Acetic acid ethanol conversion

As shown in Fig. 9, the size of the region within which a complete conversion and separation occurs depends on the feed ratio. However, in all cases the existence of such a region was confirmed. A feed ratio of 0/100 (acetic acid/ethanol) actually represents a limiting case where no reaction occurs (identical to a non-reactive SMB). Since obviously there are many operating conditions where complete conversion and separation is achieved, other criteria should be introduced... 

Selenium dioxide, Seienious acid, SeOj, HsSeOa. Mol. wts. 110.96,128.98. Suppliers Fairmont Chemical Co. K and K Laboratories Matheson, Coleman and Bell (SeOJ Fisher (HjSeO.,). Review and procedures for conversion of recovered Se into SeOa, In oxidations and dehydrogenations with either preformed seienious acid or selenium dioxide and water, usually in acetic acid, ethanol, or dioxane, the solution turns yellow and then red, and later some of the selenium separates in a red form difficult to Alter, some is retained in colloidal solution, and some is bound to an oraanic lubitrita. Elimination of all loleniuin fVom a reaction mixture often oreienti... 

The reaction occurs in the liquid phase and the conversion is kinetical ly determined. The liquid holdup on the trays should, therefore, be carefully considered. By separating the ethyl acetate as it is formed, the reaction can be driven toward completion. The feed to the column is a mixture of acetic acid, ethanol, and water. The distillate is predominantly ethyl acetate and most of the unreacted ethanol, plus small amounts of water and unreacted acetic acid. The bottoms product contains most of the water and unreacted acetic acid, plus small amounts of ethyl acetate and unreacted ethanol. 

Ethanediol. See Ethylene glycol Ethanoic acid. See Acetic acid Ethanol, 128, 130, 580-581 acidity of, 135, 740-741 and benzaldehyde, acetal from, 669 biological oxidation of, 600—602 chemical shifts, 606 conversion to diethyl ether, 592 dehydration of, 182 dipole moment of, 130, 863 by fermentation, 580-581 hydrogen bonding in, 130-131 industrial preparation of, 223, 581 physical properties of, 130, 132-133, 580 reduction of aryl diazonium salts by, 894, 907... 

Figure 10.17 represents a comparison of the concentration profiles in two different ethyl acetate synthesis modes, with and without a decanter. The investigation is performed for the pilot-scale column, with a molar feed ratio acetic acid/ethanol equal to 1.2, reflux ratio equal to 3, and a total feed rate equal to 30kg/h. The distillate-to-feed ratio is set to 0.9. The simulations reveal that the conversion with the liquid-liquid separator is about 5% higher that without a decanter, since there is less water and more acetic acid in the catalytic section. Improved conversion and product enrichment due to liquid-liquid separation result in a significant (29%) improvement of the product purity. Finally, because there is less condensed water in the reflux to be evaporated, the heat duty is reduced by up to 26%. 

The model equations were solved for predicting the acetic acid conversion using appropriate kinetics for acetic acid -ethanol, acetic acid-butanol and maleic acid ethanol systems reported in Chapters 2, 3 and 4. Other parameters required for model predictions are summarized in Table 5.3. 

METHOD 2 [89]--1M MDA or benzedrine and 1M benzaldehyde is dissolved in 95% ethanol (Everclear), stirred, the solvent removed by distillation then the oil vacuum distilled to give 95% yellow oil which is a Schiff base intermediate. 1M of this intermediate, plus 1M iodomethane, is sealed in a pipe bomb that s dumped in boiling water for 5 hours giving an orangy-red heavy oil. The oil is taken up in methanol, 1/8 its volume of dH20 is added and the solution refluxed for 30 minutes. Next, an equal volume of water is added and the whole solution boiled openly until no more odor of benzaldehyde is detected (smells like almond extract). The solution is acidified with acetic acid, washed with ether (discard ether), the MDMA or meth freebase liberated with NaOH and extracted with ether to afford a yield of 90% for meth and 65% for MDMA. That s not a bad conversion but what s with having to use benzaldehyde (a List chemical) Strike wonders if another aldehyde can substitute. 

In contrast with the well-known Embden-Meyerhof-Pamass glycolysis pathway for the conversion of hexose sugars to alcohol, the steps in conversion of ethanol to acetic acid remain in some doubt. Likely, ethanol is first oxidized to acetaldehyde and water (39). For further oxidation, two alternative routes are proposed more likely, hydration of the acetaldehyde gives CH2CH(OH)2, which is oxidized to acetic acid. An alternative is the Cannizzaro-type disproportionation of two molecules of acetaldehyde to one molecule of ethanol and one molecule of acetic acid. Jicetobacter... 

A Belgian patent (178) claims improved ethanol selectivity of over 62%, starting with methanol and synthesis gas and using a cobalt catalyst with a hahde promoter and a tertiary phosphine. At 195°C, and initial carbon monoxide pressure of 7.1 MPa (70 atm) and hydrogen pressure of 7.1 MPa, methanol conversions of 30% were indicated, but the selectivity for acetic acid and methyl acetate, usehil by-products from this reaction, was only 7%. Ruthenium and osmium catalysts (179,180) have also been employed for this reaction. The addition of a bicycHc trialkyl phosphine is claimed to increase methanol conversion from 24% to 89% (181). 

Imides (e.g. phthalimide) can be purified by conversion to their potassium salts by reaction in ethanol with ethanolic potassium hydroxide. Hie imides are regenerated when the salts are hydrolysed with dilute acid. Like amides, imides readily crystallise from alcohols and, in some cases (e.g. quinolinic imide), from glacial acetic acid. 

An example of a reversible reaction in the liquid phase is afforded by the esterification reaction between ethanol and acetic (ethanoic) acid forming ethyl acetate and water. Since, however, ethyl acetate undergoes conversion to acetic acid and ethanol when heated with water, the esterification reaction never proceeds to completion. 

Such improvements in conversion were reported for the oxidation of ethanol by hydrogen peroxide to acetic acid. This is a well-studied reaction, carried out in a continuous stirred-tank reactor (CSTR). Near-complete conversion (> 99%) at near-complete selectivity (> 99%) was found in a micro-reaction system [150]. Processing in a CSTR resulted in 30-95% conversion at > 99% selectivity. 

Oda et al. reported that under reflux conditions, the zinc-promoted reaction of 2,3-dichloro-l-propene with aldehydes and ketones in a two-phase system of water and toluene containing a small amount of acetic acid gave 2-chloroallylation products (Eq. 8.31).64 No conversion occurred when tin was used as the promoter. The absence of water completely shuts down the reaction. Interestingly, the action of 2,3-dichloropropene plus zinc powder in aqueous ethanol gives the dechlorination product, allene.65... 

Laboratory studies have been carried out to provide design data on the conversion. A stoichiometric mixture of 60 g acetic acid and 45 g ethanol was reacted and held at constant temperature until equilibrium was achieved. The reaction products were analyzed and found to contain 63.62 g ethyl acetate. 

Increasing the excess of ethanol increases the conversion of acetic acid to ethyl acetate. To carry out the calculation more accurately would require activity coefficients to be calculated for the mixture (see Poling, Prausnitz and O Connell6 and Chapter 4). The activity coefficients depend on correlating coefficients between each binary pair in the mixture, the concentrations and temperature. 

Activity of the Keggin HPW/Si02 catalyst in terms of the conversions of ethylene and acetic acid and production of ethyl acetate vs. reaction time is displayed in Figure 3. Besides ethyl acetate, ethanol and diethyl ether are also produced. It can be seen that the catalyst is quite stable over the 17 hour period on stream. Activities of the other silica-supported Keggin... 

The reaction has been improved to a satisfactory process by modifying the reaction conditions. A remarkable effect of the addition of amines on the reaction was observed (49). For example, the reaction of butadiene (4 moles) and acetic acid (4 moles) in the presence of 2-(N,/V-dimethyl-amino)ethanol (4 moles) using Pd(acac)2 (3 mmoles) and PPh3 (3 mmoles) at 90°C gave complete conversion after 2 hours. The product was found to consist of 8-acetoxy-1,6-octadiene (47) (71%), 3-acetoxy-1,7-octadiene (48) (21%) and 1,3,7-octatriene (16) (8%). Various tertiary amines, such as triethylamine, )V-methylmorpholine, Af,Af,N, N -tetramethyl-1,3-bu-tanediamine, and triethylenediamine, showed the same favorable effect. Other basic salts, such as sodium and potassium acetate, accelerate the reaction, especially at high concentrations (50, 51). The selection of solvents is also important. Arakawa and Miyake found that electron-donating type solvents (e.g., THF and triethylamine) are good solvents... 

The reaction is reversible and therefore the products should be removed from the reaction zone to improve conversion. The process was catalyzed by a commercially available poly(styrene-divinyl benzene) support, which played the dual role of catalyst and selective sorbent. The affinity of this resin was the highest for water, followed by ethanol, acetic acid, and finally ethyl acetate. The mathematical analysis was based on an equilibrium dispersive model where mass transfer resistances were neglected. Although many experiments were performed at different fed compositions, we will focus here on the one exhibiting the most complex behavior see Fig. 5. 

Fig. 9. Regions with complete conversion/separation for different feed compositions in an SMBR Acetic acid to ethanol ratio (-) 0/100 (-.-) 40/60 (—) 100/0. (Reprinted with per-...

The esterification of acetic acid with ethanol using sulfonic ion-exchange resins as catalyst/selective sorbent was studied by Mazzotti et al. [164]. The authors developed a detailed mathematical model, which was able to predict correctly the system s behavior. They succeeded in obtaining 100% conversion of acetic acid in addition to a complete separation. Several other studies involving enzymatic reactions were also carried out and will be presented in more detail in the next section. 

Electrochemical reduction of benzylic nitro compounds (27) in an ethanolic aqueous acetic acid buffer (35 65) affords a mixture of the corresponding oxime and hydroxylamine (equation 6)48. The hydroxylamine can subsequently be oxidized back to the oxime (28) (via the intermediate nitroso compound) conversions as high as 90% can be obtained. 

A typical example that illustrates the method concerns the lipase- or esterase-catalyzed hydrolytic kinetic resolution of rac-1-phenyl ethyl acetate, derived from rac-1-phenyl ethanol (20). However, the acetate of any chiral alcohol or the acetamide of any chiral amine can be used. A 1 1 mixture of labeled and non-labeled compounds (S)- C-19 and (f )-19 is prepared, which simulates a racemate. It is used in the actual catalytic hydrolytic kinetic resolution, which affords a mixture of true enantiomers (5)-20 and (J )-20 as well as labeled and non-labeled acetic acid C-21 and 21, respectively, together with non-reacted starting esters 19. At 50% conversion (or at any other point of the kinetic resolution), the ratio of (5)- C-19 to (1 )-19 correlates with the enantiomeric purity of the non-reacted ester, and the ratio of C-21 to 21 reveals the relative amounts of (5)-20 and (J )-20 (98). 

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