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A process is described that uses a silver catalyst to convert methanol into formaldehyde in the presence of less than a stoichiometric amount of oxygen. The resulting formaldehyde is reacted without isolation with propionaldehyde over a commercially available anatase titania catalyst that is shown t

A process is described that uses a silver catalyst to convert methanol into formaldehyde in the presence of less than a stoichiometric amount of oxygen. The resulting formaldehyde is reacted without isolation with propionaldehyde over a commercially available anatase titania catalyst that is shown to be catalytically active towards the formation of methacrolein from formaldehyde and propionaldehyde with conversions and selectivities close to 90%. This titania catalyst is readily available, non-toxic, and can be used with formaldehyde and a variety of other aldehyde compounds to make α,β-unsaturated aldehyde compounds. This process benefits from low raw material costs and is economically advantaged due to the elimination of catalyst separation. This process shows promising stability and selectivity during lifetime studies, particularly when performed in the presence of a hydrogen carrier gas.

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1. A process for preparing an α,β-unsaturated aldehyde compound, comprising: (i) contacting methanol with a silver catalyst and an oxygen source in a first zone to produce a vapor-phase formaldehyde source at a temperature from 450° C. to 750° C.;(ii) reducing the temperature of the vapor-phase form

1. A process for preparing an α,β-unsaturated aldehyde compound, comprising: (i) contacting methanol with a silver catalyst and an oxygen source in a first zone to produce a vapor-phase formaldehyde source at a temperature from 450° C. to 750° C.;(ii) reducing the temperature of the vapor-phase formaldehyde source to a temperature from 100° C. to 400° C. in a second zone; and(iii) contacting the vapor-phase formaldehyde source exiting the second zone, a hydrogen containing diluent gas, and an aldehyde with a heterogeneous anatase titania catalyst in a third zone under vapor-phase condensation conditions to obtain the α,β-unsaturated aldehyde compound;wherein the α,β-unsaturated aldehyde compound has the general formula (I):  wherein R is a hydrogen or a hydrocarbon group having 1-12 carbons. 2. The process according to claim 1, wherein the vapor-phase formaldehyde source and the aldehyde are contacted with the heterogeneous anatase titania catalyst at a temperature of 100° C. to 350° C. 3. The process according to claim 1, wherein the vapor-phase formaldehyde source and the aldehyde are contacted with the heterogeneous anatase titania catalyst at a temperature of 100° C. to 300° C. 4. The process of claim 1, wherein the aldehyde comprises acetaldehyde, propionaldehyde, n-butyraldehyde, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, 3-methylbutyraldehyde, 3-ethylbutyraldehyde and 3-ethylpentanal, but-3-enal, pent-3-enal, 2-cyclohexylacetaldehyde, 2-phenylacetaldehyde, or a combination thereof. 5. The process according to claim 1, wherein the aldehyde is a linear saturated aldehyde comprising acetaldehyde, propionaldehyde, n-butyraldehyde, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, or a combination thereof. 6. The process according to claim 1, wherein the aldehyde is a branched saturated aldehyde comprising 3-methylbutyraldehyde, 3-ethylbutyraldehyde and 3-ethylpentanal, or a combination thereof. 7. The process according to claim 1, wherein the aldehyde is a cyclic or an aromatic substituted aldehyde comprising 2-cyclohexylacetaldehyde, 2-phenylacetaldehyde, or a combination thereof. 8. The process according to claim 1, wherein the heterogeneous anatase titania catalyst is regenerated with a calcination step at 450° C. in air. 9. The process according to claim 1, wherein the α,β-unsaturated aldehyde compound is produced with a conversion and a selectivity above 80%. 10. The process according to claim 1, wherein the α,β-unsaturated aldehyde compound is produced with a space time yield greater than 8 moles aldehyde/kg catalyst/hr. 11. A process for preparing methacrolein, comprising: (i) contacting methanol with a silver catalyst and an oxygen source in a first zone to produce a vapor-phase formaldehyde source at a temperature from 450° C. to 750° C.;(ii) reducing the temperature of the vapor-phase formaldehyde source to a temperature from 100° C. to 400° C. in a second zone; and(iii) contacting the vapor-phase formaldehyde source exiting the second zone, a hydrogen containing diluent gas, and a propionaldehyde with a heterogeneous anatase titania catalyst in a third zone under vapor-phase condensation conditions to obtain methacrolein; wherein methacrolein has the general formula (I): 12. The process according to claim 11, wherein the α,β-unsaturated aldehyde compound is produced with a space time yield greater than 8 moles aldehyde/kg catalyst/hr. 13. The process according to claim 11, wherein the methacrolein is used to produce isobutyraldehyde, methacrylonitrile, methacrylic acid, methyl methacrylate, poly(methyl methacrylate), or a combination thereof. 14. A process for preparing an α,β-unsaturated aldehyde compound, comprising: (i) contacting methanol with a silver catalyst and an oxygen source in a first zone to produce a vapor-phase formaldehyde source at a temperature from 450° C. to 750° C.;(ii) reducing the temperature of the vapor-phase formaldehyde source to a temperature from 100° C. to 400° C. in a second zone; and(iii) contacting the vapor-phase formaldehyde source exiting the second zone, a hydrogen containing diluent gas, and an aldehyde with a heterogeneous anatase titania catalyst in a third zone under vapor-phase condensation conditions to obtain the α,β-unsaturated aldehyde compound; wherein the α,β-unsaturated aldehyde compound has the general formula (I): wherein R is a hydrogen or a hydrocarbon group having 1-12 carbons. 15. The process according to claim 14, wherein the α,β-unsaturated aldehyde compound is produced with a conversion and a selectivity above 80%. 16. The process according to claim 14, wherein the α,β-unsaturated aldehyde compound is produced with a space time yield greater than 8 moles aldehyde/kg catalyst/hr. 17. The process according to claim 1, wherein the yield of formaldehyde made in the first zone is 86-99%. 18. The process according to claim 1, wherein the amount of unreacted methanol exiting the first zone is less than 5% by weight based on the formaldehyde source. 19. The process according to claim 1, wherein formaldehyde is not isolated. 20. The process according to claim 1, wherein the vapor phase formaldehyde source exiting the first zone is not fed to a water scrubber. 21. The process according to claim 11, wherein the yield of formaldehyde made in the first zone is 86-99%. 22. The process according to claim 11, wherein the amount of unreacted methanol exiting the first zone is less than 5% by weight based on the formaldehyde source. 23. The process according to claim 11, wherein formaldehyde is not isolated. 24. The process according to claim 11, wherein the concentration of hydrogen in the diluent gas is within a range of 10 to 90 mole %. 25. The process according to claim 14, wherein the yield of formaldehyde made in the first zone is 86-99%. 26. The process according to claim 14, wherein the amount of unreacted methanol exiting the first zone is less than 5% by weight based on the formaldehyde source. 27. The process according to claim 14, wherein formaldehyde is not isolated. 28. The process according to claim 14, wherein the concentration of hydrogen in the diluent gas is within a range of 10 to 90 mole %.