Effluent treatment
United States Patent t Stander Apr. 1, 1975 {54] EFFLUENT TREATMENT 2 H1670 1/1939 Eichelberger 204/153 2 27( .3 942 204 3 1 1 2401.412 to, team 6. 20411.23  
  Kempton Park. South Attic-ti [73] Assignee: AE &amp; CI Limited. Johannesburg. Primary Examiner-G. L. Kuplan South Africa Assistant Ermniner-Auron Weisstuch Attorney, Agent or FirmCushman. Darby &amp;  
 [22] Filed. June 7. i973 Cushman I21] Appl. No.: 368.046  
 [57] ABSTRACT [30] Foreign Application Priority Data A method of treating aqueous effluent containing June :6 i972 South Africa 72 4407 Caustic Soda and Oxychlvrine Compounds p gv filling the anode and cathode compartments of an 5 US. Cl H 204/98, 204/99. 204/128 electrolytic diaphragm cell with effluent to provide an 2 4 53 electrolyte. electrolysing the effluent and reducing the 5 1 1 Int CL I I um Culh 7 o 1/40 oxychlorine compounds to chloride ions and hydroxyl [58] n w of Search H 304/98 99 g 5 ions at the cathode. recovering chlorine from the 2 7 1 4 o 97 anode compartment and sodium hydroxide solution from the cathode compartment while allowing the cf- 5 References Cited fluent to flow through the cell by introducing effluent UNITED STATES PATENTS into the cathode compartment. morass 6/1936 Ovcrdick ct ul. 204/153 7 Claims. 2 Drawing Figures l&#39;his inrcntion rclatcs to thc trcatmcnt in clcctrolysis ccll of cfflucnts containing caustic soda and o\ chlorinc compounds.  
  Aqucous cfflucnts containing caustic soda and oxychlorinc compounds such as chloritcs. hypochloritcs and chloratcs arc produccd in man industrial proccsscs. Onc csamplc of such proccsscs is thc manufacturc of chlorocarlmns.  
  Thcsc cfl&#39;lucnts also contain considcrahlc uantitics of chloridc.  
  &#39;l&#39;hc chlorinc and caustic soda containcd in thc cfflucnts arc products which can hc rccyclcd into thc proccss from which thc compounds originatc. if thc can hc rcco\crcd h cconomical mcthods.  
  (&#39;hlorinc and caustic soda arc normally prcparcd h clcctrofvsing a hrinc solution in clcctrohsis cclls.  
  Two typcs of cclls arc uscd: thc flowing mcrcury cathodc ccll and thc diaphragm ccll.  
  ln thc mcrcury ccll. chlorinc is formcd at thc anodc and sodium amalgam at thc cathodc. (&#39;austic soda is thcn ohtaincd h thc dcconiposition of thc sodium amalganr Howcwr. thc mcrcur cathodc ccll \\ill not hc suitahlc for thc rcco\ cr ot&#39;caustic soda and chlorinc from cfl&#39;lucnts containing oxychlorinc compounds. sincc thc hypochloritcs and chloritcs \\ill hc oxidiscd to chloratcs and thc cfflucnt prohlcm will not hc solrcd.  
  ln thc diaphragm ccll thc caustic soda is formcd in thc cathodc compartmcnt of thc ccll and chlorinc in thc anodc compartmcnt. &#39;lhc cathodc and anodc com partmcnts arc scparatcd h a diaphragm to avoid thc formation of hypochloritc and chloratc in thc anodc compartmcnt h thc rcaction hctwccn chlorinc and h droxyl ions. Hydrogcn is also formcd at thc cathodc and thc diaphragm also scrrcs to scparatc thc hydrogcn and chlorinc formcd in thc ccll. &#39;lhc hrinc is fcd to thc anodc compartmcnt to countcract thc migration ofthc hydrosyl ions from thc cathodc compartmcnt to thc anodc compartmcnt.  
  l&#39;o rccorcr chlorinc and caustic soda from thc cfl&#39;lucnts rcfcrrcd to ahmc. this mcthod of clcctrolysis cannot hc uscd sincc h pochloritc and chloratc arc prcscnt thcrcin and clcctrolysing thc cfflucnt in a diaphragm ccll as uscd in hrinc clcctrolysis will favour thc futmtb tion of chloratcs and crcn pcrchloratcs in thc anodc compartmcnt.  
  It is an ohjcct of thc prcscnt inrcntion clcctrolytically to dccomposc cfl&#39;lucnt containing caustic soda and oxychlorinc compounds and to rccovcr caustic soda and chlorinc from such cfflucnt. which products it dcsircd. ma hc rccyclcd to thc proccss from which thc cfflucnt originatcs.  
  According to thc prcscnt in\&#39;cntion a mcthod is prt ridcd of trcating aqucous clflucnt containing caustic soda and o\ \chlorinc compounds comprising filling thc anodc and cathodc compartmcnts of an clcctrolytic diaphragm ccll \\ith cfllucnt to proridc an clcctrolytc. clcctl&#39;oltsing thc cfflucnt and rcducing thc oxychlorinc compounds to chloridc ions and lt \Llt&#39;ti\}l ions at thc cathodc. rccmcring chlorinc from thc anodc compartincnt and sodium Iodroxidc solution from thc cathodc compartmcut uhilc allowing thc cfflucnt to flow through thc ccll h introducing cftlucnt into thc cath odc compartmcnt.  
 Ill  
  &#39;lhc anodc conipartmcnt ofthc ccll may hc fillcd ith an acidificd hrinc solution instcad of cfflucnt. to a\oid thc formation ofoxygcn at thc anodc in thc initial stagc of thc clcctrolysis causcd h thc prcscncc of hydrosyl ions in thc anodc compartmcnt.  
  Prcfcrahly. thc cft&#39;lucnt in thc anodc compartmcnt is acidificd with hydrochloric acid hcforc thc start of thc clcctrolysis to dccrcasc thc lndroxyl ion conccntration and thus avoid thc initial formation ofo\ gcn at thc anodc.  
  Thc osychlorinc compounds arc prcfcrahh rcduccd at a cathodc madc of iron or stccl. although othcr suitahlc cathodcs ma hc uscd.  
  Thc chlorinc ma hc lormcd at a carhon or graphitc anodc hilt it is prcfcrrcd to usc anodcs madc of titanium coalcd with a nictal sclcctcd from thc following clcmcnts. platinum. palladium. ruthcnium. rhodium and iridium.  
  &#39;l&#39;hc anodc and cathodc compartmcnts may hc scparatcd h a diaphragm madc of any matcrial suit-ahlc for immcrsion in a coi&#39;rosirc liquid such as. for csamplc. \\&#39;U\ cn polyvinyl chloridc cloth.  
  ln practising thc mcthod of this inrcntion. thc chlo rinc containing ions prcscnt in thc cfflucnt will hc rcduccd to chloridc ions at thc cathodc hcforc hydrogcn formation takcs placc. sincc thc oxidation potcntials of thcsc ions arc highcr than that of thc hydrogcn ions. Thc chloridc ions \\ill thcn migratc to thc anodc compartmcnt whcrc chlorinc gas will hc formcd at thc anodc. Hydroxyl ions will also tcnd to migratc to thc anodc. Howcvcr. thc hydrogcn ion conccntration in thc anodc compartnicnt is kcpt at a pH of about 4 in thc anodc compartmcnt and thc hydroxyl ion conccntration will hc ncgligihlc.  
  Thc chlorinc is rcmovcd from thc anodc compartmcnt and this causcs a conccntration gradicnt of chloridc ions hctwccn thc cathodc and anodc compartmcnts. &#39;lhcrcforc. thc movcmcnt ofthc chloridc ions to thc anodc compartmcnt will hc fast and suhstantiall purc chlorinc gas will hc ohtaincd from thc anodc compartmcnt. Hydroxyl ions and sodium ions which arc prcscnt in thc cftlucnt will not hc rcduccd at thc cathodc and can hc rcniovcd from thc cathodc compartmcnt as sodium hydrosidc solution. &#39;l&#39;hc cft&#39;lucnt is fcd continuously into thc cathodc compartmcnt. Hydrogcn formation at thc cathodc can hc aroidcd but. to lowcr thc chloridc contcnt of thc cfllucnt hy clcctrolysing thc sodium chloridc prcscnt thcrcin. hydrogcn is normally formcd at thc cathodc. (hlorinc is ohtaincd from thc anodc compartmcnt and sodium hydroxidc solution suhstantialhv frcc of oxychlorinc compounds is ohtaincd from thc cathodc compartmcnt.  
  &#39;lhc im&#39;cntion will now hc dcscrihcd with rcfcrcncc to thc accompanying drawings. without rcstricting thc scopc of thc invcntion to thc particular cmhodimcnts shown thcrcin.  
  FIG. 1 is a diagrammatic rcprcscntation of a laboratory typc diaphragm ccll which was madc for usc in thc mcthod of thc prcscnt invention.  
 FIG. 2 is a scction through a lurthcr cmhodimcnt of a ccll according to thc invcntion.  
  In Fl(iv l. sidcs II and bottom 12 of thc ccll l0 wcrc constructcd ofplatc glass. Thc lid l3 was madc of polytctraihiorocthylcnc whcrcin holcs wcrc providcd for thc conncctions to a mild stccl cathodc l4 and a graphitc anodc l5 thcrmomctcrs 16 for mcasuring thc tcmpcraturcs in thc anodc and cathodc compartmcnts l7 and 18. an inlet I) for the effluent. an outlet for the chlorine combined with an inlet 21 to introduce brine. if required. into the anode compartment 17. Further holes were provided in lid 13 for inlet 22 to introduce acid into the anode compartment 17. a pH-probe 23 to measure the pH of the anolyte and an outlet 24 for hydrogen. in one side I l of the cathode compartment 18. outlet 26 was provided to remove sodium hydroxide solution. The diaphragm 25 was a piece of woven polyv inyl chloride cloth mounted on a mild steel frame.  
  ln an experiment using the cell as shown in FIG. 1. the anode compartment 17 was filled with a 5 percent by weight sodium chloride solution the pH of which was adjusted to pH-&amp; with hydrochloric acid. An aqueous effluent containing sodium hydroxide. sodium hypochlorite and sodium chlorate was allowed to flow through the cathode compartment IS. The rate of flow and the current were so adjusted that hydrogen evolu tion just started at the cathode. indicating that all reducible osychlorine ions had been reduced and that the reduction of water and the formation of hydroxyl ions was proceeding.  
  The experiment was run during two consecutive days. hereby samples were collected at the outlet 26 and were analysed iodomctrically for hypochloritc and chlorate ions and acidimctrically for hydroxide. The results of the two runs are given below:  
 The results show that a product free of oxychlorine I ions wherein the hydroxide content is increased can be produced from the effluent. while chlorine is also produced.  
  The hydroxide solution and the chlorine are both suitable for re-use.  
  A further cell for use in the method of the invention was constructed out of dense concrete. The external dimensions ofthe cell were lot) mm wide. 440 mm long and 200 mm high.  
  Fl(i. 2 illustrates the position ofthe electrodes in this cell.  
  The cell 30 consists of cell body 31 and lid 32 con structed of 30 mm thick concrete coated with coal tar pitch.  
  The end walls and the bottom of cell body 3] worepro\ided with grooves 33 to accommodate two cathodes 34 covered on one side with a woven polyvinyl chloride diaphragm 35.  
  The cathodes 34 were made of mild steel screening. having a wire diameter of 2 mm and a spacing of St) mm. welded into a mild steel frame.  
  The cathodes 34 were fixed in the grooves 33 of cell body 3| with coal tar pitch.  
  in this way. the cell 30 was divided into three compartments. one cathode compartment 56 and two anode compartments 37.  
  The anodes 38 were suspended from lid 32 and they were made of platinum coated titanium.  
  A seal 39 was provided between the lid 32 and cell body 3! as well as cathodes 34 to prevent leakage from cell 30 and mixing of the gases formed in the cathode and anode compartments.  
  The cell 30 was further provided with outlets 40 to remove chlorine from the anode compartments 37 and outlet 4| to remove hydrogen from the cathode com partment 36.  
  The lugs 42 on lid 32 were provided to connect the anodes to a source of electricity.  
  Other inlets and outlets (not shown) are provided in the end walls ofcell body 31. such as inlets for effluent to the cathode compartment 36 and inlets for acid or anolyte to the anode com &#39;iartments 37.  
  Cathode compartment 36 is further provided with an outlet (not shown) for the caustic formed in the cell. Connections lnot shown) for the anodes 34 are also provided.  
  In an experiment using the cell 30 as illustrated in FIG 2. an effluent having the following weight/volume composition was fed to cathode compartment 36.  
 Sodium hypochlotitc oi); li Sodium hydrmlde 3 v, Sodium chloride 13 The anode compartments 37 were filled with the same effluent neutralized to a pH 4 with hydrochloric acid.  
  The effluent was clectrolyzed at a potential of 4.5 volt and a current of ampere. which gave a current density of 3(a) A/m The rate of llow of the effluent was so adjusted that hydrogen evolution just started at the cathode. indicating that all reducible osychlorine ions had been reduccd.  
  Samples taken from the flow from the cathode compartment 36 had the following weight/volume composition:  
 Sodium hypoehlorii m Sodiuni hydroyide a l Sodium chloride 33 i; m/  
  Chlorine was evolved in the anode compartments. The results indicate that this type ofeell i also suitable for use in the method of the invention. The hypoehlorite was reduced efficiently and re-usable chlorine and caustic were produced.  
  The method of the invention provides an economically attractive method for the LlLLOl&#39;nPUSlllUlt of aqueous effluents containing osychlorine compounds whereby chlorine and caustic solution are produced suitable for re-use.  
 I claim:  
  I. A method of treating aqueous effluent containing caustic soda and oxychlorine compounds comprising filling the anode and cathode compartments of an electrolytic diaphragm cell with effluent to provide an electrolyte. electrolysing the effluent and reducing the oxychlorine compounds to chloride ions and hydroxyl ions at the cathode, recovering chlorine from. the anode compartment and sodium hydroxide solution from the cathode compartment while allowing the effluent to flow through the cell by introducing effluent into the cathode compartment.  
 2. A method as claimed in claim 1 wherein the effluent in the anode compartment is acidified.  
  6. A method as claimed in claim I wherein chlorine is formed at an anode made of titanium cnated with a metal selected l&#39;rum the following elements. piaiinum. palladium. ruthenium. rhodium and iridiumv 7. A methud as claimed in claim I wherein the cathnde and anude cumpartmems are separated by a dia phragm made in woven pulyvinyl chloride cloth.