The significant surge in biodiesel production by transesterification of edible or non-edible oils have caused surplus of glycerol in the market. With its characteristics, unique structure, renewability, and bio-availability, glycerol has tremendous potential to be transformed to higher value-added chemicals. This article provides a comprehensive and critical review of glycerol dehydration to acrolein in both petroleum-and bio-based processes. Acrolein has enormous industrial applications as a significant chemical intermediate for acrylic acid, dl-Methionine and superabsorbent polymer production. The current development of several precursors on suitable support such as heteropoly acids, zeolites, mixed metal oxides, and pyrophosphates in creating superior catalytic properties for both liquid- and gas-phase processes has been discussed. The acidity and textural properties of various catalysts, as significant variables affecting acrolein yield and selectivity, are evaluated separately. Techno-economical evaluation on dehydration of petroleum- and bio-based glycerol to acrolein proved that the bio-based processes are more feasible compared to the conventional petroleum-based process. In addition, various proposed mechanisms for catalytic dehydration of glycerol to acrolein have been examined. Particularly, catalyst coking and few crude glycerol applications have been identified as the main drawbacks for immediate industrialization and commercialization of glycerol dehydration to acrolein.

Glycerol for renewable acrolein production by catalytic dehydration

This invention relates to an apparatus, comprising: at least one process microchannel having a height, width and length, the height being up to about 10 mm, the process microchannel having a base wall extending in one direction along the width of the process microchannel and in another direction along the length of the process microchannel; at least one fin projecting into the process microchannel from the base wall and extending along at least part of the length of the process microchannel; and a catalyst or sorption medium supported by the fin.

Microchannel with internal fin support for catalyst or sorption medium

This invention relates to a process for converting a hydrocarbon reactant to a product comprising an oxygenate or a nitrile, the process comprising: (A) flowing a reactant composition comprising the hydrocarbon reactant, and oxygen or a source of oxygen, and optionally ammonia, through a microchannel reactor in contact with a catalyst to convert the hydrocarbon reactant to the product, the hydrocarbon reactant undergoing an exothermic reaction in the microchannel reactor; (B) transferring heat from the microchannel reactor to a heat exchanger during step (A); and (C) quenching the product from step (A).

Process for converting a hydrocarbon to an oxygenate or a nitrile

A process for the catalytic gas-phase oxidation of acrolein to acrylic acid in a fixed-bed reactor with contacting tubes, at elevated temperature on catalytically active oxides with a conversion of acrolein for a single pass of ≧95%, wherein the reaction temperature in the flow direction along the contacting tubes in a first reaction zone before the starting reaction gases containing the reactants enter the contacting tubes is from 260° to 300° C. until an acrolein conversion of from 20 to 40% is reached, and the reaction temperature is subsequently reduced by a total of from 5° to 40° C., abruptly or successively in steps or continuously along the contacting tubes until a methacrolein conversion of ≧95% has been reached, with the proviso that the reaction temperature in this secondary reaction zone is not lower than 240° C.

Catalytic gas-phase oxidation of acrolein to acrylic acid

The invention relates to a method for preparing acrylic acid from an aqueous glycerol solution, comprising a first step of dehydration of the glycerol to acrolein, carried out in the gas phase in the presence of a catalyst and under a pressure of between 1 and 5 bar, and a second step of oxidation of the acrolein to acrylic acid, in which an intermediate step is implemented, consisting in at least partly condensing the water and heavy by-products present in the stream issuing from the first dehydration step. This method serves to obtain high acrylic acid productivity and selectivity.

Method for producing acrylic acid from glycerol

A catalyst for use in the production of acrylic acid by catalytic gas phase oxidation of acrolein, comprising active substances represented by general formula Mo.sub.(a) V.sub.(b) A.sub.(c) B.sub.(d) C.sub.(e) D.sub.(f) O.sub.(x) wherein Mo represents molybdenum, V represents vanadium, A represents at least one element selected from the group consisting of tungsten and niobium, B represents at least one element selected from the group consisting of iron, copper, bismuth, chromium, antimony, and thallium, C represents at least one element selected from the group consisting of alkali metals and alkaline earth metals, D represents at least one element selected from the group consisting of silicon, aluminum and titanium, and O represents oxygen; and further, a, b, c, d, e, f and x represent atomic ratios of Mo, V, A, B, C, D, and O respectively, and when a=12, then b=2 to 14, c=0 to 12, d=0 to 6, e=0 to 6 and f=0 to 30 and x is a numerical value determined depending upon the oxidation states of the other elements, and characterized by having a specific surface area of 0.50 to 15.0 m 2 /g, a pore volume of 0.10 to 0.90 cc/g and a pore diameter distribution in which the pore diameters are distributed concentratedly in the ranges of from 0.1 to less than 1.0 μm, from 1.0 to less than 10.0 μm and from 10.0 to 100 μm. The catalyst can be prepared, with good reproducibility, by charging an unfired catalyst material powder composition into a centrifugal flow coating apparatus to form particles having an average diameter of 2 to 10 mm, and then firing the particles.

Catalyst for oxidation of acrolein and process for production thereof

Acrylic acid can be produced efficiently by subjecting acrolein to catalytic gas-phase oxidation in the presence of a molybdenum/vanadium-based oxide catalyst prepared by using particular substances as the raw materials of the individual metal elements constituting the catalyst. A preferable example of such a catalyst is prepared by using, as the raw materials of vanadium, ammonium metavanadate and at least one vanadium oxide in which the valency of vanadium is larger than 0 but smaller than 5; as the raw material of copper, copper nitrate; and, as at least part of the raw material(s) of antimony, at least one antimony oxide in which the valency of antimony is larger than 0 but smaller than 5.

Process for production of acrylic acid

A catalyst used for producing, by catalytic gas phase oxidation of a C 3 -C 5 oelfin or tertiary alcohol, the corresponding unsaturated aldehyde and unsaturated carboxylic acid, said catalyst characterized by comprising molybdenum, iron and bismuth and having a specific surface area in the range from 1 to 20 m 2 /gr, a pore volume in the range from 0.1 to 1.0 cc/gr and a pore diameter distribution in which the pore diameters are collectively distributed in the range of each of from 1 to 10 microns and from 0.1 to less than 1 micron; and a process for preparing said catalyst by charging an unfired material power into a centrifugal flow coating device to form particles having the average particle diameter of 2 to 10 mm and then firing the particles.

Catalyst for oxidation of olefin or tertiary alcohol and process for production thereof

In a process for producing an unsaturated aldehyde or an unsaturated acid by catalytically oxidizing propylene or at least one compound selected from isobutylene, tert.-butyl alcohol and methyl-tert.-butyl ether in a gaseous phase with molecular oxygen or a molecular oxygen-containing gas using a fixed bed multipipe reactor, characterized in that (a) a plurality of composite oxides different in occupied volume, represented by formula MoaWbBicFedAeBfCgDhOx ... (I) wherein Mo denotes molybdenum; W denotes tungsten; Bi denotes bismuth; Fe denotes iron;A denotes at least one element selected from cobalt and nickel; B denotes at least one element selected from an alkali metal, an alkaline earth metal and thallium; C denotes at least one element selected from phosphorus, tellurium, arsenic, boron, niobium, antimony, tin, lead, manganese, cerium and zinc; Ddenotes at least one element selected from silicon, alminum, titanium and zirconium; Odenotes oxygen; a, b, c, d, e, f, g, h and x denote numbers of atoms of Mo, W, Bi, Fe, A, B, C, D and O; when a=2 to 12, b=0 to 10 and a+b=12, c=0.1 to 10, d=0.1 to 10, e=2 to 20, f=0.005 to 3, g=0 to 4, h=0.5 to 30 and x=value determined by an oxidized state of each element, are used as catalysts, (b) a plurality of reaction zones are provided along an axial direction in each reaction pipe of the fixed bed multipipe reactor, and (c) the plurality of the catalysts different in occupied volume are filled in the plurality of the reaction zones such that the occupied volumes become lower from the starting gas inlet side to the outlet side.

Process for producing unsaturated aldehydes and unsaturated acids

OF THE DISCLOSURE A method for the production of acrylic acid by the vapor-phase oxidation of acrolein with a molecular oxygen-containing gas in the presence of a catalyst formed of an oxide or a composite oxide of a metal element composition represented by the following formula I: MoaVbWcWudXeYf (I) wherein X is at least one element selected from the group consisting of Zr, Ti and Ce, T is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and the subscripts a, b, c, d, e, and f are such that b = t to 14, 0<c?12, 0<d?6, 0<e?10, and f = 0 to 3 where a is fixed at 12, 2.0<Cu+X?10.0 and 0.25?Cu/X?6O

Tatsuya Kawajiri

Papers

Catalyst for oxidation of acrolein and process for production thereof

Process for production of acrylic acid

Catalyst for oxidation of olefin or tertiary alcohol and process for production thereof

Process for producing unsaturated aldehydes and unsaturated acids

Method for production of acrylic acid