Azeotropic distillation

Add substance that forms minimum boiling azeotrope with one or both components. Take azeotrope off top and separate by decanting or by solvent extraction May get binary or ternary azeotrope, either homogeneous or heterogeneous

Azeotropic distillation - examples

Reverse volatilities Paraffins/aromatics add methanol to take paraffins overhead. Water wash then distill Add nitro methane to take paraffins overhead. Cool and decant

Extractive distillation
Add non-volatile substance/entrainer that modifies relative volatility of the other components. May reverse volatilities However, leads to higher T in reboiler Must separate entrainer by decanting, distillation or solvent extraction

Extractive distillation - examples

Max boiling Azeotropes Nitric acid/water or hydrochloric acid/water extract water using sulphuric acid Close Boilers Toluene/methylcyclohexane add phenol to dissolve toluene. Gives mch overhead distill phenol/toluene

Extractive distillation - examples

Reverse volatilities Paraffins/aromatics add glycol to dissolve aromatics recover glycol with water wash Propene/propane in presence of nitrogen use acrylonitrile to reverse the volatilities of propane and propene. Propene dissolves in acrylonitrile separate by flash followed by distillation

Molecular Distillation
For those classes of chemical compounds which decompose, polymerize, react or are destroyed by conventional low pressure distillation, efficient commercial high vacuum distillation equipment is available for those compounds

By centrifugal force, the material spreads in a film across the heated disc which intimately faces a large condensing surface. The lighter compound evaporates and condenses in a fraction of a second. The heavier residue which has not evaporated slides off the outer edge of the disc

 NO HEAT DEGRADATION :Low pressure and a thermal residence time of less than one second protects against decomposition. HIGHER PRODUCT QUALITY :This process can remove objectionable colors, odors, and excess reactants, adding value to product. VALUABLE BY-PRODUCTS :Materials removed from product remain intact. These waste materials become potential marketable products. LOW PROCESS COST : can be processed small or large volumes at low costs because stills use less energy, are very efficient and economical in operation.

PROCESS SMALL OR LARGE VOLUMES : throughput ranging from ounces to 2,000 pounds per hour

Food Processing Industries Provide a method for refining edible oils that result in decolorized, deodorized, pure oil, separating valuable products such as vitamins, sterols, fatty acids, and antioxidants. The centrifugal molecular distillation process provides a gentle method for purifying and fractioning essential oils. Odors, colors, and flavors can be separated without danger of hydrolysis, air oxidation or decomposition. Monoglycerides or emulsifiers can be more highly concentrated than with traditional separation techniques. Cosmetic Industries This type of distillation equipment is ideal for use in recovering lanolin from wool grease, the crude soft wax obtained from the hair of the sheep. Fragrance derived from fatty acids are also isolated through this system. Pharmaceutical Industries Government requirements concerning enrichment of food with vitamins have caused increased interest in centrifugal molecular distillation of natural vitamins A and E. Natural vitamins K-1 and K-2 are being distilled to replace synthetic K-3 and -4. Synthetic vitamin E also has been distilled by Myers molecular distillation equipment. Stills are used in a variety of purification and separation processes for many drugs, including tranquilizers.

Paint and Varnish Industry The drying properties and firm hardness of polymerized oils such as castor and linseed can be altered by distilling off low molecular weight compounds. Epoxy Resin Manufactures Manufacturers of liquid epoxy resins have discovered that this distillation technique results in desirable color reduction, lowered viscosity, and increased shelf life by removing the catalyst typically used in the formulation. Tall Oil Production Tall oil producers have benefited from Myers centrifugal molecular distillation in two ways. First, the distillation reduces the problem of tall oil pitch disposal. Secondly, the remaining fatty acids can be recovered in profitable quantities to be reused for emulsifiers, flotation agents, plasticizers, disinfectants, soaps, and cleaning agents.

 Silicon Producers Myers molecular stills are ideal for the removal of either low or high molecular weight polymers from a mixture of polymers. Wax Producers Crude paraffin, beeswax carnauba, and certain microcrystalline and high melting point waxes are purified by the Myers centrifugal molecular distillation system. Basic Research Molecular distillation has been proven successful in separating various isotopes, as well as many other research application. The Myers still is an effective tool for separating components of high molecular weight and for concentrating components for quantitative or qualitative analysis. Surfactant Producers Sugar esters and poly-oxyalkylins glycol have been routinely purified by Myers molecular distillation. Crude fatty acids and wax derivatives of fatty acids have been distilled in maximum purity concentrations without thermal damage.

Plastic Industry This method benefits plastics manufacturers. Plasticizers such as di-octyl phthalate and di-octyl sebacate are purified with the Myers stills to remove excess reactants of estererification, moisture of condensation, objectionable color, odor, and traces of catalyst. Mineral Oil Production High temperature lubricating oils and greases are commonly distilled from the C/35 - C/100 fractions of petroleum bottoms. Lube oils purified by Myers molecular distillation are more stable and protected from decomposition. Resins and bitumin are separated by the method as well. Oil Reclamation With the rising cost of oils and fluids, recovery of these materials by the Myers molecular distillation process is highly practical, profitable, and environmentally compatible by reducing disposable waste.

INTRODUCTION
Reactive distillation is a process where the chemical reactor is also the still. Separation of the product from the reaction mixture does not need a separate distillation step, which saves energy (for heating) and materials. This technique is especially useful for equilibrium-limited reactions such as esterification and ester hydrolysis reactions.

Reactive distillation can be used with a wide variety of chemistries, including the following:
Acetylation Aldol condensation Alkylation Amination Dehydration Esterification Etherification Hydrolysis Isomerization Oligomerization

PROBLEM STATEMENT
To study a proposed method of production of methyl acetate. The acetic acid is to be reacted with methanol in a catalyst filled semi batch reactor.

To simulate the reaction and see if reactive distillation is a better option than without.

RECYCLE DISTILLATION COLUMN EXTRACTIVE

MeOH

CONDENSER

STRIPPING COLUMN

MeOH
REACTIVE

MeAc HAc
REBOILER H 2O HAc

SIMPLIFIED FLOWDIAGRAM OF PRODUCTION OF METHYL ACETATE

Y 300

CHAc CMeAc CMeOH CH2O

M O L E

TIME

n-butyl acetate
C4H9OH + CH3COOH CH3COOC4H9 + H2O Market price (India): Rs.54/kg Global demand: 600,000 tpa (growth: 2-3%pa) Indian producers: Laxmi Organics, VAM Organics, RK Chemicals, Sterling Solvents etc. International producers: BASF, Celanese, DOW, Eastman Chemicals etc.

Literature survey and process selection

Conventional process
homogeneously catalyzed (H2SO4) problems of corrosion effluent treatment (tin octoate) vapor phase

Heterogeneous catalysis Catalyst selection

ion-exchange resin zeolites HPAs

Reactive distillation

BA

Reaction & Distillation Process

Mixer / Heater Recycle Stream Condensor Distillation Column

AA

Waste Stream Reflux Drum

Reactor

Product Cooler Reboiler Product Stream

Reactive Distillation Column Process

HAc Condensor Effluent Stream Decanter

BuOH

RD Column Reboiler

Product Cooler Product Stream

ADVANTAGES:
Increased speed and improved efficiency. Lower costs reduced equipment use, energy use and handling. Less waste and fewer byproducts. Improved product quality reducing opportunity for degradation because of less heat exposure.

DIFFICULTIES:
The performance of the reactive column is not optimal when equated to a chemical reactor and a distillation column seperately. It is not feasible to use a reactive distillation column when the optimum process parameters (temp,pressure etc) differ too much.

Thank you!