Distillation Rectification

Figure 2 illustrates the three-step MIBK process employed by Hibernia Scholven (83). This process is designed to permit the intermediate recovery of refined diacetone alcohol and mesityl oxide. In the first step acetone and dilute sodium hydroxide are fed continuously to a reactor at low temperature and with a reactor residence time of approximately one hour. The product is then stabilized with phosphoric acid and stripped of unreacted acetone to yield a cmde diacetone alcohol stream. More phosphoric acid is then added, and the diacetone alcohol dehydrated to mesityl oxide in a distillation column. Mesityl oxide is recovered overhead in this column and fed to a further distillation column where residual acetone is removed and recycled to yield a tails stream containing 98—99% mesityl oxide. The mesityl oxide is then hydrogenated to MIBK in a reactive distillation conducted at atmospheric pressure and 110°C. Simultaneous hydrogenation and rectification are achieved in a column fitted with a palladium catalyst bed, and yields of mesityl oxide to MIBK exceeding 96% are obtained. 

Physicochemical relationships are such that soHd potassium chloride can be converted to soHd potassium nitrate ia a one-stage operation of the simplest kiad. The conversion takes place ia a stirred reaction system (Fig. 10). The overall separation is analogous to a rectification and stripping operation ia a distillation process. 

Although all four tocopherols have been synthesized as their all-rac forms, the commercially significant form of tocopherol is i7//-n7i a-tocopheryl acetate. The commercial processes ia use are based on the work reported by several groups ia 1938 (15—17). These processes utilize a Friedel-Crafts-type condensation of 2,3,5-trimethylhydroquinone with either phytol (16), a phytyl haUde (7,16,17), or phytadiene (7). The principal synthesis (Fig. 3) ia current commercial use iavolves condensation of 2,3,5-trimethylhydroquiQone (13) with synthetic isophytol (14) ia an iaert solvent, such as benzene or hexane, with an acid catalyst, such as ziac chloride, boron trifluoride, or orthoboric acid/oxaUc acid (7,8,18) to give the all-rac-acetate ester (15b) by reaction with acetic anhydride. Purification of tocopheryl acetate is readily accompHshed by high vacuum molecular distillation and rectification (<1 mm Hg) to achieve the required USP standard. 

If a waste contains a mixture of volatile components that have similar vapor pressures, it is more difficult to separate these components and continuous fractional distillation is required. In this type of distillation unit (Fig. 4), a packed tower or tray column is used. Steam is introduced at the bottom of the column while the waste stream is introduced above and flows downward, countercurrent to the steam. As the steam vaporizes the volatile components and rises, it passes through a rectification section above the waste feed. In this section, vapors that have been condensed from the process are refluxed to the column, contacting the rising vapors and enriching them with the more volatile components. The vapors are then collected and condensed. Organics in the condensate may be separated from the aqueous stream after which the aqueous stream can be recycled to the stripper. 

Distillers employ a somewhat unique process to make various products and have tailored approaches to control and reduce ethyl carbamate to their own particular process. Some of the methods used are the use of copper packing in the rectifying section of stills, increased frequency of cleaning stills and other equipment, and using a cool-down period in the cleaning procedure. Increased rectification also reduces ethyl carbamate. Keeping the system clean is critical to minimising ethyl carbamate. 

The carbon monoxide-rich, Hquid condensate from the primary separator is expanded and exchanged against the incoming feed and is then sent to a distillation column where the carbon monoxide is purified. The bottoms Hquor from the methane wash column is expanded, heat-exchanged, and sent to the bottom section of the distillation column for methane rectification and carbon monoxide recovery. The methane bottom stream is recompressed and recycled to the top of the wash column after subcooling. A sidestream of methane is withdrawn to avoid a buildup of impurities in the system. 

Although batch distillation is covered in a subsequent separate section, it is appropriate to consider the application of RCM and DRD to batch distulation at this time. With a conventional batch-rectification column, a charge of starting material is heated and fractionated, with a vapor product removed continuously. The composition of the vapor prodiic t changes continuously and at times drastically as the lighter component(s) are exhausted from the stiU. Between points of drastic change in the vapor composition, a cut is often made. Successive cuts can be removed until the still is nearly diy. The sequence, number, and limiting composition of each cut is dependent on the form of... 

The term still is applied only to the vessel in which liquids are boiled during distillation, but the term is sometimes applied to the entire apparatus, including the fractionating column, the condenser, and the receiver in which the distillate is collected. If a water and alcohol distillate is returned from the condenser and made to drip down through a long column onto a series of plates, and if the vapor, as it rises to the condenser, is made to bubble through this liquid at each plate, the vapor and liquid will interact so that some of the water in the vapor condenses and some of the alcohol in the liquid vaporizes. The interaction at each plate is equivalent to a redistillation. This process is referred to by several names in the industry namely rectification, fractionation, or fractional distillation. 

Distillation is probably Ihe most widely used separation (mass transfer) process in the chemical and allied industries. Its applications range from the rectification of alcohol, which has been practiced since antiquity, lo the fractionation of crude oil. The separation of liquid mixtures by distillation is based on differences in volatility between the components. The greater the... 

For a constant reflux ratio, the value can be almost any ratio however, this ratio affects the number of theoretical plates and, consequently, actual trays installed in the rectification section to achieve the desired separation. Control of batch distillation is examined in Reference 134. 

This mode of batch rectification requires the continuous adjustment of the reflux to the colunrn in order to achieve a steady overhead distillate composition. Starting with a kettle obviously rich in the more volatile component, a relatively low reflux ratio will be required to achieve the specified overhead distillate composition. With time, the reflux ratio must be continuously increased to maintain a fixed overhead composition. Ultimately, a practical maximum reflux is reached and the operation normally would be stopped to avoid distillate contamination. 

Distillation calculations result in a reflux ratio L/D = 0.8, with 4 theoretical trays for rectification and 4 theoretical trays for stripping, or a total of 8 trays. The design heat balance (neglecting heat losses) is as follows ... 

Batch with Constant Reflux Ratio, 48 Batch with Variable Reflux Rate Rectification, 50 Example 8-14 Batch Distillation, Constant Reflux Following the Procedure of Block, 51 Example 8-15 Vapor Boil-up Rate for Fixed Trays, 53 Example 8-16 Binary Batch Differential Distillation, 54 Example 8-17 Multicomponent Batch Distillation, 55 Steam Distillation, 57 Example 8-18 Multicomponent Steam Flash, 59 Example 8-18 Continuous Steam Flash Separation Process — Separation of Non-Volatile Component from Organics, 61 Example 8-20 Open Steam Stripping of Heavy Absorber Rich Oil of Light Hydrocarbon Content, 62 Distillation with Heat Balance,... 

Thermal operations such as distillation, decomposition, transformation, and rectification often cause thermal degradation. Furthermore, with these processes quantitative catalyst recovery is generally not possible, which results in loss of productivity. 

It is doubtful if any design is entirely novel. The antecedence of most designs can usually be easily traced. The first motor cars were clearly horse-drawn carriages without the horse and the development of the design of the modern car can be traced step by step from these early prototypes. In the chemical industry, modem distillation processes have developed from the ancient stills used for rectification of spirits and the packed columns used for gas absorption have developed from primitive, brushwood-packed towers. So, it is not often that a process designer is faced with the task of producing a design for a completely novel process or piece of equipment. 

---