CA2074082A1 - Electrochemical process for producing chloric acid - alkali metal chlorate mixtures - Google Patents
Electrochemical process for producing chloric acid - alkali metal chlorate mixturesInfo
- Publication number
- CA2074082A1 CA2074082A1 CA002074082A CA2074082A CA2074082A1 CA 2074082 A1 CA2074082 A1 CA 2074082A1 CA 002074082 A CA002074082 A CA 002074082A CA 2074082 A CA2074082 A CA 2074082A CA 2074082 A1 CA2074082 A1 CA 2074082A1
- Authority
- CA
- Canada
- Prior art keywords
- compartment
- alkali metal
- chlorate
- ion exchange
- chloric acid
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2475—Membrane reactors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00058—Temperature measurement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00103—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger separate from the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/09—Reaction techniques
- Y10S423/13—Catalyst contact
Abstract
2074082 9112356 PCTABS00006 An aqueous solution of chloric acid and alkali metal chlorate is produced in an electrolytic cell (4) having an anode compartment (10), a cathode compartment (30), and at least one ion exchange compartment (20) between the anode compartment (10) and the cathode compartment (30). The process comprises feeding an aqueous solution of an alkali metal chlorate to the ion exchange compartment (20), electrolyzing an anolyte (12) in the anode compartment (10) to generate hydrogen ions, passing the hydrogen ions from the anode compartment (10) through a cation exchange membrane (16) into the ion exchange compartment (20) to displace alkali metal ions and produce an aqueous solution of chloric acid and alkali metal chlorate, and passing alkali metal ions from the ion exchange compartment (20) into the cathode compartment (30).
Description
2 ~
~` W091/12356 PCT/US91/00172 ACID - ~L~LI ~ LOR~T~ Tu~s This in~ention relates to a proce~ for electrochemically producing chloric acid - alkali met~l chlorate solutions.
More particularly, this invention relates to the electrochemical pro~uction of chloric &cid - ~lkali metal 5 chlorate ~olutions suitable for the generation of chlorine dio~ide.
Chlorine dio~ide h~s found wide use ~8 a di~infectant in w~ter treatment/purification, a~ ~ bleaching ~gent in pulp and paper production, a~d a number of other uses due to its 10 high o~idizing power. Ther~ is ~ variety of chlor~ne dio~ide generator systems and processes av~ilable in the marketpl~ce. Most of the very large scale generators employed, for esample, in pulp and paper production, utilize an alka}i metal chlorate salt, a reducing agenti and an w id 15 in a chemical process for pro~ucing chlorine dio~ide. These generators and the processes e~ployed al50 produce by-product salts such as sodium chloride, sodium sul~te, or sodium bisulfate. In pulp and paper mill~, the typical by-product is sodium sulfate (saltcake) which is converted into ~ sulfur 20 salt of sodium in a high temperature boiler Jnd used in the paper process. Boilers require energy and the paper mills have a limited boiler capacity. Increasing the production of chlorine dio~ide generally means increased capital in~estment to provide the added boiler capacity regu~red to process the 25 added amounts o~ saltcake by-product produced.
.
. : . .
.. . ... . ..
. ~ . , .
WO91/12356 ~ ~ ~ ~ 8 2 PCT/US~1~00172 Thu~ a proce~s ~hich ~eduoe~ the ~mount of o by-product ~alt, such ~s sodium chlori~e or 30dium sulf~te, produced wh~le efficl~ntly generating chlorine dio~lde i3 commerci~lly ~esir~able.
~.S. Patent 3,310,969 is~ued M~y l~, 1974 to A.A.
Schlumber9Pr teaches ~ process for producing chlsric ~cid by passing an aqueous solution containing rom 0.2 gram mole to ll gram moles per liter of an alkali m~t~l chlorate such ~s ~odium chlorate through a selected cationic e~change resin at a temperature from 5- to 40- C. The proces~ produces an aqueous solution containing from 0.2 gram mole to about 4.0 gram moles of HC103. This process requires the regeneration of the cationic e~change resin with acid to cemo~e the alkali metal ions and the treatment or dispos~l o~
the acidic ~nlt solution.
~.L. Hardee et al, in U.S. Patent No. 4,79B,715 issued Jan. 17,l9a9, describe ~ process for chlorine dio~ide which electroly~es a chloric acid solution produced by passing an aqueous solution of an alkali metal chlorate through an ion e~change resin. The electroly~ed solution conthins a mi~ture o~ chlorine dio~ide and chloric acid ~hich i5 fed to an e~tractor in which the chlorine dio~ide i~ stripped off. Thc ion eschange ~e5in i5 regener~ted with hydroc~loric acid 3nd an acidic solution o~ an alkali metal chloride formed.
In U.S. Patent No. 4,683,039, Swardowski et ~1 describe method for producing chlorine dio~ide in which the chlorine dio~ide i5 produced in a genetator by th~ reaction of sodium chlorate and hydrochloric acid. Ater separating chlorine dio~ide gas, the remaining sodium chloride solution is fed to a three-compartment cell to form sodium hydro~ide and an acidified liquor which is returned to the chlorine dio~ide generator.
Each of the above processes produce~ a f~ed amount and type o by-product ~alt.
2~082 : W091/12356 PCT/US91/00172 Now ~ proce~ has been discovered which permits varinbility in the composition of a chlorate solution used in chlorine dio~ide generators. Further, the process permits a reduction in the amount of acid requir~d and sub~equently the 5 amount of salt by-product produced in the chlorine dioxide generator. Still further, the process allow~ for the production o an alkali metal hydro~ide as ~ valuable by-product or ~cidic solutions of alkali metal salts at reduced energy costs. In addition, the process re~ult~ in 10 the reduction of process steps and pro~ess equipment required for the production of chlorine dio~ide.
These and other advantages are accomplished in a process for electrolytically producing an aqueous solution of chloric acid and alkali metal chlorate in an electrolytic cell h3ving 15 an anode compartment, a cathode compartment, and at least one ion e~change compartment between the anode compartment and the cathode compartment, characterized by feeding an aqueous solution of an alkali metal chlorate to the ion e~change compartment, electroly~ing an anolyte in the anode 20 compartment to generate hydrogen ions, passing the hydrogen ions from the anode compartment through a cation e~change membrane into the ion e~change compartment to displace alkali metal ions and produce an aqueous solution of chloric acid and alkali metal chlorate, and passing alkali metal ions from 2s the ion exchange compartment into the cathode compartment.
More in detail, the novel process of the present invention and its application in producing chlorine dio~ide can be carried out in apparatus i.lustrated in the following FI~URES.
Figure 1 is a sectional side elevational view of an electrolytic cell which can be employed in the novel process of the invention; and 2~0~ -W~91/12356 PCT/US9ltO0172 Figure 2 is a section~l side el~v~tional view o~ ~n addition~l electrolytic cell whi~h c~n be employed in the novel process of the in~ention.
Figure 3 is a diAgramm3tic illustr~tion of ~ ~ystem which can be employed in the process of the in~ention.
FIGURE 1 shows ~n electrolytic cell ~ divided into anode compartment 10, ion e~change compartment 20, and cathode compartment 30 by cDtion permeable ion eschange me~branes 16 and 24. Anode compartment 10 includes anode 12, and anode spacer 14. Anode spacer 14 positions porou~ anode 12 with respect to cation permeable ion e~c~ange membrane 16 and aids in the disengagement of ~nolyte gas produced. Anolyte disengager 1~ completes the disengagement of anolyte gas from the ~pent anolyte ~olut~on. Ion e~change comp~rtment 20 includes spacer material 22 which prov~des a flow channel between cation permeable ion e~change membranes 16 and 24 for the aqueous ~lkali met~l chlorate solution. Cathode compartment 30 includes cathode 32, and cathode spacer 34.
Cathode space~ 34 positions c~thode 32 with respect to cation permeable ion e~cbange membrane 24 and ai~s in the disengagement of c~tholyte ga5 pro~uced. The ~s~ngagement of catholyte gas from the spent catholyte solution is accomplished in cathode disengager 36.
In FIGVRE 2, electrolytic cell 4 has been e~panded to include a second ion e~change compartment 40 which is positioned between anode compa~tment 10 and ion e~chanqe compartment 20. Cation permeable ion e~change membrane 42 separates anode ~ompartment lO from ion e~change compartment 40. The sodium chlorate feed solution enters the lower part of ion eschange compartment 2Q, flows upward and out of ion e~chang~ compartment 20 into the upper part of ~on e~change compartm~nt 40. The HC103 ~ NaC103 product solution i~
reco~ered from the lower part of ion eschan~e compartment 40.
8:2 W091/~2356 ~ 5 ~ PCT/US91/00172 The low ~irect~on in the lon ~chan~ ~o~partment~ can ~lso be reversed, for e~ample, with the 801ut~0n Yrom the top of ion c~change comp~rtment qO being ~ed to the bottom of lon e~change compartment 20. The product solution then e~its from the top of ion e~change comp~rtment 20.
~ n aqueous ~olution of an alkali metal chlorate is fed to the single or mult~ple ion e~change comp~rt~ents o~ the electrolytic cell. Suit~ble alk~li m~t~l chlorates include sodium c~lorate, potassium chlorate and lithium chlorate. Ih o order to simpliEy the ~isclosure, the proce~s of the invention will be described using sodium chlorate, which is ~
preferred embodiment of the alk~li met~l chlorates. ~ ~hown in FIGURE 3, the ~odium chlor~te feed ~olution may be prepared, for e2ample, by di~solvin9 cry~talline ~odium chlorate ~n water. Commercial ~odium chlorate is suitable as it h~s a low ~odium chloride content and the formation of undesireable amounts of chlorine dio~ide in the electrolytic cell i5 prevented. ~queous sodium chlorate feed 301utions w~ich may be employed contain any 5uitable -oncentrations of sodium chlorate, for e~ample, solutions having a concentration in the ran9e of from about O.l ~ by weight to those saturated with NaClO3 at temper~tures in the r~nge of from ~b3ut 0- to ~out lO0-, ~nd preferably from about lS- to about 80-C.
The novel process of the invention utilizes an electrochemic~l cel} to generate hydrosen ions that displace or replace a portion of the sodium ions present ~n the aqueous sodium chlorate solution eed stream.
The generation of hydrosen ions in the process of the present invention ~n the anode compartment is accompanied, for esample, by the o~idation of water on the anode into o~ygen g~s and H~ ions by the electrode reaction as follows:
(4) 2H20~ > 2 ~ qH ~ 4e Wo91/123S6 2 0 ~ ~ ~ 8 2 PCT/USs~/00172 ~-The anode comp~rtment contaln~ Dn anolyte, which can be an a~ueou 301ut~0n of any non-osidi~ble ~ci~ electrolyte which i~ ~uitabl~ for conductin~ hydrogen ion~ into the ion e~hange comp~rtment. Non-osidi~able ~cids which may be used include ~ulfuric acid, pho~phoric acid andl the like. Where non-o~idiz~ble acid solution is used as tbe anolyte, the concentration of the ~nolyte is preferably ~electe~ to match the o~motic concentrat~on ch~r~cteristi~s of the alkali me~al chlorate solution fed to the ion e~change compartment to 10 minimize water eschange between the anode compartment and th~
ion eschange compartment. Addition~lly, an ~lkali metal choride solution can be used as the anolyte, which results in a generation of chlorine gas At the Anode. Where a chlorine generating anolyte is employed, it i8 necessary to select ~
15 cation esch~nge membrane as the ~ep~rator between the anode compartment from the ion e~change compartment which is stable to chlorine gas. The anode compartment may also employ as the anolyte electrolyte a strong acid cation e~change resin in the hydrogen form and an aqueous ~olution such as deionized 20water.
Any auit~ble anode may be employed in the anode compartment, including those which are available commercially ~8 dimensionally atable anodes. Prsferably, an anode is selected which will generate osygen gas. These anodes 25include porous or high surface area anodes. As materials of construction for the anodes metals including platinum, gold, palladium, or mistures or alloys thereof, or thin coatings of such materials on various substrates such as valqe metals, i.e. titanium, can be used. Additionally o~ides of iridium, 30rhodium or ru~henium, and alloys with other platinum group or precious meta}s metals could also be employed. Commercially available osygen evolution anodes of this type include those manufactured by Englehard (PMCA 1500) or Eltech ~TIR-2000).
Other suitable anode materials include graphite, graphite 35felt, a multiple layered graphite cloth, a graphite cloth ~ Wo91/1235~ 2 ~ 7 ~ ~ ~ 2 PCT/US91/00172 we~e, carbon, etc..
The hydrogen ions generated in t~e ~node comp3rtment pass ~hrough the c~tion ~change membrane into the ~odium c~lor~te solution in the ion e~change comp~rtment. ~s a hydrogen ion 5 enters the solution, ~ sodium ion is displaced and by electrical ion mass action passes throu9h the c~tion membrane adj~cent to the c~thode compartment to ~aint~in electrical neutrality.
The novel process of the invention as operated results in 10 the con~ersion of sodium c~lor~te to chloric acid over A wide ange, fo~ esample, from about 1 to about 99.9~, pre~erably from about 5 to about 95, and more preferably from about 15 to about 90%.
The sodium chlorate feed 501ution concentration, the 15 residence time in the ion e~chanqe compartment ~s well as the cell amperage are factors th~t ~ffect the e~tent o the conversion of ~odium chlQrate to chloric ~cid. Using very dilute solutions o~ sodium chlorate, high percentages of conversion o~ NaC103 to chloric acid ean be achieved, i.e.
20 up to 99.9~ conversion. For ~ single pass flow through system, typical residence times in the ion e~change compartment ~re between about 0.1 to about 120 minutes, with a more preferr~d r~n9e o~ about 0.5 to about 60 minutes.
Thus the concentration of sodium chlor~te in the ~olution 25 fed to the ion e~change compartment and the 10w rate of the solution through the ion exchange _ompartment are not critical and broad ranges can be selected ~or each of these parameters.
The novel process of the present invention is operated at 30 a current density of from about 0.01 KA/m to about 10 KA~m2, with a more preferred range of about 0.05 KA/m2 to about 3 XA~m .
Current efficiencies during operation of the process of the invention can be increased by employing a~ditional ion 35 e~change compartment3, as illustrated by FI~URE 2, which are adjacent and operated in a series flow pattern.
-. .
2 ~ 2 WO 91/12356 PCT~US91/00172 Adjusting th~ width of the ion e~change compartment c~nalso alter the operating cell voltage ~nd curr~nt e~ficiency. The wid~h, or spa~e between the c~tion e~c~ange membranes forming the W81ls of the ion e~ch~nge compDrtment, is in the ranqe of from ~bout O.l to about lO, ~nd prefer~bly from about 0.3 to abo~t 5 centimeters.
In ~n altern~te embodiment the ion e~cchanse compartment contains a c~tion e~change medium- Cation e~change mediums which c~n be used in the ion e~change cornpartment include cation eschange resins. Suitable cation e~change resins include those having substrates and backbones of polystyrene based with di~inyl benzene, cellulose b~sed, fluorocarbon based, synthetic polymeric types 3nd the lik~. Where more than one ion e~change compartment is employ~d, inclusion o~
the cation e~ch~nge medium is optional for each compartment.
Functional cationic ~roups on these mediums which may be employed include carbo~ylic ~cid, sulfonic or sulfuric acids, and acids of phosphorus such as p~osphonous, phosphonic or phosphoric. The cation 2~change resins are suitably ionically conductive so that a practical amount Q~ current can be passed between the cation e~change membranes used as separators. v~rious percentage mi~ture of resins in the hydrogen form ~nd the sodium orm may be useC in various sections of the ion exchange compartments on ~ssembly to compensate for the swelling ~nd conttaction of resins during cell operation. For e~ample, percentage ratios o~ hydrogen form to sodium form may include those from 50 to lO0~.
The use o~ cation exchange resins in the ion exchange compartment can serve as an active mediator which can e~change or absorb sodium ions and release hydrogen ions.
The hydrogen ions generated at the anode thus regenerate the resin to the hydrogen orm, releasing sodium ions to pass into the cathode compartment. T~eir employment i~
particul~rly beneficial when feeding dilute sodium chlorate solutions as they help reduce the cell ~oltage and increase conversion efficiency.
` WO9ltl2356 ~ ~ PCT/US91/00172 Pre~err2d ~s c~tion eschange mediums ~re 8tro~g ~c~d type cation e~c~ange resins in the hydrogen ~orm as esempli;ied by low cro~s-linked resins ~uch cs AMBERLITE~ IRC-118 ~Rohm and Ha~s Co.) ~5 well as higher c~oss-link~d resins i.e.
~M~ERLITE~ IRC-120. High surf~ce are~ macro-reticul~r or microporous type ion e~charge resins having sufficient ionic conductivity in the ion e2cb~nge compartments ~re ~lso suitable.
Physical forms of the cation e~change resin which can be o used are those which can be packed into compartments ~nd include beads, rods, fibers or a cast form with internal flow channels. Bead forms of the resin are preferred.
Cation e~change membranes selected ~s separ~tors between compsrtment~ are those which are inert membranes, and ~re substanti~lly impervious to the hydcodynamic flow of the alkali metal chlorate 501ution or the electrolytes and the passage o~ ~ny gas products produced in the anode or cathode compartments.
Cation e~change membranes are well-known to contain fi~ed anionic groups that permit intrusion and exchange of cations, an~ e~clude anions from an e~ternal source. Generally the resinous memb~ne or di~phr~gm h~s as a matris, ~
cro~s-lin~ed polymer, to whicb are attached charged radicals such 3s --S03 and~or mistures thereof with --COOH .
The ~esins which can be used to produce the membranes include, for example, fluorocarbons, vinyl compounds, polyolefins, hydrocarbons, and copolymers thereof. Preferred are cation e~change membranes sucb as those comprised of fluorocarbon polymers or vinyl compounds such as divinyl benzene having a plurality of pendant sulfonic acid groups or carbosylic acid groups or mi~tures of s~lfonic acid groups and carbos~lic Acid groups. ~he terms ~sulfonic acid groupa and ~carbo~ylic acid groups~ are meant to include salts of sulfonic acid or salts of carbosylic acid group~ by processes 3S such as bydrolysis.
WO91/12356 PCT/U~91/00172 - 10 - ' Suitable cation e~change membranes ~re r~adily available~
being sold commercially, for e~ample, by Ionics, lnc., Sybron, by E.I. DuPont de Nemours ~ Co., Inc., under the trademark ~NAFION9~, by the Asahi Chemical Company under t~e trademark ~ACIPLE~, and by Tokuyama Soda Co., under the trademark ~NEOSEPTA~". Among these are the perfl~orinated sulfonic acid ~ype membranes which are resistant to oYidation and high temperatures such as DuPont NAFIOND types 117, 417, 423, etc.., membranes from the assignee of U. S. Patent No.
4,470,888, and other polytetrafluorethylene based membranes with sulfonic acid groupings such as those sold under the RAIPORE tradename by RAI Research Corporation.
The catholyte can be any suitable aqueous solution, including alkali metal chlorides, and any appropriate acids such as hydrochloric, sul~uric, phosphoric, nitric, acetic or others.
In a preferred embodiment, deionized or softened water or sodium hydroxide solution is used as the catholyte in the cathode compartment to produce an alkali metal hydro~ide.
The water selection is dependent on the desired purity o~ the alkali metal hydro~ide by-product. The cathode compartment may also contain ~ 5trong acid cation eschange resin in a cation form such as sodium as the electrolyte.
Any suitable cathode which generates hydrogen gas may be used, including those, for example, based on nickel or its alloys, includin9 nickel-chrome based alloys; steel, including stainless steel types 304, 316, 310, etc.;
graphite, graphite felt, a multiple layered graphite cloth, a graphite cloth weave, carbon: and titanium or other valve metals as well as valve metals having coatings which can reduce the hydrogen over~oltage of the cathode. ~he cathode is preferably perforated to allow for suitable release of the hydrogen gas bubbles produced at the cathode particularly where the cathode is placed against the membrane.
~ WO~1/12356 2 0 ~ ~ O ~-2 PCT/US91/00172 Optionally a porous spacer materisl such as a chemically resistant non-conducti~e plastic mesh Ol a conductive material like graphite felt can be positioned behind the anode and/or the cathode to support the electrodes and to permit the adjustment of the gap between the electrode and the cation permeable ion e~change membrane, for e~ample, when using high open ~rea e~panded metal electrodes. The porous spacer material preferably has large holes for ease of disengagement of the gases from the anolyte ~nd/or catholyte. A thin protective spacer can also be placed between the anode and/or the cathode and the cation permeable ion e~change membranes. This spacer can be a non-conducti~e plastic or a porous conductive material like graphite felt.
The cell may be operated with the electrode in contact with the thin protective spacer and the porous spacer material, or with the membtane in direct contact with the electrode and with or without the porous spacer material.
~ t will be recognized that other configurations of the electrolytic cell can be employed in the no~el process of t~e present invention, including bipolar cells utilizing a solid plate type anode/cathode or bipolar membranes. For e~ample, a bipolar electrode could include a ~al~e metal such as titanium or niobium shee~ clad to stainless steel. The valve metal side could be coated with an o~y~en evaluation catalyst and would serve as the anode. ~n alternative anode~cathode combination which is commercially available is a platinum clad layer on stainless steel or niobium or titanium and is prepared by heat/pressure bonding.
The novel product solution contains chloric acid and alkali metal chlorate in a wide range of concentrations and ratios of chloric acid to alkali metal chlorate. For esample, the solutions produced can provide molar ratios of chloric acid to alkali metal chlorate of from about 0.1: 1 ts about 250: 1.
W~91/12356 2 0 7 ~ ~ 8 2 PCT/US91/00172 ~`
Where the product solutions are to be usl~d in the gener~tion of chlorine dio~ide, suitable molar ratios of chloric acid to alkali metal chlor~te of from ~bout 0-3: l to about 200: l, and preferably ~rom about l: l to ~bout lO0: l These solutions are highly acidic and permit a reduction in the amount of acid required ln the generatioln of chlorine dio~ide in commercial processes which react a chlorate solution with an acid in the presence of a reducing agent.
Further, the chloric acid - alkali metal chlorate solutions produced are substantially free of chloride, sulfate, phosphate, or other anionic groups which are present when an alkali metal chlorate is acidified with mineral or other acids used in the generation of chlorine dioxid~e.
Where desired, the chloric acid concentrations of these novel solutions may be increased, for e~ample, by evaporation at sub-atmospheric pressures and temperatures Oe about lOO-C.
or less. For e~ample, in the range of from about 30 to about 90C. Solutions containing up to about 40~ by weight of chloric acid may be produced in this manner.
As illustrated in FIGURE 3, the product solution can be fed directly from the electrolytic cell to a commercial chlorine dio~ide gener~tor- Typic~l commercial processes are those w~ich use sulfuric acid or hydrochloric acid with a reducing agent such as sulfur dioxide or methanol in the presence of a salt such as sodium chloride. Commercial chlorine dio~ide processes which may use the aqueous solutions of chloric acid and alkali metal chlorate of the invention include the Mathieson, Solvay, R2, R3, R8, ~esting, SVP, and SVP/methanol, among others.
The novel process of the present invention permits the production of solutions having a ~ide range of concentrations of chloric acid and sodium chlorate for use in chlorine dioYide generators.
~: Wog1/12356 2 ~`7 ~ ~ $ 2 PCT/US91/00172 The proc~s permits fle~ibility ln t~e by-product salts produced ~s ~ell as allowing the recovery of energy costs by producing, for e~ample, an alkali metal hydro~ide ~olution by-product. Further the process reduces operating costs by eliminating process steps and equipment from processes presently available. In addition novel solutions are ptocuced having a wide range of ehloric acid and al~ali metal chlorate concentrations which are substantially free of anionic or cationic impurities.
To further illustrate the invention the following e~amples are provided without any intention of being limited thereby. All parts and percentages are by weight unless otherwise s pec i ~ i ed .
,-. ~
WO91/12356 2Q7~:~8~ PCT/US9~/00172 ~
EXAMPLE ~_ An electrochemical cell of the type sho~n in Figure 1 consisting of three compartments machined from ultra high density polyethylene (UHDPE) including an anode compartment, a central ion e~change compartment, and ~ cathode compartment. The 1/2 inch (1.27 cm.) thick anode compartment contained a titanium mesh anode having an o~ygen-evolYing anode coating (PMCA 1500~ Englehard Corporation, Edison, N.J.). The anode was supported and spaced apart from the UHDPE back wall using multiple layers of polyethylene mesh having 1/4 inch square holes and being 1/16 inch in thic~nass. A polyet~ylene mesh sp~cer was positioned between the anode and adjoining membrane to provide an anode-membrane gap o~ 0.0625 inch ~0.1588 centimeters). The ~node compartment was ~illed with a 2.0 percent by weight sulfuric acid solution. The lf2 inch (1.27 cm.~ thick cathode compartment contained a 304 stainless steel per~orated plate cathode mounted flush to the surface of the cathode compartment with the polyethylene mesh spacers. The cathode w~s positioned in contact with the adjacent membrane providing a zero distance gap. The cathode compartment was initially ~illed with a sodium hydroside solution (2~ by weight) as the catholyte. Separating the anode compartment Erom the ion ~change compartment, and the ion e~change aompartment f~om the cathode compartment were a pair o~
perfluorosulfonic acid cation permeable membranes with a 985 equivalent weight, obtained from the assignee o~ U.S. Patent No. 4,470,888. The ion eschange compartment was a machined 1~4 inc~ (0.62S cm) thick frame with inlet and outlet and contained the polyethylene mesh spacers to distribute the chlorate solution as well as to support and separate the two membranes.
~- WO91tl2356 2 O ~ ~ 0 ~ 2 PCT/US91/00172 An aqueous sodium chlorate ~olu~ion containing 20 weight percent of NaClO3 was prepared by dissolving reagent grade sodium chlorate in deionized w~ter. During oper~tion of the electrolytic cell, the chlor~te ~olution was meter~d into the bottom of the ion eschange compartment in a single pass process at feed rates ~arying from 7.0 gfmin. to 14.4 g/min.
Electrolyte circulation in the anode and cathode compartments was by gas lift efect only. Tbe cell was operated employing a cell current of 24.5 amperes ~t a current density of 1.20 RA/m2. The cell ~oltage varied according to the cell operating temperature. A sample of the product solution was taken at each flow rate, the temperature measured, and the product solution analyzed for chloric acid and sodium chlorate content. The product solutions were colorless, indicating no chlorine dio~ide was formed in the ion e~change compartment. The concentrAtion of the sodium hydro~ide catholyte durlng cell operation increased to 12 per ent by weight. The results are given in Table I below.
WO 91/12356 2 ~ 7 4 ~ 8 2 PCrlUS91/00172 l:
.
-- ] 6 Z C
o, E~ ~ O
1~ ~
V ~ o~
c~ t ~3 _ ~1 `D C`J
~ 2 ~~ ~~
.....
. ,. ~ U~ X CO ,_ C:) ~ t d O C O O O O o O
Ll 1 f`') t -t U'l 11 O
C
O ~r _~ L O O ~ _I t~
~ ~ ~ O O O ~
E-l c O ~
~ ' O~ O oO O~ cO
~ X t ~, 3 C`i ~
~ O ~
JJ
C~
-- O O O O O
C~ , ~0 ~ ~ ~ ~ t U~
d ~ ~ o --~ o O O ~ ~ O ~
~ 1~ ' c~ 3 ~ t a ~ ~. O 0 ~ o C~ t~ tn ~t ~ ~t 2 ~ 8 2 ( Wosl/123~6 - 17 - ~ PCT/US91/00172 ~X~MPL~
~ he cl~ctrochemic~l cell of FIGURE 2 was employed h~in~
a second ion e~chanse compartment adj~cent to the fir3t ion e~change compartment. The anode compartm~nt cont~ining the same type of anode used in E~ample 1 w~s filled wit~ a ~trong acid hydrogen form cation e~change resin (AM~ER~ITE~ IRC-120.
plus. Rohm S Haas Comp~ny) JS the electrolyte.
perfluorin3ted sulfonic 3cid-based membrane ~Dupont NA~ION0 S17) separated the anode compartment from t~e fir~t ion eschange compartment. The two ion e~change compartments were ~o fully filled with ~MB~RLITED IRC-120 plus cation e~change resin in the hydrogen form and were separated by a Dupont NAFION~ ~17 membr~ne. The ~ame membrane wa~ cmployed to separate the second ion e~change compartment ~rom the cathode compartment. The cDthode compartment contDined ~ perforated lS 304 st~inless steel cathode, and was filled with a sodium form AM~ERLITE~ IRC-120 plus c~tion e~change resin. ~oth the anode comp~rtment and the cat~ode compartment were filled with deionized water. The sodium chlorate solution f~d to the ion e~change compartment5 ~as p~eparod from reagent gr~e sodium chlorate dissolved in deioni~d wat~r to form ~ 16 weight percent ~olution as sodium chlorate. The sodium chlorate solution at 20-C. was fed to the bottom of ion e~change compa~tment 40 adjacent to the cathode compartment at a flow rate of 6.5 grams per minute. The chloric acid -2S sodium chlorate solution flow from the upper part of ione~change compartment 40 was routed into the bottom of ion e~change compartment 20 adjacent to the anode compartment and collected fr~m the top of ion e~change compartment 20. The total residence time o the solution in the ion eschange compartments wa~ about 42 m~nut~.
', W091~12356 2 0 ~ ~ 0 82 PCT/US9]/0~172 ~t During operation of the cell, the cell current w~s set at a constant 23.0 amperes for an oper~ting current density of 1.5 ~A~m2. The cell voltage stabilized ~t 9.60 valts, and the product temper~ture was 65C. Circul~tion in the anode s and cathode compartments of the electrolyte w3s by gas lift effect and the liquid level of the gas disengagers was set at
~` W091/12356 PCT/US91/00172 ACID - ~L~LI ~ LOR~T~ Tu~s This in~ention relates to a proce~ for electrochemically producing chloric acid - alkali met~l chlorate solutions.
More particularly, this invention relates to the electrochemical pro~uction of chloric &cid - ~lkali metal 5 chlorate ~olutions suitable for the generation of chlorine dio~ide.
Chlorine dio~ide h~s found wide use ~8 a di~infectant in w~ter treatment/purification, a~ ~ bleaching ~gent in pulp and paper production, a~d a number of other uses due to its 10 high o~idizing power. Ther~ is ~ variety of chlor~ne dio~ide generator systems and processes av~ilable in the marketpl~ce. Most of the very large scale generators employed, for esample, in pulp and paper production, utilize an alka}i metal chlorate salt, a reducing agenti and an w id 15 in a chemical process for pro~ucing chlorine dio~ide. These generators and the processes e~ployed al50 produce by-product salts such as sodium chloride, sodium sul~te, or sodium bisulfate. In pulp and paper mill~, the typical by-product is sodium sulfate (saltcake) which is converted into ~ sulfur 20 salt of sodium in a high temperature boiler Jnd used in the paper process. Boilers require energy and the paper mills have a limited boiler capacity. Increasing the production of chlorine dio~ide generally means increased capital in~estment to provide the added boiler capacity regu~red to process the 25 added amounts o~ saltcake by-product produced.
.
. : . .
.. . ... . ..
. ~ . , .
WO91/12356 ~ ~ ~ ~ 8 2 PCT/US~1~00172 Thu~ a proce~s ~hich ~eduoe~ the ~mount of o by-product ~alt, such ~s sodium chlori~e or 30dium sulf~te, produced wh~le efficl~ntly generating chlorine dio~lde i3 commerci~lly ~esir~able.
~.S. Patent 3,310,969 is~ued M~y l~, 1974 to A.A.
Schlumber9Pr teaches ~ process for producing chlsric ~cid by passing an aqueous solution containing rom 0.2 gram mole to ll gram moles per liter of an alkali m~t~l chlorate such ~s ~odium chlorate through a selected cationic e~change resin at a temperature from 5- to 40- C. The proces~ produces an aqueous solution containing from 0.2 gram mole to about 4.0 gram moles of HC103. This process requires the regeneration of the cationic e~change resin with acid to cemo~e the alkali metal ions and the treatment or dispos~l o~
the acidic ~nlt solution.
~.L. Hardee et al, in U.S. Patent No. 4,79B,715 issued Jan. 17,l9a9, describe ~ process for chlorine dio~ide which electroly~es a chloric acid solution produced by passing an aqueous solution of an alkali metal chlorate through an ion e~change resin. The electroly~ed solution conthins a mi~ture o~ chlorine dio~ide and chloric acid ~hich i5 fed to an e~tractor in which the chlorine dio~ide i~ stripped off. Thc ion eschange ~e5in i5 regener~ted with hydroc~loric acid 3nd an acidic solution o~ an alkali metal chloride formed.
In U.S. Patent No. 4,683,039, Swardowski et ~1 describe method for producing chlorine dio~ide in which the chlorine dio~ide i5 produced in a genetator by th~ reaction of sodium chlorate and hydrochloric acid. Ater separating chlorine dio~ide gas, the remaining sodium chloride solution is fed to a three-compartment cell to form sodium hydro~ide and an acidified liquor which is returned to the chlorine dio~ide generator.
Each of the above processes produce~ a f~ed amount and type o by-product ~alt.
2~082 : W091/12356 PCT/US91/00172 Now ~ proce~ has been discovered which permits varinbility in the composition of a chlorate solution used in chlorine dio~ide generators. Further, the process permits a reduction in the amount of acid requir~d and sub~equently the 5 amount of salt by-product produced in the chlorine dioxide generator. Still further, the process allow~ for the production o an alkali metal hydro~ide as ~ valuable by-product or ~cidic solutions of alkali metal salts at reduced energy costs. In addition, the process re~ult~ in 10 the reduction of process steps and pro~ess equipment required for the production of chlorine dio~ide.
These and other advantages are accomplished in a process for electrolytically producing an aqueous solution of chloric acid and alkali metal chlorate in an electrolytic cell h3ving 15 an anode compartment, a cathode compartment, and at least one ion e~change compartment between the anode compartment and the cathode compartment, characterized by feeding an aqueous solution of an alkali metal chlorate to the ion e~change compartment, electroly~ing an anolyte in the anode 20 compartment to generate hydrogen ions, passing the hydrogen ions from the anode compartment through a cation e~change membrane into the ion e~change compartment to displace alkali metal ions and produce an aqueous solution of chloric acid and alkali metal chlorate, and passing alkali metal ions from 2s the ion exchange compartment into the cathode compartment.
More in detail, the novel process of the present invention and its application in producing chlorine dio~ide can be carried out in apparatus i.lustrated in the following FI~URES.
Figure 1 is a sectional side elevational view of an electrolytic cell which can be employed in the novel process of the invention; and 2~0~ -W~91/12356 PCT/US9ltO0172 Figure 2 is a section~l side el~v~tional view o~ ~n addition~l electrolytic cell whi~h c~n be employed in the novel process of the in~ention.
Figure 3 is a diAgramm3tic illustr~tion of ~ ~ystem which can be employed in the process of the in~ention.
FIGURE 1 shows ~n electrolytic cell ~ divided into anode compartment 10, ion e~change compartment 20, and cathode compartment 30 by cDtion permeable ion eschange me~branes 16 and 24. Anode compartment 10 includes anode 12, and anode spacer 14. Anode spacer 14 positions porou~ anode 12 with respect to cation permeable ion e~c~ange membrane 16 and aids in the disengagement of ~nolyte gas produced. Anolyte disengager 1~ completes the disengagement of anolyte gas from the ~pent anolyte ~olut~on. Ion e~change comp~rtment 20 includes spacer material 22 which prov~des a flow channel between cation permeable ion e~change membranes 16 and 24 for the aqueous ~lkali met~l chlorate solution. Cathode compartment 30 includes cathode 32, and cathode spacer 34.
Cathode space~ 34 positions c~thode 32 with respect to cation permeable ion e~cbange membrane 24 and ai~s in the disengagement of c~tholyte ga5 pro~uced. The ~s~ngagement of catholyte gas from the spent catholyte solution is accomplished in cathode disengager 36.
In FIGVRE 2, electrolytic cell 4 has been e~panded to include a second ion e~change compartment 40 which is positioned between anode compa~tment 10 and ion e~chanqe compartment 20. Cation permeable ion e~change membrane 42 separates anode ~ompartment lO from ion e~change compartment 40. The sodium chlorate feed solution enters the lower part of ion eschange compartment 2Q, flows upward and out of ion e~chang~ compartment 20 into the upper part of ~on e~change compartm~nt 40. The HC103 ~ NaC103 product solution i~
reco~ered from the lower part of ion eschan~e compartment 40.
8:2 W091/~2356 ~ 5 ~ PCT/US91/00172 The low ~irect~on in the lon ~chan~ ~o~partment~ can ~lso be reversed, for e~ample, with the 801ut~0n Yrom the top of ion c~change comp~rtment qO being ~ed to the bottom of lon e~change compartment 20. The product solution then e~its from the top of ion e~change comp~rtment 20.
~ n aqueous ~olution of an alkali metal chlorate is fed to the single or mult~ple ion e~change comp~rt~ents o~ the electrolytic cell. Suit~ble alk~li m~t~l chlorates include sodium c~lorate, potassium chlorate and lithium chlorate. Ih o order to simpliEy the ~isclosure, the proce~s of the invention will be described using sodium chlorate, which is ~
preferred embodiment of the alk~li met~l chlorates. ~ ~hown in FIGURE 3, the ~odium chlor~te feed ~olution may be prepared, for e2ample, by di~solvin9 cry~talline ~odium chlorate ~n water. Commercial ~odium chlorate is suitable as it h~s a low ~odium chloride content and the formation of undesireable amounts of chlorine dio~ide in the electrolytic cell i5 prevented. ~queous sodium chlorate feed 301utions w~ich may be employed contain any 5uitable -oncentrations of sodium chlorate, for e~ample, solutions having a concentration in the ran9e of from about O.l ~ by weight to those saturated with NaClO3 at temper~tures in the r~nge of from ~b3ut 0- to ~out lO0-, ~nd preferably from about lS- to about 80-C.
The novel process of the invention utilizes an electrochemic~l cel} to generate hydrosen ions that displace or replace a portion of the sodium ions present ~n the aqueous sodium chlorate solution eed stream.
The generation of hydrosen ions in the process of the present invention ~n the anode compartment is accompanied, for esample, by the o~idation of water on the anode into o~ygen g~s and H~ ions by the electrode reaction as follows:
(4) 2H20~ > 2 ~ qH ~ 4e Wo91/123S6 2 0 ~ ~ ~ 8 2 PCT/USs~/00172 ~-The anode comp~rtment contaln~ Dn anolyte, which can be an a~ueou 301ut~0n of any non-osidi~ble ~ci~ electrolyte which i~ ~uitabl~ for conductin~ hydrogen ion~ into the ion e~hange comp~rtment. Non-osidi~able ~cids which may be used include ~ulfuric acid, pho~phoric acid andl the like. Where non-o~idiz~ble acid solution is used as tbe anolyte, the concentration of the ~nolyte is preferably ~electe~ to match the o~motic concentrat~on ch~r~cteristi~s of the alkali me~al chlorate solution fed to the ion e~change compartment to 10 minimize water eschange between the anode compartment and th~
ion eschange compartment. Addition~lly, an ~lkali metal choride solution can be used as the anolyte, which results in a generation of chlorine gas At the Anode. Where a chlorine generating anolyte is employed, it i8 necessary to select ~
15 cation esch~nge membrane as the ~ep~rator between the anode compartment from the ion e~change compartment which is stable to chlorine gas. The anode compartment may also employ as the anolyte electrolyte a strong acid cation e~change resin in the hydrogen form and an aqueous ~olution such as deionized 20water.
Any auit~ble anode may be employed in the anode compartment, including those which are available commercially ~8 dimensionally atable anodes. Prsferably, an anode is selected which will generate osygen gas. These anodes 25include porous or high surface area anodes. As materials of construction for the anodes metals including platinum, gold, palladium, or mistures or alloys thereof, or thin coatings of such materials on various substrates such as valqe metals, i.e. titanium, can be used. Additionally o~ides of iridium, 30rhodium or ru~henium, and alloys with other platinum group or precious meta}s metals could also be employed. Commercially available osygen evolution anodes of this type include those manufactured by Englehard (PMCA 1500) or Eltech ~TIR-2000).
Other suitable anode materials include graphite, graphite 35felt, a multiple layered graphite cloth, a graphite cloth ~ Wo91/1235~ 2 ~ 7 ~ ~ ~ 2 PCT/US91/00172 we~e, carbon, etc..
The hydrogen ions generated in t~e ~node comp3rtment pass ~hrough the c~tion ~change membrane into the ~odium c~lor~te solution in the ion e~change comp~rtment. ~s a hydrogen ion 5 enters the solution, ~ sodium ion is displaced and by electrical ion mass action passes throu9h the c~tion membrane adj~cent to the c~thode compartment to ~aint~in electrical neutrality.
The novel process of the invention as operated results in 10 the con~ersion of sodium c~lor~te to chloric acid over A wide ange, fo~ esample, from about 1 to about 99.9~, pre~erably from about 5 to about 95, and more preferably from about 15 to about 90%.
The sodium chlorate feed 501ution concentration, the 15 residence time in the ion e~chanqe compartment ~s well as the cell amperage are factors th~t ~ffect the e~tent o the conversion of ~odium chlQrate to chloric ~cid. Using very dilute solutions o~ sodium chlorate, high percentages of conversion o~ NaC103 to chloric acid ean be achieved, i.e.
20 up to 99.9~ conversion. For ~ single pass flow through system, typical residence times in the ion e~change compartment ~re between about 0.1 to about 120 minutes, with a more preferr~d r~n9e o~ about 0.5 to about 60 minutes.
Thus the concentration of sodium chlor~te in the ~olution 25 fed to the ion e~change compartment and the 10w rate of the solution through the ion exchange _ompartment are not critical and broad ranges can be selected ~or each of these parameters.
The novel process of the present invention is operated at 30 a current density of from about 0.01 KA/m to about 10 KA~m2, with a more preferred range of about 0.05 KA/m2 to about 3 XA~m .
Current efficiencies during operation of the process of the invention can be increased by employing a~ditional ion 35 e~change compartment3, as illustrated by FI~URE 2, which are adjacent and operated in a series flow pattern.
-. .
2 ~ 2 WO 91/12356 PCT~US91/00172 Adjusting th~ width of the ion e~change compartment c~nalso alter the operating cell voltage ~nd curr~nt e~ficiency. The wid~h, or spa~e between the c~tion e~c~ange membranes forming the W81ls of the ion e~ch~nge compDrtment, is in the ranqe of from ~bout O.l to about lO, ~nd prefer~bly from about 0.3 to abo~t 5 centimeters.
In ~n altern~te embodiment the ion e~cchanse compartment contains a c~tion e~change medium- Cation e~change mediums which c~n be used in the ion e~change cornpartment include cation eschange resins. Suitable cation e~change resins include those having substrates and backbones of polystyrene based with di~inyl benzene, cellulose b~sed, fluorocarbon based, synthetic polymeric types 3nd the lik~. Where more than one ion e~change compartment is employ~d, inclusion o~
the cation e~ch~nge medium is optional for each compartment.
Functional cationic ~roups on these mediums which may be employed include carbo~ylic ~cid, sulfonic or sulfuric acids, and acids of phosphorus such as p~osphonous, phosphonic or phosphoric. The cation 2~change resins are suitably ionically conductive so that a practical amount Q~ current can be passed between the cation e~change membranes used as separators. v~rious percentage mi~ture of resins in the hydrogen form ~nd the sodium orm may be useC in various sections of the ion exchange compartments on ~ssembly to compensate for the swelling ~nd conttaction of resins during cell operation. For e~ample, percentage ratios o~ hydrogen form to sodium form may include those from 50 to lO0~.
The use o~ cation exchange resins in the ion exchange compartment can serve as an active mediator which can e~change or absorb sodium ions and release hydrogen ions.
The hydrogen ions generated at the anode thus regenerate the resin to the hydrogen orm, releasing sodium ions to pass into the cathode compartment. T~eir employment i~
particul~rly beneficial when feeding dilute sodium chlorate solutions as they help reduce the cell ~oltage and increase conversion efficiency.
` WO9ltl2356 ~ ~ PCT/US91/00172 Pre~err2d ~s c~tion eschange mediums ~re 8tro~g ~c~d type cation e~c~ange resins in the hydrogen ~orm as esempli;ied by low cro~s-linked resins ~uch cs AMBERLITE~ IRC-118 ~Rohm and Ha~s Co.) ~5 well as higher c~oss-link~d resins i.e.
~M~ERLITE~ IRC-120. High surf~ce are~ macro-reticul~r or microporous type ion e~charge resins having sufficient ionic conductivity in the ion e2cb~nge compartments ~re ~lso suitable.
Physical forms of the cation e~change resin which can be o used are those which can be packed into compartments ~nd include beads, rods, fibers or a cast form with internal flow channels. Bead forms of the resin are preferred.
Cation e~change membranes selected ~s separ~tors between compsrtment~ are those which are inert membranes, and ~re substanti~lly impervious to the hydcodynamic flow of the alkali metal chlorate 501ution or the electrolytes and the passage o~ ~ny gas products produced in the anode or cathode compartments.
Cation e~change membranes are well-known to contain fi~ed anionic groups that permit intrusion and exchange of cations, an~ e~clude anions from an e~ternal source. Generally the resinous memb~ne or di~phr~gm h~s as a matris, ~
cro~s-lin~ed polymer, to whicb are attached charged radicals such 3s --S03 and~or mistures thereof with --COOH .
The ~esins which can be used to produce the membranes include, for example, fluorocarbons, vinyl compounds, polyolefins, hydrocarbons, and copolymers thereof. Preferred are cation e~change membranes sucb as those comprised of fluorocarbon polymers or vinyl compounds such as divinyl benzene having a plurality of pendant sulfonic acid groups or carbosylic acid groups or mi~tures of s~lfonic acid groups and carbos~lic Acid groups. ~he terms ~sulfonic acid groupa and ~carbo~ylic acid groups~ are meant to include salts of sulfonic acid or salts of carbosylic acid group~ by processes 3S such as bydrolysis.
WO91/12356 PCT/U~91/00172 - 10 - ' Suitable cation e~change membranes ~re r~adily available~
being sold commercially, for e~ample, by Ionics, lnc., Sybron, by E.I. DuPont de Nemours ~ Co., Inc., under the trademark ~NAFION9~, by the Asahi Chemical Company under t~e trademark ~ACIPLE~, and by Tokuyama Soda Co., under the trademark ~NEOSEPTA~". Among these are the perfl~orinated sulfonic acid ~ype membranes which are resistant to oYidation and high temperatures such as DuPont NAFIOND types 117, 417, 423, etc.., membranes from the assignee of U. S. Patent No.
4,470,888, and other polytetrafluorethylene based membranes with sulfonic acid groupings such as those sold under the RAIPORE tradename by RAI Research Corporation.
The catholyte can be any suitable aqueous solution, including alkali metal chlorides, and any appropriate acids such as hydrochloric, sul~uric, phosphoric, nitric, acetic or others.
In a preferred embodiment, deionized or softened water or sodium hydroxide solution is used as the catholyte in the cathode compartment to produce an alkali metal hydro~ide.
The water selection is dependent on the desired purity o~ the alkali metal hydro~ide by-product. The cathode compartment may also contain ~ 5trong acid cation eschange resin in a cation form such as sodium as the electrolyte.
Any suitable cathode which generates hydrogen gas may be used, including those, for example, based on nickel or its alloys, includin9 nickel-chrome based alloys; steel, including stainless steel types 304, 316, 310, etc.;
graphite, graphite felt, a multiple layered graphite cloth, a graphite cloth weave, carbon: and titanium or other valve metals as well as valve metals having coatings which can reduce the hydrogen over~oltage of the cathode. ~he cathode is preferably perforated to allow for suitable release of the hydrogen gas bubbles produced at the cathode particularly where the cathode is placed against the membrane.
~ WO~1/12356 2 0 ~ ~ O ~-2 PCT/US91/00172 Optionally a porous spacer materisl such as a chemically resistant non-conducti~e plastic mesh Ol a conductive material like graphite felt can be positioned behind the anode and/or the cathode to support the electrodes and to permit the adjustment of the gap between the electrode and the cation permeable ion e~change membrane, for e~ample, when using high open ~rea e~panded metal electrodes. The porous spacer material preferably has large holes for ease of disengagement of the gases from the anolyte ~nd/or catholyte. A thin protective spacer can also be placed between the anode and/or the cathode and the cation permeable ion e~change membranes. This spacer can be a non-conducti~e plastic or a porous conductive material like graphite felt.
The cell may be operated with the electrode in contact with the thin protective spacer and the porous spacer material, or with the membtane in direct contact with the electrode and with or without the porous spacer material.
~ t will be recognized that other configurations of the electrolytic cell can be employed in the no~el process of t~e present invention, including bipolar cells utilizing a solid plate type anode/cathode or bipolar membranes. For e~ample, a bipolar electrode could include a ~al~e metal such as titanium or niobium shee~ clad to stainless steel. The valve metal side could be coated with an o~y~en evaluation catalyst and would serve as the anode. ~n alternative anode~cathode combination which is commercially available is a platinum clad layer on stainless steel or niobium or titanium and is prepared by heat/pressure bonding.
The novel product solution contains chloric acid and alkali metal chlorate in a wide range of concentrations and ratios of chloric acid to alkali metal chlorate. For esample, the solutions produced can provide molar ratios of chloric acid to alkali metal chlorate of from about 0.1: 1 ts about 250: 1.
W~91/12356 2 0 7 ~ ~ 8 2 PCT/US91/00172 ~`
Where the product solutions are to be usl~d in the gener~tion of chlorine dio~ide, suitable molar ratios of chloric acid to alkali metal chlor~te of from ~bout 0-3: l to about 200: l, and preferably ~rom about l: l to ~bout lO0: l These solutions are highly acidic and permit a reduction in the amount of acid required ln the generatioln of chlorine dio~ide in commercial processes which react a chlorate solution with an acid in the presence of a reducing agent.
Further, the chloric acid - alkali metal chlorate solutions produced are substantially free of chloride, sulfate, phosphate, or other anionic groups which are present when an alkali metal chlorate is acidified with mineral or other acids used in the generation of chlorine dioxid~e.
Where desired, the chloric acid concentrations of these novel solutions may be increased, for e~ample, by evaporation at sub-atmospheric pressures and temperatures Oe about lOO-C.
or less. For e~ample, in the range of from about 30 to about 90C. Solutions containing up to about 40~ by weight of chloric acid may be produced in this manner.
As illustrated in FIGURE 3, the product solution can be fed directly from the electrolytic cell to a commercial chlorine dio~ide gener~tor- Typic~l commercial processes are those w~ich use sulfuric acid or hydrochloric acid with a reducing agent such as sulfur dioxide or methanol in the presence of a salt such as sodium chloride. Commercial chlorine dio~ide processes which may use the aqueous solutions of chloric acid and alkali metal chlorate of the invention include the Mathieson, Solvay, R2, R3, R8, ~esting, SVP, and SVP/methanol, among others.
The novel process of the present invention permits the production of solutions having a ~ide range of concentrations of chloric acid and sodium chlorate for use in chlorine dioYide generators.
~: Wog1/12356 2 ~`7 ~ ~ $ 2 PCT/US91/00172 The proc~s permits fle~ibility ln t~e by-product salts produced ~s ~ell as allowing the recovery of energy costs by producing, for e~ample, an alkali metal hydro~ide ~olution by-product. Further the process reduces operating costs by eliminating process steps and equipment from processes presently available. In addition novel solutions are ptocuced having a wide range of ehloric acid and al~ali metal chlorate concentrations which are substantially free of anionic or cationic impurities.
To further illustrate the invention the following e~amples are provided without any intention of being limited thereby. All parts and percentages are by weight unless otherwise s pec i ~ i ed .
,-. ~
WO91/12356 2Q7~:~8~ PCT/US9~/00172 ~
EXAMPLE ~_ An electrochemical cell of the type sho~n in Figure 1 consisting of three compartments machined from ultra high density polyethylene (UHDPE) including an anode compartment, a central ion e~change compartment, and ~ cathode compartment. The 1/2 inch (1.27 cm.) thick anode compartment contained a titanium mesh anode having an o~ygen-evolYing anode coating (PMCA 1500~ Englehard Corporation, Edison, N.J.). The anode was supported and spaced apart from the UHDPE back wall using multiple layers of polyethylene mesh having 1/4 inch square holes and being 1/16 inch in thic~nass. A polyet~ylene mesh sp~cer was positioned between the anode and adjoining membrane to provide an anode-membrane gap o~ 0.0625 inch ~0.1588 centimeters). The ~node compartment was ~illed with a 2.0 percent by weight sulfuric acid solution. The lf2 inch (1.27 cm.~ thick cathode compartment contained a 304 stainless steel per~orated plate cathode mounted flush to the surface of the cathode compartment with the polyethylene mesh spacers. The cathode w~s positioned in contact with the adjacent membrane providing a zero distance gap. The cathode compartment was initially ~illed with a sodium hydroside solution (2~ by weight) as the catholyte. Separating the anode compartment Erom the ion ~change compartment, and the ion e~change aompartment f~om the cathode compartment were a pair o~
perfluorosulfonic acid cation permeable membranes with a 985 equivalent weight, obtained from the assignee o~ U.S. Patent No. 4,470,888. The ion eschange compartment was a machined 1~4 inc~ (0.62S cm) thick frame with inlet and outlet and contained the polyethylene mesh spacers to distribute the chlorate solution as well as to support and separate the two membranes.
~- WO91tl2356 2 O ~ ~ 0 ~ 2 PCT/US91/00172 An aqueous sodium chlorate ~olu~ion containing 20 weight percent of NaClO3 was prepared by dissolving reagent grade sodium chlorate in deionized w~ter. During oper~tion of the electrolytic cell, the chlor~te ~olution was meter~d into the bottom of the ion eschange compartment in a single pass process at feed rates ~arying from 7.0 gfmin. to 14.4 g/min.
Electrolyte circulation in the anode and cathode compartments was by gas lift efect only. Tbe cell was operated employing a cell current of 24.5 amperes ~t a current density of 1.20 RA/m2. The cell ~oltage varied according to the cell operating temperature. A sample of the product solution was taken at each flow rate, the temperature measured, and the product solution analyzed for chloric acid and sodium chlorate content. The product solutions were colorless, indicating no chlorine dio~ide was formed in the ion e~change compartment. The concentrAtion of the sodium hydro~ide catholyte durlng cell operation increased to 12 per ent by weight. The results are given in Table I below.
WO 91/12356 2 ~ 7 4 ~ 8 2 PCrlUS91/00172 l:
.
-- ] 6 Z C
o, E~ ~ O
1~ ~
V ~ o~
c~ t ~3 _ ~1 `D C`J
~ 2 ~~ ~~
.....
. ,. ~ U~ X CO ,_ C:) ~ t d O C O O O O o O
Ll 1 f`') t -t U'l 11 O
C
O ~r _~ L O O ~ _I t~
~ ~ ~ O O O ~
E-l c O ~
~ ' O~ O oO O~ cO
~ X t ~, 3 C`i ~
~ O ~
JJ
C~
-- O O O O O
C~ , ~0 ~ ~ ~ ~ t U~
d ~ ~ o --~ o O O ~ ~ O ~
~ 1~ ' c~ 3 ~ t a ~ ~. O 0 ~ o C~ t~ tn ~t ~ ~t 2 ~ 8 2 ( Wosl/123~6 - 17 - ~ PCT/US91/00172 ~X~MPL~
~ he cl~ctrochemic~l cell of FIGURE 2 was employed h~in~
a second ion e~chanse compartment adj~cent to the fir3t ion e~change compartment. The anode compartm~nt cont~ining the same type of anode used in E~ample 1 w~s filled wit~ a ~trong acid hydrogen form cation e~change resin (AM~ER~ITE~ IRC-120.
plus. Rohm S Haas Comp~ny) JS the electrolyte.
perfluorin3ted sulfonic 3cid-based membrane ~Dupont NA~ION0 S17) separated the anode compartment from t~e fir~t ion eschange compartment. The two ion e~change compartments were ~o fully filled with ~MB~RLITED IRC-120 plus cation e~change resin in the hydrogen form and were separated by a Dupont NAFION~ ~17 membr~ne. The ~ame membrane wa~ cmployed to separate the second ion e~change compartment ~rom the cathode compartment. The cDthode compartment contDined ~ perforated lS 304 st~inless steel cathode, and was filled with a sodium form AM~ERLITE~ IRC-120 plus c~tion e~change resin. ~oth the anode comp~rtment and the cat~ode compartment were filled with deionized water. The sodium chlorate solution f~d to the ion e~change compartment5 ~as p~eparod from reagent gr~e sodium chlorate dissolved in deioni~d wat~r to form ~ 16 weight percent ~olution as sodium chlorate. The sodium chlorate solution at 20-C. was fed to the bottom of ion e~change compa~tment 40 adjacent to the cathode compartment at a flow rate of 6.5 grams per minute. The chloric acid -2S sodium chlorate solution flow from the upper part of ione~change compartment 40 was routed into the bottom of ion e~change compartment 20 adjacent to the anode compartment and collected fr~m the top of ion e~change compartment 20. The total residence time o the solution in the ion eschange compartments wa~ about 42 m~nut~.
', W091~12356 2 0 ~ ~ 0 82 PCT/US9]/0~172 ~t During operation of the cell, the cell current w~s set at a constant 23.0 amperes for an oper~ting current density of 1.5 ~A~m2. The cell voltage stabilized ~t 9.60 valts, and the product temper~ture was 65C. Circul~tion in the anode s and cathode compartments of the electrolyte w3s by gas lift effect and the liquid level of the gas disengagers was set at
3 inches ~7.62cm) ~bove the height of the cell.
The product solution from the cell contained 11.44 weight percent as HC103 which represented a 90% conversion of the sodium chlorate to chloric acid. The current efficiency was determined to be 61.6% and the power consumption was 4490 RWH/Ton of HC103. The product solution was light yellow in color, indicating the presence of some chlorine dioside or chlorine in the chloric acid-sodium chlorate solution product.
. .
The product solution from the cell contained 11.44 weight percent as HC103 which represented a 90% conversion of the sodium chlorate to chloric acid. The current efficiency was determined to be 61.6% and the power consumption was 4490 RWH/Ton of HC103. The product solution was light yellow in color, indicating the presence of some chlorine dioside or chlorine in the chloric acid-sodium chlorate solution product.
. .
Claims (23)
1. A process for electrolytically producing an aqueous solution of chloric acid and alkali metal chlorate in an electrolytic cell having an anode compartment, a cathode compartment, and at least one ion exchange compartment between the anode compartment and the cathode compartment, characterized by feeding an aqueous solution of an alkali metal chlorate to the ion exchange compartment, electrolyzing an anolyte in the anode compartment to generate hydrogen ions, passing the hydrogen ions from the anode compartment through a cation exchange membrane into the ion exchange compartment to displace alkali metal ions and produce an aqueous solution of chloric acid and alkali metal chlorate, and passing alkali metal ions from the ion exchange compartment into the cathode compartment.
2. The process of claim 1 characterized in that the alkali metal chlorate is selected from the group consisting of sodium chlorate, potassium chlorate, and lithium chlorate.
3. The process of claim 1 characterized in that the anolyte is a cation exchange resin in the hydrogen form and water.
4. The process of claim 1 characterized in that the anolyte is an aqueous solution of a non-oxidizable acid.
5. The process of claim 1 characterized in that the alkali metal ions from the ion exchange compartment pass through a cation exchange membrane into the cathode compartment.
6. The process of claim 1 characterized in that the conversion of alkali metal chlorate to chloric acid is in the range of from about 1 to about 99.9 percent.
7. The process of claim 1 characterized in that the ion exchange compartment contains a cation exchange medium in the hydrogen form.
8. The process of claim 1 characterized in that the catholyte is water or an alkali metal hydroxide solution.
9. The process of claim 1 characterized in that oxygen gas is produced in the anode compartment.
10. The process of claim 1 characterized in that hydrogen gas is produced in the cathode compartment.
11. The process of claim 2 characterized in that the alkali metal chlorate is sodium chlorate.
12. The process of claim 1 characterized in that the residence time in the ion exchange compartment is from about 0.1 to about 120 minutes.
13. The process of claim 1 characterized in that the current density is from about 0.1 to about 10 KA/m2.
14. The process of claim 1 characterized in that the cathode compartment contains a cation exchange medium in the alkali metal form.
15. The process of claim 1 characterized in that the ion exchange compartment contains a cation exchange medium in the hydrogen and sodium form.
16. A process for producing chlorine dioxide characterized by:
a) feeding an aqueous solution of an alkali metal chlorate to an ion exchange compartment of an electrolytic cell having an anode compartment, a cathode compartment, and at least one ion exchange compartment between the anode compartment and the cathode compartment, b) electrolyzing an anolyte in the anode compartment to generate hydrogen ions, c) passing the hydrogen ions from the anode compartment through a cation exchange membrane into a first ion exchange compartment to displace alkali metal ions and produce an aqueous solution of chloric acid and alkali metal chlorate, d) passing alkali metal ions from the ion exchange compartment into the cathode compartment, e) feeding, in series flow, the aqueous solution of chloric acid and alkali metal chlorate from the first ion exchange compartment to a second ion exchange compartment, and, f) removing the aqueous solution of chloric acid and alkali metal chlorate from the second ion exchange compartment.
a) feeding an aqueous solution of an alkali metal chlorate to an ion exchange compartment of an electrolytic cell having an anode compartment, a cathode compartment, and at least one ion exchange compartment between the anode compartment and the cathode compartment, b) electrolyzing an anolyte in the anode compartment to generate hydrogen ions, c) passing the hydrogen ions from the anode compartment through a cation exchange membrane into a first ion exchange compartment to displace alkali metal ions and produce an aqueous solution of chloric acid and alkali metal chlorate, d) passing alkali metal ions from the ion exchange compartment into the cathode compartment, e) feeding, in series flow, the aqueous solution of chloric acid and alkali metal chlorate from the first ion exchange compartment to a second ion exchange compartment, and, f) removing the aqueous solution of chloric acid and alkali metal chlorate from the second ion exchange compartment.
17. The process of claim 16 characterized in that the aqueous solution of chloric acid and alkali metal chlorate is reacted with a mineral acid and a reducing agent to generate chlorine dioxide gas.
18. The process of claim 17 characterized in that the mineral acid is sulfuric acid or hydrochloric acid.
19. The process of claim 17 characterized in that the reducing agent is methanol or sulfur dioxide.
The process of claim 16 characterized in that the molar ratio of chloric acid to alkali metal chlorate in the aqueous solution of chloric acid and alkali metal chlorate is in the range of from about 0.1:1 to about 250:1.
21 The process of claim 17 characterized in that an alkali metal chloride is added to the reaction mixture.
22. A process for producing chlorine dioxide characterized by reacting an aqueous solution consisting of chloric acid and alkali metal chlorate having a molar ratio of chloric acid to alkali metal chlorate of from about 0.3: 1 to about 200: 1 with a mineral acid and a reducing agent to generate chlorine dioxide gas.
23. An aqueous solution characterized by chloric acid and an alkali metal chlorate, the solution having a molar ratio of chloric acid to alkali metal chlorate of from about 0.1:1 to about 250:1
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US475,603 | 1990-02-06 | ||
| US07/475,603 US5084148A (en) | 1990-02-06 | 1990-02-06 | Electrochemical process for producing chloric acid - alkali metal chlorate mixtures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2074082A1 true CA2074082A1 (en) | 1991-08-07 |
Family
ID=23888323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002074082A Abandoned CA2074082A1 (en) | 1990-02-06 | 1991-01-14 | Electrochemical process for producing chloric acid - alkali metal chlorate mixtures |
Country Status (10)
| Country | Link |
|---|---|
| US (4) | US5084148A (en) |
| EP (1) | EP0514427B1 (en) |
| JP (1) | JPH05504170A (en) |
| AU (1) | AU7221791A (en) |
| BR (1) | BR9105976A (en) |
| CA (1) | CA2074082A1 (en) |
| DK (1) | DK0514427T3 (en) |
| FI (1) | FI923249A0 (en) |
| NO (1) | NO922821L (en) |
| WO (1) | WO1991012356A1 (en) |
Families Citing this family (94)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5258105A (en) * | 1990-02-06 | 1993-11-02 | Olin Corporation | Chloric acid - alkali metal chlorate mixtures and chlorine dioxide generation |
| US5322598A (en) * | 1990-02-06 | 1994-06-21 | Olin Corporation | Chlorine dioxide generation using inert load of sodium perchlorate |
| US5084148A (en) * | 1990-02-06 | 1992-01-28 | Olin Corporation | Electrochemical process for producing chloric acid - alkali metal chlorate mixtures |
| US5242554A (en) * | 1990-02-06 | 1993-09-07 | Olin Corporation | Electrolytic production of chloric acid and sodium chlorate mixtures for the generation of chlorine dioxide |
| US5348683A (en) * | 1990-02-06 | 1994-09-20 | Olin Corporation | Chloric acid - alkali metal chlorate mixtures and chlorine dioxide generation |
| US5264089A (en) * | 1990-02-06 | 1993-11-23 | Olin Corporation | Production of chlorine dioxide employing chloric acid - alkali metal chlorate mixtures |
| US5242553A (en) * | 1990-02-06 | 1993-09-07 | Olin Corporation | Chloric acid-alkali metal chlorate mixtures for chlorine dioxide generation |
| EP0532535B2 (en) † | 1990-06-07 | 2003-07-09 | Sterling Canada, Inc. | Electrochemical production of acid chlorate solutions |
| CA2023733C (en) * | 1990-08-21 | 1998-04-14 | Marek Lipsztajn | Chlorine dioxide generation from chloric acid |
| US5284553A (en) * | 1990-08-22 | 1994-02-08 | Sterling Canada, Inc. | Chlorine dioxide generation from chloric acid |
| US5486344A (en) † | 1992-06-09 | 1996-01-23 | Eka Nobel Inc. | Method of producing chlorine dioxide |
| US5328673A (en) * | 1992-11-23 | 1994-07-12 | Olin Corporation | Process for removal of NOx and SOx oxides from waste gases with chloric acid |
| US5487881A (en) * | 1993-02-26 | 1996-01-30 | Eka Nobel Inc. | Process of producing chlorine dioxide |
| US5480516A (en) * | 1993-05-12 | 1996-01-02 | Sterling Pulp Chemicals, Ltd. | Electrolytic production of acid |
| US5478446A (en) * | 1993-07-02 | 1995-12-26 | Eka Nobel Inc. | Electrochemical process |
| US6024850A (en) * | 1993-10-27 | 2000-02-15 | Halox Technologies Corporation | Modified ion exchange materials |
| US5705050A (en) * | 1996-04-29 | 1998-01-06 | Sampson; Richard L. | Electrolytic process and apparatus for the controlled oxidation and reduction of inorganic and organic species in aqueous solutions |
| US6402916B1 (en) | 1993-10-27 | 2002-06-11 | Richard L. Sampson | Electrolytic process and apparatus controlled regeneration of modified ion exchangers to purify aqueous solutions and adjust ph |
| NZ272769A (en) * | 1994-08-18 | 1996-03-26 | Eka Nobel Inc | Process for producing chlorine dioxide by reducing chlorate in acidic reaction medium |
| SE9402856L (en) * | 1994-08-26 | 1995-11-27 | Eka Nobel Ab | Process of producing chlorine dioxide |
| US5599518A (en) * | 1994-12-01 | 1997-02-04 | Olin Corporation | Catalytic process for chlorine dioxide generation from chloric acid |
| US5616234A (en) * | 1995-10-31 | 1997-04-01 | Pepcon Systems, Inc. | Method for producing chlorine or hypochlorite product |
| US5868915A (en) * | 1996-09-23 | 1999-02-09 | United States Filter Corporation | Electrodeionization apparatus and method |
| US5792441A (en) * | 1996-10-11 | 1998-08-11 | Pulp And Paper Research Institute Of Canada | Fixed-resin bed technologies for the treatment of the chlorine dioxide generator effluent and feeds stream |
| US5882501A (en) * | 1997-08-18 | 1999-03-16 | Ppg Industries, Inc. | Method of converting amine hydrohalide into free amine |
| US5900133A (en) * | 1997-08-18 | 1999-05-04 | Ppg Industries, Inc. | Method of converting amine hydrohalide into free amine |
| US5904829A (en) * | 1997-08-18 | 1999-05-18 | Ppg Industries, Inc. | Method of converting amine hydrohalide into free amine |
| US5906722A (en) * | 1997-08-18 | 1999-05-25 | Ppg Industries, Inc. | Method of converting amine hydrohalide into free amine |
| CA2321683C (en) * | 1998-03-16 | 2005-09-27 | Pulp And Paper Research Institute Of Canada | Additives to chlorine dioxide bleaching |
| US6284124B1 (en) | 1999-01-29 | 2001-09-04 | United States Filter Corporation | Electrodeionization apparatus and method |
| US6471871B1 (en) * | 1999-10-28 | 2002-10-29 | Finnchem Usa, Inc | Method for the removal of silicon and heavy metals from aqueous streams |
| US6306281B1 (en) | 1999-11-30 | 2001-10-23 | Joseph Matthew Kelley | Electrolytic process for the generation of stable solutions of chlorine dioxide |
| GB0016846D0 (en) * | 2000-07-10 | 2000-08-30 | United States Filter Corp | Electrodeionisation Apparatus |
| US7147785B2 (en) * | 2000-09-28 | 2006-12-12 | Usfilter Corporation | Electrodeionization device and methods of use |
| FR2818922B1 (en) * | 2000-12-28 | 2003-10-03 | Atofina | METHOD AND DEVICE FOR IMPLEMENTING A REACTION IN A LIQUID MEDIUM WITH GASEOUS RELEASE |
| WO2003106736A2 (en) * | 2001-01-02 | 2003-12-24 | Halox Technologies, Inc. | Electrolytic process and apparatus |
| US6607647B2 (en) | 2001-04-25 | 2003-08-19 | United States Filter Corporation | Electrodeionization apparatus with expanded conductive mesh electrode and method |
| US6649037B2 (en) | 2001-05-29 | 2003-11-18 | United States Filter Corporation | Electrodeionization apparatus and method |
| DE60239141D1 (en) * | 2001-10-15 | 2011-03-24 | Siemens Water Tech Holdg Corp | DEVICE AND METHOD FOR CLEANING LIQUIDS |
| US20030138371A1 (en) * | 2002-01-18 | 2003-07-24 | Cdg Technology, Inc. | Method and apparatus for generating gaseous chlorine dioxide-chlorine mixtures |
| WO2004009874A1 (en) * | 2002-07-17 | 2004-01-29 | Halox Technologies, Inc. | Electrolytic process and apparatus |
| AU2002336561A1 (en) * | 2002-09-17 | 2004-04-08 | Halox Technologies, Inc. | Electrocatalytic process and apparatus |
| US7241435B2 (en) * | 2002-09-30 | 2007-07-10 | Halox Technologies, Inc. | System and process for producing halogen oxides |
| US6913741B2 (en) * | 2002-09-30 | 2005-07-05 | Halox Technologies, Inc. | System and process for producing halogen oxides |
| US7501061B2 (en) * | 2002-10-23 | 2009-03-10 | Siemens Water Technologies Holding Corp. | Production of water for injection using reverse osmosis |
| US7179363B2 (en) * | 2003-08-12 | 2007-02-20 | Halox Technologies, Inc. | Electrolytic process for generating chlorine dioxide |
| US20050076451A1 (en) * | 2003-10-08 | 2005-04-14 | Johnsondiversey, Inc. | Method of use of chlorine dioxide as an effective bleaching agent |
| US8377279B2 (en) * | 2003-11-13 | 2013-02-19 | Siemens Industry, Inc. | Water treatment system and method |
| US7604725B2 (en) * | 2003-11-13 | 2009-10-20 | Siemens Water Technologies Holding Corp. | Water treatment system and method |
| US7083733B2 (en) | 2003-11-13 | 2006-08-01 | Usfilter Corporation | Water treatment system and method |
| US20050103717A1 (en) * | 2003-11-13 | 2005-05-19 | United States Filter Corporation | Water treatment system and method |
| US7582198B2 (en) | 2003-11-13 | 2009-09-01 | Siemens Water Technologies Holding Corp. | Water treatment system and method |
| US7563351B2 (en) * | 2003-11-13 | 2009-07-21 | Siemens Water Technologies Holding Corp. | Water treatment system and method |
| US7846340B2 (en) * | 2003-11-13 | 2010-12-07 | Siemens Water Technologies Corp. | Water treatment system and method |
| US7862700B2 (en) * | 2003-11-13 | 2011-01-04 | Siemens Water Technologies Holding Corp. | Water treatment system and method |
| CA2548522A1 (en) * | 2003-12-18 | 2005-07-07 | Johnsondiversey, Inc. | Addition of salt to depress ph in the generation of chlorine dioxide |
| US7329358B2 (en) | 2004-05-27 | 2008-02-12 | Siemens Water Technologies Holding Corp. | Water treatment process |
| US20060231406A1 (en) * | 2005-04-13 | 2006-10-19 | Usfilter Corporation | Regeneration of adsorption media within electrical purification apparatuses |
| US7658828B2 (en) * | 2005-04-13 | 2010-02-09 | Siemens Water Technologies Holding Corp. | Regeneration of adsorption media within electrical purification apparatuses |
| US8045849B2 (en) * | 2005-06-01 | 2011-10-25 | Siemens Industry, Inc. | Water treatment system and process |
| US20070012578A1 (en) * | 2005-06-30 | 2007-01-18 | Akzo Nobel N.V. | Chemical process |
| US8034227B2 (en) * | 2005-06-30 | 2011-10-11 | Akzo Nobel N.V. | Chemical process |
| KR100738093B1 (en) | 2006-01-05 | 2007-07-12 | 삼성전자주식회사 | Portable pH regulating device and method for regulating pH using the same |
| BRPI0710338A2 (en) * | 2006-04-29 | 2011-08-09 | Electrolytic Technologies Corp | electrochemical generation system for producing chlorine gas, noh and sodium hypochlorite solution and process for electrolytically producing chlorine gas, there is optionally a sodium hypochlorite |
| US10213744B2 (en) | 2006-06-13 | 2019-02-26 | Evoqua Water Technologies Llc | Method and system for water treatment |
| US8277627B2 (en) | 2006-06-13 | 2012-10-02 | Siemens Industry, Inc. | Method and system for irrigation |
| US10252923B2 (en) | 2006-06-13 | 2019-04-09 | Evoqua Water Technologies Llc | Method and system for water treatment |
| US8114259B2 (en) * | 2006-06-13 | 2012-02-14 | Siemens Industry, Inc. | Method and system for providing potable water |
| US20080067069A1 (en) | 2006-06-22 | 2008-03-20 | Siemens Water Technologies Corp. | Low scale potential water treatment |
| US7820024B2 (en) * | 2006-06-23 | 2010-10-26 | Siemens Water Technologies Corp. | Electrically-driven separation apparatus |
| US7744760B2 (en) | 2006-09-20 | 2010-06-29 | Siemens Water Technologies Corp. | Method and apparatus for desalination |
| MX2010005876A (en) | 2007-11-30 | 2010-06-15 | Siemens Water Tech Corp | Systems and methods for water treatment. |
| US8568509B2 (en) * | 2008-02-27 | 2013-10-29 | National Institute Of Advanced Industrial Science And Technology | Method of recovering metal |
| EP2259854A4 (en) * | 2008-04-03 | 2011-12-07 | Siemens Industry Inc | Low energy system and method of desalinating seawater |
| CN102317244A (en) | 2009-01-29 | 2012-01-11 | 普林斯顿大学 | Carbonic acid gas is converted into organic product |
| US20110114502A1 (en) * | 2009-12-21 | 2011-05-19 | Emily Barton Cole | Reducing carbon dioxide to products |
| US8500987B2 (en) | 2010-03-19 | 2013-08-06 | Liquid Light, Inc. | Purification of carbon dioxide from a mixture of gases |
| US8721866B2 (en) | 2010-03-19 | 2014-05-13 | Liquid Light, Inc. | Electrochemical production of synthesis gas from carbon dioxide |
| US20110281959A1 (en) | 2010-05-11 | 2011-11-17 | The Government Of The United States Of America As Represented By The Secretary Of The Navy | Extraction of Carbon Dioxide and Hydrogen From Seawater and Hydrocarbon Production Therefrom |
| US20110284391A1 (en) * | 2010-05-21 | 2011-11-24 | Verein fuer Kernve. und Analyt. Rosse. e.V. (VKTA) | Process and apparatus for separating nitroaromatics from wastewater |
| US8961774B2 (en) | 2010-11-30 | 2015-02-24 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
| US8568581B2 (en) | 2010-11-30 | 2013-10-29 | Liquid Light, Inc. | Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide |
| US9090976B2 (en) | 2010-12-30 | 2015-07-28 | The Trustees Of Princeton University | Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction |
| US8845876B2 (en) | 2012-07-26 | 2014-09-30 | Liquid Light, Inc. | Electrochemical co-production of products with carbon-based reactant feed to anode |
| US10329676B2 (en) | 2012-07-26 | 2019-06-25 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
| US20140206896A1 (en) | 2012-07-26 | 2014-07-24 | Liquid Light, Inc. | Method and System for Production of Oxalic Acid and Oxalic Acid Reduction Products |
| US8641885B2 (en) | 2012-07-26 | 2014-02-04 | Liquid Light, Inc. | Multiphase electrochemical reduction of CO2 |
| US20130105304A1 (en) | 2012-07-26 | 2013-05-02 | Liquid Light, Inc. | System and High Surface Area Electrodes for the Electrochemical Reduction of Carbon Dioxide |
| US9175407B2 (en) * | 2012-07-26 | 2015-11-03 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
| US9873951B2 (en) | 2012-09-14 | 2018-01-23 | Avantium Knowledge Centre B.V. | High pressure electrochemical cell and process for the electrochemical reduction of carbon dioxide |
| US9719178B2 (en) | 2013-02-28 | 2017-08-01 | The United States Of America, As Represented By The Secretary Of The Navy | Electrochemical module configuration for the continuous acidification of alkaline water sources and recovery of CO2 with continuous hydrogen gas production |
| CN103112826B (en) * | 2013-03-20 | 2015-01-21 | 广西轻工业科学技术研究院 | Method for producing high-purity chlorine dioxide |
| US11820689B2 (en) | 2017-08-21 | 2023-11-21 | Evoqua Water Technologies Llc | Treatment of saline water for agricultural and potable use |
| CN112912544B (en) * | 2018-10-18 | 2022-07-26 | 蓝色安全有限公司 | Electrochemical system for synthesizing an aqueous oxidant solution |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2815320A (en) * | 1953-10-23 | 1957-12-03 | Kollsman Paul | Method of and apparatus for treating ionic fluids by dialysis |
| US3619350A (en) * | 1969-07-11 | 1971-11-09 | Richard Marchfelder | Chlorine dioxide pulp bleaching system |
| US3810969A (en) * | 1971-06-22 | 1974-05-14 | Hooker Chemical Corp | Process for the production of chlorine dioxide |
| FR2476077A1 (en) * | 1980-02-19 | 1981-08-21 | Rhone Poulenc Ind | NEW PROCESS FOR THE PREPARATION OF METHIONINE |
| US4362707A (en) * | 1981-04-23 | 1982-12-07 | Diamond Shamrock Corporation | Preparation of chlorine dioxide with platinum group metal oxide catalysts |
| US4486399A (en) * | 1983-07-01 | 1984-12-04 | Multifibre Process Limited | Method to reduce the potential salt cake content of chlorine dioxide generator spent acids |
| US4470888A (en) * | 1983-09-08 | 1984-09-11 | Pennwalt Corporation | Method for preparing alkali metal chlorates by electrolysis |
| US4683039A (en) * | 1985-12-24 | 1987-07-28 | Tenneco Canada Inc. (Erco Division) | Membrane pervaporation process |
| US4798715A (en) * | 1988-02-05 | 1989-01-17 | Eltech Systems Corporation | Producing chlorine dioxide from chlorate salt |
| US4806215A (en) * | 1988-07-27 | 1989-02-21 | Tenneco Canada Inc. | Combined process for production of chlorine dioxide and sodium hydroxide |
| US4915927A (en) * | 1988-10-21 | 1990-04-10 | Tenneco Canada Inc. | Production of chloric acid |
| US5092970A (en) * | 1989-12-20 | 1992-03-03 | Olin Corporation | Electrochemical process for producing chlorine dioxide solutions from chlorites |
| US5242553A (en) * | 1990-02-06 | 1993-09-07 | Olin Corporation | Chloric acid-alkali metal chlorate mixtures for chlorine dioxide generation |
| US5248397A (en) * | 1990-02-06 | 1993-09-28 | Olin Corporation | Chlorine dioxide generation from chloric acid - alkali metal chlorate mixtures |
| US5084148A (en) * | 1990-02-06 | 1992-01-28 | Olin Corporation | Electrochemical process for producing chloric acid - alkali metal chlorate mixtures |
| US5242554A (en) * | 1990-02-06 | 1993-09-07 | Olin Corporation | Electrolytic production of chloric acid and sodium chlorate mixtures for the generation of chlorine dioxide |
| US5122240A (en) * | 1990-06-08 | 1992-06-16 | Tenneco Canada Inc. | Electrochemical processing of aqueous solutions |
| SE500107C2 (en) * | 1991-06-26 | 1994-04-18 | Eka Nobel Ab | Process for the production of chlorine dioxide |
| US5284443A (en) * | 1992-08-28 | 1994-02-08 | Coltene/Whaledent, Inc. | Method of forming dental restorations |
-
1990
- 1990-02-06 US US07/475,603 patent/US5084148A/en not_active Expired - Fee Related
-
1991
- 1991-01-14 WO PCT/US1991/000172 patent/WO1991012356A1/en not_active Application Discontinuation
- 1991-01-14 EP EP91903525A patent/EP0514427B1/en not_active Revoked
- 1991-01-14 CA CA002074082A patent/CA2074082A1/en not_active Abandoned
- 1991-01-14 BR BR919105976A patent/BR9105976A/en not_active Application Discontinuation
- 1991-01-14 DK DK91903525.3T patent/DK0514427T3/en active
- 1991-01-14 AU AU72217/91A patent/AU7221791A/en not_active Abandoned
- 1991-01-14 JP JP3503566A patent/JPH05504170A/en active Pending
- 1991-09-24 US US07/765,078 patent/US5223103A/en not_active Expired - Fee Related
-
1992
- 1992-07-15 FI FI923249A patent/FI923249A0/en unknown
- 1992-07-16 NO NO92922821A patent/NO922821L/en unknown
- 1992-07-24 US US07/919,813 patent/US5296108A/en not_active Expired - Fee Related
- 1992-12-31 US US07/999,419 patent/US5354435A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AU7221791A (en) | 1991-09-03 |
| EP0514427B1 (en) | 1996-04-10 |
| US5296108A (en) | 1994-03-22 |
| EP0514427A1 (en) | 1992-11-25 |
| FI923249A (en) | 1992-07-15 |
| FI923249A0 (en) | 1992-07-15 |
| WO1991012356A1 (en) | 1991-08-22 |
| NO922821L (en) | 1992-08-06 |
| JPH05504170A (en) | 1993-07-01 |
| US5084148A (en) | 1992-01-28 |
| BR9105976A (en) | 1992-11-03 |
| US5354435A (en) | 1994-10-11 |
| NO922821D0 (en) | 1992-07-16 |
| EP0514427A4 (en) | 1993-05-12 |
| DK0514427T3 (en) | 1996-08-19 |
| US5223103A (en) | 1993-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2074082A1 (en) | Electrochemical process for producing chloric acid - alkali metal chlorate mixtures | |
| US5092970A (en) | Electrochemical process for producing chlorine dioxide solutions from chlorites | |
| US5106465A (en) | Electrochemical process for producing chlorine dioxide solutions from chlorites | |
| US4798715A (en) | Producing chlorine dioxide from chlorate salt | |
| US6254762B1 (en) | Process and electrolytic cell for producing hydrogen peroxide | |
| US4683039A (en) | Membrane pervaporation process | |
| US5246551A (en) | Electrochemical methods for production of alkali metal hydroxides without the co-production of chlorine | |
| EP0507862B1 (en) | Electrochemical chlorine dioxide generator | |
| AU648076B2 (en) | Process for the production of chloric acid and perchloric acid | |
| US4272338A (en) | Process for the treatment of anolyte brine | |
| US5248397A (en) | Chlorine dioxide generation from chloric acid - alkali metal chlorate mixtures | |
| US5089095A (en) | Electrochemical process for producing chlorine dioxide from chloric acid | |
| US5242554A (en) | Electrolytic production of chloric acid and sodium chlorate mixtures for the generation of chlorine dioxide | |
| US6159349A (en) | Electrolytic cell for hydrogen peroxide production | |
| EP0230737B1 (en) | Membrane pervaporation process for obtaining a chlorine dioxide solution | |
| US5264089A (en) | Production of chlorine dioxide employing chloric acid - alkali metal chlorate mixtures | |
| US5242553A (en) | Chloric acid-alkali metal chlorate mixtures for chlorine dioxide generation | |
| US4444631A (en) | Electrochemical purification of chlor-alkali cell liquor | |
| US5258105A (en) | Chloric acid - alkali metal chlorate mixtures and chlorine dioxide generation | |
| US5348683A (en) | Chloric acid - alkali metal chlorate mixtures and chlorine dioxide generation | |
| US5322598A (en) | Chlorine dioxide generation using inert load of sodium perchlorate | |
| RU2317351C2 (en) | Alkaline metal chlorate producing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |