CA1335974C - Electrolyzing method - Google Patents
Electrolyzing methodInfo
- Publication number
- CA1335974C CA1335974C CA 584501 CA584501A CA1335974C CA 1335974 C CA1335974 C CA 1335974C CA 584501 CA584501 CA 584501 CA 584501 A CA584501 A CA 584501A CA 1335974 C CA1335974 C CA 1335974C
- Authority
- CA
- Canada
- Prior art keywords
- ion
- chamber
- formula
- electrolyzing
- anode chamber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
Disclosed is an electrolyzing method especially for manufacturing an alkali hydroxide. The method comprises placing a solution of a compound represented by the formula A-B, wherein A is an alkali metal cation or an alkaline earth metal cation and B is an anion, in an electrolytic cell which is divided into an anode chamber and a cathode chamber by means of an ion exchange membrane, at least one of the electrodes in the two chambers being a gas permeable electrode, electrolyzing the solution while providing hydrogen evolved in the cathode chamber to the anode chamber by means of a communicating tube connecting the respective rear sides of the two electrodes, and producing a solution containing an alkali represented by the formula A(OH)X and an acid represented by the formula HyB in the cathode chamber and in the anode chamber, respectively, wherein X and Y are the valences of A and B, respectively. According to the present invention, a gas evolved in the anode chamber can be readily converted into the corresponding acid. Therefore, the operation is energy-saving .
Description
1- 133~974 The present invention relates to an electrolyzing method, and more particularly to a method for electrolytically manufacturing an alkali hydroxide or the like at a lower voltage while suppressing the formation of S surplus gases minimum.
Heretofore, many useful compounds have been made by means of various electrolyzing reactions employing an ion exchange membrane. Generally, in these electrolyzing reactions, hydrogen is generated on a cathode and oxygen or a halogen gas is generated on an anode. In the ordinary electrolyzing reactions, a main object is to obtain an alkali and an acid, and obtaining gases is not intended or is a secondary object.
The energy for generating the gases is quite high as is apparent from the fact that enormous energy is generated when these hydrogen and oxygen are subjected to combustion. In the conventional electrolyzing reaction which inevitably accompanies evolution of the above gases, a plenty of useless electrical energy has been wasted for producing the gases.
Many proposals for reducing the electrical energy in electrolysis have been made. However, many of these proposals intend to reduce the energy without suppressing evolution of the gas. An example of the proposals is an improvement of electrode material, that is, the proposal of a dimensionally stable electrode which usually comprises a _ - 2 - 1335974 titanium substrate plated with a noble metal oxide. Another example is to reduce the resistance between the electrodes by, for instance, removing an evolved gas present between an electrode and a membrane or by contacting the electrode to the membrane (for example, U.S.P No. 4,409,074). Although these two proposals have contributed to reduction of the voltage, further reduction is expected.
The invention provides an electrolyzing method in which the hydrogen gas evolved in the cathode chamber is effectively used for lowering the energy consumption in the anode chamber.
The invention is an electrolyzing method which comprises placing a solution of a compound represented by the formula A-B (wherein A is an alkali metal cation or an alkaline earth metal cation and B is an anion) in an electrolytic cell which is divided into an anode chamber and a cathode chamber by means of an ion exchange membrane electrolyzing the solution while providing hydrogen evolved in the cathode chamber to the anode chamber by means of a communicating tube connecting the both chambers, and producing a solution cont~;n;ng an alkali represented by the formula A(OH)X and an acid represented by the formula HyB (wherein X is a valency of A
and Y is a valency of B) in the cathode chamber and the anode - chamber, the anode chamber, respectively.
In this invention, at least part of hydrogen gas produced in the ~3) cathode chamber i5 provide~ into ~n anode ch~ml~er b~Y means o~ J
communic~till~ tube without takin~ it out of ~n electrolYtic cell. the hy~rogen gas is oxi~ize~ in the anode chamber to tl~ hYdrogen ion which is then combined with an anion already exiSting therein to form an ~cid. When 5 the hYdrogen ~s is not provided to the anod~ ~hflmber. the said cation already existing therein ig oxidized tO the correspvllding ~as. For ex~mple.
in Lh~ ca8e of Such a h~lo8en iOIl as a ~hlorine ion ~nd a flu~rine iOIl, they ar~ oxidi~ed to such a h~k~gen ax chlorine and fl4crille; in the c~se of a sulphatc ion ~n~l a nitr~t:e ion, theY are c~llvert~ t.rJ ~xyg-qn which is t~lken 10 out of the cell withol~t fllrther treatment; an~ in ~he ca~e of ~n vrganic aci~l ion, it. i~; oxidized and the resultant organic molecule is destroyed.
~ omParison of the ener~y quantity required for generation of ~e ~s throu~h oxidation of the chlnrine i~n and the lik~ and of that requir~d for ~ener~tion of the hydrogen ion throu~h vxidation of the h,~clrv~en ~ax revea 15 th~t th~ enery ~uantity of the l~tter is muc:l~ sm~ller. an~ efl~nolll~cal opera~i~n which greatlY decreascs ~he electric~l enel gy required f~r the produc~ion of l:he same ~uantity of ~n ~Ik~li can l~e performe~ accordin~ to th~ pre~ent invention.
l`he St~rting m~terial of th~ electrol~zing nlet.l~ocl of this illvention is 20 generally represented bY A-~. A is an alkali metal c~tinn or al~ alkallne earth me~l such as a sodium ion, a POt~S~iUm ion. a lit.h ium ion. ?l c~lcium ion an~ magne~iutn ion. B inclu~es ~ ~ulPhate ion, a h~Y~ro8ensul~ tc ion, a nitr.~te iun, a chlorine ion, a flu~rine ion ~nd an or~niu aci~l ion.
Th~refore, thc starLing material A-B of the inventisn inclu~ s f;D~lium 25 :~ul~h~tf~. sodium chlorid~, ~odiwll hy~rogen~ulph~tt~ utassillm fllloride, lithium nitr~tc~ calciurn ~ulPhate~ ~odium ox;~ alld sudiurn ci l.r . l he star~in~ material maY be a purc material or maY ~c ~ mixl.ur~ therevf, While ~ny one l~f the commerciallY avail~bl~ iun cxct~.~n~e m~mbrancs may ~4) 133S97~
be emPloYed for the Pr~sent invelltion, a ~luorine-containir~ ion exchange membrnne h~ving th~ Superior ~orrosion rç~ nc i~ preferably entl)ioye(l In Ihe case of Placing the salt solution of Lh~ rlin~ materi~l in the ~node chamber the c.q~ion exchange mem~riane is emPlo~Yed .~o that lhe ion A
S and the ion B are coll~cted to the athode chamber ~nd 1o ~he anode chalnbel, resPectively. On the other harld in the case vf placinf~ the sollltion in the cathode chamber the anion exch~nge membrane is elnploYed~
El~ctrocies t~ be emPloYed ~re desir~bly ~;o-call~ci gæ~ p~r~ Abl~
rlectrodes. The g~qs permeable electrode is one hAvin~: Ihe pro~erty uf ~:elec:tivelY le11ing a gas such ag hYdrogen or lI-e like p(rmoate ;lnd of pre~entillfS Perme~tion of such a liquid a~: w~ter 1~ ne ex;~nlple ~n clectrode ~omPrising a composite membralle con~;i.s ting of twn l;~r~ havir)~
the dif~rent propertie~; one l~yel- of which i~ ;l hydrophilic one ~Invin~ the él~ctrode flln~Lion anci facill~ the counter ele~t:rode ;~nd l.hF~ ot.h~r layer of which is a hydrol~hobic one cornPrisihg h~drophobic cari~oll hl~ck and pc~lYtetrafluoroe~hyl~ne (hereinafter referred tc~ ;ts P~FE) is kn~wn (for ex~mple ll. S P. No. 4.748.0~5). In ~clditi- ~I to the ~i.lS ~)enlleahl~
electrode aAn vrdinary sc)-c~ d dimen~;ionally ~;tal~lc electro-i- n~ay be employed.
When the g~:~ permea~le electrode is erllploytd ns th~ cathod- th~ ga~
evolved on lhF! electrode surface facin~ the ~node is led lo ilfi r~r ~;urface l~y I~Assing throllgh l.h~ electrode ~o th~t the illterele-:trvde vv It;lYe i~i not elevat~?d becausc the 8~ e~rolved does not exi:3t betW~!e~ ? e l~?clr~lcx which ~ttains muoh m~re voltage droP. and th~ itl hytlrOf~n g~S c~n be morc ~?~sily introdueed to the communicating tuh~. Wl.~n, nn l.lle olller h;~nd, ~I~eg~ permcable eleot~ode i,s emPloYed a:~ the ~n~d~, I.he hydrogen ~a~e; c~lning from the cathode ch~mher can bc easily oxidi~ y ~ir~ lY ~)rv-idi~lx the ~as to the re~r vf the anode, which t.hen passes throus3h the ;tnVIie cvlllprisirlx the 133~974 (~) gas permcable electrode to re~ch tlle electrode surf~ct~ fa~inf~ th~ cathode.
The electroly~ic cell to be ernployed is not e~eciallY r~s;îrict~d~ and any cell equipped with the communicatin~ tube for ,orovidill~ th~ hydrng~n ~a~
evolv~d in the cathode chambcr to the ~node ~halnb~r rn~ be ~.!mploy~d ln l.ho S ini~ial stage of the ~lectrolYsi~. the inl~rior ~r i.h~ eomrnunica~in~ t,lbc and of the both chambers is desir~bly repla~ed with ~ hYdros~ c~.
The electrolYsis condition:~ may be the same as those of the prior ~rt except for voltage. ~ecording ~o th~se conditions, ~h~ amount; of th~
cnn~;um~d cnc~r~y c~n be lower-ed to ol~e-fifth to one- t~nth ~f th~t ot` the 10 prior ~rt dependin~ on the electrolyte em~loyed ~nd th~ stru~tur~ of th~
electrolytic c~ll.
In the ordinary electrolysis, muc~h ell~r~y i~ re(l-llrcd fur c~nv~r~
an ~nion to the correspondin8 ga~, ror example, a chlorit-e ion Lo a chlorine ~as an~ a hydroxide ion to ~n oxYgen gas. Tn the presellt invelltion, the lS ~nioll in the anode ch~mber rn~Y be reacted wit.h the hy~lr~en ihn pro-luced from t.h~ ~id hydrogcll ~as to form thc corrcspondirl~ acid. 1 ho cnorgy required for the conver~ion of the hydroRcn gas to its i~n is mllch :~maller th~n th~t for the conver.sinn of th~ ;~ni~n to th~ corr~sp~l-din~ R;~s Accordin~3 tv the present invention. therefore, the eners~Y r~quired fol- the 20 ~volution of the ~as in the ~node chamber can be ~aved ~o th~t thc eMicient electrolYsis uper~tion can be achieved.
Furt.her, when the ~as permeable electrode is ~m~loYe<~. the ~a~; evolved on the electrode can be~e~sily t~ken out ~nd the hydro~en ~21S evolved i~l the cathode ch~mber m~Y be more smooth~Y ~ir~lllated to the ~ ode chalrlbel-, aT-d ~5 thc hydro~en ga~ provided P~sses throu~h the allode to r-ei1ch the allod~
surface f~ein~ the ~thode on which the g~ ; oxi~ t The invention will now be illu~;trated by Lhe ~'o.ll(lwin~ l xample~, which, however, ~re to be con~idered 3x merP~Iy ext?ll~plar~ o~ the~ Pra~tiGC of t~
(6) i3359~ ~
il~vention, and nvt as delimi~ive thereof.
Example l A gas perrneable electrod~ for an anode and 2~ cathode was pr~p~r~d according In thc followir~g Procedure.
A reactio n laye~ of which a Lhickno~;s was t~.l mm havir~ ele~trode function w;,s preparcd by mixin~ Platinutn fine p;~rt.icl~ ol` wllicl, a mcan Parti~le ~i7e was lO ~8L, hydruphilic c~rbon bl~ck Fin~ particle~ t~f which ~
mean ~rti~le size w~ 450 A an~i Pt~E fine p~rtiele~ of which a mean particle si~ w~s 0.3 ~I in the proportioll of 3; 3: ~. Th~ t 1~
permeable l~yer uf which ~ thicknes~ WJS 0.5 mm waS prepared b~ mlxinx hydrophobic carbvn black fil~e P~rticle~ nf which a mean particle size wz~Y
420 A and PTFr: fine p~rtictes of which a mean P~rti~le sk~ was ~3 ~ in the ProPortinn of 7: 3.
The both Iayers were joined to~ether with a cur~ t colle~tor nlacle of ~vPP~?r wirc interr~u~ed therebetween to form ~ gas per~e~hle electro~e.
An elec~rolytic cell consi~tillX of an arlode charrlI~el- and a c~tl1ode chamb~r was asscmbled empluyir~ the thII; prel~red ~ rm~able ~lectrode ~f~
the anode and the cathode. The both ch~mbers were sep~r~ted bY employing l'lafion (registered tr~demark) 117 which was a fluorine-cont.aiI-irlg c~tion exchange membr~ne of Du Pont with the interelect.rode dist~nce being 2 mm, an~ tt e the re~r surf~ces of the both electrode~ were connected by means of ~ communicatirlg tube made of polyvinyl chloride of which ~ di~meter was I
cm. ln the ~node ch~ml)er and in the e~thode chamber were l)la~ed 1~0 ~ vf a sodium suIPhate solution (1 mol/Q ) and lO0 Q of a sodium hy~iroxide svllltion ~0.1 mol~Q ~, rcspectively. The ~tmosl~t~el-e w~s replaced by flowing ;~ hydrogen gas into the both ch~mber:~ and the ~c~mmllni~ ting tube. So~lium hydroxide and suiphuric acid were manufactured bY çle~troly~in~ the ~vdiIlnl (7) 1335g79~
sulPhate with the ~urrent ~f 50 A flown between ~he both electr~des dnd with the respec~;ive electrolytes circulated in 1;he cell.
lhe interelectrode voltage durill~ tlle el~ctrt)l~si~,. the g~s evolv~d in the an~de ~ham~er an~ the cathode cham~cr and tht~ current e~ficiencY wer~
5 shown in the Table. The current efficiency was ~AIculate~ frym the valu~ of the ~odium hydrnxide produced and the vatue o~ tlle ~ rent.
Exarnple 2 Sodium hydroxid~ and sulphuric acid were manufactl~lecl br employing the ~ame ~lcctrnlytic cell ~nd the ~ame condition~ as tho~e o~ ~xample I except 10 that a ti~anium mesh havin8 an oPenin~ ratio of 40 ~ p~ tetl with platinum wa~ emPloYed a~ the cathode.
The interelectrode volta8e during Lll~ ele~trolysis. the ~as evolved i Lhe anode ~hamber and the cathod~ chamber and tlle current efficiency were shown in thc I able.
15 Examele 3 Sodium hydroxide ~nd hYd~ochloric acid werc manufa~tured by employillg ~he s~me elecLrnlytic cell and the same c~nditions as tho~e of Example I
excePt th~t a so~ium chloride solution was emplov~d as ~he ~n~ly~e.
The interelectrode volt~e during the electrolysis, the gas ~volv~d in 20 the anode chamt~er and the cathode chamb~r ~nd ~he current eff;ciencY were shown in the Table.
Compar~tiv~ Example Sodium hydroxide ~nd sulphuric acid were Manufa~tlu-ed ~y emPlo~n~ the same electrolytic cell an~ ~he ~ame con~itions as tho~e ~r Ex~mPle 2 except ~S~tha~ the communicatin~ tub~ was not equipped.
133597~
The interelecl~le voltage during the elecb~olysis, the gas evolved in the ancde cha~ber ~ the ci~tl~ 3~..~}-. an~ the current f~ff;~
were sh~n in the Table.
T A B L E
Es~ple 1 Exal~!ple 2 E}~?le 3 Canp. Exam.
Interele~L. ~e Volt~ge 1. 6 V 1. 6V 1. SV 3 . SV
lQ Gas in An~de Chaltber NQne NQne Ncme ~ch 2 Gas in Ca~le ~1~ lyr Ncne ~ch H NQne ~ch H
C~LL~lL l;'.ff;c~;~y 98 96 98 96 98 % 98 96 C~r~r;r~ the Exa~ples an~ the C~ Live Exa ~ le revealed th~t the ...~ de~l~ase of the Lnterele~LL~e voltage cculde ke achieved in the Exa~ples to cnntr;hllte to the e~yy~saving.
Heretofore, many useful compounds have been made by means of various electrolyzing reactions employing an ion exchange membrane. Generally, in these electrolyzing reactions, hydrogen is generated on a cathode and oxygen or a halogen gas is generated on an anode. In the ordinary electrolyzing reactions, a main object is to obtain an alkali and an acid, and obtaining gases is not intended or is a secondary object.
The energy for generating the gases is quite high as is apparent from the fact that enormous energy is generated when these hydrogen and oxygen are subjected to combustion. In the conventional electrolyzing reaction which inevitably accompanies evolution of the above gases, a plenty of useless electrical energy has been wasted for producing the gases.
Many proposals for reducing the electrical energy in electrolysis have been made. However, many of these proposals intend to reduce the energy without suppressing evolution of the gas. An example of the proposals is an improvement of electrode material, that is, the proposal of a dimensionally stable electrode which usually comprises a _ - 2 - 1335974 titanium substrate plated with a noble metal oxide. Another example is to reduce the resistance between the electrodes by, for instance, removing an evolved gas present between an electrode and a membrane or by contacting the electrode to the membrane (for example, U.S.P No. 4,409,074). Although these two proposals have contributed to reduction of the voltage, further reduction is expected.
The invention provides an electrolyzing method in which the hydrogen gas evolved in the cathode chamber is effectively used for lowering the energy consumption in the anode chamber.
The invention is an electrolyzing method which comprises placing a solution of a compound represented by the formula A-B (wherein A is an alkali metal cation or an alkaline earth metal cation and B is an anion) in an electrolytic cell which is divided into an anode chamber and a cathode chamber by means of an ion exchange membrane electrolyzing the solution while providing hydrogen evolved in the cathode chamber to the anode chamber by means of a communicating tube connecting the both chambers, and producing a solution cont~;n;ng an alkali represented by the formula A(OH)X and an acid represented by the formula HyB (wherein X is a valency of A
and Y is a valency of B) in the cathode chamber and the anode - chamber, the anode chamber, respectively.
In this invention, at least part of hydrogen gas produced in the ~3) cathode chamber i5 provide~ into ~n anode ch~ml~er b~Y means o~ J
communic~till~ tube without takin~ it out of ~n electrolYtic cell. the hy~rogen gas is oxi~ize~ in the anode chamber to tl~ hYdrogen ion which is then combined with an anion already exiSting therein to form an ~cid. When 5 the hYdrogen ~s is not provided to the anod~ ~hflmber. the said cation already existing therein ig oxidized tO the correspvllding ~as. For ex~mple.
in Lh~ ca8e of Such a h~lo8en iOIl as a ~hlorine ion ~nd a flu~rine iOIl, they ar~ oxidi~ed to such a h~k~gen ax chlorine and fl4crille; in the c~se of a sulphatc ion ~n~l a nitr~t:e ion, theY are c~llvert~ t.rJ ~xyg-qn which is t~lken 10 out of the cell withol~t fllrther treatment; an~ in ~he ca~e of ~n vrganic aci~l ion, it. i~; oxidized and the resultant organic molecule is destroyed.
~ omParison of the ener~y quantity required for generation of ~e ~s throu~h oxidation of the chlnrine i~n and the lik~ and of that requir~d for ~ener~tion of the hydrogen ion throu~h vxidation of the h,~clrv~en ~ax revea 15 th~t th~ enery ~uantity of the l~tter is muc:l~ sm~ller. an~ efl~nolll~cal opera~i~n which greatlY decreascs ~he electric~l enel gy required f~r the produc~ion of l:he same ~uantity of ~n ~Ik~li can l~e performe~ accordin~ to th~ pre~ent invention.
l`he St~rting m~terial of th~ electrol~zing nlet.l~ocl of this illvention is 20 generally represented bY A-~. A is an alkali metal c~tinn or al~ alkallne earth me~l such as a sodium ion, a POt~S~iUm ion. a lit.h ium ion. ?l c~lcium ion an~ magne~iutn ion. B inclu~es ~ ~ulPhate ion, a h~Y~ro8ensul~ tc ion, a nitr.~te iun, a chlorine ion, a flu~rine ion ~nd an or~niu aci~l ion.
Th~refore, thc starLing material A-B of the inventisn inclu~ s f;D~lium 25 :~ul~h~tf~. sodium chlorid~, ~odiwll hy~rogen~ulph~tt~ utassillm fllloride, lithium nitr~tc~ calciurn ~ulPhate~ ~odium ox;~ alld sudiurn ci l.r . l he star~in~ material maY be a purc material or maY ~c ~ mixl.ur~ therevf, While ~ny one l~f the commerciallY avail~bl~ iun cxct~.~n~e m~mbrancs may ~4) 133S97~
be emPloYed for the Pr~sent invelltion, a ~luorine-containir~ ion exchange membrnne h~ving th~ Superior ~orrosion rç~ nc i~ preferably entl)ioye(l In Ihe case of Placing the salt solution of Lh~ rlin~ materi~l in the ~node chamber the c.q~ion exchange mem~riane is emPlo~Yed .~o that lhe ion A
S and the ion B are coll~cted to the athode chamber ~nd 1o ~he anode chalnbel, resPectively. On the other harld in the case vf placinf~ the sollltion in the cathode chamber the anion exch~nge membrane is elnploYed~
El~ctrocies t~ be emPloYed ~re desir~bly ~;o-call~ci gæ~ p~r~ Abl~
rlectrodes. The g~qs permeable electrode is one hAvin~: Ihe pro~erty uf ~:elec:tivelY le11ing a gas such ag hYdrogen or lI-e like p(rmoate ;lnd of pre~entillfS Perme~tion of such a liquid a~: w~ter 1~ ne ex;~nlple ~n clectrode ~omPrising a composite membralle con~;i.s ting of twn l;~r~ havir)~
the dif~rent propertie~; one l~yel- of which i~ ;l hydrophilic one ~Invin~ the él~ctrode flln~Lion anci facill~ the counter ele~t:rode ;~nd l.hF~ ot.h~r layer of which is a hydrol~hobic one cornPrisihg h~drophobic cari~oll hl~ck and pc~lYtetrafluoroe~hyl~ne (hereinafter referred tc~ ;ts P~FE) is kn~wn (for ex~mple ll. S P. No. 4.748.0~5). In ~clditi- ~I to the ~i.lS ~)enlleahl~
electrode aAn vrdinary sc)-c~ d dimen~;ionally ~;tal~lc electro-i- n~ay be employed.
When the g~:~ permea~le electrode is erllploytd ns th~ cathod- th~ ga~
evolved on lhF! electrode surface facin~ the ~node is led lo ilfi r~r ~;urface l~y I~Assing throllgh l.h~ electrode ~o th~t the illterele-:trvde vv It;lYe i~i not elevat~?d becausc the 8~ e~rolved does not exi:3t betW~!e~ ? e l~?clr~lcx which ~ttains muoh m~re voltage droP. and th~ itl hytlrOf~n g~S c~n be morc ~?~sily introdueed to the communicating tuh~. Wl.~n, nn l.lle olller h;~nd, ~I~eg~ permcable eleot~ode i,s emPloYed a:~ the ~n~d~, I.he hydrogen ~a~e; c~lning from the cathode ch~mher can bc easily oxidi~ y ~ir~ lY ~)rv-idi~lx the ~as to the re~r vf the anode, which t.hen passes throus3h the ;tnVIie cvlllprisirlx the 133~974 (~) gas permcable electrode to re~ch tlle electrode surf~ct~ fa~inf~ th~ cathode.
The electroly~ic cell to be ernployed is not e~eciallY r~s;îrict~d~ and any cell equipped with the communicatin~ tube for ,orovidill~ th~ hydrng~n ~a~
evolv~d in the cathode chambcr to the ~node ~halnb~r rn~ be ~.!mploy~d ln l.ho S ini~ial stage of the ~lectrolYsi~. the inl~rior ~r i.h~ eomrnunica~in~ t,lbc and of the both chambers is desir~bly repla~ed with ~ hYdros~ c~.
The electrolYsis condition:~ may be the same as those of the prior ~rt except for voltage. ~ecording ~o th~se conditions, ~h~ amount; of th~
cnn~;um~d cnc~r~y c~n be lower-ed to ol~e-fifth to one- t~nth ~f th~t ot` the 10 prior ~rt dependin~ on the electrolyte em~loyed ~nd th~ stru~tur~ of th~
electrolytic c~ll.
In the ordinary electrolysis, muc~h ell~r~y i~ re(l-llrcd fur c~nv~r~
an ~nion to the correspondin8 ga~, ror example, a chlorit-e ion Lo a chlorine ~as an~ a hydroxide ion to ~n oxYgen gas. Tn the presellt invelltion, the lS ~nioll in the anode ch~mber rn~Y be reacted wit.h the hy~lr~en ihn pro-luced from t.h~ ~id hydrogcll ~as to form thc corrcspondirl~ acid. 1 ho cnorgy required for the conver~ion of the hydroRcn gas to its i~n is mllch :~maller th~n th~t for the conver.sinn of th~ ;~ni~n to th~ corr~sp~l-din~ R;~s Accordin~3 tv the present invention. therefore, the eners~Y r~quired fol- the 20 ~volution of the ~as in the ~node chamber can be ~aved ~o th~t thc eMicient electrolYsis uper~tion can be achieved.
Furt.her, when the ~as permeable electrode is ~m~loYe<~. the ~a~; evolved on the electrode can be~e~sily t~ken out ~nd the hydro~en ~21S evolved i~l the cathode ch~mber m~Y be more smooth~Y ~ir~lllated to the ~ ode chalrlbel-, aT-d ~5 thc hydro~en ga~ provided P~sses throu~h the allode to r-ei1ch the allod~
surface f~ein~ the ~thode on which the g~ ; oxi~ t The invention will now be illu~;trated by Lhe ~'o.ll(lwin~ l xample~, which, however, ~re to be con~idered 3x merP~Iy ext?ll~plar~ o~ the~ Pra~tiGC of t~
(6) i3359~ ~
il~vention, and nvt as delimi~ive thereof.
Example l A gas perrneable electrod~ for an anode and 2~ cathode was pr~p~r~d according In thc followir~g Procedure.
A reactio n laye~ of which a Lhickno~;s was t~.l mm havir~ ele~trode function w;,s preparcd by mixin~ Platinutn fine p;~rt.icl~ ol` wllicl, a mcan Parti~le ~i7e was lO ~8L, hydruphilic c~rbon bl~ck Fin~ particle~ t~f which ~
mean ~rti~le size w~ 450 A an~i Pt~E fine p~rtiele~ of which a mean particle si~ w~s 0.3 ~I in the proportioll of 3; 3: ~. Th~ t 1~
permeable l~yer uf which ~ thicknes~ WJS 0.5 mm waS prepared b~ mlxinx hydrophobic carbvn black fil~e P~rticle~ nf which a mean particle size wz~Y
420 A and PTFr: fine p~rtictes of which a mean P~rti~le sk~ was ~3 ~ in the ProPortinn of 7: 3.
The both Iayers were joined to~ether with a cur~ t colle~tor nlacle of ~vPP~?r wirc interr~u~ed therebetween to form ~ gas per~e~hle electro~e.
An elec~rolytic cell consi~tillX of an arlode charrlI~el- and a c~tl1ode chamb~r was asscmbled empluyir~ the thII; prel~red ~ rm~able ~lectrode ~f~
the anode and the cathode. The both ch~mbers were sep~r~ted bY employing l'lafion (registered tr~demark) 117 which was a fluorine-cont.aiI-irlg c~tion exchange membr~ne of Du Pont with the interelect.rode dist~nce being 2 mm, an~ tt e the re~r surf~ces of the both electrode~ were connected by means of ~ communicatirlg tube made of polyvinyl chloride of which ~ di~meter was I
cm. ln the ~node ch~ml)er and in the e~thode chamber were l)la~ed 1~0 ~ vf a sodium suIPhate solution (1 mol/Q ) and lO0 Q of a sodium hy~iroxide svllltion ~0.1 mol~Q ~, rcspectively. The ~tmosl~t~el-e w~s replaced by flowing ;~ hydrogen gas into the both ch~mber:~ and the ~c~mmllni~ ting tube. So~lium hydroxide and suiphuric acid were manufactured bY çle~troly~in~ the ~vdiIlnl (7) 1335g79~
sulPhate with the ~urrent ~f 50 A flown between ~he both electr~des dnd with the respec~;ive electrolytes circulated in 1;he cell.
lhe interelectrode voltage durill~ tlle el~ctrt)l~si~,. the g~s evolv~d in the an~de ~ham~er an~ the cathode cham~cr and tht~ current e~ficiencY wer~
5 shown in the Table. The current efficiency was ~AIculate~ frym the valu~ of the ~odium hydrnxide produced and the vatue o~ tlle ~ rent.
Exarnple 2 Sodium hydroxid~ and sulphuric acid were manufactl~lecl br employing the ~ame ~lcctrnlytic cell ~nd the ~ame condition~ as tho~e o~ ~xample I except 10 that a ti~anium mesh havin8 an oPenin~ ratio of 40 ~ p~ tetl with platinum wa~ emPloYed a~ the cathode.
The interelectrode volta8e during Lll~ ele~trolysis. the ~as evolved i Lhe anode ~hamber and the cathod~ chamber and tlle current efficiency were shown in thc I able.
15 Examele 3 Sodium hydroxide ~nd hYd~ochloric acid werc manufa~tured by employillg ~he s~me elecLrnlytic cell and the same c~nditions as tho~e of Example I
excePt th~t a so~ium chloride solution was emplov~d as ~he ~n~ly~e.
The interelectrode volt~e during the electrolysis, the gas ~volv~d in 20 the anode chamt~er and the cathode chamb~r ~nd ~he current eff;ciencY were shown in the Table.
Compar~tiv~ Example Sodium hydroxide ~nd sulphuric acid were Manufa~tlu-ed ~y emPlo~n~ the same electrolytic cell an~ ~he ~ame con~itions as tho~e ~r Ex~mPle 2 except ~S~tha~ the communicatin~ tub~ was not equipped.
133597~
The interelecl~le voltage during the elecb~olysis, the gas evolved in the ancde cha~ber ~ the ci~tl~ 3~..~}-. an~ the current f~ff;~
were sh~n in the Table.
T A B L E
Es~ple 1 Exal~!ple 2 E}~?le 3 Canp. Exam.
Interele~L. ~e Volt~ge 1. 6 V 1. 6V 1. SV 3 . SV
lQ Gas in An~de Chaltber NQne NQne Ncme ~ch 2 Gas in Ca~le ~1~ lyr Ncne ~ch H NQne ~ch H
C~LL~lL l;'.ff;c~;~y 98 96 98 96 98 % 98 96 C~r~r;r~ the Exa~ples an~ the C~ Live Exa ~ le revealed th~t the ...~ de~l~ase of the Lnterele~LL~e voltage cculde ke achieved in the Exa~ples to cnntr;hllte to the e~yy~saving.
Claims (3)
1. An electrolyzing method which comprises placing a solution of a compound represented by the formula A-B, wherein A is an alkali metal cation or an alkaline earth metal cation and B is an anion, in an electrolytic cell which is divided into an anode chamber and a cathode chamber by means of an ion exchange membrane, at least one of the electrodes in the two chambers being a gas permeable electrode, electrolyzing the solution while providing hydrogen evolved in the cathode chamber to the anode chamber by means of a communicating tube connecting the respective rear sides of the two electrodes, and producing a solution containing an alkali represented by the formula A(OH)X and an acid represented by the formula HyB, wherein X is a valency of A and Y is a valency of B, in the cathode chamber and the anode chamber, respectively.
2. An electrolyzing method as claimed in Claim 1, wherein A
is one or more cations selected from the group consisting of a sodium ion, a potassium ion, a lithium ion, a calcium ion and a magnesium ion.
is one or more cations selected from the group consisting of a sodium ion, a potassium ion, a lithium ion, a calcium ion and a magnesium ion.
3. An electrolyzing method as claimed in Claim 1, wherein B
is one or more anions selected from the group consisting of a sulphate ion, a hydrogensulphate ion, a nitrate ion, a chloride ion, a fluoride ion and an organic acid ion.
is one or more anions selected from the group consisting of a sulphate ion, a hydrogensulphate ion, a nitrate ion, a chloride ion, a fluoride ion and an organic acid ion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62302565A JP2648313B2 (en) | 1987-11-30 | 1987-11-30 | Electrolysis method |
| JP62-302565 | 1987-11-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1335974C true CA1335974C (en) | 1995-06-20 |
Family
ID=17910507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 584501 Expired - Fee Related CA1335974C (en) | 1987-11-30 | 1988-11-29 | Electrolyzing method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2648313B2 (en) |
| CA (1) | CA1335974C (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2008278300B1 (en) * | 2008-12-23 | 2009-07-16 | Eleryc, Inc. | Low energy electromechanical hydroxide system and method |
| US7744761B2 (en) | 2007-06-28 | 2010-06-29 | Calera Corporation | Desalination methods and systems that include carbonate compound precipitation |
| US7749476B2 (en) | 2007-12-28 | 2010-07-06 | Calera Corporation | Production of carbonate-containing compositions from material comprising metal silicates |
| US7753618B2 (en) | 2007-06-28 | 2010-07-13 | Calera Corporation | Rocks and aggregate, and methods of making and using the same |
| US7754169B2 (en) | 2007-12-28 | 2010-07-13 | Calera Corporation | Methods and systems for utilizing waste sources of metal oxides |
| US7771684B2 (en) | 2008-09-30 | 2010-08-10 | Calera Corporation | CO2-sequestering formed building materials |
| US7790012B2 (en) | 2008-12-23 | 2010-09-07 | Calera Corporation | Low energy electrochemical hydroxide system and method |
| AU2010201006B2 (en) * | 2009-02-10 | 2010-10-14 | Arelac, Inc. | Low-voltage alkaline production from brines |
| US7815880B2 (en) | 2008-09-30 | 2010-10-19 | Calera Corporation | Reduced-carbon footprint concrete compositions |
| US7829053B2 (en) | 2008-10-31 | 2010-11-09 | Calera Corporation | Non-cementitious compositions comprising CO2 sequestering additives |
| US7875163B2 (en) | 2008-07-16 | 2011-01-25 | Calera Corporation | Low energy 4-cell electrochemical system with carbon dioxide gas |
| US7887694B2 (en) | 2007-12-28 | 2011-02-15 | Calera Corporation | Methods of sequestering CO2 |
| US7939336B2 (en) | 2008-09-30 | 2011-05-10 | Calera Corporation | Compositions and methods using substances containing carbon |
| US7966250B2 (en) | 2008-09-11 | 2011-06-21 | Calera Corporation | CO2 commodity trading system and method |
| US7993500B2 (en) | 2008-07-16 | 2011-08-09 | Calera Corporation | Gas diffusion anode and CO2 cathode electrolyte system |
| US7993511B2 (en) | 2009-07-15 | 2011-08-09 | Calera Corporation | Electrochemical production of an alkaline solution using CO2 |
| US8137444B2 (en) | 2009-03-10 | 2012-03-20 | Calera Corporation | Systems and methods for processing CO2 |
| US8357270B2 (en) | 2008-07-16 | 2013-01-22 | Calera Corporation | CO2 utilization in electrochemical systems |
| US8491858B2 (en) | 2009-03-02 | 2013-07-23 | Calera Corporation | Gas stream multi-pollutants control systems and methods |
| US8834688B2 (en) | 2009-02-10 | 2014-09-16 | Calera Corporation | Low-voltage alkaline production using hydrogen and electrocatalytic electrodes |
| US8869477B2 (en) | 2008-09-30 | 2014-10-28 | Calera Corporation | Formed building materials |
| US9133581B2 (en) | 2008-10-31 | 2015-09-15 | Calera Corporation | Non-cementitious compositions comprising vaterite and methods thereof |
| US9260314B2 (en) | 2007-12-28 | 2016-02-16 | Calera Corporation | Methods and systems for utilizing waste sources of metal oxides |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1248564B (en) * | 1991-06-27 | 1995-01-19 | Permelec Spa Nora | ELECTROCHEMICAL DECOMPOSITION OF NEUTRAL SALTS WITHOUT HALOGEN OR ACID CO-PRODUCTION AND ELECTROLYSIS CELL SUITABLE FOR ITS REALIZATION. |
| US5246551A (en) * | 1992-02-11 | 1993-09-21 | Chemetics International Company Ltd. | Electrochemical methods for production of alkali metal hydroxides without the co-production of chlorine |
| KR100859176B1 (en) * | 2007-06-12 | 2008-09-19 | 삼성전기주식회사 | Electrolyte solution for hydrogen generating apparatus and hydrogen generating apparatus comprising the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL62236A0 (en) * | 1980-03-24 | 1981-05-20 | Shaw R | Apparatus and method for detecting,localizing and quantifying coronary stenoses from the body surface |
-
1987
- 1987-11-30 JP JP62302565A patent/JP2648313B2/en not_active Expired - Lifetime
-
1988
- 1988-11-29 CA CA 584501 patent/CA1335974C/en not_active Expired - Fee Related
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7744761B2 (en) | 2007-06-28 | 2010-06-29 | Calera Corporation | Desalination methods and systems that include carbonate compound precipitation |
| US7753618B2 (en) | 2007-06-28 | 2010-07-13 | Calera Corporation | Rocks and aggregate, and methods of making and using the same |
| US7931809B2 (en) | 2007-06-28 | 2011-04-26 | Calera Corporation | Desalination methods and systems that include carbonate compound precipitation |
| US7914685B2 (en) | 2007-06-28 | 2011-03-29 | Calera Corporation | Rocks and aggregate, and methods of making and using the same |
| US7887694B2 (en) | 2007-12-28 | 2011-02-15 | Calera Corporation | Methods of sequestering CO2 |
| US7749476B2 (en) | 2007-12-28 | 2010-07-06 | Calera Corporation | Production of carbonate-containing compositions from material comprising metal silicates |
| US7754169B2 (en) | 2007-12-28 | 2010-07-13 | Calera Corporation | Methods and systems for utilizing waste sources of metal oxides |
| US9260314B2 (en) | 2007-12-28 | 2016-02-16 | Calera Corporation | Methods and systems for utilizing waste sources of metal oxides |
| US8333944B2 (en) | 2007-12-28 | 2012-12-18 | Calera Corporation | Methods of sequestering CO2 |
| US8894830B2 (en) | 2008-07-16 | 2014-11-25 | Celera Corporation | CO2 utilization in electrochemical systems |
| US7875163B2 (en) | 2008-07-16 | 2011-01-25 | Calera Corporation | Low energy 4-cell electrochemical system with carbon dioxide gas |
| US7993500B2 (en) | 2008-07-16 | 2011-08-09 | Calera Corporation | Gas diffusion anode and CO2 cathode electrolyte system |
| US8357270B2 (en) | 2008-07-16 | 2013-01-22 | Calera Corporation | CO2 utilization in electrochemical systems |
| US7966250B2 (en) | 2008-09-11 | 2011-06-21 | Calera Corporation | CO2 commodity trading system and method |
| US7815880B2 (en) | 2008-09-30 | 2010-10-19 | Calera Corporation | Reduced-carbon footprint concrete compositions |
| US8869477B2 (en) | 2008-09-30 | 2014-10-28 | Calera Corporation | Formed building materials |
| US7771684B2 (en) | 2008-09-30 | 2010-08-10 | Calera Corporation | CO2-sequestering formed building materials |
| US7939336B2 (en) | 2008-09-30 | 2011-05-10 | Calera Corporation | Compositions and methods using substances containing carbon |
| US8006446B2 (en) | 2008-09-30 | 2011-08-30 | Calera Corporation | CO2-sequestering formed building materials |
| US8603424B2 (en) | 2008-09-30 | 2013-12-10 | Calera Corporation | CO2-sequestering formed building materials |
| US8470275B2 (en) | 2008-09-30 | 2013-06-25 | Calera Corporation | Reduced-carbon footprint concrete compositions |
| US8431100B2 (en) | 2008-09-30 | 2013-04-30 | Calera Corporation | CO2-sequestering formed building materials |
| US9133581B2 (en) | 2008-10-31 | 2015-09-15 | Calera Corporation | Non-cementitious compositions comprising vaterite and methods thereof |
| US7829053B2 (en) | 2008-10-31 | 2010-11-09 | Calera Corporation | Non-cementitious compositions comprising CO2 sequestering additives |
| AU2008278300B1 (en) * | 2008-12-23 | 2009-07-16 | Eleryc, Inc. | Low energy electromechanical hydroxide system and method |
| US7790012B2 (en) | 2008-12-23 | 2010-09-07 | Calera Corporation | Low energy electrochemical hydroxide system and method |
| AU2010201006B2 (en) * | 2009-02-10 | 2010-10-14 | Arelac, Inc. | Low-voltage alkaline production from brines |
| US8834688B2 (en) | 2009-02-10 | 2014-09-16 | Calera Corporation | Low-voltage alkaline production using hydrogen and electrocatalytic electrodes |
| US9267211B2 (en) | 2009-02-10 | 2016-02-23 | Calera Corporation | Low-voltage alkaline production using hydrogen and electrocatalytic electrodes |
| US8491858B2 (en) | 2009-03-02 | 2013-07-23 | Calera Corporation | Gas stream multi-pollutants control systems and methods |
| US8883104B2 (en) | 2009-03-02 | 2014-11-11 | Calera Corporation | Gas stream multi-pollutants control systems and methods |
| US8137444B2 (en) | 2009-03-10 | 2012-03-20 | Calera Corporation | Systems and methods for processing CO2 |
| US7993511B2 (en) | 2009-07-15 | 2011-08-09 | Calera Corporation | Electrochemical production of an alkaline solution using CO2 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01142093A (en) | 1989-06-02 |
| JP2648313B2 (en) | 1997-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1335974C (en) | Electrolyzing method | |
| US20160222524A1 (en) | Electrochemical production of hydrogen | |
| US11560638B2 (en) | Electrochemical method of ammonia generation | |
| US5219671A (en) | Hydrogen generation and utility load leveling system and the method therefor | |
| US4316782A (en) | Electrolytic process for the production of ozone | |
| US6063258A (en) | Production of hydrogen from water using photocatalyst-electrolysis hybrid system | |
| JPH02197590A (en) | Redox reaction method and electrolytic bath for it | |
| JP2000290791A (en) | Electrochemical production of lithium | |
| US4156635A (en) | Electrolytic method for the production of lithium using a lithium-amalgam electrode | |
| CN102839389B (en) | Novel production method of electro-depositing and refining metal chloride by membrane process | |
| CN113603059B (en) | Molten salt, electrochemical purification method of molten salt and electrochemical device | |
| US5004527A (en) | Continuous electrolytic production of alkali metal perchlorates | |
| US5496454A (en) | Method for the operation of electrolytic baths to produce Fe3 O4 electrophoretically in a three compartment cell | |
| Huissoud et al. | Electrochemical reduction of 2-ethyl-9, 10-anthraquinone (EAQ) and mediated formation of hydrogen peroxide in a two-phase medium Part II: Production of alkaline hydrogen peroxide by the intermediate electroreduction of EAQ in a flow-by porous electrode in two-phase liquid–liquid flow | |
| JPH11140679A (en) | Electrolytic cell for production of hydrogen peroxide | |
| KR890002059B1 (en) | Electrolytic process for manufacturing pure potassium peroxydiphosphate | |
| IL98516A (en) | Alkali metal hydroxide generation system and the method therefor | |
| KR890002060B1 (en) | Electrolytic process for manufacturing potassium peroxydephosphate | |
| US4256549A (en) | Hybrid process for producing hydrogen | |
| CN114672826B (en) | Double cathode electrolytic tank capable of producing hydrogen peroxide or hydrogen in switching mode | |
| CN114016083B (en) | Method for regenerating alkali metal reducing agent in process of preparing metal by alkali metal thermal reduction of metal oxide | |
| SU1033576A1 (en) | Method for preparing antimonous hydride | |
| Yanagase et al. | The production of hypochlorite by direct electrolysis of sea water-influence of electrode gap | |
| US4582584A (en) | Metal electrolysis using a semiconductive metal oxide composite anode | |
| CH679437A5 (en) | Aluminium gas battery with reduced hydrogen evolution - has acid electrolyte and aluminium@ (alloy) electrode contg. lithium, beryllium, magnesium, calcium, zinc, etc. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |