Sodium Hydroxide Production from Electrolytic Cell with Ceramic Membrane

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Europaisches Patentamt European Patent Office

OffOffice europeen des brevets © Publication number : 0 559 400 A2

12) EUROPEAN PATENT APPLICATION

@ Priority : 28.02.92 US 843509 @ Inventor : Joshi, Ashok 3377 South 2410 East Salt Lake City, UT 84105 (US) @ Date of publication of application : Inventor : Liu, Meilin 08.09.93 Bulletin 93/36 1346 East 4170 South Salt Lake City, UT 84124 (US) Inventor : Bjorseth, Alf @ Designated Contracting States : Staverbakken 14 AT BE CH DE DK ES FR GB GR IE IT LI NL PT N-1300 Sandvika (NO) SE Inventor : Renberg, Lars c/o Storal Swedish Match, PO Box 16100 S-103 22 Stockholm (SE) © Applicant : CERAMATEC INC. 2425 South 900 West _ Salt Lake City, Utah 84119 (US) © Representative : Rees, David Christopher et al Kilburn & Strode 30 John Street London WC1N 2DD (GB)

(57) An electrolytic cell (10) for producing caustic soda from sodium salts through a thin membrane (15) of ceramic or ceramic composite electrolyte. The membrane 15 separates anode and cathode chambers (12,11) and conveniently comprises NASICON.

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LU Jouve, 18, rue Saint-Denis, 75001 PARIS EP 0 559 400 A2

The present invention relates to the production of caustic, and concurrently, strong acids via electrolysis of a sodium salt in an electrolytic cell. Electrolytic cells employing composite polymeric membranes are currently used to produce caustic solutions. Examples of such electrolytic cells are disclosed in an article entitled "Use Electrodialytic Membranes 5 for Waste Recovery", Nicholas Basta, Chemical Engineering, March 3, 1986 and an article entitled "The Be- haviour of Ion Exchange Membranes in Electrolysis and Electrodialysis of Sodium Sulphate", J. Jorissen and K.H. Simmrock, Journal of Applied Electrochemistry 1991. Such cells have polymeric membranes which are not efficient at higher concentrations of caustic and acid as well as at higher conversion ratios of salt to acid although they are resistant to strongly acidic and basic solutions. The operational life of such polymeric mem- 10 branes is very sensitive to impurity contaminations. For example, such cells are limited generally to caustic production at a maximum concentration of about 20% and to salt to acid conversion of about 50%. Higher caustic concentrations or salt to acid conversions severely limit the efficiency of the process. For instance, at a fifty percent conversion of salt to acid, the current or energy efficiency is only about sixty percent. According to one aspect of the invention, there is provided an electrolytic cell for the production sodium 15 hydroxide from a sodium salt derived from a strong acid comprising: an anode chamber; a cathode chamber; an acid resistant, electronically conductive anode in the anode chamber; an alkali resistant, electronically conductive cathode in the cathode chamber; and a membrane separating the anode chamber from the cathode chamber; characterised in that the membrane is solid, impervious, sodium ion conducting, electronically insulating, and resistant to acid and alkali. 20 The invention also extends to an electrolytic process for producing concentrated sodium hydroxide solution from an aqueous sodium salt solution having anions derived from a strong acid, which comprises: introducing electrons into an aqueous catholyte solution containing sodium hydroxide; removing electrons from an aqueous anolyte solution containing sodium cations and anions producing oxygen gas in the anolyte; producing hydrogen gas in the catholyte; and producing an acid from the anions in the anolyte; from an acid; characterised by 25 conducting sodium ions through a solid integral, monolithic anolyte/catholyte separator containing mobile sodium ions in its lattice to produce a concentrated solution of sodium hydroxide in the catholyte solution. The electrochemical cell of the present invention is particularly useful for producing, through electrolysis, a concentrated caustic (NaOH) solution from a sodium salt solution, preferably concentrated, in which the salt has an anion derived from a strong acid, especially sulphuric acid. The cell has an anolyte chamber, a catholyte 30 chamber, a pair of electrodes and a cation-conducting ceramic membrane, such as NASICON, separating the anolyte chamber from the catholyte chamber. Contrary to polymeric membranes, electrochemical cells having a ceramic membrane display high current efficiency such that at a one to one, proton to sodium ion, conversion rate (fifty percent), the current efficiency is about 94% or greater. At about 80% salt to acid conversion, the current efficiency is about 86%; polymers 35 drop to about 20% at this level. The cell of this invention operates at a relatively low temperature, generally less than 100°C, to produce a concentrated caustic solution in the catholyte chamber and a relatively concentrated acid, for example, sulphuric acid, in the anolyte chamber. The cell can operate either continuously or batchwise. Hydrogen gas is produced in the catholyte chamber while oxygen is produced in the anolyte chamber through the electrolysis 40 of the water present in each chamber. The cell may also be used to produce caustic and chlorine from NaCI solutions. The cell is unique in its ability to employ a unitary ceramic or a composite ceramic membrane which is durable in a concentrated caustic solution and a strong acid. The ability of the cell to produce caustic in concentrations up to about 50% NaOH is very advantageous. Conventional polymeric membrane electrolytic cells 45 are limited to caustic concentrations of about 20% NaOH, and so requires considerable evaporation to achieve concentrated caustic or dry, solid NaOH. Evaporation is an energy-inefficient operation. In addition, unlike polymeric membranes which can be damaged by trace amounts of alkaline earth metal cations (Ca++, Mg++), ceramic membranes are relatively less affected by impurity contaminants. Accordingly, for the systems based on polymeric membranes, pretreatment of a feed sodium salt solution to remove con- 50 taminants is an expensive process. The invention may be carried into practice in various ways and some embodiments will now be described by way of example with reference to the accompanying drawing, in which: Figure 1 is a schematic representation of a caustic electrolytic cell having a unitary (monolithic) ceramic membrane; 55 Figure 2 is a schematic representation of a caustic-producing electrolytic cell employing tubular ceramic electrolytes; Figure 3 is an elevation of a thin-film ceramic electrolyte sandwiched between two porous support mem- bers; 2 EP 0 559 400 A2

Figure 4 is a graph showing results from a laboratory cell for NaOH production of the ceramic membrane; Figure 5 is a schematic representation of an electrodialysis cell employing sodium ion-conducting membranes alternating with proton-conducting membranes; Figure 6(a) is a graph illustrating initial impedance spectra for a typical NASICON tube; 5 Figure 6(b) is a graph illustration initial ionic conductivity of the NASICON tube as a function of temperature; Figure 7(a) is a graph illustrating the impedance evolution of NASICON tubular cell; Figure 7(b) is a plot of the tube resistivity determined from the spectra of Figure 7(a); Figure 8 is a graph illustrating typical l-V characteristics of a tubular cell at two testing temperatures; Figure 9 is a plot of cell performance as a function of increasing cell temperature; 10 Figure 10 is a plot of cell performance as a function of NaOH concentration in the catholyte; Figure 11 is a plot illustrating the effectiveness of certain electrode materials; Figure 12 is a graph illustrating the characteristics of several electrolytic cells having NASICON tubes of differing conductivity; Figure 13 is a schematic section through a composite ceramic-polymer electrolyte; 15 Figure 14 is a schematic section through a polymer-wrapped ceramic tube electrolyte; Figure 15 is a graph illustrating cell performance using sodium chlorate at an operating temperature of 50°C; Figure 16 is a graph illustrating cell performance using sodium chlorate operated at room temperature; Figure 17 is a graph illustrating the effect of salt to acid conversion on current efficiency of polymeric mem- 20 branes; and Figure 18 is a graph illustrating the effect of NaOH and acid concentrations on the current efficiency of polymeric membranes. Figure 1 shows a cell having a corrosion resistant container 10, a catholyte chamber 11, an anolyte chamber 12, an anode 13, preferably porous WC, a cathode 14, preferably porous silver, and a ceramic sodium ion- conducting electrolyte 15. In the cell of Figure 1, the ceramic membrane is a very thin unitary ceramic such 25 as NASICON (Trade Mark), which is structurally supported by the cathode and the anode, each of which is porous. NASICON is a cation-conducting ceramic material having the following composition:- Na2.94Zr1.49P0.8O10.85 While a thin ceramic ion-conductive membrane is very effective and efficient, it is not necessary for either 30 the cathode or anode to contact the electrolyte. Both the catholyte and anolyte are ion-conductive so that from an electrical standpoint the electrodes may be remote from the sodium ion-conductive membrane. In such an event, a thin-film dense ceramic membrane may be deposited on a porous substrate, which does not have to be an electrode. A sodium salt, such as an aqueous solution of sodium sulphate, is charged into the anolyte chamber. A 35 very dilute solution of NaOH is charged into the catholyte chamber. It is desirable to start with an electrolyte solution of some sort in the catholyte chamber since pure water is not a very good electrolyte. An example of an overall electrolytic reaction, using sodium sulphate, is as follows: Equation (1): Na2So4 + 3H20 2NaOH + H2S04 + V2O2 + H2 The half-cell reactions may be summarised as follows: 40 Equation (2): (anode) Na2S04 + H20 -» 2Na+ + H2S04 + 2e + 1/202t Equation (3): (cathode) 2Na+ + 2H20 + 2e -» 2NaoH + H2t The above-identified reactions are electrolytic reactions, i.e. those which take place under an induced current wherein electrons are introduced or are removed to cause the reactions. The reactions proceed only so long as a current is applied to the cell. 45 In contrast to the electrolytic reactions occurring in electrolysis cells, galvanic reactions may occur when an applied potential to the cell is removed, which tends to reduce the efficiency of the electrolysis cell. Galvanic reactions are the source of electricity produced by storage batteries. The overall galvanic reaction for the cell is as follows: 2NaOH + H2S04 -» 1/202 + H2 + Na2S04 + H20 so The galvanic reaction is the reverse of the preferred electrolytic reaction. It is preferred that only electrolytic reactions occur in the cell and that galvanic reactions should be elim- inated or, at least, greatly minimised. The electrolytic membranes which are preferred in the present invention are those which eliminate or min- imise galvanic reactions and promote only electrolytic reactions and have the following characteristics: 55 (1) High ionic conductivity with minium, preferably negligible, electronic conductivity; (2) High selectivity to preferred ionic species; (3) Physical separation (low porosity of electrolyte) of the anolyte from the catholyte. One of the significant advantages of the present invention is that ceramic electrolytes, especially NASI- 3 EP 0 559 400 A2

CON, are impermeable to both the catholyte and anolyte solution. Adistinct advantage of ceramic electrolytes, such as NASICON, is their low (negligible) electronic conductivity, virtually eliminating any galvanic reactions from occurring when an applied potential or current is removed. Ceramic membranes typically are very selective to a specific ion and hence have a high transference number of the preferred species, implying very low 5 efficiency loss due to electrodialysis or dialysis. Polymeric membranes generally have a low transference number of the preferred species and therefore have a low current efficiency due to electrodialysis. As shown in Figure 1 7, at a one-to-one ratio of protons to ions, a salt to acid conversion rate of 50%, the current efficiency of a pure NAFION (Trade Mark) (polymeric) membrane is about 60%. Under similar conditions, the current efficiency of ceramic membranes is about 94% or greater. 10 Preferred membranes for the present invention are those which have very mobile sodium ions (high ionic conductivity), low electronic conductivity and corrosion resistance. Examples of materials for such ceramic membranes include NASICON, sodium phosphotungstate and soda glasses having high ionic conductivity. Similar glasses of this type have been disclosed by Dow Chemical Co. for use in sodium-sulphur batteries. Such glasses, however, must be resistant to leaching by either strong bases or strong acids. 15 The preferred membrane material is NASICON since it fulfils all the requirements of a good membrane. Membranes of NASICON may be formed by conventional ceramic processing. Such membranes may be in the form of very thin sheets (tape cast) supported by porous ceramic plates, e.g., porous NASICON or alpha alumina, or by porous electrodes, or in the form of thicker sheets (plates) or tubes. A cell 31 employing NASI- CON tubes 32 is illustrated in Figure 2 in which concentrated caustic (sodium hydroxide) is formed in the cath- 20 olyte 35 inside the tubes. Each tube 32 includes a cathode 33 and there is an anode 34 in the Na2S04 + H20 anolyte 36. In Figure 2, the anolyte and catholyte chambers may be reversed. From an energy efficiency standpoint, very thin ceramic membranes are preferred. These have the small- est ohmic resistance and energy loss. Thin sheets of NASICON, for example, may be formed by tape casting. Sheets as thin as about 25 micrometers to 0.5mm may readily be produced. Such thin sheets are preferably 25 supported on or between porous structural supports. Such structural supports may be the electrodes as shown in Figure 1 where the porous silver cathode may supply the necessary support. Alternatively, the structural supports may be porous ceramic sheets or plates as shown in Figure 3 where a NASICON film 36 has a porous ceramic sheet 37, 38 on each side. The porosity of such ceramic supports is preferably quite high so that the liquid solutions on either side of the supports may be in intimate contact with a large area of the electrolytic 30 membrane. Porosity, as a percent of total volume for electrolyte supports, ranges from about 30 to about 90% porosity. Ceramic electrolytes, e.g. NASICON, may be vapour deposited (sputtered or plasma sprayed) onto a porous substrate to form membranes which are very thin, e.g. about 5p.m or even thinner. The porous substrate must have similar thermal expansion and good bonding with the membrane as well as good mechanical 35 strength. If electrode materials are employed as structural supports, then similar characteristics for these must be present. Layered ceramic-polymer composite membranes are also particularly suitable for use as electrolytes in the present invention. Layered ceramic-composite membranes generally comprise ionic-selective polymers layered on a ceramic electrolytic membrane, such as NASICON or beta-alumina. Polymer materials have the 40 disadvantage of having poor selectivity to sodium ions resulting in low current efficiency and low salt to caustic conversion, yet they demonstrate high chemical stability. Therefore, composites of sodium-selective ceramics with chemically stable polymer layers are very suitable for use in the electrolytic cell of the invention. The types of polymer material which may be used in the layered ceramic-composite structure include NA- FION and polyvinyl chloride (PVC). Suitable polymers for use in the composite membrane are those which have 45 high chemical stability, high ionic conductivity, good adhesion to ceramic materials and are insensitive to impurity contamination. Such polymers may be polyelectrolyte perfluorinated sulphonic or carboxylic acid polymers, matrix-based polymers, co-polymers or block-polymers. The electrode materials must be good conductors and must be stable in the media to which they are ex- posed. A particularly suitable electrode material is DSA (dimensionally stable anode) which is comprised of so ruthenium oxide coated titanium (Ru02 ■ Ti). Good anodes can also be formed from nickel, cobalt, nickel tung- state, nickel titanate and the like or from noble metals. Lead, graphite, tungsten carbide and titanium diboride are also useful anode materials. Good cathodes can be formed from metals such as nickel, cobalt, platinum, silver and the like and alloys such as titanium carbide with small amounts (up to about 3%) of nickel, FeAI3, NiAI3 and the like. Graphite is also a good cathode material. 55 The electrochemical cells of the present invention may be operated batchwise or continuously. Continuous operation of a cell involves the continuous introduction of water to the catholyte and the removal of concentrated aqueous caustic solution while a feed salt solution is introduced to the anolyte concurrent with the removal of concentrated sulphuric acid containing some salt. As with any chemical reaction, removal of the re- 4 EP 0 559 400 A2

action products assists the reaction, removal of the reaction products assists reaction proceeding in the desired direction. However, if dilute (unconcentrated) caustic solution is removed from a cell, then expensive energy is consumed in evaporating the caustic solution to achieve concentrated caustic solution or crystalline NaOH. Thus, some balancing is necessary to select the proper concentration of caustic and sulphuric acid to be re- 5 moved from the cell. Batchwise operation involves charging the cell with a feed salt solution as the anolyte, dilute caustic solution as the catholyte and operating the cell at the desired temperature and voltage until a concentrated aqueous caustic solution is obtained. Cells of the instant invention employing NASICON membranes may be operated in caustic solutions of 10 50% by weight concentration and in sulphuric acid up to four molar (approximately 40% by weight) concentration. The invention will now be illustrated in the following Examples.

EXAMPLE 1 15 An electrochemical (electrolysis) cell containing a caustic/acid resistant container of polypropylene (PP) material. The cell has a configuration as illustrated in Figure 1 wherein a thin, approximately 2mm in thickness, impervious NASICON ceramic membrane with an area of about 8 to 9cm2 was sandwiched between a porous tungsten carbide anode and a porous silver cathode. The sandwich type structure was used primarily to provide 20 structural support to the NASICON membrane since the electrodes also operate effectively when remote from the membrane. The porous silver cathode has a porosity of about 50% by volume and a thickness of about 0.5-1 .0mm. The porous tungsten carbide (WC) anode had a porosity of about 30-50% by volume and a thickness of about 0.5-2.0mm. Both electrodes were deposited on a NASICON tube with wall thickness of 1.5mm and diameter 25 of 3/8 inch (9.5mm). The membrane was sealed in the PP container to separate the container into an anolyte compartment and a catholyte compartment. A concentrated solution of sodium sulphate was placed in the anolyte compartment while a very dilute solution of caustic (NaOH) was placed in the catholyte compartment. A voltage of 3 volts was applied while operating the cell at a temperature of 80°C. Acurrent density of about 30 50 mA/cm2 was observed. As the cell operation was continued, the pH of the respective electrolyte compartments was monitored. The pH of the catholyte increased, indicating the continual production of NaOH while the anolyte pH decreased, including the production of sulphuric acid. The operation of the cell was also conducted at various temperatures and voltages. The resulting currents from these operations are illustrated in Figure 4. As can be seen from the data in Figure 4, the current density 35 increased diproprotionally with increases in temperature, i.e. a voltage increase of thee volts resulted in a current increase from about 1 50 mAto over 400 mA. The current density at 3 volts and 80°C was about 50 mA/cm2 while at 2 volts and 80°C the current density was less than 10 mA/cm2, indicating a large increase in current density due to increases in voltage. This indicates that the electrode kinetics at the interfaces between the electrodes and the solution contribute significantly to the total cell impedance. Therefore, better electrode ma- 40 terials can dramatically enhance cell performance. The cell temperature was maintained at a maximum of 80°C since the boiling point of water is 100°C and it is generally desired to operate below the boiling point of the aqueous anolyte and catholyte. Operation at even higher temperatures is desirable from an energy standpoint although corrosion and other problems may exacerbate such operation. Operation at temperatures greater than 100°C requires superatmospheric pres- 45 sures. Achieving higher current densities through a higher operating temperature is only partially successful inasmuch as gases are released during the electrochemical reactions proceeding within the cell. Increased pressure in the anolyte and cathode chambers subdues the reaction proceeding in the desired direction when gas is a reaction product. However, the retardation of the reaction by an increase in pressure may be more than offset by the increases in the electrical efficiencies from the increased conductivity of the electrolytes so and the ion conducting membrane.

EXAMPLE II

Electrolysis Cells 55 For simplicity, tubular electrochemical cells were used in this study. NASICON ceramic tubes were employed as sodium ion conductive membranes. The densities of those tubes typically ranged from 91% to 97% of theoretical density. The outside diameter of the tubes was about 10 mm whereas the wall thickness was in 5 EP 0 559 400 A2

the range of 0.9 to 1.5mm. The length of the tubes was between 40 and 65mm.

(1) Cathode materials.

5 The cathode materials used in this example were nickel and silver metals. Porous silver electrode was applied by brushing a silver slurry on a NASICON tube and subsequent firing at 750°Cfor2 hours. Nickel electrode was in a mesh form which was usually wrapped around a NASICON tube. Unless otherwise stated, nickel mesh was used as the standard cathode throughout this example since early observations indicated that nickel mesh delivered higher current densities than porous silver. 10 (2) Anode materials.

The anode materials used in this example include silver, nickel, lead, graphite, WC, and TiB2. The selection of the anode is based on the catalytic activity and the chemical stability of the materials in the severe oxidising 15 environment. Among these anodes, Ni and Ag were used in mesh forms, WC and TiB2 were as cylinders, and graphite and lead were solid rods.

(3) Cell construction.

20 A NASICON ceramic tube was suspended in a plastic chamber containing NaOH solution. (The arrangement was similar to Figure 3, except that only a single NASICON tube was employed) An aqueous solution saturated with Na2S04 was poured into the tube. In order to evaluate the strength of products obtainable from this process, the concentrations of NaOH in the cat hodic solution was varied from 0 to 40% by weight whereas the concentration of H2S04 in the anodic solution was fixed at about 30 wt%. 25 Electrochemical Characterisation

Applied potential

30 A potentiostat was used to apply a steady voltage to the electrolytic cell. The voltage was varied from 1 to 5 volts to determine the effect of applied voltage on operating current densities.

Operating temperature

35 Electrolytic cells were immersed in a constant temperature circulating bath (Haak, Model F3) to control cell temperature with fluctuation of + 0.2 K. The operating temperature was varied between 35° and 85°C.

Initial ionic conductivity

40 Typical impedance spectra of as-prepared NASICON materials are shown in Figure 6(a). The initial ionic conductivity of the NASICON tubes, determined from the spectra, is plotted as a function of operating temperature in Figure 6(b). It was observed that materials obtained from three batches showed different conductivities, indicating that the electrical properties of these materials depend critically on processing. 45 Ionic conductivity during cell operation

The impedance of electrolytic cells was periodically monitored during cell operation. A number of cells have been continuously operated for over 100 hours. It was observed that the conductance of the cell changed dur- 50 ing operation. The impedance evolution of the cell is shown in Figure 7(a). The resistivity of the electrolyte determined from the spectra shown in Figure 7(b) as a function of operating time. It was this deterioration in electrolyte resistance which brought an inconsistency in electrochemical characterisation; the observed current densities at a given applied potential decay during operation. Fortunately, the deterioration rate in resistance attenuated gradually and after about 80 hours operation, the cell performance became relatively stable. Ac- 55 cordingly, the following results on cell performance appear to represent the steady-state performance after 80 hours of operation. The increase in electrolyte resistivity may be due to either impurity blocking or electrochemical degradation of the materia. Impurity blocking has been observed in beta"-alumina, a sodium ion conductor having much 6 EP 0 559 400 A2

less water resistance than NASICON. For instance, divalent cations such as Ca++ may diffuse into the con- duction plane of beta"-alumina and block the transport of Na+ in the material. Such a problem, if occurring with NASICON, can be avoided either by eliminating undesirable impurities in the electrolytic bath or by frequent reversing of the polarity of the applied potential to condition the material. 5 Performance of Electrochemical cells

The tubular electrolytic cells were constructed and tested. The Ph of the solutions in both sides of the cell were continuously monitored. As electrolysis proceeds, the solution the cathodic compartment becomes more 10 basic (pH increases), indicating the formation of NaOH, whereas the solution the anodic compartment becomes more acidic (pH decrees), indicating the formation of H3S04.

I-V characteristics

15 The performance of electrochemical cells was typically evaluated in terms of the current density as a function of applied potential. Figure 8 shows some typical l-V characteristics of a cell at two testing temperatures. Clearly, when the applied voltage is close to the EMF of the cell, the observed current density was very small. When the applied potential is sufficiently high, the current density reaches a plateau, indicating that the overall process is limited by mass transport. The minimum potential at which the current plateau occurs will set the 20 maximum operating potential for a given system. The limiting current can be expressed as

j, =

Effect of operating temperature

35 Since both the charge transfer and mass transfer are the thermally activated processes, cell performance improves with the increase of operating temperature, as shown in Figure 9.

Effect of electrolyte concentration

40 The effect of NaOH concentration in the cathodic solution on cell performance is shown in Figure 10. Cur- rent densities initially increase with NaOH then decline gradually with further increases in NaOH concentration. This phenomenon is probably related to the proton reduction and hydrogen evolution occurring at the electrolyte-cathode interface.

45 Effect of electrode materials

Among the six electrode materials evaluated in this example, nickel mesh showed the highest catalytic activity for oxygen evolution in a sulphuric acid medium (see Figure 11). All the ceramic electrodes exhibited very similar behaviour which was characterised by little dependence of the current density on the applied po- 50 tential when Va is above a certain value. The chemical stability of ceramic electrodes such as WC and TiB2 is superior to that of metal electrodes. However, Ni is not stable in H2S04. Accordingly, DSA has been used as an anode.

Effect of resistance of ceramic membrane 55 It was also observed that the resistance of ceramic membrane plays an important role in the electrochemical process. Figure 12 shows the l-V characteristics of several electrolytic cells with NASICON tubes having different conductivity. The cell with NASICON electrolyte having a conductivity of the order of 10"3Q-1 cm-1 7 EP 0 559 400 A2

showed exponential-like dependence of current on applied potential, indicating the overall process was con- trolled by electrode kinetics. On the other hand, cells with resistive NASICON electrolytes (of the order of 1CHQ-1 cm-1) showed a linear dependence of the current density on the applied potential. Accordingly, cell performance may be greatly enhanced through improved electrolyte conductivity. 5 Production rate

Initially, when the NASICON tube was fresh, a current density of more than 50 mA/cm2 was observed at 80°C and an applied potential of 3 volts (the thickness of the tube was about 1 .5mm). Unfortunately, the re- 10 sistance of the NASICON tube increased during operation, leading to a decay in the current density. The steady-state current density was about 36 mA/cm2 at 85°C and 28 mA/cm2 at 65°C (Figure 8) after about 80 hours of operation (the conductance of the electrolyte was decreased by about one order of magnitude). The conductance of the electrolyte may be improved by an order of magnitude by reducing the thickness of the electrolyte from 1.5mm to 0.15mm by means of tape casting techniques, resulting in an optimised current 15 density of the order of 500 mA/cm2 at 85°C. At this operating current density, the production rate of NaOH, H2S04, H2, and 02 would be 18, 21.9, 0.45 and 3.58 grams per cm2 per day, respectively.

Current efficiency

20 Current efficiency is primarily determined by the properties of the membrane materials, including selectivity to Na+, electronic conductivity, as well as permeability toother ionic species. For the production of NaOH based on a solid-state electrolyte membrane, the current efficiency increased with the ionic transport number for sodium ions in the membrane. NASICON membrane has demonstrated higher selectivity to Na+ than any polymeric cation selective membranes. The current efficiency for the process based on NASICON membranes 25 is about 94f% at a 50% salt to acid conversion ratio, which is greater than that for an analogous process based on a polymeric membrane such as NAFION membranes which has an efficiency of 60%. A higher current efficiency results in a lower energy loss due to undesirable electrochemical reactions. Energy efficiency for the process will be the product of current efficiency and voltage efficiency. The production rate for cells of the present invention are capable of yielding 40 kg NaOH, 49 kg H2S04, 1 30 kg or 11 .2 standard cubic meters of hydrogen and 8 kg or 5.6 cubic meters of oxygen from 72 KW hours. Aceramic membrane, such as NASICON, which has been contacted with a chemically stable polymer may be used as the electrolyte in the electrochemical cell in accordance with the invention. Polymers which are particularly suitable are those which exhibit high ionic conductivity, good adhesion to the ceramic membrane and insensitivity to contamination from impurities in the feeding solutions. Examples of such polymers are NA- 35 FION and polyvinyl chloride (PVC). NAFION is a polymer having the following chemical structure

-[(CF2CF2)n - (CF2CF)]ra- • 0-CF2CFCF3 40 ' O - CF2CF2S03H

where "n" denotes a possibility of more than one CF2CF2 sequence, and where "m" indicates a longer polymer chain. Polymer material may be contacted to the ceramic membrane in several different ways, including the 45 following examples:

EXAMPLE III

Protective sheet contacted to ceramic 50 A NAFION sheet was cut ot the size of a NASICON disc and immersed in 3 M H2S04 solution for one hour, allowing the NAFION to swell with the solution. After rinsing it with water, the swollen sheet 43 was laminated onto one side of the NASICON disc 41 which had been precoated with NAFION solution 42 (duPont Company; stock No. 27.470-4 from the 1990-91 Aldrich Catalog: contains 5% NAFION dissolved in an ethanol-water 55 mixed solvent, where the equivalent weight of NAFION is about 1100.) The NAFION solution 42 acts as a glue to bind the NAFION sheet 43 to the NASICON disc 41. The laminated disc is shown in Figure 13. The disc was used as an electrolytic membrane in a cell where DSA (Permascand, Sweden) was used as the anode immersed in a solution containing 10% H2S04 and 10% Na2S04 and nickel mesh was used as the 8 EP 0 559 400 A2

cathode immersed in a 10% NaOH solution. The polymer-coated side of the membrane was oriented in the cell towards the anodic compartment and the side without the polymer was orientated at 60°C under a constant applied potential of 4.0 volts. Titration analysis of the anodic and cathodic compartments contents indicate that sodium sulphate was electrolysed with a 94% current efficiency. No apparent degradation was observed in 5 the NASICON disc although some cracks appeared.

Polymer wrapped ceramic tube

A sheet of NAFION 53 was cut to fit around the exterior surface of a tube 51 of NASICON. The exterior 10 surface of the NASICON was coated with NAFION solution (not shown) and the sheet 53 was wrapped about the tube 51. The NAFION-wrapped tube was dried at 120°C for three hours. Aschematic representation of the tube is shown in Figure 14. The prepared tube was used as the electrolyte of a cell where DSAwas used as the anode and nickel mesh was used as the cathode. The cell was operated at 60°C and at 4.0 volts for 120 hours. The tube appeared to have a number of cracks, suggesting a break in the seal between the sheet and 15 the membrane. Although the cell worked efficiently initially, the NAFION sheet 53 eventually delaminated from the nasicon membrane. However, the weight loss of the ceramic tube during the testing was very small indicating that the ceramic was chemically protected by the polymer.

Polymer film coating 20 Clean-fired NASICON tubes were preheated to 70°C and were then dipped in a NAFION solution. In order to achieve a dense coating having no pin-holes, the tubes were dipped four times. Evaluation through scanning electron microscopy indicated a smooth film with no pin-holes was achieved with four coatings which produced a thickness of about eight urn. The tubes were then dried at a temperature of from about 50°C to about 70°C 25 for about one hour and then cured further at about 120°C to about 150°C for about 20 minutes. It was observed that the coating maintains greater integrity and mechanical strength with increased curing temperature. Good adhesion of the polymer is important to provide protection to the ceramic membrane. Adhesion, it was observed, increases with increase in curing temperature. A NAFION coating may be applied to a NASICON tube by shrink-wrapping in which a nested sheet of NA- 30 FION is placed about NASICON tube. As the NAFION is placed about a NASICON tube. A NAFION cools it adheres to the outer surface of the NASICON tube. A mechanical coherence is established. A further example of electrolysis of sodium-containing salts involves aqueous sodium chlorate solutions. The reaction is as follows: 2NaC103 + 3H20 -» 2NaOH + 2HC103 + H2t + 1/202t 35 The half-cell reactions may be written as follows: (anode) 2NaC103 + H20 -» 2Na+ + 2HC103 + 1/202t + 2e" (cathode) 2Na+ + 2H20 + 2e" -» 2NaOH + H2t Three electrolytic cells, each comprising a NASICON membrane, an Inconel (Trade Mark) (78% Ni, 13% Cr, 6% Fe) or other high nickel alloy metal anolyte containing 40% NaC103 and a nickel mesh catholyte con- 40 taining 10% NaOH were operated at 50°C. The results of the tests are shown in Figure 15. The observed cell current was about 450 mAat an applied voltage of 4 volts. When the cells were operated at room temperature, however, as shown in Figure 16, the observed cell current was about 150 mAat an applied voltage of 4 volts. Further examples of electrolytic reactions to produce caustic using sodium-containing salts include the aqueous solutions of sodium carbonate, sodium nitrate, sodium phosphate, sodium hypochlorite, sodium chlor- 45 ite, and sodium perchlorate. Aqueous solutions of sodium-containing salts are electrolysed in a cell as follows:

EXAMPLE IV

An electrolytic cell was constructed comprising a NASICON tube, nickel mesh as the cathode and a pla- 50 tinum mesh as the anode. The NASICON tube was placed in a plastic chamber containing NaOH solution. An aqueous solution containing about 40% Na2C03 (sodium carbonate) was introduced into the tube. A voltage of 3.0 volts was applied to the electrochemical cell at ambient temperature. It was observed that the concentration of NaOH in the chamber increased, while the concentration of carbonic acid increased within the tube. This can be represented by the following reactions: 55 Na2C03 + 3H20 -» 2NaOH + H2C03 + 1/202t + H2t the half cell reactions being: anode: Na2C03 + H20 -» 2Na+ + H2C03 + 2e" + 1/202t cathode: 2Na+ + 2H20 + 2e" -» 2NaOH + H2t 9 EP 0 559 400 A2

EXAMPLE V

An electrolytic cell was constructed comprising a NASICON tube, nickel mesh as the cathode and a platinum mesh as the anode. The NASICON tube was placed in a plastic chamber containing NaOH solution. An 5 aqueous solution containing about 40% NaN03 (sodium nitrate) was introduced into the tube. A voltage of 3.0 volts was applied to the electrochemical cell at ambient temperature. It was observed that the concentration of the NaOH in the chamber increased while the concentration of nitric acid increased within the tube. This can be represented by the following reactions: NaN03 + 11/2H20 -» NaOH + HN03 + 1/202 + 1/2H2t w anode: NaN03 + 1/2H20 -» Na+ + HN03 + e" + 1/202t cathode: Na+ + H20 + e" -»NaOH + 1/2H2t

EXAMPLE VI

15 An electrolytic cell was constructed comprising a NASICON tube, nickel mesh as the cathode and a platinum mesh as the anode. The NASICON tube was placed in a plastic chamber containing NaOH solution. An aqueous solution containing about 40% Na3P04 (sodium phosphate) was introduced into the tube. A voltage of 3.0 volts was applied to the electrochemical cell at ambient temperature. It was observed that the concentration of the NaOH in the chamber increased while the concentration of phosphoric acid increased within the 20 tube. This can be represented by the following reactions: 2Na3P04 + 9H20 -» 6NaOH + 2H2P04 +3/202t + 3H2t anode: 2Na3P04 + 3H20 -» 6Na+ + 2H3P04 + 6e" +3/202t cathode: 6Na+ + 6e" + 6H20 -» 6NaOH + 3H2t

25 EXAMPLE VII

An electrolytic cell was constructed comprising a NASICON tube, nickel mesh as the cathode and a platinum mesh as the anode. The NASICON tube was placed in a plastic chamber containing NaOH solution. An aqueous solution containing about 40% NaC102 (sodium chlorite) was introduced into the tube. A voltage of 30 3.0 volts was applied to the electrochemical cell at ambient temperature. It was observed that the concentration of the NaOH in the chamber increased while the concentration of chlorous acid increased within the tube. This can be represented by the following reactions: 2NaC102 + 3H20 -» 2NaOH + 2HC102 + 1/202 + H2 anode: 2NaC102 + H20 -» 2Na+ + 2e" + 2HC102 + 1/202t 35 cathode: 2Na+ + 2H20 + 2e" -» 2NaOH + H2t

EXAMPLE VIII

An electrolytic cell was constructed comprising a NASICON tube, platinum mesh as the anode and a nickel 40 mesh as the cathode. The NASICON tube was placed in a plastic chamber containing NaOH solution. An aqueous solution containing about 40% NaC104 (sodium percolate) was introduced into the tube. A voltage of 3.0 volts was applied ot the electrochemical cell at ambient temperature. It was observed that the concentration of the NaOH in the chamber increased while the concentration of perchloric acid increased within the tube. This can be represented by the following reactions: 45 2NaC1 04 + 3H20 -» 2NaOH + 2HC1 04 + 1/202t + H2t anode: 2NaC104 + H20 -» 2Na+ + 2e" + 2HC104 + 1/202t cathode: 2Na+ + 2e" + 2H20 -» 2NaOH + H2t

EXAMPLE IX 50 An electrolytic cell was constructed comprising a NASICON tube, platinum mesh as the anode and a nickel mesh as the cathode. The NASICON tube was placed in a plastic chamber containing NaOH solution. An aqueous solution containing about 40% NaC10 (sodium hypochlorite) was introduced into the tube. A voltage of 3.0 volts was applied to the electrochemical cell at ambient temperature. It was observed that the concentration 55 of the NaOH in the chamber increased while the concentration of HC1 increased within the tube. This can be represented by the following reactions: 2NaC10 : 3H20 -» 2NaOH + 2HC10 + 1/202t + H2t anode: 2NaC10 + H20 -» 2Na+ + 2e" + 2HC10 + 1/202t 10 EP 0 559 400 A2

cathode: 2Na+ + 2H20 + 2e" -» 2NaOH + H2t Although cell operation has been described, in particular, as being very effective in producing caustic from sodium sulphate solutions, with the consequent production of hydrogen and oxygen, these cells can also produce caustic and chlorine from the electrolysis of sodium chloride solution. Cells which electrolyse sodium sul- 5 phate solution are particularly desirable inasmuch as sodium sulphate is produced through the absorption of S02 by sodium carbonate solution. The cell may be used to electrolyse sodium nitrate as well, to produce sodium hydroxide, hydrogen and nitric acid. An effective multiple cell arrangement can be constructed by employing alternate sodium ion conductors and proton conductors. Acell of this type is illustrated in Figure 5. This particular cell assembly contains a plur- 10 ality of chambers which are operated in series. The anode chamber 16 contains an anode 17, preferably constructed of TiB2 (titanium diboride) and an anolyte of aqueous Na2S04 and H2S04. As electrolysis proceeds, Na2S04 is converted to H2S04. Make-up Na2S04 is added to the chamber 16 while anolyte containing predominately H2S04 and a small amount of Na2S04 is removed. Oxygen is generated at the anode 17 while sodium ions are transported through the so- 15 dium ion conducting electrolyte 18 into the catholyte-type chamber 19 containing aqueous sodium hydroxide. In the chamber 16, Na2S04 is electrolysed to sodium ions and sulphate ions. The sodium ion is electrolyt- ically transported through the ceramic membrane 18 (preferably dense NASICON) to form sodium hydroxide and a hydrogen ion (proton) is transported through a proton conducting membrane 20 to form an acid. Although only the membrane 16 and 27 contain electrodes (anode and cathode, respectively), for the pur- 20 poses of this invention, the chambers 16, 21 and 25 are considered anolyte chambers since electrolysis (dis- association) of Na2S04 or some other salt occurs in each of these chambers. While in each catholyte chamber, sodium hydroxide is formed from the reaction of a sodium ion with water and the release of a proton, the proton in the catholyte chamber is transported through the proton transporting membrane into an adjoining anolyte chamber. 25 In the assembly of cells shown in Figure 5, positively charged ions (sodium ions and protons) travel from the anode-containing chamber 16 through the various cells, resulting in the release of hydrogen at the cathode in the cathode-containing chamber 27. Electrons are provided at the cathode from an external direct current power source. Electrons are released at the anode in accordance with Equation 2 (The Anode Half-Cell Reaction), while the reaction at the cathode 30 occurs in accordance with Equation 3 (Cathode Half-Cell Reaction). The electrodialysis structure shown in Figure 5 produces less oxygen and hydrogen gas than would be the case with electrolysis such as shown in Figure 1. In a cell such as that shown in Figure 1, one mole of hydrogen and one-half mole of oxygen are produced for each mole of sulphuric acid and each two moles of sodium hydroxide produced. One mole of sodium sulphate is consumed for two moles of NaOH or one mole 35 of H2S04 produced. In the cell assembly of Figure 5, only one-half mole of oxygen and one mole of hydrogen are produced for each three moles of H2S04 or six moles of NaOH produced. The number of half-cells (chambers 16, 19, 21, 23, 25 and 27) may beany desired number although internal resistance of such an assembly of cells is additive and the energy consumed by each electrolyte reaction is not altered by this serial arrangement of half cells. 40 However, whenever maximum production of NaOH and/or H2S04 is desired with the minimum production of gases (H2 and 02), then an electrodialysis structure such as that illustrated in Figure 5 is very useful. Proton conductors suitable for use in the present invention include NAFION, barium cerate (BaCe03), strontium cerate (SrCe03) and the like. Suitable proton conductors operable at the modest temperatures in- volved and having acid and alkali resistance, especially ceramic proton conductors, are well known in the art. 45

Claims

1. An electrolytic cell (10) for the production sodium hydroxide from a sodium salt derived from a strong acid so comprising: an anode chamber (12); a cathode chamber (11); an acid resistant, electronically conductive anode (13) in the anode chamber (12); an alkali resistant, electronically conductive cathode (14) in the cathode chamber (11); and a membrane (15) separating the anode chamber (12) from the cathode chamber (11); characterised in that the membrane (15) is solid, impervious, sodium ion conducting, electronically insulating, and resistant to acid and alkali. 55 2. An electrolytic cell as claimed in Claim 1, characterised in that the membrane (15) is a ceramic material, for example Nasicon.

11 EP 0 559 400 A2

An electrolytic cell as claimed in Claim 2, characterised in that the ceramic material has a theoretical density which is greater than 95% of the theoretical density.

An electrolytic cell as claimed in Claim 1, characterised in that the membrane (15) is a composite of ceramic and polymer materials.

An electrolytic cell as claimed in Claim 4, characterised in that the ceramic material is Nasicon and the polymer has the formula:

10 -[(CF2CF2)n - (CF2CF)]m - I 0-CF2CFCF3 O - CF2CF2S03H

15 where n^1 and msl

6. An electrolytic cell as claimed in any preceding Claim, characterised in that inorganic portion of the membrane (15) has a thickness of less than 1.5mm.

20 7. An electrolytic cell as claimed in any preceding Claim, characterised in that the membrane (15) is a thin, substantially planar structure or is in the form of a closed end tube.

8. An electrolytic cell as claimed in any preceding Claim, characterised in that at least two anode chambers are present and/or at least two cathode chambers are present. 25 9. An electrolytic process for producing concentrated sodium hydroxide solution from an aqueous sodium salt solution having anions derived from a strong acid, which comprises: introducing electrons into an aqueous catholyte solution (11) containing sodium hydroxide; removing electrons from an aqueous anolyte solution (12) containing sodium cations and anions producing oxygen gas in the anolyte; producing hy- 30 drogen gas in the catholyte; and producing an acid from the anions in the anolyte; from an acid; characterised by conducting sodium ions through a solid integral, monolithic anolyte/catholyte separator (15) containing mobile sodium ions in its lattice to produce a concentrated solution of sodium hydroxide in the catholyte solution.

35 10. A process as claimed in Claim 9, characterised in that the concentrated solution of sodium hydroxide includes up to 40% by weight of NaOH.

11. A process as claimed in Claim 9 or Claim 10, characterised in that the anolyte solution contains a sodium salt selected from sodium sulphate, sodium chloride, sodium chlorate, sodium chlorite, sodium nitrate, so- 40 dium phosphate, sodium perchlorate, sodium nitrite and sodium carbonate.

12. A process as claimed in any of Claims 9 to 11 , characterised in that the temperature of operation is up to 100°C, preferably about 85°C, and/or the operating pressure is atmospheric or superatmospheric.

13. An electrolytic cell system characterised in that it comprises a plurality of cells as claimed in any of Claims 45 1 to 8 positioned serially with a proton conducting membrane (20) alternating with the sodium ion conducting membranes (18).

14. An electrolytic cell system as claimed in Claim 13, characterised in that one terminal cell is a catholyte cell (27) containing a cathode (28) and the other terminal cell is an anolyte cell (16) containing an anode 50 (17).

12 EP 0 559 400 A2

A 0 © / / / 74- / ■13 / / / / 77- / / y / / / 10- / / ■Na+ — / NaOH+H20 No250/h +H20 / / / / / / / / / /

Figl

13 EP 0 559 400 A2

(NaOH + H20) (NaOH+H20) 35 35

■33 '33 -33

■32 '32 -32

^ O ^ - (Na2S0u +H20) — 36

Fig.2.

Fig. 3.

14 EP 0 559 400 A2 EP 0 559 400 A2 EP 0 559 400 A2

17 EP 0 559 400 A2

45n

40- +

35- AFTER U8 HOURS

■^30- gz>5-

o ' 75- V + 10- v o V ,+ 0+0 5- |

0 ^0 UO 60 80 100 120 %0 160

Z'(Ohms)

Fig.7(a).

4.5-1 4.4- 4.5-

4.2-

4.7- 4.0- / 3.9- / / CL 3.8- / 3.7- / 3.6- / / 3.5-

54-

3.2% 0 20 40 60 80 100 TIME (HOURS)

Fig.7(b).

18 EP 0 559 400 A2

40- NLHpO/WBE 7/NiJNa250^H2S0/h 35-

I 30- " 85'C /

e * 65-c / +^-+ 25_ / / / / g 20- I / / is /

1 "/

2 / + 5- //

0- , ! , , j ! j_ 2 3 4 5 APPLIED POTENTIAL (V)

Fig.8.

NLH20/TUBE l/WC,NQ2SO+H2Sty 7" ^ APPLIED POTENTIALSPOTENTIAL: A

I 6-

/ 5- g / * / i — , ■ R 4- / & / 5 3- / / /

20 60 80 | 40 t e\x 25'c TEMPERATURE CO

Fig.9.

19 EP 0 559 400 A2

74- Ag.NaOH/TUBE 4/WCM2S04+H2S04 13- 12- 55 r 11- 10- 9- / \ 8- / \ 7- / \ 6- / \ 25 r f 5<; \ I 4-

3-, 2- N 7- +

u 10 20 30 40 CONCENTRATION OF NaOH (wt%) Fig.10.

70-i

9- CATHOLYTE: 10wt% Na0H(45X) ANOLYTE: Na2SO^H2S04 I 8- CATHODE: Ni 7- ANODE: WC I I + TUBE 4 i 6- ■ TUBE 1 I I o I 5- TUBE 6 I 1

4- I 3- xS>u

/ 1-

1 2 3 APPLIED POTENTIAL (V) Fig.12.

o r EP 0 559 400 A2

Fig.13.

~ ' 53^ Ct¥> HzSOi

Fig.%.

22 EP 0 559 400 A2

23 EP 0 559 400 A2