PREPARATION OF UNSATURATED ACIDS AND ESTERS

Abstract: An improved process for the preparation of unsaturated acids and esters comprising the catalytic vapor-phase conden­ sation of formaldehyde, or formaldehyde derivatives, with sa­ turated monocarboxylic acids or derivatives wherein the reac­ tion is conducted in the presence of oxygen.

Description: PREPARATION OF UNSATURATED ACIDS AND ESTERS This invention relates to an improved process for the production of unsaturated carboxylic acids or esters. The condensation reaction of saturated carboxylic acids and esters with carbonyl compounds to produce unsaturated acids and esters is known and various catalysts for this reaction are known. Such condensations are usually carried out by passing the vaporized reactants alone or with an inert carrier gas over a catalyst and are not oxygen-promoted. U.S. Patent No. 4,165,438 discloses the production of acrylic acids and esters by reacting a lower alkanoic acid or a lower alkyl ester thereof with formaldehyde in the presence of a vanadium orthophosphate catalyst. U.S. Patent No. 4,339,598 and 4,324,908 disclose vanadium-antimony catalysts and promoted phosphate catalysts, respectively, as being effective for the vapour phase condensation of saturated monocarboxylic acids or esters with formaldehyde, to produce unsaturated carboxylic acids or esters. It has now been discovered that over typical condensation catalysts, in the condensation of formaldehyde or formaldehyde derivatives with saturated acids or esters, the product yields of corresponding unsaturated acids or esters are greatly improved when the reaction is conducted in the presence of oxygen. This advance over the art significantly increases the economic incentive for the production of important monomers, such as methyl acrylate, from starting materials easily available from synthesis gas, such as methanol, formaldehyde, acetic acid and methyl acetate. SUMMARY OF THE INVENTION Greatly improved yields of unsaturated acids and esters are obtained when the condensation of formaldehyde, or its derivatives, with saturated monocarboxylic acids or esters over condensation catalysts is conducted in the presence of oxygen. DETAILED DESCRIPTION OF INVENTION The present invention is an improved process for the catalytic vaporph-ase condensation of formaldehyde, or formaldehyde derivatives, with saturated monocarboxylic acids or esters, by conducting the reaction in the presence of oxygen. This oxygen-promoted condensation reaction is conducted similarly to a condensation reaction which is not oxygen-promoted. The reactant mixture is vaporized and the vapors passed along with oxygen or an oxygen-containing gas over a suitable catalyst in a reaction zone. The reactant mixture consists of formaldehyde, or its derivatives, and carboxylic acids or their derivatives. Formaldehyde in an aqueous solution may be used. Any formaldehyde derivative capable of undergoing a condensation reaction with a carboxylic acid or its derivative may be used. The preferred formaldehyde derivatives are methylal and trioxane. Any saturated monocarboxylic acid or its ester capable of undergoing a condensation reaction with formaldehyde or formaldehyde derivatives can be used. The preferred acids and esters are acetic acid and acetates and propionic acid and propionates. A preferred aspect of the invention is to prepare acrylic acid and methacrylic acid derivatives from formaldehyde and acetic or propionic acid and their esters. After the reactants are mixed in the desired ratio, the mixture is vaporized and the vapors passed along with oxygen or an oxygen containing gas over a suitable catalyst. Air is a convenient source of oxygen. Ad diticnal diluents such as nitrogen or steam may be used. The molar ratio of the acid or acid derivative to methylal or formaldehyde may range from 1:10 to 10:1. The preferred molar ratio is from 2:1 to 10:1. The molar ratio of oxygen to methylal or formaldehyde can be from 0.2:1 to 10:1 with the preferred ratio being from 3:1 to 6:1. The reaction temperature may range from 200"C to about 5000C, preferably from 3000C to 4500C. The average residence time may be from 2 to about 60 seconds, but a residence time of from 3 to 15 seconds is preferred. Especially good results are obtained with catalysts selected from among those described in US Patents Nc. 4,324,908 and 4,339,598, herein incorporated by reference. Thus, mixed iron phosphates promoted with molyhdenum or compositions containing vanadium and antimony give excellent results. Suitable catalysts are those having the empirical formulas: a) V SbmOx where in m = 0.5-40; and x is determined by the nature and oxidation state of the other elements; b) VSbmA a B bCcOx wherein m = 0.5-40; and A = alkali metal, alkaline earth metal, T1, La, rare earth metal, Th, or mixtures thereof, B = Cu, Ag, Fe, Co, Ni, Mn, Cr, Nb, Ta, Ti, P, As, Sn, B, U or mixtures thereof; C = Mo, W, Te, Bi, or mixtures thereof; a = 0-1; b = 0-1; c = 0-1; and x is determined by the nature and oxidation state of the other elements; and c) AaBbCcPOx wherein A is Fe, Ni, Co, Mn, Cu, Ag or mixtures thereof; B is alkali metal, alkaline earth metal, T1 or mixtures thereof; C is Se, Y, La, rare earth metal, Th, Nb, Mo, Te, Cr, Ta, As, Sb, U or mixtures thereof; and A = 0.2-3.0; b = 0-1.5; c = 0-2.0; and x is determined by the nature and oxidation state of the other elements. Other suitable catalysts include the following: molybdates, tungstates, vanadates and chromates of various transition elements, optionally promoted with alkali-and alkaline earth metals; heteropoly acids of molybdenum and tungsten, and their salts; crystalline alumino-silicates including zeolites X and Y, mordenites, the ZSM-series, and the like, suitably exchanged and/or impregnated with alkali metals and other elements such as Fe, V, Sb, Pt, Ag, Mo, or W. The catalysts may be used unsupported, but the use of a suitable carrier, such as silica, alumina, amorphous silica-alumina, mixtures of silica and alumina, titania, zirconia, natural clays, and the like is preferred. The concentration of the active catalyst on the support may range from about 10t to about 80% by weight. Specific Embodiments Example 1 A catalyst having the composition 50% K 4 Cry 1 Fe047Mo, POx + 50% A1203 was prepared according to the procedure given in US Patent No. 4,324,908 at column 3, incorporated by reference. Five cc of the catalyst was charged to a fixed-bed microreactor equipped with a preheat leg serving as a vaporizer and immersed in a temperature-controlled salt bath at 3500C. In Experiment A, liquid feed consisting of a mixture of methyl acetate and an aqueous formaldehyde solution in a molar ratio of methyl acetate/formaldehyde/water = 10/1/3 was injected by a syringe pump into the reactor, through the preheat leg, over a period of 70 minutes, at such a rate that the feed vapors passed over the catalyst at an average contact time of 5 seconds. The reactor effluent was condensed, weighed and analyzed by gas chromatography. The condensation products were methyl acrylate and acrylic acid. The combined per pass conversion (ppc) to these condensation products, based on formaldehyde charged, was 33%. In Experiment B, using a fresh batch of catalyst, the same liquid feed was injected into the reactor, but with air added as a carrier gas. The molar ratios were methyl asetate/formaldehyde/water/air = 10/1/3/23.8; the molar ratio of oxygen to formaldehyde was 5:1; the temperature was 3500C and the average residence time of the total feed was 5 seconds. The combined per pass conversion to methyl acrylate and acrylic acid, based on formaldehyde charged, was 75%. As can be seen from the summary of results in Table I, the results of experiments A and B show the improvement of the condensation yield when air is added to the feed. Example 2-4 ln Examples 2-4, methylal, CH2(0CH3)2, served as a formaldehyde source. The condensations were carried out with methyl acetate and with methyl propionate. In each example, one condensation reaction was carried out with nitrogen as an inert carrier gas and another reaction with air. The molar ratios were: ester/methylal/N2 (or air) = 10/1/22. In the case of air as a carrier gas, the 02/methylal ratio was 4.6:1. The temperature was 3500C; the average residence time of the total feed was 4.3 seconds. The catalyst of Example 2 was prepared according to the procedure disclosed in U.S. Patent No. 4,339,598 at column 3, previously incorporated by reference. The catalysts of Examples 3 and 4 were prepared as indicated in Example 1. The results are summarized in Table II wherein each Example shows the percentage (%) per pass conversion (ppc) to condensation products obtained, based on methylal charged, utilizing the inert nitrogen carrier gas as compared to reaction results obtained utilizing oxygen. The results clearly show that in the presence of oxygen, the yield of the condensation products is greatly increased. TABLE I EXAMPLE 1 - CONDENSATION OF METHYL ACETATE WITH FORMALDEHYDE EFFECT OF AIR VS. NITROGEN Experiment Reactants Carrier Gas % ppc (molar ratio) of Total Condensation Products A methyl acetate/formaldehyde/water -- 33 10/1/3 B methyl acetate/formaldehyde/water/air Air 75 10/1/3/23.8 TABLE II CONDENSATION OF METHYLAL WITH METHYL ACETATE and PROPIONATE EFFECT OF AIR VS: NITROGEN Example Catalyst Ester Carrier % ppc Total Gas Condensation Products 2 42% VSb5Ox+42%Al2O3+16%SiO2 Methyl Acetate N2 43.6 1 AIR 82.9 3 50% K0.2Mn0.25Fe0.49Mo0.1 Methyl Acetate N2 41.1 1 POx+50%Al2O3 AIR 100.1 4 50% K0.2Cr0.1Fe0.47Mo0.1 Methyl N2 49.7 2 POx+50%Al2O3 Propionate AIR 67.4 1 Methyl Acrylate + Acrylic Acid 2 Methyl Methacrylate + Methacrylic Acid

Claims: CLAIMS: 1. A process for producing unsaturated carboxylic acids and esters comprising passing into a reaction zone, a vaporous mixture of a saturated monocarboxylic acid or its ester with formaldehyde or a formaldehyde derivative in the presence of oxygen over a condensation catalyst. 2. A process as claimed in claim 1 characterized in that the ester is methyl acetate or methyl propionate. 3. A process as claimed in claim 1 characterized in that the formaldehyde derivative is methylal or trioxane. 4. A process as claimed in any of claims 1 to 3 characterized in that the saturated monocarboxylic acid is acetic acid or propionic acid. 5. A process as claimed in any of claims 1 to 4 characterized in that the catalyst comprises V Sb O mx wherein m = 0.5-40; and x is determined by the nature and oxidation state of the other elements. 6. A process as claimed in any of claims 1 to 4 characterized in that the catalyst comprises VSbmAaBbCcOx where in m = 0.5-40; and A =,alkali metal, alkaline earth metal, T1, La, rare earth metal, Th, or mixtures thereof, B = Cu, Ag, Fe, Co, Ni, Mn, Cr, Nb, Ta, Ti, P, As, Sn, B, U or mixtures thereof, C = Mo, W, Te, Bi, or mixtures thereof; a = 0-1; b = 0-1; c = 0-1; and x is determined by the nature and oxidation state of the other elements. 7. A process as claimed in claim 6 characterized in that m is 3-15. 8. A process as claimed in claim 6 or claim 7 characterized in that the catalyst is on a support comprising silica and alumina. 9. A process as claimed in any of claims 1 to 4 characterized in that the catalyst comprises AaBbCCPOX where in A is Fe, Ni, Co, Mn, Cu, Ag or mixtures thereof; B is alkali metal, alkaline earth metal, T1 or mixtures thereof; C is Se, Y, La, rare earth metal, Th, Nb, Mo, Te, Cr, Ta, As, Sb, U or mixtures thereof; and A = 0.2-3.0; b = 0-1.5; c = 0-2.0; and x is determined by the nature and oxidation state of the other elements. 10. A process as claimed in claim 2 characterized in that the ester is methyl acetate, the formaldehyde derivative is methylal and the catalyst comprises VSbmOX wherein m = 0.5-40; and x is determined by the nature and oxidation state of the other elements. 11. A process for producing methyl acrylate and acrylic acid comprising passing into a reaction zone, a vaporous mixture of methyl acetate and formaldehyde, in the presence of oxygen, at a temperature of from 300"C to 4000C in the presence of a catalyst comprising A,BbC,PO x wherein A is Fe, Ni, Co, Mn, Cu, Ag or mixtures thereof; B is alkali metal, alkaline earth metal, TL or mixtures thereof; C is Se, Y, La, rare earth metal, Th, Nb, Mo, Te, Cr, Ta, As, Sb, U or mixtures thereof; and A = 0.2-3.0; b = 0-1.5; c = 0-2.0; and x is determined by the nature and oxidation state of the other elements. 12. A process as claimed in claim 11 characterized in that the catalyst comprises V SbmAaBbCc x wherein m = 0.5-40; and A = alkali metal, alkaline earth metal, T1, La, rare earth metal, Th, or mixtures thereof, B = Cu, Ag, Fe, Co,'Ni, Mn, Cr, Nb, Ta, Ti, P, As, Sn, B, U or mixtures thereof, C = Mo, W, Te, Bi, or mixtures thereof; a = 0-1; b = 0-1; c = 0-1; and x is determined by the nature and oxidation state of the other elements. 13. A process as claimed in claim 11 or claim 12 characterized in that the vaporous reaction mixture consists of methyl propionate and methylal and the products are methyl methacrylate and methacrylate acid.

Inventors: GRASSELLI, ROBERT KARL, GUTTMANN, ANDREW TYTUS
Applicants: THE STANDARD OIL COMPANY
Application year: 1984
Main classification: C07C57
IPC codes: B01J27, C07C57, C07C69, C07C51, B01J23, C07B61, C07C67