Patent GB-797624-A (GB)
Title: Treatment of solutions comprising similarly charged monovalent and polyvalent ions to concentrate the polyvalent ions
IPC: B01J47/10
Filed: 1956-04-16
Abstract: An aqueous starting solution containing mono- and poly-valent ions of the same sign is contacted to concentrate the polyvalent ions with an ion exchange agent suitable for absorbing the polyvalent ions and the ion exchange agent is then contacted with a solution having a composition corresponding with that of the diluted regenerate liquor referred to below and thereafter with an aqueous solution containing a higher concentration of monovalent ions than the starting solution, whereby a regenerate liquor is obtained richer in the polyvalent ions.  A portion of said regenerate liquor may be diluted with at least an equal volume of liquid consisting of water and/or starting solution to form a solution which may be used as described above in subsequent cycles.  Examples refer to the partial separation and concentration of solutions of calcium chloride from a mixture with sodium chloride or hydrogen chloride, of sodium sulphate from a mixture with sodium <PICT:0797624/III/1> chloride and of magnesium chloride from sea water: in each case the final eluting liquid contained the second component of the starting mixture (in the case of sea water, sodium chloride or sodium chloride with a small amount of calcium chloride).  Also mentioned are the concentration of calcium nitrate from solution with potassium nitrate using sodium nitrate eluent, of aluminium nitrate from solution with nitric acid, with nitric acid as eluent and of phosphates from nitrate solutions. The three steps of contacting the ion exchanger with solutions may take place batchwise by successively treating in a single column, if desired with intermediate washing, or may be performed continuously, e.g. by means of a moving stream of resin in three columns (as in Fig. 2) or two columns (as in Fig. 3, not shown, in which the first two columns of the three-column embodiment are replaced by a single column and the corresponding zones may be separated if desired by a perforated plate).  When treating sea water (or a similar brine) by the apparatus of Fig. 2, to extract magnesium therefrom as chloride, the sea water after dilution (e.g. 0.5 to 10 times) and/or removal of some of the calcium ions (as described in Specification 791,364) if desired is fed to column 1 at inlet 13. Cation exchange resin is removed via star valve 5 and is passed through line 4 by means of water or other liquid, e.g. sea water injected through line 6 to the top of column 2, where it is contacted with the diluted regenerate liquid.  The saturated resin is then similarly passed to the top of column 3 where a solution of sodium chloride, preferably in at least 10 per cent by weight concentration, passing upwardly from inlet 14 meets it and elutes the absorbed magnesium ions.  The resin is then returned in a similar way to column 1.  The eluate is withdrawn via line 15, e.g. as a 10-14 per cent solution for recovery of magnesium, e.g. by evaporation and crystallization and a portion forms the product whilst the remainder, e.g. 0.1 to 0.3 volumes, is mixed with between 0.5 and 100 volumes of water and/or sea water from line 17, and pumped to column 2.  In one example calcium is removed from this diluted liquor before passage to column 2 with sodium carbonate.  A liquid-liquid interface is maintained between the offtake of the produce and the outlet 24 for the carrier liquid, e.g. by means of the device described in Specification 736,276.  The rates of circulation of exchange material and liquid feed in column 1 are preferably such that the solid falls to the bottom of the column whilst absorbing a major portion of the magnesium ions in the feed solution: in column 3 the interface should be maintained. Alternatively the exchange material can be forced up the columns whilst the liquors pass downwardly or the separate columns could be arranged differently.  When using a single column, the sea water may if desired be initially passed in undiluted and thereafter diluted to effect better absorption; the feed of starting solution may be continued until the eluate approaches the same concentration; the feed of final eluent may be similarly continued, or discontinued when the concentration of sodium ions in the eluate increases; the final eluent solution usually contains 15 per cent or more of sodium chloride and is preferably saturated.  Cation exchange materials referred to are zeolite (sodium aluminium silicate), sulphonated coal, insoluble carboxylated resins such as the alkali insoluble copolymers of maleic acid, styrene and divinyl benzene, and alkali-insoluble sulphonated resin such as the nuclear sulphonated phenol-formaldehyde resins or the nuclear sulphonated copolymers of a major amount of one or more monovinyl aromatic hydrocarbons such as styrene and ethylvinylbenzene and a minor amount of divinyl benzene. For use in absorbing magnesium ions from the sea water the exchanger is preferably in the form of sodium salt but may be in acidic, ammonium or potassium form or may be rich in sodium ions but have a minor proportion of magnesium ions.  Anion exchange materials referred to are strongly basic resins containing quaternary ammonium radicals, e.g. those obtained by reacting tertiary amines such as trimethylamine or dimethanolamine with a solid chloromethylated copolymer of styrene, ethylviny benzene and divinyl benzene.  In an example such a resin is used in the chloride form.  Examples (1) and (2) describe procedures (which are not claimed) of a generally similar kind in which a column of resin is successively contacted with a starting solution of sodium chloride and calcium chloride or sodium chloride and sodium sulphate, then with a more concentrated sodium chloride solution, then with a solution corresponding to a portion of the effluent after dilution and finally with a more concentrated sodium chloride solution. Concentration of the polyvalent ion was achieved.  U.S.A. Specification 2,387,898 also is referred to.  Reference has been directed by the Comptroller to Specification 736,276.