US2059543A - Apparatus for fusions - Google Patents

Description

Nov. 3,1936.

J. F. WAIT APPARATUS FOR FUSIONS Filed April 11, 1935 3 Sheets-Sheet 1 Nov. 3, 1936. F WAIT 2,059,543

APPARATUS FOR FUSIONS Filed April 11, 1933 3 Sheets-Sheet 2 Nov. 3, 1936. I J F. WAlT 2 ,59,543

APPARATUS FOR FUSIONS Filed April 11, 1933 3 Shets-Sheet 3 Patented Nov. 3, 1936 7 UNITED STATES PATENT OFFICE Justin I. Wait, New York, N. Y. Application April 1 1, 1933, Serial N0. 655,560

This invention is a modification of that described in Ser. No. 385,597 filed August 13, 1929 which matured into Patent No. 1,913,143 and is related thereto and is in part a continuation thereof. It relates chiefly to methods of preparation of alkali metals or solutions of these metals and their compounds in compounds of alkali metals, and the use of such compounds and solutions in fusions as in the manufacture of organic chem icals and to apparatus therefor. I have found that by using apparatus and the methods as described herein it is possible to greatly reduce operating hazards and to lower cost of manufacture of alkali metals and compounds thereof, and to decrease the cost of production of organic chemicals whose manufacture involves the use thereof. The apparatus involves certain prescribed combinations 'which make improved operation possibleand which overcome prior objectionable features. The improvements are such as to form apparatus which are commercially acceptable for previously used action and reactions and further to render acceptable the application of like or similar principles to new actions and reactions which could not be carried out by means previously known. The invention is a continuation in part of that disclosed in my application Ser. No. 482,267 filed September 16, 1930.

In many chemical processes, mixtures of com- P unds of alkali metals are used and it isdesirable to alter the proportion of the metals involved. In these, mixtures have generally been held for long periods whereas by my invention freshly prepared or freshly treated compounds may be used. For examplefreshly electrolyzed hydroxide of alkali metal may be used with improved results. Again, as in mixtures of the hydroxides oi the alkali metals it is often desirable to decrease the hydroxide content. This is done by subjecting the concentrated or fused compounds thereof to electrolysis thus depositing one of the metals such as breaking sodium hydroxide into "its parts and producing metallic sodium, and at times the further. conversion of sodium as into sodamide by the action of ammonia.

By the term fused is meant that state existing when a solid compound is heated to the point where its properties approach those of a ,liquid, this point usually being near the melting point of the compound involved. An effect of moisture and other foreign products is to alter the fusion point so that it does not equal the true melting point of the pure compound. Another effect is what I regard a chemical one in that moisture content is undesirable in some treatments especially of organic substances to be a1- tered. As a salt or hydroxide containing water is concentrated as by evaporation, it gradually 24 Claims. (01. 204-19) approaches the condition of dehydration which term is applied in the art to the condition of being approximately water free in the sense that most of the water has been removed, as compared with the state of absolute dehydration wherein all of the water has been removed except traces of water which may be in definite chemical or physical equilibrium with the conditions involved.

The invention may be used to produce a state of dehydration of compounds of such alkali metals, wherein the water content is decreased or entirely removed by electric power. Relatively cheap electricity is thus substituted for more expensive chemical heating or other means as has been used in the past. As an example of this, the moisture content of a commercially and partially dehydrated hydroxide of sodium may be removed by electrolysis of the fused mass thus producing a state of complete dehydratiom. It is to be noted that there are instances where chemical treatmentto produce dehydration is feasible and economical.. Furthermore, vacuum may be applied to the operation, to assist in carrying oil gaseous products of the electrolysis producing the metal and other gases and vapors such as may be formed in connection with the treatment of an organic substance. In cases where an excess of a dehydrating agent is required, the electrolysis may be continued past the dehydration point, thus creating an excess of free sodium or other similar active metal. In operating a cell continuously for this purpose it is therefore but necessary to discharge both fused hydroxide and metal as contrasted with the usual method of operation whereby sodium alone is discharged in one system, the isolated metal being later added to a hydroxide. My invention provides means for maintaining fluidity and quickly forming the desired mixture and quickly using it for alternation .or action or reaction,

With an alternate method of dehydrating the fused material, it is economical to add to the partially dehydrated compound, a mixture or solution of the compound containing free metal or some derivative thereof as, for example, a solution or mixture of sodium or sodamide in fused salt of soda as elsewhere explained the alkali metal may be converted in part to alkali hydroxide by reaction and in such and similar instances the metal and the compound may be used to dehydrate'fused material and be electrolyzed. In accord with common commercial practice of adding excess of a reagent the fused mass to be electrolzed (formed as above or otherwise) may thus contain some free metal. This method eliminates some of the corrosive and hazardous conditions involved in electrolysis of such compounds when mixed with small amounts of water. When a chloride is electrolyzed such corrosion is marked especially whencombined with the high temperature of the melting point of a single alkali chloride. By my method of using a mixture of two salts or hydroxide or salt and hydroxide and flowing the same to yield one to the almost exclusion of the other, resulting greater fluidity raises the efliciency of operation and results detrimentally occurring by reason of light temperature may be reduced or eliminated from a practical angle.

In using alkali metals and compounds thereof for the preparation or treatment of chemicals it has been the usual practice to isolate the metal, solidify the same, pack, store and ship the same. Thus thereafter the metal or compound would again be made fluid and used. This has involved unusual hazards affecting both life and health and has caused a loss in yield due in part to handling and exposure to the elements.

My invention involves the use of a closed system which greatly reduces the hazard and prevents air and other elements from acting in a deleterious manner. It results in less costs of labor, yield and insurance and greatly improves the safety and the health of the operators, and otherwise improves operation.

Another feature of the invention is storage and/or use of the alkali metal or its derivative such as its amide, in relatively dilute solution or suspension in a fluid material such as fused alkali compound or a petroleum product or mixture thereof. The compound itself may react or be a catalyst or merely used as -a vehicle. This method of using an inert fluid such as alkali compound or oil in combination with an alkali compound which is treated with an alkali metal or a derivative such as an amide or other equivalent dehydrating or reacting substance gives excellent results in organic reactions as for synthesis. In some instances such fluid may be practically inert as far as change of itself is concerned but it is used because of its influence, by dilution or otherwise, on the substance treated and altered.

Careful control of the temperature of reaction is essential to obtain good energy and current efficiencies and to obtain maximum capacity for a cell unit. As a very satisfactory method for obtaining this control and to abstract relatively large quantities of heat, I have adopted or added a new method of heating to electrolysis. By using boiling mercury or alloys thereof, it is possible to eliminate many mechanical difficulties previously experienced. By controlling the pressures on the mercury or the composition of the alloy, the desired temperatures are accurately maintained and the reaction economically controlled. This control may also be used in the operation of other processes as indicated herein. I regard fairly precise temperature control during reaction as quite desirable and even essential in some instances. In view of the operations at about or above the indicated temperature of fusion of alkali hydroxide and other compounds the problem of temperature control is one requiring careful and proper solution.

Temperature control by means of direct fired apparatus, oil circulating systems and other equivalent systems have been attempted heretofore, but these have not proved as satisfactory where accurate and quick control is essential, as for increase in capacity, delicate chemiml reactions and increased efficiency.

In the electrolysis of fused hydroxides, passage of a gas through the mass assists in removing the products of the reaction and if an amide of the metal is desired, ammonia gas is passed into the mix thus converting the metal directly into the amide. In treatment gases over vapors may be utilized to similarly carry away easily volatilized substances which are formed and reduced pressure is preferred when the volatile matter is of high boiling point. In fusing and electrolyzing a mixture containing sodium hydroxide for example, it .is possible to obtain a: solution of sodamide in alkali directly by this means and without the usual isolation, cooling, air exposure or other undesirable procedure commonly employed. The solution of sodamide or sodium or both may then be used as for dehydration or other treatment of a dyestuff intermediate or other organic substance and for removing water from fused compounds which are partially dehydrated.

Fusions or other reactions carried out in mixtures of compounds of alkali and like metals or in contact therewith have the advantage of greater fluidity of mix and make it possible to operate at a temperature below the melting point of a single compound. Such fusions or reactions may so be carried out with the use of a dehydrating agent as an alkali metal or other metal with an unpaired eiectron or a compound thereof. On the recovery of the hydroxides or chlorides or other salts from a reaction it is often desirable to readjust the ratio of the component parts which may be done by electrolysis. sodamide is used as a dehydrating agent in a mixture of sodium and potassium hydroxides, the sodamide is decomposed into sodium hydroxide asit reacts, thus altering the ratio of sodium and potassium hydroxides. The caustic mixture may then be recovered and readjusted to its original state by electrolysis, yielding the free metal which may then be converted into the amide by the action of ammonia. In prior processes it has been customary to remove the excess sodium that was formed during the reaction by pure chemical means as by conversion into carbonate and mechanically separating it. This required subsequent readjustment and dehydration as for example by the addition of caustic potash and sodamide.

An improved method for the manufacture of sodamide from sodium, in preparation for its addition to fused alkali to form a fusion mixture, is covered by my Patent No. 1,646,372. While I prefer to use features of this process as it involves the required quick reaction, I have found that it is expensive and dangerous as compared with the above process involving the cycle indicated. I prefer to utilize quick reaction to reduce the time of existance of free metal to less than about an hour and preferably to a matter of minutes and to immediately form a solution of the amide thus avoiding storage thereof. When a solution of sodamide in alkali hydroxides is desired, economical operation may be had by preparing a solution of sodium in hydroxide and treating the mixture with ammonia. By proper operation of special apparatus the two steps may be carried out simultaneously, or the metalmay be delivered beyond the zone of electrolysis and immediately reacted as in a separated zone.

In the operation of the ordinary electrolytic cell such as has been used for the treatment of an alkali metal or compound thereof, the material has been charged into the cell in approximately the exact amount required for decomposition. In most instances, the flow of the products has been in a different direction from the natural If for example,

reduction in the diffusion which is detrimental to highyield and efficiency. It is also possible to so control the feed and the electrolysis as to yield a final product containing the desired percentage of alkali metal or its derivative. By flowing a mixture of two or more compounds of metals it is possible to release or decompose one preferentially to the other.

The lowering of the meltingpoint as by use of. a mixture of two alkali compounds renders the system more positive and less hazardous. The increased fluidity also makes it possible to operate at lower temperatures than is otherwise possible. In the electrolysis of mixtures of compounds of two metals it is possible to set free two metals in a proportion depending upon their natural properties and the controlled conditions including current, temperature and velocity.

In usual processes it has been necessary to discard the used salts or hydroxides or for example to recover the hydroxide or chloride component of fusion mixtures by evaporation, filtration, dehydration, etc. My invention provides for the control of I conditions such that concentrations may be made of the compound desired" ina portion of the hydroxide and the remaining portion of the hydroxide, which is relatively free from the chemical, may be readjusted as to its components and again used in a subsequent fusion without product thereat.

the expense'of dilution, concentration and dehydration. My invention also permits the use of components left therein which would be destroyed if the hydroxide or salt were put through a regular recovery system. Among these components is the required excess of free metal which may be introduced into the cell. Large savings may also be made in those processes where, after fusiomthealkali 'content'is wasted as by neutralization with an acid. V

After the fusion orreaction has been completed for the step, organic salts so formed may in some cases be recovered by concentration or nearly complete separation from the fused compound as by. filtering. If a fluid material such as a mineral oil is added it may facilitate this separation as by dilution or solvent action or otherwise. I prefer this oil method and therefore provide an oily means for flushing out or otherwise carrying away altered organic matter which has been withdrawn from the zone of reaction by the alkali metal, alkali hydroxide mixtures thereof or other similar treatingagent. The oil may carry the altered product to another region and be separated therefrom thus concentrating that portion of altered Vaporous or gaseous portions of altered or treated organic substance or other volatilized product of reaction may have been and preferably is elsewhere removed as directly from the reaction zone rather than via the separating zone. In this case the alkali compound or part thereof may be recovered and received without such a large expense of diluting as is ordinarily resorted to.

In many such treatments the active or more activeagent such as sodium or sodamide may re-. act to form sodium hydroxide or sodium salt which is decomposable by electric current. Such matter I prefer to electrolyze. Thus sodium hydroxide may be reconverted into free metal or a portion thereof may be reactivated by electrolysis and used immediately thereafter. The temperatures required are those indicated (of the order of that for fusion of alkali hydroxides) and preferably in the described range up to the described temperatures of about 875 C. to 425 C. whereat I have found sodium to be exceptionally reactive. I recognize that some organic substances are dissociated or on the verge of dissociation'at such temperatures and the improved results obtainable by my apparatus and method are due in part to the excitation or activation of such compounds at the indicated temperaturesof above about 300 C. The treating agent and the treated substance are thus maintained at especially active tempera: tures. The treating agent is recovered and reused in active form. High fluidity is maintained and air is excluded throughout. Means for these have not heretofore been provided.

This description and the examples mentioned above show some of the possible applications of given as a particular illustration of an arrange-' ment of apparatus for carrying out the invention.

In the drawings Fig. l is a vertical section through a cell for treatment or recovery or activating and in Fig. 2 is a somewhat diagrammatic arrangement of apparatus that carrying out the invention.

The electrolytic cell shown in Fig. 1 consists of a container I with an inlet 2 for a fused alkali compound, such as sodium hydroxide for example, and an outlet 3 so adjusted as to maintain the desired liquid level. The drawolf is provided to give uniform fiow from electrolyzing area. A second outlet not shown may be used to uniformly withdraw liquid from the annular zone about 8. The fused material is passed in any convenient way through the electrolysis zone 4 which may be annular in shape. The electrodes 5 and 6 are connected to a source of direct current thus causing fiow of electricity radially across the zone 4 whereby electrolysis takes place, the alkali metal being released at the surface of the electrode 5. I consider it essential that a definite controlled size and shape of electrolysis zone be provided and that velocity be used especially when the fused mass contains organic substance or when reactive gas is in association therewith.

A fine gauze I is placed so as to prevent diffusion of deposited molecular substances including the alkali metal. This gauze is preferably hung from a support 8 carried by the cover plate 9. An open ing I0 may be provided in the cover 9 for inspecmay be used in tion and to release gases. A removable cover may be provided, if desired, to close the opening Ill. The construction is preferably such as to be substantially gastight at nonatmospheric pressure.

Gases liberated at the surface of the electrode 6 may be collected in an annular chamber I I and vented through the outlet I2. Thus chlorine may be obtained therefrom when chlorides are being electrolyzed. Gases liberated at the electrode 5 may be collected in the dome I3 and vented through the utlet I 4. The cover plate I 5 ispreferably removable and gas inlet I6 provided connecting with a gas distributing ring I! having outlets I8. The ring II or its equivalent may be located at or below or above the annular electrolysis zone 4.

l through the liquid mass.

perature control substance, such as mercury. One or two electrodes may be so provided. Vapors may be introduced through the pipe 29 and condensate drawn off through the pipe 2i. When cooling is required, a connection to pipe 2i may be provided to maintain a liquid mass in the chamber IS, the piping being such that the exothermic heat may be absorbed by causing the liquid in the chamber l9 to boil, the vapors passing to condensers connected to the pipe 20. Other means may be used for dissipating the heat but I consider it essential that such means be provided either at the cell or at other point of reaction. The flow ofundecomposed compound assists in carrying away heat formed.

One side of a source of a unidirectional or direct current is connected to the pipe 22 which is connected to the electrode 5 and insulated from .the opposite side by the insulating material 23. The other side of the electric current line is-connected to the container land is thus connected to the electrode 6. The current passes through the zone 4 acting upon the fused alkali compound the chemical and mineral oil that may be passing through the cell.

The deposited metal or migrated substance accumulating at or near the surface of the electrode 5 or 6 passes upwardly in and/or through the current of the fused compound. Should its deposition or occurence exceed the solubility, the metallic and/or other substance would rise more rapidly if and when its density is less than that of the alkali compound. Upon entering the region below the dome 13 the alkali metal, if sodium, may be acted upon by the gas which, if

ammonia, produces sodamide. The resulting soduction of indigo by the fusion and dehydration of a salt of phenylglycine.

The entire process may be carried out as indicated in Fig. 2, the cell i being made as described above in connection with Fig. 1. The fusing of the organic salt, such as phenylglycine for example, is carried out in the fusion pct 24 the gaseous ammonia effluent being carried off through the outlet 25 as the reaction, aided by agitation, progresses. The organic salt may be charged gradually through a mechanical feed hopper 21, the finished fused mass being discharged through the outlet 28 into the dilution tank 29 previously charged with recovered or fresh water through the 'pipe 3| and bubbled The use of a cooling means, such as a flaker for example between the fusion pot 24 and the dilution tank 29 sometimes results in higher chemical yields.

' When using the aqueous method, the indigo may be withdrawn from the tank 29 through the outlet 32 and concentrated and separated from the dilute caustic by countercurrent flow through thickeners 33 and 34 in series and the continuous filter 35. The thickened slurry from the thickener 33 is preferably mixed with water in the agitation chamber 31. I have found it preferable in some instances to blow air through the thickener to elevate the solids that the discharge may be from at or near the surface. The liquid from the thickener 34 contains some caustic and is used in the dilution tank 23, that from the thickener 33 is evaporated in the evaporator 36 which may be single stage or multi-stage. It is provided with steam connections 31' and a for some reaction or other purpose.

vacuum connection 38. The indigo delivered by the filter 35 will be of suitable composition for drying or standardizing as a paste.

The concentrated caustic from the evaporator 36 will pass through its outlet 39 and into a 5 heated dehydrator 40 wherein the caustic liquor of 45-55% .strength may be concentrated by heat to a moisture content of about 0.3% especially when vacuum is employed. Thereafter the caustic is preferably passed from the dehydrator 40 1 into a storage tank M which may also function as a secondary dehydrator, this tank acting as such when it receives sodamide-caustic solution from the cell i. The fused caustic then containing only traces of water may be charged through .1 the inlet 2 into the cell i, where it is electrolyzed and reacted upon thus completing the cycle.

Ammonia gases liberated from the cell I, the fusion pct 24 and the dehydrator 4| may be recovered by collection in the absorbtion towers 42 and 43. The towers 42 and 43 are provided with water connections 44 and 45. The gaseous ammonia is regenerated in the ammonia generator 46 that is provided with steam connection." and water connection 48. Evolved hydroge" "gas is vented from 49 and wasted or could used Cooling coil connections 50 are preferably connected with cold brine or the ammonia system may be used as shown in my Patent No. 1,452,009. Other gases or vapors released from the reaction zone may be recovered by appropriate means such as,absorption or condensation.

For the manufacture of indigo, a mixture of approximately equal parts of sodium and potassium hydroxides have been found to be quite satisfactory for fusion purposes. Its relatively low melting point is'also of assistance in flowing the mass through the system and in controlling the cell operation. Other organic substances may be similarly treated.

Substances such as phenolic bodies made as by replacement of the sulfo or a halide radical may be similarly treated as in the case of phenol or naphthol. Sulfur containing substances such as those in coal tar oils or petroleum are generally more conveniently treated in the vapor phase If the sulfur is high a less active or relatively inert oil, which may also be benefited by the treatment, may be mixed therewith. In such cases I prefer vapor phase treatment although liquid phase treatment is often quite effective and it is of advantage when portions of the treated mass are slightly volatile. Where heavy or high boiling lubricating oil is to be treated and light carrier vapors or gases are not effective or found ineffective or inefiicient, the heavy oil to be treated may be diluted as with relatively inert mineral or equivalent oil and liquid phase treatment resorted to. The added oil is then separated as by distillation thereof and generally with a few percent or so of light oil formed from heavy oil by rearrangement.

The use of molten alkali hydroxide requires a temperature of above about 800 C. or 320 C. Thus for fluidity of alkali compounds and for the desired activity of the free metal or amide or the" like a temperature of between about 360 C. and 425 C. isdesirable as previously indicated. Such temperature is quite in contrast with that previously employed where alkali metals have been involved. At such temperatures and with the reduced pressure and. the associated oil when used, there appears to be a decided volatilization of alkali metal which may account for its un- 7 usual activity. In treating substances which are not easily volatilized and with the indicated temperatures considerable vacuum is required. This may be such as to yield an absolute pressure of between about one and ten millimeters of mercury. While mixtures such as that of sodium and potassium hydroxides are fluid at lower temperatures, I prefer to utilize the indicated temperatures except possibly for preliminary treatment. The temperature range is that at which organic matter is exceeding active at which some cracking or rearrangement of oils occur. The ordinary time of contact of such fusions is generally from about two to several hours, the temperature being materially less. With the precise control and quick reaction obtainable with freshly prepared treating agent and the elevated temperatures the time required is considerably less as for example a matter of a second or so or less if the organic substance is vaporized and a matter of seconds or minutes being less than the usual two hours or thereabouts.

A simple arrangement of the parts of my invention is schematically illustrated in Fig. 3. Cell 5! may be of the type described and as illustrated in Fig. 1. The electrolyzed compound such as anhydrous sodium hydroxide or sodium. or

both may be passed through line 52 terminating in a distribution within contact zone 53 whereat the organic substance to be treated and altered is in vaporous form in association with vapors of relatively inert mineral oil or fixed gases are introduced as by inlet 54. Substances remaining in vaporous form are passed through outlet 55 and then to an absorber or condenser 'not shown. The stream of treating agent descends to the discharge line 56 and may carry with it associated altered matter which may be considered as having chemically and physically condensed to a less volatile or non-volatile form.

Separating means 57 is illustrated as being provided with an oil inlet 58 and outlet 59 for oil and altered substance which may be subsequently treated as for recovery of one or more contained products. The construction of separator 5! is dependent upon the nature of the treating agent and treated product thereat. It may be of baiiied, agitated, filtered or other form depending upon the experimentally found requirements for the particular case under consideration. The hydroxide which is recovered may be that passed through line 52 or that formed in reaction zone 53 or both. It is illustrated as passing through line 60 for treatment in cell 5| however a portion, or all at times, may be passed directly to zone 53. Reaction'zone 53 may be in multiple with the organic matter passing in series therethrough and temperature control means to give the same or different temperatures in each. The product in line 56 or preferably in line 60 may be flowed through a second or other contact zones before passing to cell 5!. Y

In Fig. 4 is illustrated an arrangement for treatment We modified method. Cell 6| supplies treatment agent which maybe for example a mixture of hydroxides of sodium and potassium containing a small amount of free sodium. The mixture passes through line 62 to reaction zone 63 which may be for example similar to Fig. 3 of Patent No. 1,765,386, with agitator shaft 64 and outlet for gaseousor vaporous fluid 65 and outlet for fused substance 66. Line 61 represents the inlet from hopper or feeding device preferably feeding material in the form as described in Patent No. 1,820,684. With some organic substances it is of advantage to form a mixture, suspension or solution thereof in inert mineral oil or coal tar distillate and to then contact the mixture or solution. Such oil may be formed by prior contact thereof with the same or similar treating agent until it becomes inert or stable under the conditions of the contact zone. The oil may be evaporated inpart or all while in contact with the fusion mass or quickly thereafter. Vessel 68 may be similar to vessel 63 with outlet 69 corresponding to 66 and with drive shaft 10. Vessel 63 may be in greater multiple such as is desired to permit of continuous operation to further the reaction especially where a longer time of contact is desired. The fused mass is illustrated as passing through line Ii to vessel 72 which is preferably in multiple and in parallel connection so as to successively receive product from line it. Relatively inert oil may be introduced as indicated by inlet 13 and mixed as by an agitator connected with drive shaft 74. The temperature in vessel 12 may be lowered a little to facilitate separation, the hydroxide or metal therefrom being later elevated. The mixture may then be passed through outlet 75 to one or more separating vessels 16 which may operate with intermittent agitation resulting from turning of shaft ill. After settling oil with associated organic matter may discharge through line 16 to a. rotating drum dryer 19 with vapor outlet 80 connecting with condenser 8i and outlet 82 for recovered oil which may be in association with altered organic substance or of it. Discharge line 82 may be connected with pressure control means as high vacuum when intense drying is required.

With some organic substances the drum I9 or another operating therewith may be used to perform as described in Patent No. 1,863,735. There are some substances which do not require oil to be added in vessel 12 to effect concentration and with which careful temperature control will result in desired crystal formation that settling or filtration may be employed for concentration or nearly complete separation. In instances a portion of the treating agent is preferably concentrated with organic substance and then mixed with water or an alcohol to effect recovery, the. so recovered hydroxide or other agent then being dehydrated as illustrated in Patent No. 1,734,699

after which it is preferably mixed with product from line 62 to effect substantial dehydration before charging into cell 6|. Flushing with oil may be combined with crystallization for concentration or for separation. Refen'ing to Figures 2 and 4, reaction vessel 24 may be replaced by vessels such as 63, 68, I2 and 16. I do not limit my claims to the exact parts as described but intend to include other equivalent parts and designs.

The apparatus parts are constructed so as to exclude air and to withstand pressure or vacuum as may be required. Insulation and temperature control means are required to maintain the mass fluid for flow and for evaporation and reaction and for that found necessary for concentration or separation. Pumps or other transfer or elevating means are required to effect the indicated passage in the illustrations.

A feature of the structure involved in my invention is the indicated direct and short connections between the zones of electrolysis, treatment and separation whereby quick passage is effected. Circulating means to remove altered organic substance from the treating or reacting zone is provided as well as means to concentrate altered substance and return the recovered treating agent to the reacting zone. Oil may be used to facilitate separation. The arrangement permits maintenance of fluidity and exclusion of air. Means for applying unusual temperatures is provided thus promoting more rapid and better action or reaction by virtue properties which are characteristic of the treating agent and the treated substance at those temperatures. The exact combination of parts and arrangement and treating agent and other factors can be selected only after tests and by cut-and-try methods such as a skilled technician may arrive at by following the general procedure described herein or the equivalent thereof such as he might be expected to substitute to meet the particular requirements of the case at hand. The selection of equipment to fit the requirements of the empirically selected process is a relatively simple matter in view of the present state of the art.

I claim:

1. In apparatus for producing and treating metal released by electrolysis of fused metallic compound the combination of electrodes spaced a short distance apart and forming therebetween an upwardly disposed channel and closely defining and limiting the electrolytic decomposition zone therebetween, positive means for flowing the compound through the zone at-a rate in ex- 30 cess of decomposition, a reaction zone comprised of a separate chamber located beyond the electrolytic decomposition zone and close thereto, means for quickly passing the electrolyzed compound from the electrolytic decomposition zone to the reaction zone and means for introducing a reacting substance which will react with a product of the electrolytic decomposition zone into the reaction zone.

2. In combination, a chamber adapted to contain fused alkali compound and to exclude air under non-atmospheric pressure, a pair of electrodes therein closely spaced and forming a defined zone of electrolysis, means for applying a decomposing potential to the electrodes to decompose compound therebetween andto prevent substantial current flow in contacting masses of compound beyond the zone, means for continuously withdrawing released alkali metal and quickly passing it into a separately constructed reaction zone located beyond but close to the zone of electrolysis, means for introducing into the reaction zone a substance reactable with the metal, means for excluding air throughout under non-atmospheric pressure and means for retaining the metal molten and at a temperature of above about 300 C. throughout.

3. The combination of a treating zone adapted to dehydrating fused alkali metal compound by a dehydrating agent, means to flow. the dehydrated and fused compound to a defined zone of electrolysis between two closely spaced electrodes, an electrical potential for decomposing compound therebetween and forming free metal therefrom, a separately constructed reaction zone located beyond and close to the zone of electrolysis means for quickly passing formed free metal from the zone of electrolysis to the reaction zone and means for contacting a reactable substance with the free metal in thereaction zone.

4. In an apparatus for treating an alterable organic substance with alkali metal, the combination of a defined zone of electrolysis contained between two closely placed electrodes and designed to prevent substantial flow of current outside of the defined zone, mechanical means for passing a fused decomposable alkali compound through the zone of electrolysis, conductor means for applying a potential to the electrodes to decompose the compound to form free metal, pipe means for flowing the free metal through a nearby reaction zone, tower-like means for contacting the organic substance with the metal at the reaction zone comprised of circulating means for continuously flowing a stream of metal within a tower-like chamber, flush out means for applying mineral oil and effecting separation of altered organic substance from the metal to recover the metal, heated pipe means for returning the recovered metal to the reaction zone, means for withdrawing altered substance from the apparatus, heating means to maintain metal and compound molten through their occurrence in the apparatus and means for applying high vacuum to the apparatus within the reaction zone.

5. In an apparatus for treating organic substance with anhydrous alkali hydroxide, the combination of a zone of electrolysis formed by two closely placed electrodes, a means for applying decomposition potential to form alkali metal from the hydroxide, a discharge line for hydroxide containing. free metal connecting with a reaction zone, means for introducing organic substance into the reaction zone, a connected separating zone to recover hydroxide with lowered organic content, a connection to return recovered hydroxide to the zone of electrolysis, temperature control means to maintain fluidity of the hydroxide throughout and means to exclude air therefrom.

6. In apparatus for treating oil containing organic substance alterable with alkali metal, the combination of a cell for forming alkali metal,

- a closely placed reaction zone, means for contacting the oil and freshly prepared alkali metal with the oil, oily means for separating altered organic matter associated with used metal, means for returning the so recovered metal to the reaction zone and means for maintaining the metal at a temperature of above about 300 C. throughout.

7. In apparatus for treating oil containing organic substance alterable with alkali metal, the combination of a cell for forming alkali metal, a closely placed reaction zone, means for contacting the oil and freshly prepared alkali metal with the oil, oily means for separating altered organic matter associated with used metal, means for returning the so recovered metal to the reaction zone, means for passing hydroxide associated with the metal through the cell to form metal therefrom and means for maintaining the metal at a temperature of above about 300 C. throughout.

8. In an apparatus for altering organic substance contained in oil by contact with alkali metal, the combination with a cell, of a connecting reaction zone which is located within piping distance of the cell and heated pipe lines therefrom and means adapted to quickly convey alkali metal from the cell to the reaction zone and with means to introduce substance to be altered into the reaction zone, a closely connected separation zone which is structurally distinct and provided with means to fiow altered substance from the reaction zone thereto and provided with means to remove altered organic substance from the metal, means to return the metal to the reaction zone and means to maintain fluidity of the metal throughout and to exclude air therefrom. 9. In an apparatus for treating organic matter with water-free alkali hydroxide and a dehydrating agent, the combination of a cell for electrolyzlng fused hydroxide to render the same 'substantially anhydrous, means to form a mixture or dehydrated hydroxide and a dehydrating agent, means to contact the mixture with substance to be altered, means to separate altered organic substance from the hydroxide, means for returning a portion of the hydroxide to the cell for electrolysis and means for maintaining the hydroxide molten and substantially anhydrous and air-free throughout.

10. In apparatus for treating organic matter with alkali metal diluted with alkali metal compound, the combination of a zone for forming the diluted metal contained in alkali metal compound, a connection with a closely located re' action zone, means for introducing organic matter to be altered with relatively inert oil, means for discharging gaseous 'fluid from the reaction zone, means for discharging diluted alkali metal and altered organic compound simultaneously to a closely connected separating means adapted to flush out altered organic matter and means to return the so recovered alkali metal to the reaction zone and wherein means for maintaining the metal fluid and at above about 300 C. throughout is provided.

11. In apparatus for treating oil containing organic substance alterable by treatment with alkali metal, the combination of a zone oi. electrolysis contained between two concentric electrodes, means for flowing alkali metal compound therethrough to release free metal therefrom, a potential to decompose a portion of the compound into metal, a closely connected reaction zone, means for passing oil and freshly prepared metal through the reaction zone to effect contact therebetween at above about 300 0., means for circulating the metal through the reaction zone and means to maintain the metal fluid and exclude air therefrom throughout the apparatus. a

12. In apparatus for treating oil containing alterable organic substance, the combination of a, cell forming a zone of electrolysis for fused alkali compound and provided with means for applying and controlling potential and flow of compound to definitely control the extent of electrolytic'decomposition of the compound, a directly connected reaction zone, a separating zone directly connected with the reaction zone with means for separating organic matter from alkali'compound and means for circulating the alkali compound through the three zones and means for passing organic substance through the reaction zone.

13. In apparatus for forming and using active water-free alkali hydroxide in beneficially altering organic matter, the combination of a cell with closely spaced electrodes and channel means to flow substantially all of the electrolyzable compound therebetween whereby successive portions will be treated alike adapted to form active waterfree alkali hydroxide, a connected contact zone and means for circulating the hydroxide through the contact zone and maintaining fluidity of the hydroxide and means for passing organic matter through into the contact zone and mechanical means tor concentrating organic matter with respect to hydroxide and withdrawing an organicconcentrated portion simultaneously with its associated hydroxide while another portion of hydroxide of substantially lower organic control ,is recovered and is separately withdrawn and means to return portions of recovered hydroxide to the cell and to reactivate the same therein.

14. In apparatus suitable for electrolyzing' an alkali compound and treating alkali metal so formed, the combination of electrical means to dehydrate the compound and render it subcompound and to flow it through an electrolytic zone of decomposition and heating means to maintain the compound and the metal fluid and enclosing to exclude air from within the apparatus.

15. In an apparatus suitable for desirably treating alterable organic substance and recovering alkali metal used for alteration thereof, the combination of means for flowing vapors of alterable organic substance through a reaction zone, means for recirculating alkali metal through said zone and in a manner so that altered portions are discharged from said zone continuously and substantially as formed, temperature control means to hold the organic vapors and circulating metal at a temperature of above about 300 0., connected means in the circulating line of the metal for separation and recovery of altered matter removed from the contact zone by the circulating metal by contacting the used metal with relatively inert mineral oil and flushing away impurities from the metal thereby, pipe means to return recovered metal to the treating zone, and mechanical means to practically continuously add freshly prepared alkali metal to the metal in circulation as make-up that the amount in circulation is substantially constant and means for excluding air from the zone of contact and circulating means, and heating means for maintaining the metal fluid and at above about 300 C. from the time of its formation and throughout its use in the circulating system.

16. In an apparatus adapted to produce an alkali metal from a mixture of fused compounds thereof and to eliminate hazards and supply freshly formed metal of use, the combination of an electrolytic cell with defined zone of electrolysis, means for precisely controlling the temperature of an electrode of the cell, means for preparing a fused mixture of alkali compounds of different decomposition potential and flowing it through the defined zone of electrolysis at a selected rate and so that successive portions are treated alike, means for applying a potential for electrolysis to form free metal and means of control of flow and potential so that one of the alkali compounds may be decomposed preferentially to and almost to the exclusion of another and means to exclude air from the cell and to deliver alkali metal and compound to a point of use beyond through a pipe line heated to maintain fluidity.

17.'In apparatus suitable for treating an organic substance which may be rearranged by an alkali metal freshly obtained from a compound thereof, the combination of a chamber adapted to contain a fused mixture containing a decomposable alkali compound and to exclude air under non-atmospheric pressure, a pair of electrodes therein closely spaced and forming a defined zone of electrolysis, means for applying a decomposing potential to the electrodes to decompose compound therebetween and to prevent substantial current flow in contacting masses of compound beyond the zone, means for continuously withdrawing released alkali metal and quickly passing it into a separately constructed reaction zone located beyond but close to the zone of electrolysis, means for introducing into the reaction zone a vaporous organic substance which may be beneficially reacted with the metal and to quickly dis charge metal and associated liquidous substance formed by said metal, means for excluding air throughout under non-atmospheric pressure, means for retaining the metal molten and at a temperature of above about 300 C. throughout, and means for recovering the metal in free form and to reuse recovered metal in cyclic manner.

18. In apparatus adapted toelectrolyzlng a compound of alkali metal which may be decomposed to yield free metal, the combination of a cell with closely spaced electrodes forming a defined zone of electrolysis, conductor means for applying potential to the electrodes, mechanical means to fiow the compound between the electrodes while preventing substantial current flow in contacting masses beyond the zone and appreciable flow of compound otherwise than between the electrodes, mechanical means for controlling the potential and velocity of flow so that the compound is practically decomposed in predeterminate manner as it flows in substantially its entirety between the closely spaced electrodes and a connected chemical reaction zone with organic reactiv means for lowering the free metal content and means for recycling portions of the compound of lowered metal content through the zone of electrolysis.

19. In an apparatus suitable for treating an organic substance which may be desirably altered by contact with a fused mass containing alkali metal compound and a dehydrating agent of freed alkali metal, or derivative thereof, the combination of an electrolytic cell with a defined zone of electrolysis contained between closely spaced electrodes, mechanical means for flowing fused decomposable alkali compound through the electrolytic zone of decomposition, electrical means to decompose like portions of successive amounts flown through the zone and mechanical means to form a mixture of predetermined content of dehydrating agent, an agitated vessel closely connected wtih pipe means to quickly flow compound with dehydrating agent, an agitated vessel closely connected with pipe means to quickly flow compound with dehydrating agent thereto and for introducing and contacting alterable organic substance in the dehydrating-agent-compound-containing vessel, a vessel closely connected therewith with means for introducing oil and flushingout altered portions of treated organic substance and to discharge the so formed mixture into a closely located zone of quick evaporation under high vacuum and in association with such lighter portions of solid matter as may be obtained by settling, condenser means for liquifying vapors and mechanical means for withdrawing residual matter freed from lighter volatilized substance.

therein and designed to treat subsequent portions of the compound alike and to avoid appreciable escape of current through compound without the defined zone of electrolysis, a pipeconnected reaction zone and means to deliver a product of electrolysis quickly to the reaction zone, means to substantially continuously and uniformly recirculate the product of electrolysis through the reaction zone, and into intimate contact with vaporous content of the reaction zone and to remove altered organic portions from the zone about as formed, means to fiow the vapors of the oil through the reaction zone and into contact with the product of electrolysis circulated therethrough, whereat portions are altered and removed, a connected zone of separation to recover and separate a product of electrolysis which has so been used in a form of lowered content of altered organic matter, and mechanical means to flow the same to the reaction zone, means to flow portions of electrolyzed product which has passed through the reaction zone through the zone of electrolysis of the cell, means to exclude air from the fused electrolyzed product, and temperature control means to maintain the temperature in the reaction zone at above about 300 C.

21. In combination with the apparatus of claim 20 evaporation and pressure control means for forming the oil vapors under high vacuum and maintaining them thus in the reaction zone.

22. In apparatus for fusing an organic substance such as a salt of phenylglycine with a mixture of alkaline hydroxide and sodamide, the combination of a cell with a closely defined zone of electrolysis, suitable for forming sodium, a pipe-connected reaction zone adapted to receive freshly formed, metal from the cell, means to fiow dry ammonia into the reaction zone and through and into intimate contact with the metal thereof to form sodamide, means to hold the temperature of the reaction zone at a temperature of the general range of 360 to 425 degrees centigrade, means to form a solution of sodamide and sodium and potassium hydroxide of a concentration suitable to desirably fuse the organic substance, a second reaction zone with temperature control means to hold the temperature at below that of the first reaction zone and at a fusion temperature, means to add the organic substance and the solution of sodamide to the second reaction zone and to contact them intimately thereat, recovery means to save the released ammonia, means to discharge the treated mass to a separation zone, means to maintain the sodium molten and free from air throughout and to avoid the accumulation of sodium in substantial amounts.

23. In apparatus for desirably fusing an organic substance such as a salt of phenylglycine, in combination with the apparatus substantially as stated in claim 22,0f separating means adapted to form two portions of the treated fused mass and to discharge one portion high in organic component and a second portion low in organic matter, and pipe means to return portions of low organic matter to the second reaction zone, and means to exclude air from the second portion and to maintain it molten throughout.

24. The combination of the apparatus substantially as stated in claim 22, with pipe-connected means to receive portions of the discharged treated mass and to cool it and render it substantially solid, and means to exclude air from the fusion mass until it has been so solidified.

JUSTIN F. WAIT.

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