Current efficiency membrane

Current Efficiency. Current efficiency for caustic production in diaphragm and membrane cells can be estimated from collection of a known amount of caustic over a period of time and from a knowledge of the number of coulombs of electricity passed during that time period. An alternative method involves analysis of the gases evolved during electrolysis and determining the anolyte composition. Material balance considerations (7) show the expression for the caustic efficiency for membrane cells to be... 

Data, for a 32% caustic concentration at 90°C and a current efficiency of 96.0%, obtained in laboratory cells using a DSA anode and an activated cathode, where the membrane is against the anode at a 3-mm gap. 

The anode and cathode chambers are separated by a cation-permeable fluoropolymer-based membrane (see Membrane technology). Platinum-electroplated high surface area electrodes sold under the trade name of TySAR (Olin) (85,86) were used as the anode the cathode was formed from a two-layer HasteUoy (Cabot Corp.) C-22-mesh stmcture having a fine outer 60-mesh stmcture supported on a coarse inner mesh layer welded to a backplate. The cell voltage was 3.3 V at 8 kA/m, resulting ia a 40% current efficiency. The steady-state perchloric acid concentration was about 21% by weight. 

For a profitable electrochemical process some general factors for success might be Hsted as high product yield and selectivity current efficiency >50%, electrolysis energy <8 kWh/kg product electrode, and membrane ia divided cells, lifetime >1000 hours simple recycle of electrolyte having >10% concentration of product simple isolation of end product and the product should be a key material and/or the company should be comfortable with the electroorganic method. 

A.sahi Chemical EHD Processes. In the late 1960s, Asahi Chemical Industries in Japan developed an alternative electrolyte system for the electroreductive coupling of acrylonitrile. The catholyte in the Asahi divided cell process consisted of an emulsion of acrylonitrile and electrolysis products in a 10% aqueous solution of tetraethyl ammonium sulfate. The concentration of acrylonitrile in the aqueous phase for the original Monsanto process was 15—20 wt %, but the Asahi process uses only about 2 wt %. Asahi claims simpler separation and purification of the adiponitrile from the catholyte. A cation-exchange membrane is employed with dilute sulfuric acid in the anode compartment. The cathode is lead containing 6% antimony, and the anode is the same alloy but also contains 0.7% silver (45). The current efficiency is of 88—89%, with an adiponitrile selectivity of 91%. This process, started by Asahi in 1971, at Nobeoka City, Japan, is also operated by the RhcJ)ne Poulenc subsidiary, Rhodia, in Bra2il under Hcense from Asahi. 

Commercially available membranes are usually reinforced with woven, synthetic fabrics to improve the mechanical properties. Several hundred thousand square meters of IX membranes are now produced aimuaHy, and the mechanical and electrochemical properties are varied by the manufacturers to suit the proposed appHcations. The electrochemical properties of most importance for ED are (/) the electrical resistance per unit area of membrane (2) the ion transport number, related to current efficiency (2) the electrical water transport, related to process efficiency and (4) the back-diffusion, also related to process efficiency. 

The ion transport number is defined as the fraction of current carried through the membrane by counterions. If the concentration of fixed charges in the membrane is high compared to the concentration of the ambient solution, then the mobile ions in the IX membrane are mosdy counterions, co-ions are effectively excluded, and the ion transport number then approaches 1. Commercial membranes have ion transport numbers in dilute solutions of ca 0.85—0.95. The relationship between ion transport number and current efficiency is shown in Figure 3 where is the fraction of current carried by the counterions (anions) through the AX membrane and is the fraction of current carried by the counterions (cations) through the CX membrane. The remainder of the current (1 — in the case of the AX membranes and (1 — in the case of the CX membranes is carried by co-ions and... 

Major differences between ED and other processes are, first, the solute is transferred across the membrane against water in the other technologies discussed below, whereas only ionic species are removed by ED. As noted, two different membranes (anionic and cationic) are employed. Current consumption depends primarily on the TDS concentration. You should look at this very closely when comparing the operating cost benefits and tradeoffs of this technology to other options. Current efficiency can be calculated from the following formula ... 

A number of metal porphyrins have been examined as electrocatalysts for H20 reduction to H2. Cobalt complexes of water soluble masri-tetrakis(7V-methylpyridinium-4-yl)porphyrin chloride, meso-tetrakis(4-pyridyl)porphyrin, and mam-tetrakis(A,A,A-trimethylamlinium-4-yl)porphyrin chloride have been shown to catalyze H2 production via controlled potential electrolysis at relatively low overpotential (—0.95 V vs. SCE at Hg pool in 0.1 M in fluoroacetic acid), with nearly 100% current efficiency.12 Since the electrode kinetics appeared to be dominated by porphyrin adsorption at the electrode surface, H2-evolution catalysts have been examined at Co-porphyrin films on electrode surfaces.13,14 These catalytic systems appeared to be limited by slow electron transfer or poor stability.13 However, CoTPP incorporated into a Nafion membrane coated on a Pt electrode shows high activity for H2 production, and the catalysis takes place at the theoretical potential of H+/H2.14... 

Electrolysis of water contained within a perfluorinated sulphonic acid membrane (Membrel water electrolysis) developed by ABB [133,201-205] and Sasakura [200]. Current efficiencies reach 14-15% at current densities of 10000 A m2 and more. The cells are generally immersed directly in the water so that ozone is introduced directly into the water to be treated, Fig. 18. 

The current efficiency for pure Cr(III)-sulfuric acid is in the range of 90%. Organics, present in the industrial liquors, especially higher dicarboxylic acids, interfere, thus necessitating the use of divided cells. The scheme of the membrane cell used is shown in Fig. 29. 

This type of cell is limited by the performance of the anion-exchange membrane. The membrane can tolerate only a limited concentration of acid in the anolyte before backdiffusion of protons through the anion membrane becomes rather significant, causing a decrease in the cell s current efficiency, and acid gets into the salt stream. Unconverted salt in the product solutions can be eliminated by the use of the three compartment device, but this option substantially adds to the capital costs and operating complexity of the plant. 

In the brine system, sulphate ions are mixed with raw salt. These ions deposit on membranes in the electrolysis process and cause loss of current efficiency [3, 4]. 

In the brine electrolysis system, silica is also contained in raw salt. Silica will precipitate on to membranes in the presence of calcium, strontium, aluminium and iodine resulting in the loss of current efficiency [8-10]. Silica can also be removed in a column filled with ion-exchange resin containing zirconium hydroxide, just like the iodide ion. 

As indicated in Fig. 17.2, the membrane process has long been characterised by substantial reductions in electric power consumption, through constant advances in membrane, electrolyser and electrode technologies. In the early years of its commercial establishment, some 25 years ago, it yielded a caustic soda concentration of 20% or lower, with less than 90% current efficiency. Today, the caustic soda concentration is 33%, the current efficiency is 97%, and the ohmic drop of the membrane has been lowered by approximately 1.0 V. During the same period, advances in electrolyser design have improved the uniformity of intracell electrolyte concentra-... 

Asahi s investigations showed that a Na+ concentration of 1.1 N was necessary in compartment II to maintain a current efficiency of 96% in the carboxylic membrane during operation with 3.5 N brine in compartment I and 32% caustic soda in compartment III. The Na+ concentration in compartment II was generally far lower than that in compartment I, and clearly indicates the tendency for depression of the Na+ concentration at the interface of the sulphonic and carboxylic layers in the normal... 

The limiting current density may be defined as the current density at which the depression of the Na+ concentration at the interface of the membrane s sulphonic and carboxylic layers results in an abrupt rise in cell voltage and drop in current efficiency. 

The circulation conditions obtained in the small laboratory cell cannot be attained in a full-scale cell. The effects of Na+ diffusion to the membrane and non-uniformity in its intracell concentration cannot be entirely eliminated, and a greater decrease in current efficiency will tend to occur at high current densities. 

For high current efficiency at high current densities, it is essential that the electrolyser provides efficient mass transfer to the membrane surface. The most important... 

The ML32NCH electrolyser equipped with the Aciplex F-4401 membrane has been in commercial operation at 6 kA m-2 for approximately one year at Asahi Chemical s chlor-alkali plant. As shown in Figs 17.16 and 17.17, the electrolyser has achieved a cell voltage of 3.17 V and a current efficiency of 96%, while operating at 6kA m-2. This operation is continuing the present plan is to investigate the performance of the ML32NCH at a current density of 8 kA m-2. 

The F-8934 seems attractive to any commercial plants operational in the range of 3-4 kA m-2. This membrane has already been supplied to such end-users. As a result, they have obtained a 30-40 kWh tonne-1 reduction in power consumption compared to the power consumption of the F-893 membrane. Figure 19.11 shows the current efficiency plots from two AZEC plants in the current density range just touched on. 

Several test runs have been carried out using 1.5 dm2 laboratory cells with the F-8934 at 8kA m-2. The current efficiency at 8kA m-2 was about 1% lower than that at 5kAnT2, and no further decline was observed. F-8934 has also had a similar evaluation result in full-scale pilot cells at 8 kA m-2. AGC has been obtaining slightly lower current efficiencies than its desired target of 97% at the beginning of the membrane lifetime. This has led AGC to ensure that the other stepped-up design concept should be applied to the membrane for 8 kA m-2 operation. 

AGC has modified the carboxylic polymer and prepared one experimental membrane. This membrane is similar to F-8934 in the arrangement of the sub-structure, and it is almost the same as the F-8934 in both mechanical strength and ohmic resistance. Figure 19.13 illustrates the current efficiency trend of this experimental membrane in a laboratory test run at 8 kA irf2, compared with the F-8934 tested under the same conditions. The absolute value of the membrane s current efficiency is approximately 97.5%. No decline in current efficiency has been observed. AGC is now evaluating the stability and is optimising the carboxylic polymer feature and fabrication process for commercial production of this type of membrane. 

Fig. 19.13 Plot of current efficiency stability at 8 kA nrf2 operation in a laboratory cell using the F-8934 membrane.

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