Cell Caustic Systems

Membrane-cell caustic systems that require the dilution and recirculation of product to the cells are the most complex. Some operate with the direct addition of water, but this section is based on the more comprehensive case. 

Many caustic evaporator suppliers have schemes to separate the two types of caustic whilst making 50% solutions of both. A particularly good option is to install an extra first-effect evaporator for the membrane caustic soda and split the steam usage between the diaphragm first-effect and the new membrane first-effect, then recombine the steam again to feed to the rest of the diaphragm cell evaporator system. 

Evaporation of membrane-cell caustic is simple concentration, and there is no need to handle crystallized salt. With the smaller steam demand and the higher BPRs in the system, fewer effects can be justified, and Section 9.3.3.1 points out that the usual number is two or three. Very small plants may have only one effect. 

This section describes the controls for a triple-effect membrane-cell caustic evaporator. Section 9.3.3.1 explains some of the reasoning behind the selection of the number of effects and the progression of flow of caustic through the evaporators. To illustrate the control systems here, we assume backward feed of the caustic. 

Water, after the preliminary treatment methods of Section 12.4.1, can be called purified. Here, we use the term to refer to the higher levels of purification in Table 12.1 or to those processes which remove dissolved contaminants. In the chlor-alkali process, the major uses of purified water are dilution of catholyte, processing of membrane-cell caustic liquor, preparation of ion-exchange system regenerants, manufacture of hydrochloric acid, acidification of brine, and, sometimes, dissolving of salt. It also serves as utility and seal water in the membrane preparation area and in certain parts of the process. 

Chlorate corrosion in anhydrous caustic evaporator systems is prevented by decomposing chlorates with additions of sucrose or sugar [49]. The amount of sugar added with mercury-cell caustic is generally around 0.24 to 0.36 kg per dry ton of NaOH. 

In selected markets, such as the rayon industry, low salt levels are required (typically 100 ppm). Mercury cell and membrane cell caustic are ideally suited for these markets. Diaphragm cell caustic is purified further in a few installations, but primarily to remove NaC103, which is corrosive to the equipment used to manufacture anhydrous caustic. Chlorate alone may be removed by reaction with a reducing agent, such as sugar, which is injected into the hot caustic feed to the anhydrous concentrator system. This has the disadvantage of increasing both the salt and the carbonate levels in the caustic. 

To remove chlorate and other salts, the 50 percent diaphragm cell caustic may be extracted with liquid ammonia in a pressurized system. The ammonia fraction then is processed through a stripper to remove and recycle the ammonia. The alkaline stripper bottoms are useful in neutralizing acidic waste streams. The purified caustic is evaporated further, and then fed to an anhydrous concentrator, typically an Inconel falling film evaporator, heated with molten salt. The anhydrous caustic, containing at least 97.5 percent NaOH, is marketed as one solid mass in drums, as flake caustic, or more desirably as beads or prills. The last are marketed in bulk or bags. 

The reaction mixture is filtered. The soHds containing K MnO are leached, filtered, and the filtrate composition adjusted for electrolysis. The soHds are gangue. The Cams Chemical Co. electrolyzes a solution containing 120—150 g/L KOH and 50—60 g/L K MnO. The cells are bipolar (68). The anode side is monel and the cathode mild steel. The cathode consists of small protmsions from the bipolar unit. The base of the cathode is coated with a corrosion-resistant plastic such that the ratio of active cathode area to anode area is about 1 to 140. Cells operate at 1.2—1.4 kA. Anode and cathode current densities are about 85—100 A/m and 13—15 kA/m, respectively. The small cathode areas and large anode areas are used to minimize the reduction of permanganate at the cathode (69). Potassium permanganate is continuously crystallized from cell Hquors. The caustic mother Hquors are evaporated and returned to the cell feed preparation system. 

There have been a number of cell designs tested for this reaction. Undivided cells using sodium bromide electrolyte have been tried (see, for example. Ref. 29). These have had electrode shapes for in-ceU propylene absorption into the electrolyte. The chief advantages of the electrochemical route to propylene oxide are elimination of the need for chlorine and lime, as well as avoidance of calcium chloride disposal (see Calcium compounds, calcium CHLORIDE Lime and limestone). An indirect electrochemical approach meeting these same objectives employs the chlorine produced at the anode of a membrane cell for preparing the propylene chlorohydrin external to the electrolysis system. The caustic made at the cathode is used to convert the chlorohydrin to propylene oxide, reforming a NaCl solution which is recycled. Attractive economics are claimed for this combined chlor-alkali electrolysis and propylene oxide manufacture (135). 

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