This is the file Marc mentioned (he sent me the pdf and I extracted the text).

Best

Keith Addison
Journey to Forever
Handmade Projects
Tokyo
http://journeytoforever.org/



Separating Ethanol From Water Via Differential Miscibility

Alcohol for combustion could be purified more economically.

Langley Research Center, Hampton, Virginia

The differential miscibility of castor oil in ethanol and water would 
be exploited to separate ethanol from water, according to a proposal. 
Burning the separated ethanol would produce more energy than would be 
consumed in the separation process. In contrast, the separation of a 
small amount of ethanol (actually an ethanol/water solution poor in 
ethanol) from water by the conventional process of distillation 
requires more energy than can be produced by burning the resulting 
distillate. As in the process described in the preceding article, 
"Separating Ethanol From Water Via Differential Solubility" 
(LAR-14894), the proposed alcohol/water separation process could be 
exploited industrially to produce clean fuel from fermented vegetable 
matter.

In one version of this process, castor oil would be added to an 
ethanol/water solution. The ethanol would mix freely with castor oil, 
which is insoluble in water. The resulting ethanol/castor-oil phase, 
which would contain less than 1 percent water, would collect as the 
top layer, the bottom layer being the remainder of the ethanol/water 
solution somewhat depleted in ethanol. Heating this two-layer mixture 
to a temperature slightly below the boiling temperature of ethanol 
(78.5 deg C) would cause the partial pressure of ethanol above the 
top layer to be much greater than the partial pressure of either 
castor oil or water. This vapor-phase ethanol could be condensed in a 
relatively pure state.

Although heating an isolated ethanol/water solution like that in the 
bottom layer would normally raise the vapor pressure of both ethanol 
and water above the solution, this would not be the case in the 
presence of the top castor-oil/ethanol layer for the following 
reasons: The amount of water that could dissolve in the top 
castor-oil/ethanol layer would increase only slightly upon heating. 
On the other hand, ethanol could readily cross the interface between 
the two layers and enter the top layer. As long as the total mix was 
kept at a temperature below the boiling temperature of ethanol 
(thereby preventing agitation of the layers by boiling), the 
diffusion of water through the castor-oil/ethanol phase would be 
inhibited.

In an alternative version of this concept, the upper 
castor-oil/ethanol layer would be skimmed off and heated to obtain 
the ethanol. Once the ethanol was driven off, the castor oil could be 
returned to an ethanol/water solution to dissolve more ethanol to 
repeat the process. This concept could readily lend itself to a 
continuous process. Substances other than castor oil (one of its 
components perhaps, or another substance) could be used in this 
process or to extract other compounds from other mixtures by using 
this upper-of-two-phases vaporization technique.

This work was done by Renaldo V. Jenkins of Langley Research Center. 
No further documentation is available. LAR-14895

Separating Ethanol From Water Via Differential Miscibility 
file:///E|/Tech/Fuels/EtOHmix.html



Separating Ethanol From Water Via Differential Solubility

Alcohol for combustion could be purified more economically.

Langley Research Center, Hampton, Virginia

The differential solubility of sulfur in ethanol and water could be 
exploited to separate ethanol from water. The energy that could be 
produced by burning the separated ethanol would be more than that 
required in the separation process. In contrast, the separation of a 
small amount of ethanol (actually an ethanol/water solution poor in 
ethanol) from water by distillation requires more energy than can be 
produced by burning the resulting distillate. The proposed 
alcohol/water separation process could be exploited industrially to 
produce clean fuel from fermented vegetable matter.

In one version of this concept, sulfur would be added to an 
ethanol/water mixture: a slight amount of sulfur that depends on the 
temperature of the mixture would be dissolved by the ethanol. (All 
three forms of sulfur are insoluble in water, even at its boiling 
temperature, but the a form of sulfur is slightly soluble in ethanol 
and the b form is more soluble in ethanol, according to the CRC 
Handbook of Chemistry and Physics.) The sulfur/ethanol mixture would 
settle to the bottom of the container, where it could be bled off. 
This small part of the original mixture could then be heated to 
separate the volatile ethanol from the significantly less volatile 
sulfur. The hot sulfur left after the distillation could be added to 
another batch of the ethanol/water mixture.

In comparison with the energy consumed in the conventional 
distillation process, a significant amount of energy would be saved 
in this process because only the small bled-off portion of the 
original mixture would have to be heated. Because of its solubility 
in ethanol, the b form of sulfur would be used when the separation 
process was carried out at room temperature and atmospheric pressure. 
Finely divided sulfur that was not dissolved by the ethanol would 
float on the mixture.

In an alternative version of this concept, the ethanol/water/sulfur 
mixture would be placed in a retort, where it could be heated and 
pressurized to a temperature above the critical temperature and 
pressure of ethanol [243 deg C and 63 atm (6.4 MPa), respectively] 
but below the critical temperature and pressure of water [374.1 deg C 
and 218.3 atm (22.12 MPa), respectively]. The mixture would be 
retorted at a temperature slightly above 243 deg C and at a pressure 
slightly above 63 atm (6.4 MPa), putting the ethanol in the 
supercritical state, in which it should easily dissolve all three 
forms of sulfur (including the form, which is insoluble at ambient 
temperature and pressure). The water, on the other hand, would still 
be well below its critical state and still should not dissolve 
sulfur. The sulfur/ethanol mixture would settle to the bottom of the 
retort, where it could be piped away under pressure and at high 
temperature. The sulfur/ethanol mixture would then be expanded to a 
lower temperature and pressure at which not as much sulfur could be 
dissolved in the ethanol and at which ethanol would partially 
separate from the mixture.

Further heating of the remaining mixture at a pressure of 1 atm (0.1 
MPa) would separate most of the remaining ethanol and sulfur. The 
sulfur could be reused, and the high-pressure hot water could be used 
to cook more mash to be fermented or to preheat a charge going to 
another retort.

This second version is probably the most suitable for an industrial 
process, and could be aided by the addition of a centrifuge to 
separate the initial two-phase mixture. The role of sulfur in both 
versions could be played by another substance. However, the low 
toxicity and very low vapor pressure of sulfur at the boiling 
temperature of ethanol appear to make it the best candidate.

This work was done by Renaldo V. Jenkins of Langley Research Center. 
No further documentation is available. LAR-14894

Separating Ethanol From Water Via Differential Solubility 
file:///E|/Tech/Fuels/EtOHsol.html

Biofuel at Journey to Forever:
http://journeytoforever.org/biofuel.html
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