United States Patent (1 (1) Patent Number: 5,070,061 ‘Langerbeins [45] Date of Patent: Dec, 3, 1991 [s#] HETEROPOLYMOLYBDATE CATALYSTS 568801 1/1986 Simian ct a sox AND METHOD FOR "20875 1/1988 Gruber souls OXYDEHYDROGENATION [75] Inventor: Klaus Langerbeins, Mannheim, Fe, Rep. of Germany [73] Assignee: Rohm GmbH, Darmstadt, Fed. Rep. of Germany [21] Appl. No 625,69 [22] Filed: Dee. 7, 1990 Related U.S. Application Data [63] Comtinuation.in-part of Ser. No. 390:487, Avg. 1,198, abandoned, which is a continuation of Ser. No. 78.223, [30] Foreign Application Priority Data ‘Avg. 2, 1986 [DE] [3 Fed. Rep. of Germany son. 3626256 Bois 27/186 ‘02/211; 502/209, 502/210, 502/212; 502/213; 502/214; 562/399 [s8] Field of Search .. '$02/209, 210, 211, 212, 502/213, 214; 562/599 56] References Cited US. PATENT DOCUMENTS 44061,673 12/1977 Onods et 562/599 41146575 3/1979 Onods et “423/295 427676 1981 Matsumoto eta. aes #522938 6/1985. Shom et a. s02/200 FOREIGN PATENT DOCUMENTS 119s01$. 9/1985 Canada 531729. 7/1981 Europeen Pat. OF. (079491 5/1983 European Pat. OF, (0113064 7/1984 European Pat. Of 2722575 12/1877 Fed. Rep. of Germany 3019731 12/1981 Fea. Rep. of Germany 3243600. 7/198 Fed. Rep. of Germany 2401022 5/1979 France 1525889 9/1978 United Kingdom OTHER PUBLICATIONS ‘Tsigdinos, Ind. Eng. Chem, Prod. Res. Develop. 13, 267-274 (1974), Otake et el, Studies Surface Science and Catalysis 7, 780-791 (1981) Primary Examiner-—William R. Dison, Jt ‘Assistant Examiner—Anthony 3. Gre 17 ABSTRACT Catalysts containing molybdenum, vanadium, phospho- rus, and oxygen, optionally together with one or more etal ions, as their active constituents, are prefersbly isposed on an inert carrier for the oxidative dehydro- genation of isobutyric acid or its lower esters to meth- acrylic acid or its lower esters. 9 Claims, No Drawings5,070,061 1 HETEROPOLYMOLYBDATE CATALYSTS AND ‘METHOD FOR OXYDEHYDROGENATION ‘This application is a continustion-in-part of applica: tion Ser. No. 07/390,487, filed Aug. 1, 1989 and now sbandoned, which in turn is a continuation of applica: tion Ser. No. 07/078,223 filed July 27, 1987 and now sbandoned, The present invention relates to mixtures of beteropolyacid compounds, particularly to mixtures of ‘phosphomolybdic acid and vanadium-containing deriv- atives of phosphomolybdic acid and their slis, and to ‘methods for the oxydehydrogenation of isobutyric acid or its esters to methacrylic acid or is esters using such mixtures as catalysts, ‘THE PRIOR ART 12.Molybdophosphoric acid, HsPMo10.0 - xH:0, ‘ko known as phosphomolybdic acid, can be prepared, for example, by reacting molybdenum trioxide in heated dilute phosphoric acid, in other words, hydrothermally, [Tsigdinos, Ind. Eng. Chem., Prod. Res. Develop. 13, 267 (974). ‘This phosphomolybdic acid can be used as a heteropalyacid catalyst in the oxydehydrogenation of isobutyric acid to methacrylic acid, which proceeds by heterogeneous catalysis, However, the selectivity of this catalytically active substance for methacrylic acid hasan unsatisfactory value of only 40 percent. [O:ake et al, Studies Surface Science and Catalysis 7, 780-791 (1981). In contrast thereto, a heteropolyacid catalyst with HxPMo;eV20u, a vanadium derivative of phos- phomolybdic acid with a selectivity for methacrylic ‘acid of 73 percent, is considerably more selective and has practically the same activity, according to the same futhors. Vanadium derivatives of phosphomelybdic acid such as HsPMogV20u or HsPMoy1 VOw can be prepared inter lis hydrothermally, as described in Ger- man Patent Publication 27 22 375, (US. Pat. No. 4,146,514) by heating stoichiometric amounts of Mo and V20s in water containing H:PO ‘As the applicant's own tests have shown, oxydehy- Arogenation catalysts containing the heteropolyacic HAPMoy;VOu as the catalytically active substance, Which catalysts have a selectivity for methacrylic acid ‘of about 60 percent, are significantly less selective than coxydehydrogenation catalysts containing HsPMoio V0, While HsPMo1z0.is quite unsuitable for use as, 1 catalyst in a commercial process because of its low selectivity, HsPMor;VOu used asa catalyst, and espe- Gilly the relatively selective HsPMoioV:0u9 or HePMosV ;Oupcatalysts, lack the fong term characteris- tics required from the technical and economic points of Catalysts prepared from metallic salts of heteropol ids, for example HrgCua2PMooVOss or its anhy- ride, CupPMoyoVO3s2, which are known from Ger- man Patent Publication 32 48 600 for the oxydehy- drogenstion of isobutyric acid or its esters and which are prepared hydrothermally in the presence of a cop- per compound and have high selectivities for meth- acrylic acid of up to about 83 percent in the oxydehy- rogenation of isobutyric acid, also exhibit an unsats: factory long term behavior. s 2s ” 45 6 2 ‘THE OBJECT AND THE INVENTION Thus, there has been 2 need for developing heteropolyacid derivatives comprising phosphomoly®- ic acid which, when used as catalysts for the oxydehy- drogenation of isobutyric acid oF its esters to meth acrylic acid or its esters, exhibit not only good activity fand selectivity but also exhibit long term behavior which is technically satisfactory. ‘According tothe present invention, it has been found that compositions of various heteropolyacids compris- ‘ing phosphomolybdic acid which have an atomic ratio of Mo:V wherein Mo is ereater than 9 and less than 12, land V is O11 or grester but less than 3 surprisingly have Jong term stability when used as oxydehydrogenation catalysts, The heteropolyacid derivatives used in accor. dance with the invention are compositions of various hheteropolyacids comprising phosphomolybdic acid, such as HsPMor0. and/or Hs..,PMoi2—:V,0x ‘wherein x is 1,2, or 3, or salt derivatives thereof, and they may be mixtures of the various starting Ieteropolyacids or their salts as well as mixtures con- taining farther compounds formed during preparation, The invention thus relstes 10 catalysts containing ‘molybdenum, vanadium, phosphorus, and oxygen, and ‘optionally one or more mets! ions, as the ative consti tents, which catalysis are preferably disposed on an inert carrier and are useful for the oxidative dehydro- genation of isobutyric acid or its lower esters to form methacrylic acid or its esters. The catalytically active constituent of the catalyst is, or is formed from, @ hheteropolymolybdate mixture of phosphomolybdic acid, HaPMoy:0., or its salts and/or its vanadium derivatives, Hs-+sPMoi2—,V Ou wherein x is 1, 2, of 3, and/or their salts ‘The catalyst corresponds to a heteropolymolybdate sixture ofthe formula HaMsPMogV.O,, wherein M is ‘cation of one or more of the metallic elements Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Zn, Cd, Al, Ce, Th, Zr, Sa, Sb, Pb, Bi, Cr, Mn, Fe, Co, Ni, Cu, Ag, or As and 2s grester than 0.1 but less than 6, b has a value from 003, chasa value from 0.5 0 1.5, é hasa value greater ‘than 9 but less than 12, ¢ has a value from 0.1 10 3, and has a value determined by the valences and amounts of the other elements represented in the formula. The heteropolymolybdate mixtures preferably contain Cu, Cs, Rb, Ky Ti, Ce, Mn, Fe, Bi, Cr, or As as component M. ‘Surprisingly, the catalysts prepared from the compo- sitions in accordance with the invention have 2 life longer by a factor of from $ to about 100 than prior art HsPMojeV20« or Cug2PMoioVOxs2 heteropolyacid catalysts that are catalytically active and selective in ‘onydehydrogenation. Hence the new catalysts have @ correspondingly higher productivity, expressed, for ‘example, as kg of methacrylic acd per gram of catalyt- cally effective heteropoly acids, and thus offer a deci- sive advantage over the prior art oxydehydrogenation catalysts, ‘The novel catalysts for the oxydehydrogenation of isobutyric acid or its esters are heteropolyacid and/or heteropolyacid salt mixtures comprising phosphomo- Iybdic acid which are characterized in thatthe mixtures have an atomic ratio of Mo:V wherein Mo is greater than 9 but less than 12 and V is 0.1 or greater but les, than 3, with an Mo:P atomic ratio wherein Mo is srester than 9 but ess than 12 and P is from 0.5 to 1.5, preferably 15,070,061 3 PRACTICE OF THE INVENTION From the Mo-V-P atomic ratios indicated, which ratios are not limited 10 integers, its apparent that the novel compositions, for example mixtures of various known heteropolyacids or their salt derivatives, such as of HsPMO;2049 with HsPMoyiVOw and/or with HsPMo1oV2049 and/or with Hz sCunsPMo},VOw, or also of H4PMo1i Vw with HsPMoroV20s0, may have different molar ratios and, as has been found, can be prepared by intensive mixing of such constituents. ‘When used as catalysts in the oxydehydrogenation of isobutyric acid or its esters, mixtures ofthe heteropolya- ids, such as 2 1:1 molar mixture of H3PMo1;040 and HsPMoriVOw which then has the overall composition H35PMoy, sVosELa, exhibit not only good activity but also significantly improved long term behavior. ‘However, it as further been found thatthe selectiv- ity of the inventive mixed heteropolyacid catalysts is improved sill more, and considerably 50, they contain ‘metal ions. Heteropolyacid mixtures containing, metal ions can be prepared, as indicated above, by admixing ‘an appropriate metallic salt of a heteropolyacid, or by ‘eacting at least a portion ofthe heteropolyacids present in the heteropolyacid mixture with further metal com > pounds to give their metallic salts. In this way, catalysts ‘re obtained which not only have good activity and considerably improved long term properties, but also substantially better selectivity for methacrylic acid. A ‘content of copper ion in the heteropoly acid mixtures has proved particularly advantageous. Such composi- tions are obtained, for example, by reacting heteropoly acid mixtures according to the invention with copper hydroxide, for example. With a composition of the in- vention such as H ;Cug2PMo}) sVasO,pused as acata- lyst, selectivities for methacrylic acid of about 70 per- cent have been obtained, which represents an increase ‘of more than 20 percent over that ofa copper free cata- lyst. Substantial stabilization of this selectivity is se- ccured by adding further metal fons, for example in @ ‘Cu/Cs metal ion combination ‘Thus, the catalysts of the present invention are (A) a ‘mixture of at least two members selected from the ‘group consisting of () H42PMox2— VO, wherein x is 1, 2, or 3 and (i) metals salts thereof, the molar ratio of any member ‘oF combination of members to any other member in such a mixture being from 0,99:0.001 to 0.01088, or ‘consisting essentially of (B) a mixture of at lest one member selected from the ‘group consisting of (A)() and (AM) and at least one member selected from the group consisting of| ii) HgPMor20q and (Gv) metal salts thereof, ‘the molar ratio of said member or members (A)(i) and (AN) to said member or members (BX) and (BY(Wv) being from 0.9.01 to 0.1.03. ‘The composition of the inventive heteropoly acid ‘mixture containing metal cations can be represented by the formula HMPMod Op ‘wherein M signifies one or more ofthe elements Li, Na, K, Rb, Cs, Be, Mg, Ce, Sr, Ba, Zn, Cd, Al, Ce, Ti, Zr, ‘Sn, Sb, Pb, Bi, Cr, Mn, Fe, Co, Ni, Cu, Ag, or As and ‘wherein ab, 6,4, e, and f have the values given earlier. ‘The preparation of the heteropolyacid metallic salts, fn admixture with free heteropolyacid is advanta- $ 6 4 scout carcied out by adding metal compounds such as etal hydroxides, meta carbonates, metal nits, oF metal phosphates to mixtures of heteopolyacds, which Inter ean be made for example, a paste with water 10 improve. mining. For teller conversion to. the heteropolyacid metalic sl, the mixture may be heated fora short time to about 100°C. “The preperation ofthe heteropolymolybdate mixture in the presence of a solid carrier particularly pre- ferred for preparation of the catalyst systems in accor dance with the invention, Inert carser materials com- prising onygen compounds ofslrinum, titanium, and Particularly silicon, or mixtures of various such oxygen ompounds, oF silicon carbide, ae prefered “The ratio ofthe catalytically active substance, tat i ofthe heteropolymolybdate mixtre ofthe general for. mula HAM APMoavOp to the carrer may vary within certain limits. In general, the catalytically active substance will be from § to £0 percent, and preferably from 15 10 70 percent, of the total weight including the carrier. For use as a catalyst system, the product so obtained may be put into a proper size and shape, for example by granulation, pel- letizing, or tableting. The size and shape ofthe catalysts, to be used depend mainly on the reaction technique employed in the oxydehydrogation, for example reac tion ina fixed bed reactor. Shaping may be followed by annealing of the catalyst system for from about 1 hour to about 24 hours, for example at temperatures ranging From 200° C. to 400" C. ‘The catalyst system in accordance with the present invention is distinguished by good activity and selectiv- ity and at the same time by technically appropriate long, term behavior in'the oxidative dehydrogenation of isobutric acid or its esters, the latter being primarily the lower esters having from one to three carbon atoms in the alcohol group of the ester, and particularly isobu- tyric acid methyl ester. The conversion is effected at temperatures ranging from about 250" C. to about 400° Cand preferably between 300" C. and 380° C. The dwell time generally ranges from 0.1 to $ seconds. ‘The oxydehydrogenation method in accordance with the present invention isa gas phase reaction with oxy gen as the oxidizing agent, for example in the form of air. In addition to the isobutyric acid or ester and oxy {gen reagents, the gas mixture used in particular contains nitrogen and, optionally, also water in the form of steams, The molar ratio of the components of the gas ‘mixture, in the order indicated, advantageously ranges from 1x1-4)(4-20)(0-5) moles, the preferred molar ratio being 1:(1-2)(4-10)0.5-2). Experience has shown thatthe presence of water has a favorable effect on the reaction. The inventive mixed ‘heteropolymolybdate catalysts can be used in the reac tors commonly employed, for example using pressure ‘Suitable pressures range from 0.1 to 5 bar and are pref- erably from 0.5 to 2.5 bar. The catalysts should be adapted with respect to size and shape to the reaction technique to be used. ‘A better understanding of the present invention and of its many advantages will be had from the following Examples, given by way of illustration.5,070,061 5 EXAMPLES (A) Preparation of mixed catalysts Example 1 Hy PMoyi sVos040 0.063 mole of HsPMoy1VOs is introduced into @ reactor as a 10 weight percent aqueous solution and (0.063 mole of HsPMo;:0,9 is then added. ‘The mixture is heated to reflux for 30 minutes at 100° . The clear orange colored solution is mixed with 80.5, 8 of diatomaceous earth (kieselguht) and 16.1 g of pow- ‘ered silica gel and evaporated with stirring t0 leave a paste. The latter is oven dried for 1 hour at 110° C. and for 3 hours at 200° C. The catalyst is then calcined in 3 muffle furnace for 3 hours at 300° C. and erushed into pieces about § mm in sie, Example 2 (Cag Hs :P Mons sVos040 0.063 mole of HyPMonVOw is introduced into @ reactor as a 10 weight percent equeous solution and 0.063 mole of HxPMo;20wand 0.0252 mole of CuO are added. ‘Alter brief boiling (for § minutes), 81.4 g of diatoma. ** cous earth and 163 g of powdered silica gel re added, Further processing is carried out as in Example 1 Example 3 (Cep2HasPMor sVas0u0 6 ‘Comparative Example 3 Ceo Hs9PMoniVOu0 0.063 mole of HaPMoy1V Oay is used a5 # 10 weight percent solution and 0.0032 mole of CsyCOs is added. ‘The further preparation of a 70 percent catalyst is ear- ried out as described in Example 3 Example 4 CuosCso 3H 3PMoy sVos00 0.063 mole of Cug HsaPMoy/VOu is used as a 10 weight percent aqueous solution and 0.053 mole of HaPMo1204 and 0.0063 mole of Cs:CO3 are add. ‘The mixture is heated in a liter beaker for 30 min- tes, mixed with 814 g of diatomaceous earth and 16.3, 8 of powdered silica gel, and processed further as de- scribed in the other Examples. (B) Oxydehydrogenation of isobutyric acid Examples 1 to 4 and comparative Examples 1 10 3 General testing procedure A vaporous mixture of isobutyric acid and oxygen (as sit) in a molar ratio of 1:15 is reacted over the 70 per- cent catalysts (Gee following Table 1) in a circulating reactor known in the art (ef, published German Patent Application DOS 30 19 731) at 320° C. and with a dwell time of 0.6 second. The catalyst loading is 2.5 ke of Jsobutyric acid per kg of catalytic mass per hour. The reaction gas is then analyzed by gas chromatography TABLE oT COMERIONGY SELECTING 5 prepared in Catyictyefeve subwance 6) Co Caan 8) Sx Sem Example! HssPMonsVas0u0 mn BS Compursine HAEMoy VOW sn @ @ 8 @ Exnpie? Ceara Pon sVasOe ere a Congarsive (CensHs PMoiNv Oa os 2 = Row SF cumple? Exieple 3 CooztsPMoi.sVos0.0 6 8 2 8 & @ Comparative Cea oPMer 0a, 6 & 8 8 & 6 sranpie Example CenesCeoiH PMO Neon Sw ‘No Compare example 0.063 mole of H4PMo1;VOm is used 38 a 10 weight percent aqueous solution and 0.063 mole of HsPMo Example 5 204 and 0.0126 mole of Cs:COs ae added. The mixtze is mixed with 81.4 g of diatomaceous earth and 163 g of powdered silica gel, evaporated with stiring to leave a paste, and further processed as de- scribed in Example I. Preparation of comparative catalysts Comparative Example 1 HAPMoyVOw ‘The heteropolyacid was prepared as described in US. Pat, No. 4,146,574. The preparation ofa 70 percent catalyst was carried out as described in Example 1 ‘Comparative Example 2 (Cua 6P Mou VO ‘The preparation of the 70 percent Cup2Hs¢PMo), ‘Vou catalyst was carried out as described in Example 2 55 CroatisaPMoy0sV1s04) A10 percent by weight solution of 0.063 mole of H:PMo1:VOq and a 10 percent solution of 0.063 mole of HsPMojoV204 are combined at room temperature and then further mixed with a 10 percent solution of (0.025 mole of Crs, ‘The resulting solution is combined with 80.5 g of kieselguhr and 16.1 g of powdered silica gel and further ‘worked up as in Example 1 Example 6 Feo2BioH: 3PMo11sVo Ow 0.063 mole of H4PMos; VOwo is prepared as 2 10 per- ‘cent aqueous solution and 0.063 mole of HsPMo1:040is added. 0.025 mole of iron(IIInitrate - H20 and 0.025 ‘mole of bismuth(UDnitrate - 5H;0 are dissolved in about 15 ml of HNOS and are added to the solution of, HssPMo11 sVosO4s5,070,061 1 ‘The solution is combined with 80.5 g of kieselguhr and 16.1 g of powdered silica gel and further worked up. as in Example 1 Examples 7-10 ‘The preparation ofthese catalysts follows the proce- dures given in Example 5. For dosing with metal ac- cording to the formulas given in following Table Il, Ce ‘was added as Ce(NO3}s, Mn as Mn(CO3);, Ti as TH(O- propyl, Cu as CuO, and Cs as Cs:C0s, Example 11 (Cup Hz PMo13 ¥020.0 0.1 mole of HsPMo1z0.is dissolved together with (0.025 mole of CuO in 300 ml of H:O with stirring at 100° C. and subsequently combined with 0.025 mole of HsPMo1iVOu (20 percent solution by weight). ‘The clear solution is combined with 82.2 g of Kiesel- ‘guhr and 164 g of powdered silica gel and further ‘worked up as in Example 1 Example 12 (Cun2Asy H23PMoy1sVe0.0 0.1 mole of HsPMo1:0y is dissolved together with (0.0063 mote of As20s and 0.025 mole of CuO in 500 mi ‘of HO with stirring at 100° C. and subsequently com- bined with 0.025 mole of HsPMo1;VO4 (20 percent solution by weight). The clear solution is combined ‘with 822 g of kieselguhr and 1644 g of powdered silica gel and further worked up as in Example 1 Example 13 HygPMojosV 16010 13 mole of MoO) are heated for 24 hours at 100° C together with 0.1 mole of VaOsand 0.125 mole of HaPs (85.9 percent) in 2000 g of distilled water. repre Emme Comparaive Eumle Bump comparative Exsmpe 7 Example Expl Comparative Enea Example 10 ‘No Compantive Example Eepiet Compara No Comparative Example Etample 1 s 2» 0 3s 8 ‘The solution is worked up as in Example 1 Example 14 Rbo3H1s3PMo11 sVos0w 0.063 mole of HsPMo12049 and 0.025 mole of RbNOs are added toa 10 percent aqueous solution of 0.063 mole of HaPMo1 VO. ‘The mixture is combined with 805 g of distomaceous earth and 16.1 g of powdered slice gel and worked up as in Example 1 Example 15 Ke,:Hy4PMoyosVis0.0 ‘The catalyst is prepared as in Example 5. K is added as KNOs in an amount required by the formula, Preparation of the Comparative Catalysts ‘The catalysts for comparative Examples $-9, 11, and 13 are prepared by a procedure analogous to that used in the Examples 10 which they pertain by combination of the relevant metal compound with HsPMo)0V204 (or HsPMoi:VOun. B. Onydehydrogenation of Isobutyric Acid The catalysis of Examples 5-15 and comparative ‘Examples 5-9, 11 and 13 were used for the oxydehydra- tion of isobutyric acid using the following general test procedure: ‘A vaporous mixture of isobutyric acid, onygen (from sir), and nitrogen in a mole ratio of I:1.5:7.71 is reacted by passing it over the 70 percent catalyst (ef. Table 1) ina circulating reactor at 340° C. with a dwell time of 1 second. The loading of the catalyst is 1.25 kg of isobu- tyric acid /kg of catalytic mass/hr. The reaction gas is subsequently anslyzed by gas chromatography. Conversion and selectivity as a function of time are reported in Table I. TABLE Il Casialy eave Saiiiiiaioe Ge ae SE Ee i custintine Se oy) Ee cnturiniioo ee Sa te de esting ea D vinsage fe BS Sh Ba rertomince GG BS eee een eyes coconanmnivion & fe SB Eg catmontede SSH SB, Be Ee craniininooe GS Sa ie i Munowide «Se Se Sa te5,070,061 9 TABLE I-continued peated ‘stance Conprsive HePMoKVIOH Enampie 13 Enample 1 Rb sHssPMor1Vas0up Eampie 15 KosMasPMoiesVis0s CoC flo S38 What is claimed is 5 1. A composite heteropolymolybdate catalyst, adapt- able to the oxydehydrogenstion of isaburyric acid oF @ lower ester thereof to methacrylic acid or a lower ester thereof, respectively, said composite catalyst being @ having the formula, for the composite of HALFOMOe Op wherein M is at least one member selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Zn, Cd, Al, Ce, Ti, Zr, St, Sb, Pb, Bi, Cr, Mn, Fe, Co, Ni, Co, Ag, and As, a is greater thas 0.1 but less than 6, bis 010 3, cis 05 to 1.5 dis areater than 9 but less thas 12, eis 01 to 3, and fhas a value determined by the valences and amounts of the elements other than 3 oxygen, and consisting essentially of (A) 2 mixture of at least two members selected from the group consisting of @¥b.:PMoi2- 2:0. wherein xis 1,2,0r 3 and (Gi metals salts thereof, the molar ratio of any member or combination of members to any other member in such e mixture being from 0.99:0001 to 00014089, of consisting essentially of (B)s mixture ofa least one member selected from the 40 ‘Broup consisting of said mixture (A)() and (ANG) 3s 4s 50 ss 10 on Sie Ce So Se feb Gs 365 oat and at least one member selected ftom the group consisting of Gi) H5PMo},0.9 and (Gv) metal salts thereof, the molar ratio of said member (A)() and (Ai) 0 ssid member or members (B)(ii) and @)Gv) being from 09:01 to 0.1.09. 2. A catalyst asin claim 1 wherein b is 005 to 2. 3.4 catalyst asin claim 1, wherein Mis Cu, Cs, Rb, K, Ti, Ce, Mn, Fe, Bi, Cr, or As ‘4. A catalyst as in claim 1 wherein M is at least one ‘member selected from the group consisting of copper and cesium ', A catalyst as in claim I present on an inert carrer. 6 A method for the oxidative dehydrogenation of ‘sobutyrie acid or a lower ester thereof to methacrylic acid or a lower ester thereof, which method comprises Contacting a gaseous misture of said isobulytic acid or a lower ester thereof and oxygen in the presence of @ catalyst as in elim 1. 7A method asin claim 6 wherein bis 0.05 to 2. 8. A method as in claim 6 wherein M is at least one member selected from the group consisting of Cu, Cs, Rb, K, Ti, Ce, Mn, Fe, Bi, Cr, and As 98, A method asin claim 6 wherein M is at least one member selected from the group consisting of copper and cesium,