Formaldehyde, from methanol

An example of a series reaction system is the production of formaldehyde from methanol ... 

In methanol—formaldehyde—water solutions, increasing the concentration of either methanol or formaldehyde reduces the volatility of the other. Vapor-hquid-equihbrium data (8,27) for several methanolic formaldehyde solutions ate given in Table 2. The flash point varies with composition, decreasing from 83 to 60°C as the formaldehyde and methanol concentrations increase (17,18). 

A third possible route is to produce formaldehyde from methyla1 that is produced from methanol and formaldehyde (112,113). The incentive for such a process is twofold. Eirst, a higher concentrated formaldehyde product of 70% could be made by methyla1 oxidation as opposed to methanol... 

The carbon dioxide removed in synthesis gas preparation can be reacted with ammonia, to lonn urea CO(NH2)2- This is an excellent fertilizer, highly concentrated in nitrogen (46.6%) and also useful as an additive in animal feed to provide the nitrogen for formation of meat protein. Urea is also an important source of resins and plastics by reacting it with formaldehyde from methanol. 

This derivative is stable to TsOH/benzene at reflux and to Cr03/H. It is also stable to NBS/hv In the formation of a related derivative, formaldehyde from formalin (containing methanol) converted a C,-hydroxyl group to the C -methoxymethyl ether. Paraformaldehyde can be used as a source of methanol-free formaldehyde to avoid formation of the ethers. ... 

Removal of formaldehyde from aqueous 2-butyne-l,4-diol, or a similar solution, which is relevant in the subsequent manufacture of c -2-butene-l,4-diol, by batch reactive distillation with methanol or ethylene glycol in the presence of Indion 130 as catalyst has also been reported 98% conversion of formaldehyde was obtained by reactive distillation with 7 times the stoichiometric quantity of methanol, compared to 15% conversion obtained in a closed system (Kolah and Sharma, 1995). 

One of the considerations regarding the use of methanol as a fuel is that it emits higher amounts of formaldehyde, which is a contributor to ozone formation and a suspected carcinogen, compared to gasoline. Proponents of methanol dispute this, saying that one-third of the formaldehyde from vehicle emissions actually comes from the tailpipe, with the other two-thirds forming photochemically, once the emissions have escaped. They state that pure methanol vehicles produce only one tenth as much of the hydrocarbons that are photochemically converted to formaldehyde as do gasoline automobiles. 

Instead of methanol, formaldehyde can be used as an intermediate derived from syngas. As is exemplified in Table III, various chemicals can be derived directly from formaldehyde. 

An ozone-sensitized oxidative conversion of methane to methanol has been reported.54 A double-layered Sr on La203 then M0O3 on a silica catalyst bed exhibited significantly higher yields of formaldehyde from a methane-air mixture than did M0O3 on silica alone.55... 

However, if the photochemical reaction is run in the presence of oxygen, then of course, the methyl radicals are oxidized, and one obtains instead methanol, formaldehyde, and their decomposition products. Now, if the vessel is pumped out after a photo-oxidation and once again a normal photolysis of acetone is run, the products in the first 10 or 15 minutes are still oxidation products rather than hydrocarbon products. It takes from 15 to 30 minutes to remove whatever it is that is attached to the wall before the normal photochemical decomposition of pure acetone products are produced. These results should remind us that oxidation system do produce species, some of which are not known or understood. 

The main products were hydrogen peroxide, methanol, formaldehyde, acetaldehyde, and water. The change in mole ratio of propane and oxygen in feed from 2 to 8 had almost no influence upon the hydrogen peroxide formation. The yields of methanol, formaldehyde, and acetaldehyde increased and that of water decreased with decreasing mole ratio... 

Emissions from methanol vehicles are expected to produce lower HC and CO emissions than equivalent gasoline engines. However, methanol combustion produces significant amounts of formaldehyde (qv), a partial oxidation product of methanol. Formaldehyde is classified as an air toxic and its emissions should be minimized. Formaldehyde is also very reactive in the atmosphere and contributes to the formation of ozone. Emissions of NO may also pose a problem, especially if the engine runs lean, a regime in which the standard three-way catalyst is not effective for NO reduction. 

Ozone decomposition in airplanes Selective catalytic reduction of NOx Arrays of corrugated plates Arrays of fibers Gauzes Ag Methanol -> formaldehyde Pt/Rh NO production from ammonia HCN production from methane Foams Catalytic membranes reactors... 

Let us note once again that comparison of the results on methanol oxidation with hydrogen peroxide with methane oxidation data under atmospheric pressure (refer to Table 4.3, Figures 4.10 and 4.11) indicates significant differences in these processes. Methane is oxidized to formaldehyde at a higher rate and higher selectivity than at methanol oxidation. Low methanol yields at methane oxidation compared with formaldehyde confirm parallel proceeding of formaldehyde and methanol synthesis from methane. 

The activation of methane [1] is also included as one of the most desired yet not technically viable reactions. Abundant amounts of methane occur with crude oil and as gas in remote locations it is also produced in large quantities during hydrocarbon processing. A large fraction of this methane is flared, because economical use or transportation is not possible. This gas and the abundant resources of methane gas hydrates would make a very suitable feedstock for higher hydrocarbons, if its activation to produce molecules other than synthesis gas were feasible. Despite enormous fundamental and practical efforts [1-5], no applicable method has yet been found for creation of ethylene, methanol, or formaldehyde from methane. 

Tetrahydrofolate functions as a carrier of one-carbon units. There are numerous metabolic reactions that require either the addition or removal of a one-carbon unit of some specific oxidation state. THF binds one-carbon units of three oxidation levels the methanol, formaldehyde, and formate states. These are shown in Table 6.4 along with their origins and uses. The various one-carbon units are interconvertible, as shown in Figure 6.5. Nicotinamide coenzymes are involved. In addition, the one-carbon unit may be released as C02. The methanol-level THF-bound one-carbon unit 5-methyl-THF is the storage and transport form. Once formed, its main pathway of metabolism is to form methionine from homocysteine, a reaction that requires vitamin B12 in the form of methylcobalamin (see Figure 6.2 and Chapter 20) ... 

Formaldehyde SR [Series Reactor] A process for making aqueous formaldehyde from methanol. Developed by Haldor Topsoe. Three plants had been built by 2005, and three more were under construction. 

A catalytic reactor is used to produce formaldehyde from methanol in the reaction... 

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