid is placed in a tray and dried again in an oven at a temperature of 1707°C. The dry material is cooled to room temperature and placed in an oven, where it is roasted at a temperature of 0075 C for a period of 4: 16 hours. The temperature is raised from Ye at room temperature to 0758°C at a rate of 17°C (/min) and thereafter the temperature is held at 0075°C (for ; hours. The improved catalyst is formulated into uniform granules using a sieve of size − + and the ( test ) The catalyst in the propane oxidation reaction. The catalyst is evaluated at a temperature of m using a nutrient mixture containing propane, oxygen, nitrogen at a ratio of 1:70 Ye: 70. The reaction products showed the following results: transformation of propane 776.40 selectivity of acrylic acid 771 acrylic acid

YY

771 acetic acid selectivity 7 acrolein selectivity 7/47 Cox selectivity . The results showed a total of “75 oxygenated products and 7; 7 Complete oxidation products, for example?

MO: Vo,308 Gases 20: Nbo.1225T€0.23 Lay as much as lanthanum nitrate at the end, except for adding the required amount of lanthanum nitrate, example 1. Step in preparation The roasted catalyst is formulated in the form of regular granules using a sieve of size 0001 M and evaluated in the propane oxide reaction. The catalyst is rated at a temperature of te - 0

Ver 00: Yo (using a nutrient mixture containing propane: oxygen: nitrogen at a ratio of 0: reaction results. The following results showed 771 acrylic acid selectivity of acrylic acid 771/771 propane conversion of propane

YY acetic acid selectivity acetic acid / 1 acrolein selectivity 7/19 Cox selectivity . The results of the reaction showed a total of 70 oxygenated products and 775 complete oxidation products

DY A: Manal 1/101 17 with 0 and with yoyo Nbo.125T€0.23 22-5 except for adding the required amount of zinc nitrate and acid: 1 Same steps as the example. In the last step in the preparation of telluric acid, the roasted catalyst is formulated in the form of regular granules using a sieve of size Ye av 00. The catalyst is evaluated at a temperature of 0 and evaluated in the propane oxidation reaction 01-6 L.: 01: 01 using a nutrient mixture containing propane: oxygen: nitrogen for the ratio: Explain the results of the reaction as follows:

JAR acrylic acid A 0 propane 711 acetic acid A 0 acrolein Yo

VY

7/58 Cox Selective . The total results of the reaction showed 772 oxygenated products and 7715 complete oxidation products. The catalyst is evaluated at a temperature of 9107 C (using a feed mixture of 10 - 460 C using a sieve containing propane: oxygen: nitrogen for a ratio of 45.76: 75; show the reaction results: the following results: 740.06 acrylic acid Acrylic acid 77 propane Propane conversion 70,0 acrolein (ly SY) selectivity ARE oxygen acid 0 758 Cox selectivity 70,0 acetic acid selectivity acetic acid The results showed a total of 777 products. Oxygenated and 777 complete oxidation products e0 ethanal MO; Vo 308 Gai as pdi 210012251 mo and the roasted catalyst is formulated in the form of regular granules: 1 the same steps as the example Ye km (using a mixture Feed 0.0 b to 1 and the catalyst is evaluated at a temperature of 0 ¢ using a sieve Show reaction results Results 01: 0 Contains propane: oxygen: nitrogen for the ratio: the following / 001 . Oxygen conversion 4 propane Propane conversion 7,5 | Acrylic ages) /Ye,0 acrylic acid 0 7/2501 Cox selectivity / 01 acetic acid selective acetic acid. Complete oxidation products 701 The results showed a total of 749 oxygenated products and 1 Manal MO Vo 398 Ga Eos Pdi 155.04 Nbg125Teo 30 ye

Pd except for the addition of different amounts of: 1 The preparation steps are the same as the example steps The roasted catalyst is formulated in the form of regular granules using . tellurium and tellurium, and the catalyst is evaluated at a temperature of 0070 °C using a feed mixture containing 0 - 00 sieves. The results of the reaction showed results: Ve: 01: Ye on propane: oxygen: nitrogen for the ratio: the following: 0 7 001 Nigskala conversion 7/4 propane conversion of propane 7 selectivity of acrylic /Yo,0 acrylic acid selectivity of acrylic acid 771 Cox selectivity 701 acetic acid selectivity of acetic acid. The results showed the total reaction; 77 oxygenated products and 777 complete oxidation products to 01 from +1 - 1 for the catalysts described in BET. The surface area varies by 01 . DMG 1 The X-ray code pattern of the catalyst according to one of the applications of the invention is illustrated in the figure The catalysts suspended in the present invention have a structural composition which results in a diffusion pattern and a very broad signal at (A) angstroms YY Or poor crystalline with a strong reflection signal at, and in general, to obtain this structural composition, it is necessary to prepare (A (la angstrom) (xy m) is a type of A very broad signal at 3.75 angstrom 0 catalyst By the previously described methods, the diffusive signals, which are difficult to attribute to any single phase, although when these catalysts are acidified at high temperatures, several known reflections will appear, and these reflections are inactive to activate the alkanes on the catalysts of the present invention. Perfect reductive properties and lead to the effectiveness of Jad) Example No. 7 This purifies the catalysts of the invention Yo. And a high transition of the catalyst towards partial oxidation products of the data resulting from the etching process. The general properties of the announced catalysts can be collected in Les: In The current version is as follows: In acrylic acid temperatures, high transition catalysts for acrylic acid appear (1): . Low Yo 19 C = 01 The protan oxidation reaction shows a spectrum change in temperatures between (1). My father has a positive feedback on the design of the reactor.

The specific selectivity of the oxygenated compounds depends on the composition of the catalyst, the temperature of the reaction, the reaction temperature, the alkane oxygen, the velocity, the pressure, and the feed composition (the alkane).

MO; Woo Nbg 125Tep 23 ° The composition of the catalyst and the steps are the same as those declared in the European Patent No. For comparative purposes the catalyst is calcined at 08°C (as described in the European patent version 7). An X-ray diffraction pattern is shown The catalyst and form as LA 5.7;¢ 00 at two values of “FLY 78,777,1 clear reflections at” are described in the European patent issue The roasted catalyst is formulated as 0 and the catalyst is evaluated at Oxidation reaction of skipper Te - £0 regular particles using a sieve of volume C using the nutrient mixture containing Ave C and temperature 00 at temperature. : Nitrogen : propane on propane The catalyst is inactive at these two temperatures The previous description of the invention was prepared for clarification and not limitation Ve can make many changes and modifications in the applications described by skilled persons in this field This can be done without departing from the spirit or purpose of the invention. 1 YA

Claims (1)

protection pale 1-1 A one-step catalytic process for the conversion of polymeric propane into acrylic acid Y and acrolein by means of a propane oxidation reaction which x includes propane oxidation In a reaction mixture comprising: (i) propane or propane / propylene (i) °oxygen or an oxygen-capable compound 28 in reaction range 1 in the presence of system Catalytic The catalytic system contains a catalytic composition comprising: Nb, X¢ v quenching Mo, Vy, A and in which: aX 4 at least one of the elements selected from Ge, Te, La, 177.18 , 81.20 00 dohy 1 - MN 5 is from 0.1 to 0.1 . 1 © is greater than 0 to 0.7 0". L is from 0.6006 0000 to SY pee is greater than 0 to DY AF 1 is greater than 0 to 0.5 11 and so that the numeric values 2, 6, 17, d, c, b, a represent the specific atomic ratios in grams for the elements O, X, Nb, Pd, Ga, V, Mo 17, respectively, in The catalyst and the elements are present in combination VA with oxygen 1 ?- A process according to claim 1 in which the reaction mixture also includes an alkane (when. 1 “- Process according to the claim? ; Allg in which the alkane is ethane ¢ propane vy and isobutane and the general n-butane or a mixture of them. 1>- A process according to Claim 1, in which the aforementioned catalyst is in the form of a fixed layer, and in which the “oxidation reaction takes place using a mixture prepared to include the feeding of propane in the oy range of the reaction. 11 VY; In which the aforementioned catalyst is in the form of a fixed layer and in which 1 process is carried out according to the protection element 0 1 in the range of propane using a mixture prepared to include feeding propane oxidation oxidation reaction 0 . interaction ¥ . Operation according to protection element © ; in which the feed mixture includes air — 1 process according to claim © ; in which the nutrient mixture contains oxygen 7-1. Y oxygen pursuant to claim ©; in which the nutrient mixture contains oxygen Adee =A 1 by volume. 70 0 -_ in a proportion ranging from zero to “according to the © claim; In which the feed mixture is dried by steam with an amount ranging from 1-4 dle. From zero to 7760 by volume by oxidation process according to the protection element; ; In which the oxidation reaction is carried out 0-1 bar 50 to 1 to 0049 C under a pressure of 100 in gaseous media at a temperature between . 01 to 1.1 seconds, and the contact time between the reaction mixture and the catalyst is between 801758 | +” oxidation selectivity of the protective agent; ; in which the oxidation reaction ly process 1-11 and acetic acid acrolein and acrolein are dried for the oxygenated compounds (acrylic acid 717 glossy) at a ratio of v as a process propylene product according to the claim; ; In which propylene 1-1 is not detected as side products using propane oxidation to oxidize propane Y. of the nutrient mixture 75900 to 1.01 whose percentage ranges from molecular oxygen?-oxygen process according to the protection element; ; Involves the multi-step addition of oxygen 1-1 into the nutrient mixture to increase the yield and selectivity or both the yield and the selectivity of the desired compounds. Catalytic comprising - Mo, Vb Ga, Pd4y Nb, Xs Vv YA W,In,Si,Zn,Ge,Te,La is at least one of the selected elements of Xo in which ¢ is p 8° . »,1 to 0.1 is from 0 0.7 greater than zero to aC SY to 00960605000 is from 0 A 0.7 is greater than zero to 1 0.5 is greater than zero to Ye for a catalytic chemical reaction comprising the step of adding the reactant to the liquid medium idee —Vo 1 The range of the reaction containing the catalyst having the catalytic composition and which can be prepared Jala to : by the method comprising Steps to form a mixture with the following ratio: 75 Nbe Pde 08. Ve Mo A- Mixing the elements Mo, Vy, Ga, Pdg Nb. Xt © in which Alls x W,In, Si, Zn, Ge, Te, La at least one of the elements chosen from a= XV 1 is 8 A . 0.1 to 1.1 < is from 04 0.7 is greater than zero to © 0 SY to 200006610 l is from 11 0.7 is greater than zero to ©» 1 0 is greater than 0 to 7 0 of the said mixture. calcining b. Roasting 1 process of claim 10; In which the catalytic chemical reaction shifted one or -1-1 . More than one of the reactants of the liquid medium to one or more of the products of the liquid medium; the catalytic chemical reaction Led; which oxidizes V0 process according to protection element -117-1 to the corresponding acid 266:09. alkene or alkene Cg-C; Alkanes Alkanes catalytic chemical VA) process pursuant to claim 176; and in which one or more of the reactants of the liquid medium include tropane and one or more of the products of the liquid medium contain 0 acrylic acid. -11-1 process pursuant to claim 116; in which one or more of the reactants of the liquid medium include unsaturated beta aliphatic aldehydes and one or more led + or more of the products of the liquid medium contain unsaturated carboxylic acids; except - alpha -beta iw . -71-1 Process pursuant to claim 1; In which the catalyst is in the form of a solid mobile layer 0 and in which the oxidation reaction takes place using the nutrient mixture that includes propane or ¥ propane / propylene within the reaction range. 11 Y.A