US1264535A - Electrolysis of chlorids. - Google Patents

Description

K. P. McELROY.

ELECTROLYSIS 0F CHLORIDS.

APPLICATION FILED DEC.9,I915.

Patnted Apr. 30, 1918.

3 SHEE1S-SHEET I.

K. P. McELROY.

ELECTROLYSIS 0F CHLOBIDS. APPLICATION FILED DEC. 9. l9l5.

3 SHEEIS- SHEET 2.

Patented Apr. 30, 1918. v

K. P. McELROY.

ELECTROLYSIS 0F CHLORIDS.

APPLICATION FILED DEC. 9. 1915.

mwmm, Patented Apr. 30,1918.

3 SHEEISFSHEET a.

amuwnlo z Witwaoo KARL P. MeELnoY, or wasnmeron, msrmcr or COLUMBIA, assrelvon T cnnmcar.

DEVELOPMENT COMPANY, a CORPORATION Or MAINE.

ELECTROLYSIES 0E CHLORIDE.

Application filed December 9, 1915. Serial No. 65,983.

To all whom it may concern:

Be it known that I, KARL P. MOELROY, a citizen of theUnited States, residing at Washington, in the District. of Columbia, have invented certain new and useful Improvements in Electrolysis of Chlorids, of which the following is a specification.

This invention relates to the electrolysis of chlorids; and it comprises an improvement in the method of electrolyzing aqueous solutions of. potassium chlorid and sodium chlorid for the manufacture of alkali and chlorin wherein the production of chlorin as such is obviated and in its lieu are obtained other and more valuable volatile products,

such volatile products being removed in the vapor form from the zone-of electrolysis as fast as formed for condensatlon elsewhere,

the electrolytic liquid being maintained hot,

ture of olefins is introduced into the electrolytic apparatus in the vicinity of the anodeand the vapors of volatile products formed by reaction of such gas or vapor with the chlorin evolved at the anode are removed and condensed; and it further comprises as .a new organization of apparatus elements an electrolytic cell adapted for the electrolysis of aqueous chlorid solutions, means for heating the same, means for introducing hydrocarbon gases or vapors in proximity'to the anode and means for removing and condensing vapors of volatile products; all as more fully hereinafter set forth and asclaimed.

. In the manufacture of alkali by the eleotrolysis of solutionsof potassium chlorid and sodium chlorid, corresponding. amounts of free chlorin are necessarily produced while the market demand for chlorin is not as great as that for alkali. .][t is one of the objects of the resent invention to improve the alkali-maklng process by the substitution of the'produ'ction of other and more valuable productsfor that of chlorin. To

this end, in the electrolytic operation the chlorin evolved at the anode is caused to react within the cell with unsaturated hydrocarbons to produce various volatile bodies of value for solvent and other purposes, the re:- action being carried on at such a temperature that the new products are maintained in vapor form while the vapors are removed from thezone of reaction as fast as formed.

Olefin hydrocarbons, of the general formula CnH such as ethylene, C 11,, and its homologs, react with chlorin by simple addition, forming olefin chlorids, C H Cl In thecase of ethylene, (3 1L61 ethylene chlorid or Dutch liquid, is produced. These olefin chlorids are volatile liquids insoluble in water and of value for solvent purposes though not now made commercially.

As I have, discovered, and have elsewhere described and claimed, the action'of chlorin upon the unsaturated gaseous hydrocarbons,

Specification of Letters Patent. Patented Apr. 3@, lfillfi.

such as the olefins, is however, not necessarily one of simple addition. Ethylene, for example, in contact with chlorin under-certain conditions does not form Dutch liquid by simple addition but may instead form ethylene 'chlorhydrin, O H,OHCI; a body which is nearly related to ordinary ethyl alcohol G H Oll-l, difi'ering from it by containing' an atom of chlorin in lieu of one of hydrogen. The other olefins, propylene, the butylenes, the amylenes, etc, form chlorhydrins in a similar way. These chlorhydrins re all bodies'more or less soluble in water, of fragrant alcoholic odor and of excellent solvent properties for varnish making, celluloid manufacture, etc. The chlorhydrins of the lower or gaseous olefins, ethylene, propylene and the butylenes as well as of the amylenes all have nearly the same boiling points.

A necessary condition for the formation of chlorhydrins from the olefins and chlorin is the presence of water in relatively large amount, either as liquid water or as steam.

:Under these conditions, half the chlorin re-. acts with part of thehydrogen of the water to form hydrochloric acid while the remaining' chlorin and the remainin O and H of the water or steam unite with the olefin formingaa chlorhydrin. If the reaction be performed in the presence of steam, at

. 971Q0 G. thechlorhydrin is formed and remains in the vapor state. While the olefin chlorhydrins are relatively high boiling olefin being caused to contact together in an atmosphere of steam at a temperature around 100 C. Under these circumstances olefin chlorhydrins are formed and pass out of the apparatus as vapor to be subsequently condensed. Half the chlorin is converted into hydrochloric acid which condenses and remains in the apparatus and which may be drawn off as an aqueous solution. The process is there described and claimed as being particularly suitable for treatment of the mixture of olefins which is contained, to the extent of 40 to 60 per cent, in oil gas made from petroleum oils at relatively low temperatures.

- In the present invention in lieu of separately preparing chlorin and then admixing it with the olefinic gases, I directl introduce the gases into the electrolytic ce l, forming the chlorhydrins'in the cell and withdraw- .ing them therefrom as vapors which are subsequently condensed.

To this end I perform the electrolysis of a solution of salt (NaOl) or of any other suit able chlorid in any suitable form of cell now used to manufacture chlorin and alkali; but I maintain the temperature of the cell considerably higher than is usuall the case. This is for a number of reasons. ne is that I wish to maintain an atmosphere of steam within the cell and another s that I wish to produce and maintain the chlorhydrins invapor state until they can be removed from the cell; and therefore do not wish'them to condense in the electrolyte.

While the present process is applicable to the treatment of pure olefins such as ethylene, propylene, the butylenes, the amylenes, the hexylenes, etc., I shall hereinafter speak more specifically of the treatment of oil gas, 1t being understood that such gas is merely typical of gases containing olefins and of the gaseous olefins themselves, or of vaporized low boiling olefins such as are contained in unsaturated gasolene.

Oil gas when properly made is a mixture of saturated and unsaturated hydrocarbons.

The saturated hydrocarbons, methane,ethane, propane, etc, are inert in the present process.

A little hydrogen may be present but this is sired to remove the butylenes, amylenes, etc., leaving the ethylene and propylene, the gas may be com ressed and chilled to condense out liquefiab e gases and vapors; or it may be washed with chilled oil. Or it may be both pressed and chilled and scrubbed with chilled oil. However, for most purposes the presence of the amylenes and the butylenes does no harm. Chlorhydrins of ethylene,

and propylene, and of the amylenes and buty-. lenes-all boil within a' narrow range, between 127 and 135 (3.; so that a mixture of such chlorhydrins such 'as is obtained on directly treating unpurified oil gas by the present recess is,f0r most purposes, a unitary body in the sense that it does not have const1tuents which can be readily separated by fractional distillation. For many solvent purposes this mixture is more desirable than the several pure bodies composin it. The boilin point of a mixture-of chlor ydrins obtainet l from crude oil gas ranges, in the dry state, as stated, between 127 and 135 C. In the presence of suificient' water the mixture will boil between 9799 C.

On passing the oil gas over or through ahot electrode evolving chlorin and at a tem er- I ature between 97100 C. the chlorin an the chlorhydrins containing some water and water carrying dissolved chlorhydrins. This mixture may be settled and the oil and water separated. The water solution on redistillation in a column still gives oily chlorhydrins and saturated solution. The aqueous solution formed on condensin the efiluent vapors from a cell where muc steam goes forward, may be similary distilled to recover the chlorhydrins in the oily form. The oily chlorhydrins may be dehydrated by distillation or by treatment with salt followed by distillation. In dry form, without separation of the individual components the condensed chlorhydrin mixture forms an excellent solvent capable of dissolving cellulose acetate and many other coatlng materials and capable of replacing amyl acetate and other expensive solvents for many uses.

Under the stated conditions, the hydrochloric acid formed in the action is condensed, dissolvesin the cell electrolyte and is relectrolyzed to furnish more chlorin.

If the temperature of the vapors above electrolyte be over 100 C. as may be the casein supplying live steam to such space, or is very much under 100 C. there is usually some formation of olefin chlorids. Superheated steam, that is steam-"over 100 'C. at

' forme atmospheric pressure does not have as much of the tendency favoring the production of ohlorhydrins as steam at 100 C. while at temperatures much below 100 0. there is often not enough water vapor in the reaction space. Where olefin chlorids are produced,

, they separate from the aqueous condensate,

being wholl insoluble in water. They however as'a rue carry more or less chlorhydrins. Where olefin ehlorids and chlorhydrlns are both roduced in the cell, the separation g is a turbid whitish looking material, sometimes floating on the water and compOSed of mutually dissolved chlorids, chlorhydrins and water. These whitish oil separations on washing with water-give clear olefin chlorids, the chlorhydrins going into solutionwith the water. Washing with water may be used for the purpose of separating.

horizontal diaphragm types, it may be blown along the surface of the electrolyte in the anode chamber. 1

While chlorhydrin may be formed in chlorin evolving cells at a lower temperature; a temperature such that they do not volatilize to any material extent but remain in the electrolyte or separate from it physically as oils, this matter ll do not herein claim, it forming part of the subject matter of my copending application 35505, filed June 22, 1915; the present invention relating more specifically to a process wherein the chlorhydrins are formed in the cell in the vapor state and are removed as such.

In the accompanying illustration I have shown more or less diagrammatically certain cheap, simple and effective types of cell. In this showing,

' Figure 1 is a central vertical section of a horizontal type of diaphragm cell;

Fig. 2 is a central vertical section, certain accessory parts being in elevation, of a type having a vertical diaphragm;

Fig. 3 is a vertical cross-section'of a come pact type of cell, having a plurality of units adapted for use in series; and

Fig. 4 is a fragmentary central longitudinal vertical section of two such units; and

Fig. 5 is a central longitudinal vertical section of still another form of cell.

In the showing of Fig. 1 element 1 isan alkali chamber which may bemade of concrete or any other suitable non-conducting material. At. its base it is provided with valved alkali outlet At a high point it is,

Any of the ordinaryv types of cell may be employed for the present purposes if it be.

provided with hydrogen escape 3. At a lower point it is provided with steam inlet 4:.

Within this chamber is hung the cell proper. The side walls of the chamber inclosing the cell are spaced somewhat away to give a steam space 5 therebetween. The walls carry a mark row iron plate 6 on which rest angle irons 7 extending the full length of the cell and serving to support it. be built of a frame of expanded metal or wire netting 8 bent into the proper form. Within thisnetting is placed a lining 9 of tile or other acid resistant 'material.

slate does very well. The metal framework and slate lining being in positionthe sides of the cell are plastered with a thin layer ofeconcrete 10 extending nearly to he cell proper may.

Ordinary the top of the slate lining and to its base i and rigid with the stated angle irons. This layer grips the lining and makes the structure unitary. The expanded metal or wire netting may extend across the bottom of the cell to form cathode 11. This cathode may be of copper, iron, or any other metal and may, as stated be the same piece of netting that forms the side Walls of the cell or it may be anotherpiece laced .to the side walls. Extending longitudinally along this cathode bottom is supply pipe 12 which may be of iron or other metal and may serve as a 'current lead to.the cathode. It carries short glass or earthenware nipples 13 extending upwardly beyond a diaphragm layer 14.

This diaphragm may be of asbestos having its pores filled with mineral matter such as barium sulfate, talc, etc. Or asbestos fabric may be simply soaked in solution of silicate rous concrete may be employed. Above this diaphragm have shown a second diaphragm 15 which may be of concrete or asstos. For this second diaphragm, asbestos treated with water glass or silicate of soda solution is useful. The second or false diaphragm serves to form a brine space between ,it and the lowermost diaphragm. Immediately above the falsediaphragm are horizontalanodes 16 which'may be of carbon or graphite. Above these anodes ll may suspend a secondary cathode 17 for a purpose hereinafter set forth. At the top the cell may be closed by slab 18 of soapstone or slate. They may be notched at 19 to receive the upper extremlties of the slate slabs forming the linin The cell may be provided with steam in ets 20 and with vapor outlets 21 leading to any suitable .condenser tnot shown). Gas may enter at special inlet-.ZQQ or be min led with the steam by meanslof inlet 23. nlet 90 may supply chlorin from any othersource mixed with steam from 91.

llll

In the use of the above described structure the cell isfilled with brine through 12 to a point above the anodes 16. It is best to [use a saturated brine. Weak brines may be used but there is no advantage in this. Steam is now led into the interior of the cell through and into the chamber belowand around the cell through 4 until the liquid as sumes a temperature of 97 100 C. as shown by thermometer 25. Thermometer 26 indicates the temperature of the vapor space. Gas is now led in through inlet 22 or 23 and mixes with the steam passing in at 20. The mixture of steam and gas passes forward over the surface of the hot liquid and meets the chlorin which escapes from the electrolyte in admixture with more or less water vapor. Under these conditions the stated reaction takes place with formation of chlorhydrin vapors and HCl. The temperature of the vapors being 97 or higher the chlorydrin vapors do not condense; but the hydrochloric acid, for the clearly soluble in water. If whitish drops which are not completely soluble in water form, olefin chlorids are being produced. With a cell of the type shown, if the vapor space above the normal liquid level is 5 or -6 inches in-the clear, the formation of olefin chlorids will not ordinarily occur, with proper regulation of the feed of gas and steam. With proper operation of the cell the gases passing beyond the condenser will be nearly free of olefins (as indicated by analysis with the bromin absorption test). A slight amount should always remain to insure presence of an excess over the chlorin 1n the reaction zone. They may be scrubbed with a little water to remove acid and used for supplying gas engines to furnish the power for the supply of electric current to be used 1n carrying out the operation. In this type of cell I sometimes employ the sup'.

plemental cathode 17 placed directly above the anodes. This cathode tends to form, by well understood reactions, hypochlorites which in theboiling solution are converted by the chlorm into chlorids and hypochlorous acid, HClO, which is freely volatile in water solutions at 97 (land above and which likewise unites with the olefins to form chlorhydrins. It inay be that the aclike that shown in Fig. 2 or may be any simple type of worm.

The temperature of 97100 C. indicated is that of the vapor space in operating at the ordinary atmospheric pressure. If a greater or less pressure is used, the temperature range will vary correspondingly. The temperature should be within two or three degrees of that at. which water wilTboil at the pressure used but below the boiling point of the brine used. It is not desirable to have the electrolyte actually boil if it is a saturated solution.

In the showing of Fig. 2 I illustrate a vertical type of cell wherein gas or a mixture of gas and steam is blown through the electrolyte instead of along its surface. If the electrolyte becomes dilute by reason of condensation ofsteam, less steam is blown in with the gas. In this showing element 30 is a concrete housing or hydrogen and I alkali chamber which may be made of concrete, brickwork or any other suitable material. It may be either cylindrical or rcctangular in shape. At a point near the top it carries outlet 31 for hydrogen and at a point near the bottom outlet 32 for caustic soda. Inlet 33 allows introduction of steam in this chamber. On the floor of this chamber is a slate or soapstone slab 34 on which the cell proper rests, making a liquid tight union at its base with the slab. The slab is in effect the floor of the cell proper. Through the floor of the cell passes outlet 35 for brine. At the top is brine inlet 35'. The side walls of the cell as shown areucomposed of cathode 36 which may be of copper or iron; and may be made of wire ga uze or perforated or expanded metal. W1th1n this cathode is diaphragm 37 which may be of porous concrete, asbestos, or any other suitable material. For the present purposes, since there is considerable agitation within the cell which is apt to disintegrate asbestos in its ordinary form, if asbestos be used it is best first treated with a concentrated solution of water glass. Under the influence of the saturated brine of the electrolyte this glass is precipitated within the pores of the asbestos as a stifi, mechanically stron colloid mass, which, while not interfering materially with electric conductivity or the passage of the ions has nevertheless considerable mechanical strength. Near this diaphragm are placed anodes 38 which may be of carbon or graphite. Inch rods spaced a quarterof an inch apart form a very good anode. for the present purpose. These rods pass through and are held by ring cover 39 which may be of slate or other acidresistant material. As shown, it, rests on the top of the cathode and diaphragm,.,. being notched to receive their upper extremity and form a gas tight union therewith. Any suitable lute may be used in this joint. Resting on this ring is hollow tile 40 of terra cotta or the like, forming a vapor dome wherein reactions may be completed. This is closed-by cover 41 through which passes gas introduction pipe 42 depending to the bottom of the cellwhere it carries lateral extensions 43 adapted to bubble gas up along the anodes. Carried by the cover is a steam pipe 44 which may be of stoneware or of metal as may be desired. It made of metal, it may be copper or iron; but in such event it is connected to the source of energy in such manner as to act also as a cathode. As'shown thissteam pipe is coiled into a spiral shape and lies as near the anodes as may be. The use of this heating pipe as a cathode considerably increases the output of the cell as it enables both sides of the anodes to be active but it results in the tormation of some chlorate. Also passing through the cover is vapor pipe 45 flanged at 46. By this flanged union it connects through pipe 47 with adiagrammatically shown column still 48 0t stoneware or any other acid resistant material. At the top this still carries thermometer 49 and vapor outlet 50. The vapor outlet is continued through worm 51 in tub 52. Condensate from the worm'isreceived in tub 53 having gasoutlet 54. The condensate in this tub will divide itself into two layers, a lower one of oily chlorhydrins and chlorids which may be withdrawn from time'to time through outlet 55, and an upper layer of a saturated solution of .chlorhydrins which may be returned to the still through pipe connection 56 for re-distillation.

The operation may be controlled in accordance with the appearance and odor of the condensate in 53. In normal operation no smell of 'chlorin should occur at this drops also tend to take a conoidal shape,-

elongating downwardly centrally (something like a wasp nest) with the end of the cone breaking ofl and sinking from time to time.

In Figs. 3 and 4 I have shown another type of vertical cell designed for compactness, capacity and economy of power. It is assembled by providing a longitudinal chamber or casing Which may be of any convenient non-conductive material and as shown is built up of hollow tiles 60 for the sake of heat-insulation, these tiles being laid in concrete wall 61. Within this casing may is brine outflow pipe 67, rising to the normal liquid level within the unit and leading outward past valve 68 to discharge in trough 69, leading to a resaturator (not shown). This pipe and trough are of non-conductive material. Brine is supplied from main 70 to funnel 71 on pipe 72. This pipe extends Within the unit at 73 and has a drain connection 74. Gas is sup lied at 75, and passes through a glass sighteed device 76. Steam is introduced with it by means of connection 77. Beneath the anodes is a perforated gas distribution pipe 7 8 of glass or terra cotta. Near the top of the unit vapor discharge 79,

which may be a glass tube, leads outward,

being given a slight angle to permit reflux of any condensate. This discharge communicates withvapor trunkl80, leading to a condenser (not shown). "As many as may be desired of these units are assembled together as more fully shown in Fig. 4. As there shown, the unit is composed of two diaphragm walls, 81. Beyond these diaphragms are cathodes 82 which may be of any of the usual mater'ials- Asshown, however, they are composed of a porous or open textured mass of copper oxid having embedded copper wire or gauze 83, tor the sake of conductivity. The unit being intended for use in series, the two cathodes, ar-'a of unit A are connected through 84 with the anode of unit B. There being a potential dropbetween the two cathodes a and b of units and B, the chamber between them is divided into two parts, 0 and D, or

subchambers, by partition 85 of slate or the I like. On each side of this partition is an alkali outlet, 86, a steam and air inlet 8-7 and a steam or hydrogen outlet 88.

In the use of this structure, the operation, so far as the chlorhydrin making operation is concerned, is much the same as that in Fig. 2. The steam and gas pass up around the anodes from 78 and form chlorhydrin vapors which are led away through 79 to 80;

the latter serving both as a vapor trunk and as a reaction chamber. Cathodes 82 however operate in a novel'manner. Air being introduced with steam at 87 and the whole apparatus being at about 100 0., the copper oxid of the cathodes acts as a regenerated depolarizer, the reduced copper being oxidized by the air. It is best to free this air of CO by washing with air or a little cause tic soda.

If-no air be introduced, the cathodes 0perate in the usual manner; and in this event they may be of iron or any other suitable material. For depolarization while other bodies, may be used, such as manganese oxids, I regard the copper oxid as well adapted.

In Fig. 5 I have shown a cell intended for the recovery of the chlorin converted into hydrogen chlorid in the reaction. This cell which has no diaphragm is composed of a casing 100 of wire netting or expanded metal, lined with slate 101 held in place by the gripping action of fine concrete plastering 102. Suitably supported below normal liquid level 103 are anode 104 and cathode 105.. The latter is intended to serve also as a heatingmember and may be composed of copper or lead tubing and be connected to steam conduit'l0'6 Drain 107 is provided for cleaning out. Chlorin is introduced at 108 and gas or vapor at 109. Steam may be introducedwith the gas by 110. Vapors are led off to a condenser by vertical conduit 111 which may be of any suitable size or material and may lead to an auxiliary reaction chamber.

In the operation of this structure chlorin from another source is introduced at 108 and reacts with gas from 109. The hydrochloric. acid roduced in the reaction condenses with tl i her and joins the liquid layer while chlorhydrinvapors pass outward through 111.

- The heater cathode 105 keeps the liquid at or near the boilingpoint to furnish the aqueous vapor needed in the reaction while cathode and anode cooperate to reconvert the hydrochloric acid into chlorin and keep the hydrochloric acid concentration of the liquid at a low-point; which is desirable.

- water.

ward with the chlorhydrin.

e aqueous vapors of the chamgassing for-* Other olefin rich gas, such as that from coking coal, charring wood, etc., may be employed. The richest oil gas is that made by passing heavy oils, such as gas oil, through a hot retort at say 700 C. It should not be fixed by reheating to a high temperature. Gases from cracking stills in petroleum refineries may be used in lieu of specially made gas.

Instead of using gaseous olefins, (those normally gaseous at say 20 (1.), the volatile liquid olefins contained in unrefined cracked gasolenes may be employed. The operation is exactly the same as hereinbefore described save that gasolene vapors are used in lieu of oil gas. I

By lowering the cell temperatures somewhat or by restricting the amount of water vapor in the reaction zone, olefin chlorids may be produced in lieu of chlorhydrins. They distil over at somewhat lower temperatures. For some purposes simultaneous production of both chlorids and chlorhydrins is desirable; as in producing mixed solvents containing both.

Bromhydrins may be produced in the same manner as chlorhydrins by substituting a bromid, such as sodium bromid, for the chlorid in the electrolytic cell.

As stated, chlorhydrins may be made without electrolysis by minging gaseous chlorin from any suitable source with steam and olefins in a suitable reaction chamber (ap--.

plication No. 34678). This results in the production of vapors of chlorhydrins and of hydrogen chlorid (HCl or hydrochloric acid), as in the present invention. In the present invention, this hydrochloric acid is reelectrolyzed to form more chlorin. The two inventions may be usefully. combined, chlorin from another source being blown into any of the cells shown through inlet 90 by means of steam from 91. With introduction of supplemental chlorin, in addition to that which is generated in the cell, the chlorhydrin output of the cell can of course be considerably increased; but this is at the expense of the alkali production. If sufiicient supplemental chlorin be so introduced, the function of the cell may be (as shown more specifically in Fig. 5) simply the electrolysis of the hydrogen chlorid produced in the chlorhydrin formation; and in this event no sodium or potassium chlorid is used in the electrolyte. Ordinarily however in such a combination operation I use some sodium chlorid.

The hydrochloric acid formed in the operation need not be returned to the cell for reelectrolysis, although this is usually done in the present embodiment of my invention, but may be removedv for use elsewhere. In the apparatus of Fig. 2 for example a solution of HCl may be removed at valved drain 200. In Fig. 3, trunk 80 may be inclined wearer vapors generated. will send HCl in greater or less amount beyond the cell. The HCl'solution may be used for chemical generation of chlorin for making chlorhydrins; or may be used for replenishing the chlorin where chlorhydrins are made with the aid of reducible, autoxidizable. chlorids such as GuCl Fecl etc. I

What I claim is:

1. The process of preparing solvent bodies which comprises electrolyzing a hot aqueous chlorid solution in a suitable electrolytic cell, having an anode and during electrolysis supplying an olefin into the vicinity of the anode while removing vapors of produced chlorinated products.

2.. The process of preparing solvent bodies which comprises electrolyzing a hot aqueous chlorid solution in a-suitable electrolytic cell having an anode and during electrolysis supplying a gaseous olefin into the vicinity of the anode While removing vapors of produced chlorinated products.

3. The'process of preparing solvent bodies which comprises electrolyzing a. hot aqueous chlorid solution in a suitable electrolytic cell having an anode and during electrolysis supplying oil gas into the vicinity of the anode while removing vapors of produced chlori nated products. I

4. The process of preparing chlorhydrins which comprises electrolyzing a hot aqueous solution of a chlorid in a suitable cell having an anode and during the electrolysis supplying an olefin into the vicinity of the anode under conditions permitting presence of an ample amount of water vapor to dilute such olefin during its reaction with chlorin evolved at the anode. I

5. The process of preparing chlorhydrins [which comprises electrolyzing a hot aqueous solution of a chlorid in a suitable cell having an anode and durin the electrolysis supplying a gaseous ole 11 into the vicinity of the'anode under conditions kpermitting presence of an ample amount 0 water vapor to dilute such olefin during its reaction with chlorin evolved at the anode.

6. The process of preparing chlorhydrins which comprises electrolyzin a hot aqueous solution of a chlorid in a sultable cellhaving an anode and during the electrolysis supplying oil into the vicinity of the anode under conditions ermitting presence of an evolved at the anode. I

7. The process-of making solvents which comprlses electrolyzing. a chlorid solution in a suitable cell at a temperature around 100 G, removing andrecovering the alkali produced and during electrolysis supplying an yvater vapor to dilute. such 011 gas during its reaction with chlorinolefin tosuch cell at a rate sufficiently rapid to combine with the chlorin as fast as produced by electrolysis and removing vapors of chlorinated products as fast as formed.

8. The process of making solvents which comprises electrolyzing a chlorid solution in a suitable cell at a temperature around 100 (3., removing and recovering the alkali produced and during electrolysis supplying a gaseous olefin to such cell at a rate sufliciently rapid to combine with the chlorin as fast as produced by electrolysis and removing vapors of chlorinated products as fast as formed.

9. The process of making solvents which comprises electrolyzing a chlorid solution in asuitable cell at a temperature around 100 (3., removing and recovering the alkali produced and during electrolysis supplying oil gas to such cell at a rate sufiiciently rapid to combine with the chlorin as fast as pro duced by electrolysis and removing vapors of chlorinated products as fast as formed.

10 In the manufacture of solvents, the process which comprises electrolyzing a chlorid solution in a diaphragm cell having an anode chamber and during electrolysis. continuously introducing an olefin and steam into such anode chamber while continuously removing vapors of products formed from such olefin.

process which comprises electrolyzing -a-' chlorid solution in a diaphragm cell having an anode chamber and during electrolysis 11. lln the manufacture" of solvents, the";

return an aqueous condensate and further coolin the vapors to condense and collect the chlorinated products.

13. In the manufacture of solvents, the process which comprises electrolyzing a hot aqueoussolution of a chlorid in a suitable chamber, durin electrolysis introducing 011 gas into such c amber in proximity to the anode, removing aqueous vapors and vapors of chlorinated products formed, cooling the removed vapors somewhat to condense and return an aqueous condensate and further a cooling the vapors tocondense and collect the chlorinated products.

14:. The comblnation, with an electrolytic cell arranged for the electrolysis of chlorids, and means for heating such cell, of means ineluding a source of olefinic gases for comremoving the products of reaction of the chlorin and olefinic gases.

15. In an electrolytic apparatus, a cell adapted for the electrolysis of chlorids', means for feeding steam into such' cell, means for feeding olefinic gases or vapors into such cell and means for removing vapors therefrom,'such means including means for refluxing and returning aqueous portions of such vapors.

16. In an electrolytic apparatus, a cell adapted for the electrolysis of chlorids, means for feeding steam into such cell, means for feeding olefinic gasesor vapors into the anode chamber of such cell and means for removing vapors therefrom.

17. In an electrolytic apparatus, a cell adapted for the electrolysis of chlorids,-

means for feeding steam into such cell, means for feeding olefinic gases or vapors into such cell and means for removing and condensing vapors therefrom, such means including means for refluxing and returning aqueous portions of such vapors.

18. In an electrolytic apparatus, a cell having a diaphragm and adapted for the electrolysis of chlorids, means for introducing ole nic gases into the anode chamber of water vapor, leading off the the resultantvapors and recovering the halogenated products therefrom.

20. The process which consists in simultaneously heating and electrolyzing an aqueous solution of a halogen compound to drive off a mixture of halogen and Water in gaseous and vapor form, commingling an unsaturated hydrocarbon in gaseous state with said mixture of water vapor and halogen, leading off the resultant vapors and recovering the halogenated products therefrom.

In testimony whereof, I allix my signature.

K. P. McELROY.

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