Azeotropic distillation, recycling

In the first class, azeotropic distillation, the extraneous mass-separating agent is relatively volatile and is known as an entrainer. This entrainer forms either a low-boiling binary azeotrope with one of the keys or, more often, a ternary azeotrope containing both keys. The latter kind of operation is feasible only if condensation of the overhead vapor results in two liquid phases, one of which contains the bulk of one of the key components and the other contains the bulk of the entrainer. A t3q)ical scheme is shown in Fig. 3.10. The mixture (A -I- B) is fed to the column, and relatively pure A is taken from the column bottoms. A ternary azeotrope distilled overhead is condensed and separated into two liquid layers in the decanter. One layer contains a mixture of A -I- entrainer which is returned as reflux. The other layer contains relatively pure B. If the B layer contains a significant amount of entrainer, then this layer may need to be fed to an additional column to separate and recycle the entrainer and produce pure B. 

Wastewater leaves the process from the bottom of the second column and the decanter of the azeotropic distillation column. Although both these streams are essentially pure water, they will nevertheless contain small quantities of organics and must be treated before final discharge. This treatment can be avoided altogether by recycling the wastewater to the reactor inlet to substitute part of the freshwater feed (see Fig. 10.36). 

Another process employs a pH maintained at 4—7 and a catalyst that combines a divalent metal cation and an acid. Water is removed continuously by azeotropic distillation and xylene is recycled. The low water content increases the reaction rate. The dibenzyl ether groups are decomposed by the acid the yield of 2,2 -methylene can be as high as 97% (34). 

Generally more favorable for maximum boiling azeotrope because the recycles between columns are bottoms streams, pure products are distillates recycle not as energy-intensive, products distilled once. 

With reversible reactions, recycling is warranted when improvement in conversion can be realized by removing some of the product in a separator and returning only unconverted material. In some CSTR operations, the product is removed continuously by extraction or azeotropic distillation. The gasoline addi-... 

The first three of these are solely X T.E-based approaches, involving a series of simple distillation operations and recycles. The final approach also relies on distillation (X T.E), but also exploits another physical phenomena, liqnid-hqnid phase formation (phase splitting), to assist in entrainer recovery. This approach is the most powerful and versatile. Examples of industrial uses of azeotropic distillation grouped by method are given in Table 13-18. 

The choice of the appropriate azeotropic distillation method and the resulting flowsheet for the separation of a particular mixture are strong functions of the separation objective. For example, it may be desirable to recover all constituents of the original feed mixture as pure components, or only some as pure components and some as azeotropic mixtures suitable for recycle. Not every objective may be obtainable by azeotropic distillation for a given mixture and portfolio of candidate entrainers. 

Exploitation of boundaiy curvature for breaking azeotropes is veiy similar to exploiting pressure sensitivity from a mass-balance point of view, and suffers from the same disadvantages. Separation schemes have large recycle flows, and in the case of minimum-boiling azeotropes, the recycle streams are distillates. However, in the case of maximum-boihng azeotropes, these recycles are underflows and... 

Consider azeotropic distillation to dehydrate ethanol with benzene. Initial steady-state conditions are as shown in Fig. 13-108. The overhead vapor is condensed and cooled to 298 K to form two hquid phases that are separated in the decanter. The organic-rich phase is returned to the top tray as reflux together with a portion of the water-rich phase and makeup benzene. The other portion of the water-rich phase is sent to a stripper to recover organic compounds. Ordinarily, vapor from that stripper is condensed and recycled to the decanter, but that coupling is ignored here. 

If the system forms azeotropes, then the azeotropic mixtures can be separated by exploiting the change in azeotropic composition with pressure, or the introduction of an entrainer or membrane to change the relative volatility in a favorable way. If an entrainer is used, then efficient recycle of the entrainer material is necessary for an acceptable design. In some cases, the formation of two liquid phases can be exploited in heterogeneous azeotropic distillation. 

With reversible reactions, sufficient improvement in conversion sometimes can be realized from removing the product to warrant a recycle operation. This can be done by sending the product to a separator and returning only unconverted material. Some systems, moreover, lend themselves to continuous removal of product in equipment integrated with the reactor. Extraction is thus employed in problem P4.06.13 and azeotropic distillation in problems P4.06.14 and P4.06.15. The gasoline additive, methyl-tert-butyl ether, is made in a distillation column where reaction and simultaneous separation take place. 

Batch Stirred Tank H2S04/Oleum Aromatic Sulfonation Processes. Low molecular weight aromatic hydrocarbons, such as benzene, toluene, xylene, and cumene, are sulfonated using molar quantities of 98—100% H2S04 in stirred glass-lined reactors. A condenser and Dean-Stark-type separator trap are installed on the reactor to provide for the azeotropic distillation and condensation of aromatic and water from the reaction, for removal of water and for recycling aromatic. Sulfone by-product is removed from the neutralized sulfonate by extraction/washing with aromatic which is recycled. 

Most of the energy is consumed in the distillation section, namely for VAM recovery and purification. The reboiler duty for the azeotropic distillation of VAM is particularly high, of about 30 MW. It can be observed that this is due to the large recycle of VAM necessary to carry out the water formed by reaction (3 mole VAM per mol water). Thus, any measure is welcome that can reduce the water content in the crude VAM/acetic acid mixture. Figure 10.8 shows an ingenious method known as gas dehydration [1]. The reactor outlet, cooled up to the dew point,... 

ETBE is recovered as the bottoms product of the distillation unit. The ethanol-rich C4 distillate is sent to the ethanol recovery section. Water is used to extract excess ethanol and recycle it back to process. At the top of the ethanol/water separation column, an ethanol/water azeotrope is recycled to the reactor section. The isobutene-depleted C4 stream may be sent to a raffinate stripper or to a molsieve-based unit to remove oxygenates such as DEE, ETBE, ethanol and tert-butanol. 

Step 1. For this process we must be able to set the production rate of vinyl acetate while minimizing yield losses to carbon dioxide. During the lifetime of the catalyst charge, catalyst activity decreases and the control system must operate under these different conditions. To maintain safe operating conditions, the oxygen concentration in the gas loop must remain outside the explosivity region for ethylene. The azeotropic distillation column must produce an overhead product with essentially no acetic acid and a bottoms product with no vinyl acetate. The absorber must recover essentially all of the vinyl acetate, water, and acetic acid from the gas recycle loop to prevent yield losses in the CCf removal system and purge,... 

Step 5. The azeotropic distillation column does not produce the final salable vinyl acetate product. Its primary role is to recover and recycle unreacted acetic acid and to remove from the process all of the vinyl acetate and water produced. So we want little acetic acid in the overhead because this represents a yield loss. Also, the bottoms stream should contain no vinyl acetate since it polymerizes and fouls the heat-exchange equipment at the elevated temperatures of the column base and the vaporizer. Hence we have two control objectives base vinyl acetate and top acetic acid compositions. And we have two manipula-... 

To provide an illustration, the flow sheet of the IFP process shown in Fig. 3.12 comprises two possible variants. The simpler corresponds to the direct use of the etherified solution in the gasoline pool, without separating e excess methanol contained. Operations are conducted with two reactors in series the first with an upflow stream and expanded bed with recycle of part of the previously cooled effluent for better control of the temperature rise, and the second with a downflow stream and a fixed bed. The more complex involves the recovery of excess methanol, first by azeotropic distillation in a depentanizer with part of the unconverted hydrocarbons, and then by water washing of this raffinate. The hydrocarbon phase is added to the bottom of the depentanizer. The water/methanol mixture is distilled to recover and recycle the alcohol to the etherification staee. 

If n-pentane is selected as the entrainer for an azeotropic distillation scheme, an ethanol product containing less water than that obtained in the extractive distillation method is easily obtained with entrainer-etha-nol ratios of 2.S-3.5, mole basis (10). For a ratio of 3.214, the water content of the ethanol is less than 3 ppm. Only 18 equilibrium trays are required in a column of less than 5 feet diameter. The heat loads in millions Btu/hour are about 10.7 for the reboiler and 11.3 for the condenser. A stripper is used to recover n-pentane and ethanol from the aqueous phase. The recovered n-pentane and ethanol can be recycled either to the feed or to the reflux stream of the azeotropic distillation column. 

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