Feed alcohol

Polyisocyanate + Alcohol —> Urethane Feed alcohol Into Isocyanate over 2 hours Allow temperature to rise to 100°C, then hold at 95°C Heat of Reaction 9 K cals/mol... 

The quality of the plasticizer can be increased by removal of dissolved oxygen from a feed alcohol.This reduces formation of colored products which reduce quality of the plasticizer or require more rigorous after treatment. 

Alcohol ammoxidation provides an option to augment the production of HCN and/or acetonitrile in a propylene ammoxidation process for producing acrylonitrile (103). This is accomplished by co-feeding alcohol or alcohol mixtures with propylene over conventional molybdate or antimonate ammoxidation catalysts under typical process conditions for propylene ammoxidation. 

Inorganic-organic composite membrane and the MMM was developed in the initial article of te Hennepe et al. in the Journal of Membrane Science in 1987 for the separation of alcohol and water by PV (te Hennepe et al. 1987). They incorporated silicate-1 in the membrane made of rubbery PDMS to enhance the sorption of alcohols in the membrane over water, thus attempting to improve PV performance for the concentration of alcohols in the permeate from feed alcohol-water mixtures. The idea woiked successfully, as shown by Table 17.5. From the table, it is obvious that both the separation factor and total volumetric flux inaeased with an inaease in silicate content in the membrane. 

In general, the best way to deal with a feed impurity is to purify the feed before it enters the process. Let us return to the isopropyl alcohol process from Fig. 10.3. Propylene is fed to the process containing propane as a feed impurity. In Fig. 10.3 the propane is removed from the process using a purge. This causes waste of... 

The Fischer-Tropsch reaction is essentially that of Eq. XVIII-54 and is of great importance partly by itself and also as part of a coupled set of processes whereby steam or oxygen plus coal or coke is transformed into methane, olefins, alcohols, and gasolines. The first step is to produce a mixture of CO and H2 (called water-gas or synthesis gas ) by the high-temperature treatment of coal or coke with steam. The water-gas shift reaction CO + H2O = CO2 + H2 is then used to adjust the CO/H2 ratio for the feed to the Fischer-Tropsch or synthesis reactor. This last process was disclosed in 1913 and was extensively developed around 1925 by Fischer and Tropsch [268]. 

The conventional electrochemical reduction of carbon dioxide tends to give formic acid as the major product, which can be obtained with a 90% current efficiency using, for example, indium, tin, or mercury cathodes. Being able to convert CO2 initially to formates or formaldehyde is in itself significant. In our direct oxidation liquid feed fuel cell, varied oxygenates such as formaldehyde, formic acid and methyl formate, dimethoxymethane, trimethoxymethane, trioxane, and dimethyl carbonate are all useful fuels. At the same time, they can also be readily reduced further to methyl alcohol by varied chemical or enzymatic processes. 

Acetylene-Based Routes. Walter Reppe, the father of modem acetylene chemistry, discovered the reaction of nickel carbonyl with acetylene and water or alcohols to give acryUc acid or esters (75,76). This discovery led to several processes which have been in commercial use. The original Reppe reaction requires a stoichiometric ratio of nickel carbonyl to acetylene. The Rohm and Haas modified or semicatalytic process provides 60—80% of the carbon monoxide from a separate carbon monoxide feed and the remainder from nickel carbonyl (77—78). The reactions for the synthesis of ethyl acrylate are... 

The stoichiometric and the catalytic reactions occur simultaneously, but the catalytic reaction predominates. The process is started with stoichiometric amounts, but afterward, carbon monoxide, acetylene, and excess alcohol give most of the acrylate ester by the catalytic reaction. The nickel chloride is recovered and recycled to the nickel carbonyl synthesis step. The main by-product is ethyl propionate, which is difficult to separate from ethyl acrylate. However, by proper control of the feeds and reaction conditions, it is possible to keep the ethyl propionate content below 1%. Even so, this is significantly higher than the propionate content of the esters from the propylene oxidation route. 

The reaction is initiated with nickel carbonyl. The feeds are adjusted to give the bulk of the carbonyl from carbon monoxide. The reaction takes place continuously in an agitated reactor with a Hquid recirculation loop. The reaction is mn at about atmospheric pressure and at about 40°C with an acetylene carbon monoxide mole ratio of 1.1 1 in the presence of 20% excess alcohol. The reactor effluent is washed with nickel chloride brine to remove excess alcohol and nickel salts and the brine—alcohol mixture is stripped to recover alcohol for recycle. The stripped brine is again used as extractant, but with a bleed stream returned to the nickel carbonyl conversion unit. The neutralized cmde monomer is purified by a series of continuous, low pressure distillations. 

The olefin product contains 1.1% of residual / -paraffins. Essentially similar results have been obtained in commercial operations on Cg—C q and C g feedstocks. The desorbents used are generally hydrocarbon mixtures of lower boiling range than the feed components. The concentrated olefin stream may then be used for production of detergent alcohols. 

Study of the mechanism of this complex reduction-Hquefaction suggests that part of the mechanism involves formate production from carbonate, dehydration of the vicinal hydroxyl groups in the ceUulosic feed to carbonyl compounds via enols, reduction of the carbonyl group to an alcohol by formate and water, and regeneration of formate (46). In view of the complex nature of the reactants and products, it is likely that a complete understanding of all of the chemical reactions that occur will not be developed. However, the Hquefaction mechanism probably involves catalytic hydrogenation because carbon monoxide would be expected to form at least some hydrogen by the water-gas shift reaction. 

Eigure 2 shows that even materials which are rather resistant to oxidation ( 2/ 1 0.1) are consumed to a noticeable degree at high conversions. Also the use of plug-flow or batch reactors can offer a measurable improvement in efficiencies in comparison with back-mixed reactors. Intermediates that cooxidize about as readily as the feed hydrocarbon (eg, ketones with similar stmcture) can be produced in perhaps reasonable efficiencies but, except at very low conversions, are subject to considerable loss through oxidation. They may be suitable coproducts if they are also precursors to more oxidation-resistant desirable materials. Intermediates which oxidize relatively rapidly (/ 2 / i — 3-50 eg, alcohols and aldehydes) are difficult to produce in appreciable amounts, even in batch or plug-flow reactors. Indeed, for = 50, to isolate 90% or more of the intermediate made, the conversion must... 

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