KYAMBOGO

UNIVERSITY

FACULTY OF ENGINEERING DEPARTMENT OF MECHANICAL AND PRODUCTION ENGINEEERING

BACHELORS OF ENGINEERING IN AUTOMOTIVE AND POWER ENGINEERING

POWER PLANT II ASSIGNMENT A REPORT ON THE METHODS OF ETHANOL DEHYDRATION AND ITS RELEVANCE IN THE PETROLEUM INDUSTRY

BY: ALETI ABELE EMMANUAL 11/U/1300/APE/PE LECTURER: MR. KAKEBE ROBERT

A report on the explanation of the following methods of ethanol dehydration; a A!"#$%&'#( M)&*#+

This uses a principle that water dissolves in rock salt, but Ethanol does not. For this method, Ethanol can be dehydrated by circulating the Ethanol !ater through dry salt. P$#,)+-$) ". Ethanol is mixed with calcium salt, or any other preferred salt in a container, there after which the container is sealed off to close the contents within. #. The container is shaken vigorously to make sure that the salt and water combine, after which it left to settle for $% minutes. This makes salt water to separate from ethanol making the dividing line to be clearly seen $. The ethanol is filtered or siphoned off from the top, leaving water laden salt at the bottom of the &ar, '. The water laden salt is poured on a cookie sheet, as a way of recovering the salt, The salt is oven dried, or laid in the sun until its completely dry, and it can be re(used ! D$.'(/ 0'&* L'1) This is the oldest method of drying alcohol, and it is still used on a laboratory scale. )t is similar to the salt absorption method &ust described above except that, with this method, water is removed by a chemical reaction. P$#,)+-$) *rdinary lime +calcium oxide, reacts with water to form calcium hydroxide +-a+*.,#,. -a* / .#* -a+*.,#

The water(containing alcohol is mixed with lime at a ratio of about $0 pounds +or more, of lime for each gallon of water to be removed +as determined with a hydrometer, and allowed to 1slake2 for "#(#' hours with occasional stirring.

The lime reacts with the water to form calcium hydroxide.

The calcium hydroxide is insoluble in the alcohol and so the relatively pure +33.04, alcohol goes to the top of the container and the calcium hydroxide settles to the bottom.

The usual method of separating the lime and calcium hydroxide from the alcohol is by distillation.

Alternately, but less desirable, the alcohol can be carefully drawn off +decanted, and filtered to remove any suspended particles that give it a milky appearance.

A still head with thermometer +no reflux column is needed, and condenser should be added to allow simple distillation.

Also, a small gate valve located 5(6 inches from the bottom +above the level of the lime, will allow the alcohol to be decanted, if desired.

After slaking in the apparatus, the alcohol should be distilled off through the simple still head and condenser.

7uring distillation, the temperature should remain exactly at the boiling point of pure alcohol.

8emaining after the pure alcohol has been distilled or decanted is wet calcium hydroxide and lime.

9ome alcohol will also be trapped in the residue. To recover it, the distillation process is continued The still head temperature will rise above ":$ degrees F indicating that water is coming over with the remaining alcohol.

!hen the still head reaches #%6(#"# degrees F all of the alcohol has been removed. The water alcohol distillate should be added to the beer for the next run in the reflux distillation apparatus.

The calcium hydroxide may be converted back into calcium oxide and re(used.

.owever, the temperatures re;uired are ;uite high unless a vacuum drying oven is used.

<ut since lime is relatively cheap, this process is not recommended. , A2)#&$#%', D'"&'33a&'#(

A=eotropic distillation uses a solvent with an intermediate boiling point to introduce new a=eotropes to the mixture and at the same time to generate two li;uid phases that allow, in a combined way, separating ethanol from water. This solvent can be cyclohexane. P$#,)"" #4 A2)#&$#%', D'"&'33a&'#( The process has two columns and one decanter. The first heterogeneous a=eotropic distillation column is designed to obtain high(purity ethanol product at the column bottom while obtaining minimum boiling ethanol(water(cyclohexane a=eotrope at the top of the column. The a=eotrope obtained at the top is heterogeneous and the top vapor stream is then condensed to form two li;uid phases in the decanter. The organic phase containing mainly cyclohexane is refluxed back to the heterogeneous a=eotropic distillation column. The a;ueous phase is drawn out from the decanter to be sent to the entrainer recovery column where at the bottoms stream is obtained water essentially pure and at the top is removed cyclohexane to be recycled to the first column. -omparison of the main ethanol dehydration technologies through process simulation

Flow sheet for a=eotropic distillation with cyclohexane + 5)#3'&) M#3),-3a$ S')6)" This is a material with selective adsorption properties capable of separating components of a mixture on the basis of a difference in molecular si=e and shape since Ethanol molecules are '.' angstroms and water is #.6 angstroms +in diameters, P$#,)+-$) The surface of the =eolite +crystalline alumino(silicates,, has the ability to retain the water molecule. Their uni;ue structure allows the water of crystalli=ation to be removed, leaving a porous crystalline structure. These pores have a high affinity to re(adsorb water or other polar molecules. Aided by strong ionic forces +electrostatics fields, caused by the presence of cations such as sodium, calcium and potassium, and by the enormous internal surface area of close to ">%%% m# g, molecular sieves will adsorb a considerable amount of water or other fluids. This strong adsorptive force allows molecular sieves to remove gas li;uid impurities to very low levels.

5)#3'&) D)*.+$a&'#( T),*('7-) 4#$ S1a33 P$#+-,)$" The =eolite has a maximum amount of water that it can hold, if you incorporate it into the distilling process then you will load it up while the alcohol is still ;uite wet and thus making it unproductive.

P$#,)+-$) ?re dry your =eolite when dry ?our about $ gallons of alcohol into it. wait about #% minutes and then ?our off the alcohol and 9tore in an air tight container @ess than $ gallons will be reali=ed, the rest of the alcohol will be stuck inside the =eolite. To recover the alcohol, pour the =eolite full of water, &ust enough to cover it. the water will push out the rest of the alcohol, !ait about #% minutes and then drain your alcohol water mixture out and put it into the next batch that you are going to distill.

The =eolite can now be dried for reuse ) D'44)$)(&'a3 M'",'!'3'&.

The differential miscibility is done by mixing castor oil in ethanol to separate ethanol from water. )n 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 " percent water, would collect as the top layer, the bottom layer being the remainder of the ethanol water solution somewhat depleted in ethanol. .eating this two(layer mixture to a temperature slightly below the boiling temperature of
ethanol +:6.0 %-, 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 reasonsA The amount of water that could dissolve in the top castor(oil ethanol layer would increase only slightly upon heating. *n 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. )n an alternative version of this concept, the upper castor(oil ethanol layer would be skimmed off and heated to obtain the ethanol. *nce 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. 9ubstances 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 vapori=ation techni;ue. 4 D'44)$)(&'a3 S#3-!'3'&. ". The differential solubility of sulfur in ethanol and water could be exploited to separate ethanol from water. #. 9ulfur 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 soluble in ethanol. sulfur that is not dissolved by the ethanol will float on the mixture $. The sulfur ethanol mixture settles to the bottom of the container, where it could be bled off. This small part of the original is then heated to separate the volatile ethanol from the significantly less volatile sulfur. The hot sulfur left after the distillation could be added to another batch of the ethanol water mixture. R)3)6a(,) #4 E&*a(#3 D)*.+$a&'#( &# &*) P)&$#3)-1 I(+-"&$. <elow is a discussion of the relevance of ethanol dehydration to the petroleum industry, it shows both positive and negative effects. Anhydrous ethanol +dehydrated ethanol, means an ethyl alcohol that has a purity of at least ninety(nine percent, exclusive of added denaturants, that meets all the re;uirements of the American 9ociety of Testing and Baterials +A9TB, 7'6%5, the standard specification for ethanol used as motor fuel. Ethanol anhydrous is used as an addictive in gasoline, as a way of reducing the use of fossil fuels. Adding ethanol anhydrous to gasoline has substituted the use of the toxic tetraethyl

lead, a lead compound that had significant adverse impacts on the environment. .owever, ethanol anhydrous cannot be used pure in vehicles, as other types of ethanol with higher water content can, such as hydrous ethanol. The alcohol water separation process could be exploited industrially to produce clean fuel from fermented vegetable matter. )n transportation, ethanol is used as a vehicle fuel by itself +E"%%,, blended with gasoline +E60,, or as a gasoline octane enhancer and oxygenate +"% percent concentration,. 8esearch strongly suggests that there is an 1optimal blend levelC of ethanol and gasoline D most likely E#% or E$% D at which cars will get better mileage than predicted based strictly on the fuelEs per(gallon <tu content. The #%%: flex(fuel -hevrolet )mpala utili=ed in midlevel blends testing revealed a "04 increase in fuel efficiency using the .ighway Fuel Economy Test +.!FET, for E#% in comparison with unleaded regular gasoline. For the same vehicle, the highway fuel economy was greater than calculated for all tested blends, with an especially high peak at E#%. The new study, co(sponsored by the F.9. 7epartment of Energy +17*EC, and the American -oalition for Ethanol +1A-EC, also found that mid( range ethanol blends reduce harmful tailpipe emissions. The disadvantage of using ethanol gasoline blends is that the ethanol must be anhydrous, re;uiring a dehydration step in production. )f non(anhydrous ethanol is mixed with gasoline, the blends will separate into a gasoline phase and a water ethanol phase, causing erratic engine performance. )n addition to its use in gasoline(fueled automobiles and in truck or tractor engines, ethanol can be used in other types of engines. For example, small, four(cycle gasoline engines found in small(scale agricultural e;uipment +e.g., tillers, small tractors, can often burn 6% to 30 percent ethanol as a direct replacement for gasoline. 9uch engines fed by ethanol re;uire minimal modifications. The use of ethanol in specially designed two(cycle engines has been demonstrated on a limited basis. The problem of using ethanol in these engines is that the ethanol does not blend well with lubricating oil. To get around this problem, research is under way to find lubricating oils that are not affected by ethanol.

Though ethanol use in diesel(fueled engines is feasible, it has its limitations. Ethanol does not ignite under compression and does not mix well with diesel fuel. Therefore, ethanol cannot be used as a direct replacement for diesel fuel or blended with diesel fuel for use in compression ignition engines. Ethanol can be used as a replacement for diesel fuel only if the engine is fitted with glow plugs. Ethanol can be used in supercharged diesel engines for up to about #0 percent of the total fuel. This is done by carrying the ethanol in a separate fuel tank and in&ecting it into the diesel engine through a supercharger airstream. Ethanol can also replace aviation fuel in aircraft engines. Ethanol is most commonly used in transportation and agriculture to fuel internal combustion, four(cycle, spark(ignition engines. )t is used as a direct replacement for gasoline, or it is blended with gasoline as an extender and octane booster. The use of ethanol to replace gasoline re;uires modifications to the carburetor, fuel system components, and often the compression ratio. The efficient conversion of existing gasoline engines re;uires skilled, knowledgeable technicians. Engines specifically designed and manufactured to operate on ethanol fuel will generally be more efficient than modified gasoline engines. Ethanol concentrations of between 6% and 30 percent can be used as fuel, which eliminates the need for sophisticated dehydration systems and simplifies distillation. )n many cases, the conversion of engines to operate on ethanol may be simpler and more cost efficient than ethanol dehydration. The disadvantage of engine conversion is that vehicle travel distance is limited by the available supply and distribution of ethanol. 9ome 2dual fuel2 systems((that is, engines with a carburetor that can operate either on ethanol or on gasoline((have been developed on a limited basis. )n <ra=il, a significant portion of the transportation fleet uses ethanol fuel in automobiles with specially designed engines, manufactured by ma&or international automobile companies.

)n unmodified engines, ethanol can replace up to #% percent of the gasoline. <lending ethanol with gasoline extends the gasoline supply, and improves the ;uality of gasoline by increasing its octane value. As an octane enhancer, ethanol can replace lead compounds in gasoline. There are advantages to using gasoline ethanol blends rather than pure ethanol. <lends do not re;uire engine modification. )n this way, ethanol can be integrated rapidly with existing gasoline supply and distribution systems. 8eplacing lead compounds with ethanol removes one of the principal air pollution problems associated with gasoline. C#(,3-"'#( A $(54 increase in ethanol production accompanied by a decrease in energy costs, plus an increase in fuel efficiency, will help to increase ethanol sales and profit margins for ethanol producers. Existing gasoline pipelines will be able to utili=e midlevel hydrous ethanol blends as a much more compatible blendstock. This will dramatically reduce transportation costs by allowing petro(refineries and blenders to leverage existing infrastructures for distribution of hydrous ethanol. Gew turbocharged engines designed for ethanol only, FFH, and ethanol hybrid vehicle technologies allow for utili=ing hydrous ethanol in E60 and E"%% fuels in con&unction with electric power to provide unprecedented power, fuel efficiency and emissions reductions. 9uch combinations can substantially reduce and eventually eliminate dependence on fossil fuels. )n summary, a transition from anhydrous to hydrous ethanol for gasoline blending is expected to make a significant contribution to ethanolEs cost( competitiveness, fuel cycle net energy balance, and greenhouse gas emissions profile.