Acrylic acid from acrolein

The V-Mo-O oxides are well-known industrial catalysts for the synthesis of acrylic acid from acrolein and maleic anhydride from benzene more recently, V-P-0 systems are being utilized for maleic anhydride production from -butane. The V20s/Ti02 combination was employed for phthalic acid production from o-xylene. V-Fe-O catalyzes oxidation of polycyclic aromatic hydrocarbons to dicarboxylic acids and quinones. Methyl formate is produced by the oxidation of methanol over V-Ti-0 catalysts [58]. For many of these processes, it has been experimentally proved that the catalytic reaction follows a Mars-van Krevelen mechanism. The surface coverage with active oxygen 0 in the steady state of the redox reaction following Mars-van Krevelen mechanism is given by... 

Heterogeneous oxidative processes operate at high temperatures (250-450 6C) and are useful for the synthesis of acrolein and acrylic acid from propylene over bismuth molybdate catalysts, the synthesis of maleic and phthalic anhydrides from the oxidation of benzene (or C4 compounds) and naphthalene (or o-xylene) respectively over vanadium oxide,101 arid the synthesis of ethylene oxide from ethylene over silver catalysts.102... 

Acrolein and Acrylic Acid from Propylene for Super-Absorbent Polymers, Paints, and Fibres... 

The significance of industrial acrolein production may be clearer if one considers die two major uses of acrolein—direct oxidation to acrylic acid and reaction to produce mediionine via 3-metiiylmercaptopropionaldeliyde. In acrylic acid production, acrolein is not isolated from die intermediate production stream The 1990 acrylic acid production demand in die United States alone accounted for more than 450,000 t/yr (28), widi worldwide capacity approaching 1,470,000 t/yr (29). Approximately 0.75 kg of acrolein is required to produce one kilogram of acrylic acid. The mediionine production process involves die reaction of acrolein widi methyl mercaptan. Worldwide mediionine production was estimated at about 170,000 t/yr in 1990 (30). (See Acrylic ACID AND DERIVATIVES AMINO ACIDS, SURVEY.)... 

For the same reason, the synthesis of acrylic acid from propylene must be carried out in two separate reactors, one for the oxidation of propylene to acrolein and one for the oxidation of the aldehyde to acrylic acid. This is due to the fact that the requirements needed for the two steps make the two reactions incompatible. Acidity is needed in the second step, to favour the desorption of acrylic acid and save it from unselective consecutive reaction, while on the other hand, acidity is detrimental for the first reaction, because it favours the transformation of propylene to undesired products. Therefore, the development of a process for the one-step transformation of propane to acrylic acid will be possible when a catalyst is developed which possesses active sites able to perform quickly the complete transformation of adsorbed propane to the acrylic acid, the latter being the only product which finally desorbs into the gas phase. Accordingly, best performances in the oxidation of propane to acrylic acid have been reported to be obtained on heteropolyoxomolybdates (26), which are known to couple tuneable acid and redox properties. In this case, acid properties may facilitate the desorption of acrylic acid. 

Figure 24.6. Selective oxidation of propane (a) and propylene (b) over a MoVTeNbO catalyst at 380°C and a C3/02/H20/He molar ratio of 4/8/30/58. Symbols , = acrylic acid, = propylene, = acrolein. From Ref. 92.

Acetic acid (qv) can be produced synthetically (methanol carbonylation, acetaldehyde oxidation, butane/naphtha oxidation) or from natural sources (5). Oxygen is added to propylene to make acrolein, which is further oxidized to acryHc acid (see Acrylic acid and derivatives). An alternative method adds carbon monoxide and/or water to acetylene (6). Benzoic acid (qv) is made by oxidizing toluene in the presence of a cobalt catalyst (7). 

Transition metal oxides or their combinations with metal oxides from the lower row 5 a elements were found to be effective catalysts for the oxidation of propene to acrolein. Examples of commercially used catalysts are supported CuO (used in the Shell process) and Bi203/Mo03 (used in the Sohio process). In both processes, the reaction is carried out at temperature and pressure ranges of 300-360°C and 1-2 atmospheres. In the Sohio process, a mixture of propylene, air, and steam is introduced to the reactor. The hot effluent is quenched to cool the product mixture and to remove the gases. Acrylic acid, a by-product from the oxidation reaction, is separated in a stripping tower where the acrolein-acetaldehyde mixture enters as an overhead stream. Acrolein is then separated from acetaldehyde in a solvent extraction tower. Finally, acrolein is distilled and the solvent recycled. 

The main use of acrolein is to produce acrylic acid and its esters. Acrolein is also an intermediate in the synthesis of pharmaceuticals and herhicides. It may also he used to produce glycerol hy reaction with isopropanol (discussed later in this chapter). 2-Hexanedial, which could he a precursor for adipic acid and hexamethylene-diamine, may he prepared from acrolein Tail to tail dimenization of acrolein using ruthenium catalyst produces trans-2-hexanedial. The trimer, trans-6-hydroxy-5-formyl-2,7-octadienal is coproduced. Acrolein, may also he a precursor for 1,3-propanediol. Hydrolysis of acrolein produces 3-hydroxypropionalde-hyde which could he hydrogenated to 1,3-propanediol. ... 

Co-adsorption experiments show a complex role of the nature and concentration of chemisorbed ammonia species. Ammonia is not only one of the reactants for the synthesis of acrylonitrile, but also reaction with Br()>nsted sites inhibits their reactivity. In particular, IR experiments show that two pathways of reaction are possible from chemisorbed propylene (i) to acetone via isopropoxylate intermediate or (ii) to acrolein via allyl alcoholate intermediate. The first reaction occurs preferentially at lower temperatures and in the presence of hydroxyl groups. When their reactivity is blocked by the faster reaction with ammonia, the second pathway of reaction becomes preferential. The first pathway of reaction is responsible for a degradative pathway, because acetone further transform to an acetate species with carbon chain breakage. Ammonia as NH4 reacts faster with acrylate species (formed by transformation of the acrolein intermediate) to give an acrylamide intermediate. At higher temperatures the amide may be transformed to acrylonitrile, but when Brreform ammonia and free, weakly bonded, acrylic acid. The latter easily decarboxylate forming carbon oxides. 

Fig. 15.13 Illustration of the selective oxidation of acrolein to acrylic acid on carbon. Adapted with permission from [87]. Copyright (2011) Wiley VCH.

Well, not quite. First, they sound similar because at one time, one of them, acrylonitrile, was based solely on manufacture from acrolein, a pungent liquid whose roots in Latin are aca- meaning sharp, and oiere, meaning smell. Acrylonitrile was made from acrolein, and acrylates were derivatives of acrylonitrile. But acrylates also are made from acrylic acid, which is also a derivative of acrylonitrile. So the name, acrylo, covers an extended farnily of relations. 

The important role Transmission Electron Microscopy (TEM) can play in this process is demonstrated on the development of an oxidation catalyst for the production of acrylic acid. Acrylic acid is produced by BASF in quantities of several 100.000 tons per year in a two step gas phase oxidation process starting from propene, which is oxidised to acrolein in the first step and then further oxidised to acrylic acid in a second step, each step requiring a special developed catalyst. Acrylic acid is used as a base material for the production of superabsorbents for nappies, dispersions and emulsions for adhesives and construction materials. 

The cationic chiral Lewis acids 10, generated from the corresponding oxazaboroli-dines by protonation by trifluoromethanesulfonic acid, are excellent catalysts for the enantioselective reaction of 2-substituted acroleins, a-unsaturated a,p-enones, a-unsaturated acrylic acid esters, and a-unsaturated acrylic acids with a variety... 

The two bands at around 1700 cm may be reasonably attributed to Vc=o two different adsorbed species, probably acrolein and acrylic acid. In this compound, in fact, the vc=o band is found at a frequency about 20 cm higher than in acrolein (9). In these adsorbed compounds [for example, on V-Mo oxides (9)], the vc=c band is expected at a nearly the same value as in 7C-bonded propylene (around 1625 cm ), whereas other IR active bands are covered by the stronger bands due to physisorbed propane. A more clear identification of the above species, therefore, is not possible. The shoulder at about 1425 cm" may be attributed to VsCOO in adsorbed acrylate, but the VasCOO band expected at around 1550 cm is absent. A more reasonable interpretation is the formation of alkene oligomers. In fact, propene adsorbed on HNaY gives rise to the formation of a main band at about 1460 cm (9), apart from vch 5ch bands that, in our case, are covered by the band of physisorbed propane. However, all adsorbed species are removed by evacuation, indicating their weak interaction with the surface. 

Oxidation of the allylic carbon of alkenes may lead to allylic alcohols and derivatives or a, 3-unsaturated carbonyl compounds. Selenium dioxide is the reagent of choice to carry out the former transformation. In the latter process, which is more difficult to accomplish, Cr(VI) compounds are usually applied. In certain cases, mixture of products of both types of oxidation, as well as isomeric compounds resulting from allylic rearrangement, may be formed. Oxidation of 2-alkenes to the corresponding cc,p-unsaturated carboxylic acids, particularly the oxidation of propylene to acrolein and acrylic acid, as well as ammoxidation to acrylonitrile, has commercial importance (see Sections 9.5.2 and 9.5.3). 

Acrylic acid [79-10-7] - [AIR POLLUTION] (Vol 1) - [ALDEHYDES] (Vol 1) - [ALLYL ALCOHOL AND MONOALLYL DERIVATIVES] (Vol 2) - [MALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) - [POLYESTERS, UNSATURATED] (Vol 19) - [FLOCCULATING AGENTS] (Vol 11) - [CARBOXYLICACIDS - SURVEY] (Vol 5) -from acetylene [ACETYLENE-DERIVED CHEMICALS] (Vol 1) -from acrolein [ACROLEIN AND DERIVATIVES] (Vol 1) -acrylic esters from [ACRYLIC ESTER P OLYMERS - SURVEY] (Vol 1) -from carbon monoxide [CARBON MONOXIDE] (Vol 5) -C-21 dicarboxylic acids from piCARBOXYLIC ACIDS] (Vol 8) -decomposition product [MAT. ETC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -economic data [CARBOXYLIC ACIDS - ECONOMIC ASPECTS] (Vol 5) -ethylene copolymers [IONOMERS] (Vol 14) -in floor polishes [POLISHES] (Vol 19) -in manufacture of ion-exchange resins [ION EXCHANGE] (V ol 14) -in methacrylate copolymers [METHACRYLIC POLYMERS] (Vol 16) -in papermaking [PAPERMAKING ADDITIVES] (Vol 18)... 

ACRYLIC ACID AND DERIVATIVES. [CAS 79-10-7]. Acrylic acid (propenoic acid) was first prepared in 1847 by air oxidation of acrolein. Interestingly, after use of several other routes over the past half century, it is tins route, using acrolein from the catalytic oxidation of propylene, that is currently the most favored industrial process. 

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