US1072373A - Process of producing cyanogen compounds and the like. - Google Patents

Description

C. E. ACKER.

PROCESS 0F PRODUCING CYANOGEN COMPOUNDS AND THE LIKE;

APPLICATION FILED AUG. 3o. 1910.

1,072,373. 4 Patented sept. 2, 1913.

3 SHEETS-SHEET 1.

C.' E. ACKER. PROCESS OF PRODUGING GYANOGEN COMPOUNDS AND THE LIKE.

APPLICATION FILED AUG. 3o. 1910.

1;O'72,373, .Patented Sepnz, 1913.

3 SHEETS-SHEET 2.

WLM/wonen vw@ wko@ G.B.AGKBR.l

PROCESS OP PRODUCING CYANOGEN COMPOUNDS AND THE LIKE.

APPLICATION FILED AUG. so, 1910.

1 ,072,8'73, Patented Sept. 2, 1913.

3 SHEETS-'SHEET 3.

.metallic barium. It was stated in the appli- UNITED STATES PATENT OFFICE.

CHARLES E. ACKER, OF OSSINING, NEW YORK, ASSIGNOR TO THE NITROGEN COMPANY,

A CORPORATION OF NEW YORK.

PROCESS OF PBODUCING CY'ANOGEN COMPOUNDS AND THE LIKE.

Specification of Letters Patent.

Patented Sept. 2, 1913.

Application filed August 3o, 1910. serial No. 579,763.

To all whom t may concern:

Be it known that I, ClrARLEsE. Aonnn, a citizen of the United States, residing at OS- sining, in the county of Vestchester and State of New York, have invented certain newand useful Improvements in Processes of Producing Cyanogen Compounds and the Like, of which the following is a full, clear, and exact description.

This invention relates to a process for the manufacture of alkali metal cyanids, cyanamide and the like, and,more particularly to .certain improvements in the process described in my United States application Serial No. 485,344, tiled March 23, 1909, the process therein disclosed consisting in initially reacting on a particularly reactive metal, such as barium, lithium, calcium,` strontium, manganese, etc., with carbon. or a carbonaceous reagent, for the purpose ot producing a carbid of such' metal, e. g.,

arium carbid; in then treating this carbid with nitrogen or a nitrogenous reagent, for the purpose of producing the cyand of suoli metal, 1n this case barium cyanid; and in inallyreacting on the barium cyanid with an alkali metal, e. g., sodium with the cousequent production of sodium cyanid and cation aforementioned that the reactive metall e; g., barium, might combine directly with nitrogen to form barium nitrid, which would then react with the carbonaceous reagent to form barium cyanid; and that this cyanid would in turn be decomposed by sodium as above with formation ,of sodium cyanid and metallic barium. It was further stated that both carbid and nit-rid might be formed under the conditions of the process, and that these products might in turn then react together to 'form reactive metal cyanid, e. g., barium cyanid, which would then be similarly decomposed by metallic sodium.

While it is possible to bring about the reactions substantially asl hereinabove described, I nd, as a result of further investigation of the phenolrwnon, that in practice by far the greater part of the snal product is produted as the result of the initial ,iermation ofixjactive metal carbid, in what,

seems to be a particularly favorable physical condition, such carbid when insuch con-- dition readily absorbing and combining` with nitrogen; and that as a consequence, but a comparatively .small proportion of the final product is obtained as a result of the initial formation of reactive metal nitrid this small proportion of course combinin with carbon in the maunerabove descried to form the cyanid, etc. Sutiicient free carbon being present, I consider that the principal reactions are as follows:

It anhydrous ammonia is employed instead of free nitrogen, the second of the above equations will be as follows:

The reactive metal e. g., barium, and the alkali metal, e. g., sodium, may be cmployed in the manner then stated, to wit, either in the pure state, in the form of an alloy with each other, or in the form of an alloy with certainrelatively inert metals, such as lead, tin, etc. The nitrogen may be employed in the orin of pure or diluted gas, ammonia or other nitrogenous rea; gcut;l while the carbonaccous reagent may be elnployed in the form of finely divided, granular, or lump charcoal, coal, coke, or a hydrocarbon gas, fuel oil, lamp black, or-

cyanids 4or cyanamids. It the source of carbon is a gas,- fuel oil or lamp black, the resultant carbid produced by the combination of the reactive meial with carbon as pointed out in the patent application above referred to, is found to be present solely in finely divided form.

I have discovered that the carbid produced in the present process is apparently amorphous and impa pable, which is evidentlyv a result of the very low tcmpcratu-e at Vwhich it is produced, generally below 900 C. and under most radically different conditions :from theiiupure., hard, iriclescent, crystalline carblds which. are pretion, one of suoli conduits is shown in sec-` vtion in FigJl and has been designated 17 ai passage. 18 leading down into it .from chamber. #if and acorrespoiiding passage 19,

leadingrlrom it-to chamber 5. The second' ronduit- 20 is in communicationl with the further .sides of the respective .chambers through. passages 21, 22,:the conduit 20leading therefrom to a suitable pump 23. This puinpis preferably of the centrifugal type, but any. suitable apparatus may be employed for. lthis purpose. The; movement of Athe either interinitteiitly or continuously by,

mass .of fiuid alloy throughv the chambers, resultsin stirring upthe respective Amolten salt-msince such bodies float-.upon the surfaces of the alloy in the respectivechambers. The circulation of this alloymay be effected mechanical means or. otherwise,- and suitable means, such as a hopper M, may 'beprovided for )`ermitting the continuous or .intermittent introduction of the salt required in the elcctrolytic chamber. The plunger lis ajdjustablcin the air tight cover 12 and has a liole.. extending through fits. shank, the

upperpart of which-is fittedwith a valved pipel2ffor introducing nitrogen or ammo,- niainto. the `.inolten mass. infthe reaction regulated quantities into the reaction cham- A4 chamber; aiidfis also fitted .with an oil feed de if'ice 26, .through which .fueloil or other hydrocarbon maybe vintroduced in carefully bei".A "An auxiliary supplypipe 27 extends through. the side of the reaction chamber,

-whichpipe may be -usedto .introduce nitrogen or liydmcarbon, or j both, directly intol the.. rinafi'ssjof molten metal, whendesired.

AfThev coi-2er 12'is lalso fittedwith a- Specially constructed hopper 2 8, which has anA air tiglitfcoverf'aiid is so -arrangedthat itmay be .filled'w'itli charcoal. and then subjected to a vacuum forthe purpose of exhausting theair from Itliehopper and the charcoal The containetl'thcrein, before it is charged into the ,reaction chamber, 'the vconnections for exhausting @the air being. indicated at 29.

iiioltenvfcyaiiidfis produced iii the 'reaction 'chamber and normally rises to ai'elatix-'ely highlevelbefore it ispermitted to' v rlfin off' through the .spout 1l;V this spout being tciiii'iorari'ly .zlosed, when desired, to

if' uin'clilord, ata sufficiently-high voltage-and` 'current permitftlie cyanid tol accumulate -in ythe cli'ainberbe'fo'rc being tapped off.' In starting the appa ratus the electric current is passed through' ythe electrolyte in the electrolytic chati'iber. such electrolyte consist ing, 'for example, of barium chlorid and sodiboth'.n'i'et'allicj barium -and* sodium on the surfalcefof the lmolten leadconstituting the cathode and electrical Contact with flange o fv'gwall 6.1 .liberated metals combine with lielead WQ-formen. alloy. of barium. sddi'nin 'd flead',. iirhicli iai conducted yin to densit to simultaneously liberate or circulated through the reaction chamber to'a point where its lower surface or face is submerged in theinolten alloy. Fuel oil 4under pressure may then `be lintroduced in contact'with. the red hot alloy below the surface of the plunger, 'at 'which temperature the oilwill be broken up. into finely divided-carbon .(lampblack) and hydrogen, the latter of which iv'villescape'"through the 'overflow spoilt 11. If. there is suicient barium .in the allo the carbon of the c iircbalor with'l th'e caroil to form barium carbid, some of which will be held submerged in the, alloy. against the lower surface of tlie plunger, and some of .which will .be forced out 'by theescaping 'hydrogen u y y throughpipe'2'5 and will then pass dovn the Avlower surface thereof, and then `Spread out in 'the Yform of athin layerbetwecn the face of the plunger and theniolten alloy and thus come into more or' less effective contact ,with the carbide which will have been produced in accordance with the reaction herenitrogen which comes into' reactive contact with some of the barium carbid then combines barium in the.barinm cyanid is'v then disthe -consequent production of sodium c vtion of more carbid. As soonas a suicient 4inetal) has been incorporated into the valloy to react readily with the carbon it becomes unnecessary to supply inore for the reason that the reactive metal is, used over and over again and therefore no more utrolyte'. Ifany loss of available barium oc,

curs in th'efalloy or of. bariumcarbid or cyanid in the melt through any unavoidable by means of the centrifugal pump. The

shaped casting or plunger may be flowered.

it will combine. with bon produced by the .decomposition of the Nitrogen may be introduced,

through the hollow shank of the plungerto f therewith to prodncebarium cyanid. The' placed by metallic sodium in the alloy with anid and metallic barium; the barium imme' diately becoming' available for the pi'oducproportion of barium (or,l other reactive barium chlorid `need be'added to the elecor inadvertent. circumstance; or if as in some cases. acertain proportion of the bariallowed to be drawn olf 4taogcther withthe sodium cyanid produced, or

i for.. any @der ma the, de'iema .Wilbe through the oil feed vdevice and will come los inbefore referred to. That portionfof the .supplied from time to time by adding presence of this fluid mass permits vthe amorphous barium carbid and finely divided carbon to become dili'used therein; being mixed andsuspendcd to a considerable extent and thus much more easily brought and held in reactive contact with the nitrogen or nitrogenous reagent. The entire mass of cyanid is practically saturated with impalp able carbid and if a sample of the molten cyanid be withdrawn duringthe process, and

moistened with water, the presence of carbid is very evident fromthe odor of theevolved.

acetylene, although no lumps or'crystals of carbids-whatsoever'` may be visible. The-carbid is therefore present in a very fine state of division, and is probably entirely amorphous, although it is possible that it may in part, at least, be in-actual solution.

W'hen the cyanidv is examined under the microscope the :pure colorless crystals of cyanid loom up very largeand'clcar, and squeezed in between'the crystals is the dark gray or black carbid apparently in the form of a film. The moisture-in the vair attacks this film of carbid between'the crystals at the exposed edges-*of the film and minute bubbles of gas are .constantly given olf all along the exposed edges. l

Evidentlythe carbid is in very soft condition since it is squeezed into the thin spaces between the crystals of the cyanid in the manner described; but it is impossible to examine it directlyin the open air on account of the minute.- bubbles of gas which instantly cover its surface.

. vThe specific gravity of some carbids, e, g.,

barium carbid, is considerably greatertllan that of molten sodium cyanid, but'owing to the fact that these carbids are apparently in amorphous condition, very little agitation is re uired to maintain'them in suspension'. little fuel oil injected into the alloy or into the molten cyanid .and used primarily as a source of carbon', suices to produce all the agitation, requiredto maintain both the carbon'a'nd amorphous carbid in suspension in the molten cyanid; and if there is then. escaping around the edge of the .plungerl and' passing up through the alloy an excess of nitrogen orfa'mmonia, I

find that such gases arismgin the form of.A bubbles into the superimposed body of mol-- ten c vanid, also keep the carbon and carbid m suspension and that mtrogeror ammonia there advantageously reacts with the sus- 'pendediggnd impalpable, or possibly even dissolved-barium carbid, to form barium cya-nid. The latter compound, dissolving in the molten sodium'cyanid, is then or aflterward easily brought into contact with the necessary alkalimetal or alkali metal alloy and transformed into sodium cyanid and metallic barium. This 4liberated barium soon seizes uponfmore carbon-to reform amorphous barium carbid which again becomes suspended in the molten cyanid ready to combine with more nitrogen, ammonia, or other nitrogenous reagent; this cycle being indefinitely repeated.' I have discovered, furthermore, in employing either free nitrogen or ammonia as the nitrogenous reagent, that it is not necessary at any time to bring the gas into actual contact with the molten metal,

either at the surfaceofl the molten alkali metal, reactive metal, when Iused'in a pure state, or molten alloy, .containing-either of them; nor to inject it into the mass',"z'. e.`,.

below thesurface thereof, provided therev is present on the surface of the alloy a suticient-body of molten cyanid. The plunger may, hence, -in such case, be raised so that its lower surface is entirely above the molten alloy, but still submerged in the cyanid.

'lfheabsorption of free or nolecularnitroT;`

' genA by the pure suspended barium fcabidg" formed under the conditions of the process,.

when heated, mayube attributed to either one or both oftwo things; namely, the amorphous condition of such carbid, in which res'pect it is radically different from the hard crystalline lpure 'carbid which `Moissan stated (Comptes Rendus 1894, page 503) would not a absorb free nitrogen; and because the m'olten cyanogen compound in which the carbid is suspended apparently assists the absorption in away not as yet u 'derstood The temperature of th lower end of the plunger when` submerged in the red hot alloy, is of course, substantially equal to that of the molten metal itself; butif the face of the plunger be raised above this efficient metallic heat cpnductor, I find that sufiioient heat may be conducted away through the tion of the nitrogen of the ammonia with the amorphouscarbid suspended in the molten 1cyanid takes place with great rapidity and,"-

eciency owing to the fact that the nitrogen is liberated in nascent form directly in con- `l t a `:t lyi rith the carbid; wher-eas if the ammonia. were irstintroduced into the red hot alloy, ,.1

lit would be partly decomposed into free nitrogen and hydrogen, and this free nitrogen rising into the molten cyanid does notcombine withal@ ,carbid with anything like rhs-aso.

shank of the plunger, to the outside of the 'same degree of avidity as'it does when in a nascent state. The absorption of Ifree nitrogen, in other words, is eiected much more slowly than the absorption of nascent nitrogen. lVhle it is prejudicial for this reason to first introduce ammonia into the molten metal, this objection does no't hold with free or molecular nitrogen, which may in fact be advantageously introduced in the molten metal, for the purpose of pre-heating such nitrogen before it comes in contact with the carbid, whether t-he carbid is suspended in the molten' metal .or in the molten cyanid, or bot-h. It may7 hence be desirable, in some cases, to introduce nitrogen through the pipe 27 directly into the body of the molten alloy while simultaneously introducing ammonia into the cyanid mass thereabove through the instrumentality of the hollow lunger.

In practicing this process o nefecting reactions within a body .of the molten cyanid itself, I prefer to introduce` the necessary cyanid in the reaction chamber at .the outset instead of building it up carefully as described.

After the process has been carried on for some time and the reaction vessel is sulficientlyfull of cyanid, the flow of gas should be stopped and the alloy should be circulated a short time longer in order to insure the decomposition of all of the barium cyanid by sodium, after which the mass should be allowed to settle.

For certain purposes, as for example in the extraction of gold from ores, it 1s not always essential that the sodium cyanid be absolutely pure; and a small percent-age of barium cyanid which will react in substantially the same manner as the sodium cyanid may be permitted to remain. In such case it is not necessary to allow the mass tosettle in the manner above described. Barium carbid, which has a specific gravity somewhat greater than sodium cyanid will settle out together with the excess carbon to the surface of the alloy Vin the course of time, after which the clear sodium cyanid or part of it may be tappedof at one of the .spouts above 'the sodium alloy.

The apparatus which I have just described is adapted to the more or less continuous utilization of the alkali metal in the alloy, and while in practically free communication with the alloy in the electrolytic charnber.v

In my previous application, above referred to, I pointed out that the reaction chamber might be quite distinct and Widely separated from the electrolytic chamber, and adapted to the continuous or intermittent treatment. of a very large body of alloy, the product, for instance, of several large electrolytic,furnaces. In this connection therefore it is obvious that'the alloy produced in the apparatusshown in Figs. l, 2, 3 and Il need .not be utilized in situ; but a portion of therefore simpl be used as a storage reservoir for the al oy, preparatory to tapping ofi' a portion thereof; and not as a reaction chamber. The alloy may be run from a number of such furnaces into a single reac tion vessel, such as that shown in Fig. 5,

which is adapted to treat several tons of alloy at one time 5 and suitable removable pipe connections 3l may be provided for this purpose between the valved pipe 30 and the Y, or like connection 32, shown in Fig. 5. The connection 32 is disposed adjacent a section of pipe, the opening leading from which may be closed by any suitable means, such as that indicated at The alloy may be conducted through the pipe sections 30 by gravityor it may be impelled by vacuum,

as pressure, or suitable mechanical means rom one vessel to the other.

The reaction vessel or pot shown in Fig. 5 i

consists of a large cast iron pot 34 which is flanged at the top and fittedwith a gas tight cover 35 which is bolted thereto; the pot being provided with a mixing or stirrmg device comprising one or more flat disks or plates 36 and 37 such plates having ribbed 4projections on theirl upper sides and beingl mounted on a vertical hollow shaft 38 which passes through a stufling box 39, preferably located at some distance above the cover so as to be out of the hot zone. This hollow shaft connects above the bearings with a stationary supply pipe 40 by means of a gas tight slipsjoint 41. The shaft is steadied within the pot by means of a carbon bearing ring @t2 which is held in position upon the cover by means of a suitable sleeve 43, this sleeve carrying a bracket tl wherein is journaled suitable driving mechanism for rotating the said shaft.

The pot and all its fittings should be adapted to withstand heat; and pressure as high as 75 pounds per square inch may be employed. The pot should be iitted with a pressure gage 45, a'pyrometer 46, a hopper 47, such hopper having a valved pipe 48 for' permitting the exhaustion of air from the hopper, and an oil feed device 49, connecting with the stationary supply pipe 40, for introducing nitrogen, ammonia, or a mixture thereof, and oil, which will pass downwardly through the hollow shaft escaping fromA the lower end thereof near the bottom of the pipe. If, however, a plu be removed from the orifice 50, which 1s isposed just below the disk 37, the gas will be discharged at. a much higher level and above the surface of the alloy. The nitrogenous gas and fuel oil may be either simultaneously or alternately introduced througfgh the hollow shalt; or in any other suitable manner..

rlhe residual hydrogen troni ituel oil. or ammonia, or any residual nitrogen gas which may accumulate in the pot and tend to raise the pressure above the working limit, ina-y escape ironi a safety valve 51. Such may, obviously, if desired, be collected and further utilized. The pot may be lit-ted with valved pipes near the bottom thereof and at different levels, as shown at 52, and 54; which devices together with pipe 30 may be used for receiving and discharging the materials required and produced in the process. .An opening may be provided .tor perinitting examination ol' the interior oit the pot betere starting the process. Air must in all cases, however, be excluded While operating.

The reaction vessel or pot inay be heated electrically; or externally by the combustion of suitable Lluel, to a Working temperature approximating a red heat; a fuel oil burner being indicated at 5G 'which inay be used for external heating'.

The barunieodiuni alloy, or the like, may be charged in the reaction vessel up to the level desigi'iated 5T; and charcoal in lii'iely di vided or lump torni, or both, nlay thou be charged through the hopper ell. ,llhe air must be euhausted from the pot in all cases before starting in order to eliminate onu l and for the saine reason air and moisture should also be removed troni the charco-al. lit the charcoal has been stored alter prv paring it, it is advisable to heet it uiuler a vacuum in order to thoroughlyv .tinore mois ture and occluded gases; aiuL such charcoal should be chargedinto the reaction :riot tvi thout again coming into contact f the air.

lnstead oiE using charcoal, `fuel oil, which does not contain oxygen, inay be used 'to ad vantage; the oil being bruinen up into its constituents at the temperature and under the conditions of the process and 'hue sup* plying' the necessary carbonq The ineeluiuical stirring device may then le started and the contenus of the pot ith gen or aininenia, or beenn lulcrot tu or aininonia gas may heintreduoed eil:l er be low or above the siuface et the iuolteu alloy, depending; on Whether the opening be opened or closed; and sullicieut be introduced at one time to produc, sure oit" 753 pounds or loss, per sauf Within the vessel, The bariuui or other reA acti'veunetal, c. g., lithium in the alloy 'will combine directly with both the nitrogen and carbon and the action will lproceed in the presence col." metallic sodium to produce sodiun'i cjjvanid, which Vwill 'then accumulate above the alloy; but lu star i the operaa separate reaction 'ves el it" is de 1d more convenieni to introduce a z marge ol alkali. inet-al cyaniddi* gen on the alloy; such latter operation being both inellicient audtedious. s

After a sufficient body of molten cyanid has been introduced or accumulated the gaseous nitrogei'l or annuo-nia. may be siinply injected into the body of molten cyanid itselit' through the orifice 50; or may even be silnply brought in Contact with the surface oit the cyanid and not injected into the alloy at all in order to react eliiciently When the barium or lithiuin carbid, or other finely divided carbide in suspension, solution, or both. ll, however, the gaseous nitrogen or ammonia escapes at the lower extremity of the hollow shaft, orifice 50 being plugged, the bubbles el gas will then rise through the alloy and strike the lower surface of the plate 3o, which at first will be submerged in the `rich bulky alloy. The bubblesjof as can only escape by passing along the un e' surface of this plate tothe periphery thereot, atte-r' which they will rise and strike the underside of the baille plate 58, and `Will then nass along to the center of this plate in intimate Contact with the alloy. Any uneonibined gas will then bubble up through the surface et this alloy lmesing through the orifice 59 in 'the center of plate 58, and strike the under surface o't plate 37, Which is preferably submerged in the molten cyanid ,troni the beginning action of the operation, The nitrogen introduced on the under side el? plate 37, is thus held subinergedin the niet n cyanid by this plate or disk which insures most favorable conditions for absorption. Any uuabsorbed nitrogenous gas or. residual hydrogen may then pass around the periphery oit the plate 3T and escape to the upper part oit the vessel. If the orifice .30 is open the gaseous nitrogen or ammonia 'will obviously not pass through the bottom of the shaft, but will pass through the cyanid below the plate 37. The impoverished alloy in the pot Which extends up to the line G0 may be returned. to the electrolytie fuiA nace by means of compresser gases such as hydrogen, nitrogen, ammonia, or oil gas, actingr on the surface of the alloy, or of the superimposed cyand in the pot. Pressure `then forces the. fluid alloy up through the discharge pipe 31 from the bottoni of the pot. The pipe 31, which extends outside of the brick-work ol the pot and of the electrolytie furnace, may be inclosed in any suitable manner so as to leave a passage-way or flue therearound to permit independent heating oit such pipe by a gas flame, or the like. The alloy may, however, be returned by any suitable lifting device for luid metal if desired. Such device maybe located 'somewhat near, but below, the reaction vessel so When the reaction pot is suliiciently full of cyanid, the How of gas should be stopped and the agitator should run a short time longer in order to insure decomposition of all of the barium cyanid by sodium, after which the agitator should be stopped and the mass allowed to settle. The clear molten sodium cyanid or apart of it may be tapped ott' at one of the openings above the surface 'of theI alloy, which latter, after the abstraction of the, lightmetals therefrom will have greatly diminished in volume so that its surface may be as low as level GO, It Will be observed by considering reactions No. l to No. 4 (representing the principal steps of the process) that the reactive metal c. g. barium passes from the metallic state, to carbid, from carbid to cyanid, and from cyanid back to the metallic state, and then over the same course again and again durine numherless cycles. It' there is insufiicient free carbon present, some of the reactive metals e. g., barium, lithium, etc., will combine with a portion of combined carbon in the sodium cyanid itself to form barium carbid and sodium cyanamid (dialkali eyanamid) probably according to the following equation:

but the cyanamid thereafter on the introduction ot free carbon into the molten mass,

is prompt-ly reconverted into cyanid. It.

however, free carbon is not supplied the reduction of the cyanid to cyanamid by the barium or other reactive metal will proceed until the entire mass of cyanid is1 converted.' into cyanamid, and for this reason the process may be used for the production of alkali cyanamids, Well as cyanids.

I regard it as likely, in View of the fact that barium does reduce molten sodium cyanid to sodium eyanamid by combining with some of its combined carbon, and in view of the fact that molten sodium cyanid is in intimate and close contact with the barium at. the moment of its liberation,--pressed against itl in fact by the Weightl of the supernatantluid cyanid, and in 'view oi the impalpable and amorphous character of the barium carbid produced in the process at so lou'v a temperature (below 900O C.) that the greater part of the barium carbid, Whirh is concerned in the synthesis ot sodium cyanid by this process is produced by barium combining- 1` Awith a portion of carbon in theA cyanid itscl.t,--it being `understood, of course, that but a very small proportion of the whole mass of cyanid would be thus momentarily reduced,-and that the free oarbon float-ing' around therein quickly reconverts the reduced portion back to cyanid.

The element lithium m( f be regarded as being characterizable both as a reactive metal and as an "alkali metal, since it is usable in the process in eithercapacity. In-

deed, it may be used in the process in both capacities, as for example, when the alloy contains lithium as the reactive metal and the molten bath. comprises lithium cyanid or cyanamid.

It will be apparent thata carbid, nitrid, cyanid, or cyanamid, it of sutlicicnt purity and in suitable physical condition, may be employed at. the out-set instead of the reactive metal itself; that beingpossible by reason of the fact that the initial carbid or nitrid, under the conditions ot' the process, Will beconverted into either cyanamid or cyanid of the i alkali metal sodium, or potassium will thereupon liberate or set free the reactive metal in metallic form.

Other reactive metal salts may be similarly introduced and decomposed with consequent liberation of a free reactive metal but the method is slightly objectionable for the reason that it introduces an impurity or diluent, c. g., sodium ch'lorid. into the final cyanid. Thus barium chlorid, lithium chlorid, etc., if introduced into the molten cyanid Will melt and dissolve therein and come into contact with the sium in the alloy, which will then decompose such chlorids with the formation of sodium or potassium chflorid and metallic barium or metallic lithium, which latter will be liberated according to the following equation:

(o) Licorne.; NaCl-l-Li (free reactive metal It will bc apparent from a consideration of the above reactions, that ya free reactive metal must be employed at some point .in the cycle or in lieu thereof a compound which will yield a free reactive met-al at some point in the cycle, and that the usc oi any salt or compound which when introduced into the molten mass or vemployed under any of the conditions ot the process, will' yield such reactive mel-al at some point in the process, is within the scope'ot my inventlon. 4Other reactive metals may be employed instead .of barium,--notably lithium, strontium and calcium, in which event the reactions will be quite similar to those indicated for barium.

The reactive metals manganese, eerium, chromium, titanium, vanadium, etc., have the property when heated ot' combining direct-ly 'with carbon to form carbide, and

'with free nitrogen to form stable nitride,

and although they do not themselves form the base metal of stable cyanide under the conditions of the process, they will nevertheless bring about the synthesis of sodium or potassium cyanid under the process-the mechanism of some of the i ntennediate reac- 'tions being necessarily different from those sodium or potas-A fill :lier "which equaliions are given in lfhie specilicalionwand lacing in fact, uol; clearly/f un- The process also werke eomewhal more slowly when manganese, ceriuin1 elc. are employed instead of barium, lilhiunn etc. Pure iron will also combine with car-V hon lo form a carbid in 'the proccwf: huli il will not combine with free nitrogen 'lo form a sizable nilrid and will not accoi'nplieh 'lhe synl'hesic oil alkali cyanid under the procees..

lll finely divided or amrgvrphous :man ganese ie hroughlinlo Contact with carbon in a cyanid hath, nanganese carhid will he readiliT formed and nitrogen or annnonia will reacl` therewith to form a manganese nilrid, that will settle lo the surliice oil? ille sodiumdead alloy9 and ldiere in Contact with sodium und carbon will he formed so-dirun cyanid and linely divided in escT 'lhe loller probably in :nur hous condition. The manganese will ncl, in l al lzhc temperarlaure of the (meralion and will nel alloy with the lead. rlhe Same siepe may he -followed Willi chromium, ccriunn elc. lli the allraliH moral is employed in che pure. sialicj instead oli in the 'lorm ol an alloy `with a heavyT metal, or il liolh pure allie" 'al and alloyr he used, "che reactions une Lhe linel resulll will he suhslanliially llie same lilioec already described. lhe purr c liiun or potassium will float on lthe euriface of molten cyanid, lio-Wever, or on port-ion ol:A the eur lace, which may he reslricled Vlor instance inside of a cylindrical casing 5l shown .in die large pol; in Fi. 5.

The ascending nilrogen or ammonia will in euch case pass up wardlT into 'the cyanid adjacent die Walls of che pot and ourside oil the cylinder, and may hence pues enlirely through the mass of cyanid,` il' no'lJ co-npletcly ahsorlocd ltherehjyg wilihou l; passing thrmigh lhe molten allmli melal lf ammonia loe employed inslead of pure nitrogen and come or il; comes in physical contacuwith pure eodiunn illus floating on llie surface oli die mollen cyanirh another ser of Ver); lranei'lory inlzermediale reactions may come into p1" lio a email ex" teni and likewise reeulll in the production of sodium cyanid; out die l'ree carhon suspended in the cyanid *will continue jo reacl Willi lhe reactive metal l in equation l, and 'the process will proceed substantially according lo equal-ions l, el and l Wish lio define lha't in l'he cleirne 'lie scope olf 'lhe herrn lnilrogenous rcagcniu includes any7 rea gent which will )Yield nitroa gen under lhe'condilions ci 'lhe process, us, for example, eilher nlprogcn, nitride, or ammonia; and similarly, 'that C carboini-` ceous reagcnh includes any,7 reagent whi h, 'will yield carbon under euch condilionsn lor eilan'iple, charcoal, :fuel oih coul, oyeron cyanamide9 etc.

ln conclusion l desire lo call alle die l'acl; that iron when healed does sluhle ni rids, although they' do not form cyanids lilac die alkaline earth and alkali metals.

lll-'rlich l claim, is:

l. ln a jnocess oil producing cyanogcn compounds and the like, the step which con sisls in reacting on an impalpahle amen phone carbid with a nitrogenous reagent, at a len'iperalure alcove SOOO C.

2. yllie procese of producing cyanogen compounds and Athe like, which comprises ellecting a chemical. reaction between a nilrogenoue reagent and a quantity of noncrjslalline carhid al; a, temperature below the 'fusing point of said cai-hid hut above 500O C.

E. 'lhe procese of producing cyanogen which combine Willi free nitrogen to form compminds and the like, which comprises 4 compounds and the like7 which comprises reacling 'with a nitrogenous reagent on a carbid held in suspension in and dill'used through a fluid compound the radical forming conetituente of Whichvconstitute a con eiderahle percentage of eaid compound and which conenituenls are `the Same as those of lloc compound 'which is to he produced, at a lcnrperalime ahorn 500 C.

llhe procese of producing cyanogen compounds an ehe like which comprises ellecling a reactioiii between a, nitrogenous reagent end 'Elie carbid of a reactivemetil,w the latter being in impalpeble noncryselline condition and held 1u suspencion in and dilfueed through a mass of non-u aqueous llnid comprising a compound the dical loruiing constituents ofV which are 'the une those of the compound which is Vlo he producedU 6., A pre eee olf producing cyanogen compounds and the lillej 'which comprises form- 1 un amorphous carbid by bringing toi lr carbid. :lorn'ling elements at a tem-- ililiouc cuii'hid with e nitrogeuous reagent.

'" lho procese oil.E producing allcalnmetal cyanogen compounds and the like, which includes reacting with a nitrogenous rea ent on a carbid of a reactive-metal W ile said carbid is contained in a fused mass which contains carbon and nitrogen, the

Y fused mass ybeing in contact with a fused body of alloy containing analkali-metal as one of the constituents thereof.

8. The process of producing alkali-metal cyanogen compounds and the like, which includes reacting with a nitrogenous reagent on a carbid of a reactive-metal while said carbid is contained in a fused salt which contains carbon and nitrogen, and dissociating the product 'of such reaction, in the presence of an alkali metal thereby causing the carbon and nitrogen to unite with said alkali-metal to form the product sought.

9. The process of producing alkali-metal cyanogen compounds and the like, which includes reacting with nitrogen on a carbon compound of a reactive-metal while said compound is contained in a nitrogenous salt, `the nitrogenous salt being in contact with a fused body of alloy, containing an alkali-metal. as one of the constituents thereof, said salt being maintained at a lower temperature than that of the alloy.-

10. In a process of producing cyanogen compounds and the like, the steps which consist in forming a carbid of a reactivemetal at a temperature below that at which such carbid will fuse, thereby substantially avoiding subsequent crystallization thereof, and effecting a reaction between such carbid and a nitrogenous reagent within a mass of nitrogenous salt.

11. In a process of producing cyanogen compounds and the like, the steps which consist in forming a carbon compound at a temperature below that at which, such compound will fuse, and effecting a reaction, between such compound and a nitrogenous rezligent Within a mass of fluid nitrogenous sa t.

12. A `process of reducing cyanogen compounds and the 1i e, which comprises forming an amorphous carbid by bringing together carbid formng elements at a red heat, and reacting on said amorphous carbid with a nitrogenous reagent.

13. A recess of producing cyanogen compounds andthe like, which comprises forming an amorphous carbid at a temperature below the fusing point of said carbid, and reacting on said carbid with a nitrogenous reagent at a temperature also below that at which saidvcarbid will fuse.

14. A rocess of roducing cyanogen coinpoun s and the li e, which comprises forming a carbid at a given temperature within a fused bulk of a ycompound having radical forming constituents which constitute a considerable percentage of said compound, and which constituents are the same as those of the compound which is to be produced, and reactiugon said carbid at a temperature substantially the same as that of the given temperature aforesaid.

15. In a process of roducing cyanogen compounds and the li e,I the step which comprises reacting on amorphous lithium carbid with a nitrogenous reagent.

I1G. In a process of producing cyanogen compounds and the like, the step which comprises reacting on lithium carbid with a nitrogenous reagent.

17. In a process of producing cyanogen compounds and the like, the step which includes reacting o-n a substance which comprises lithium, with 'free nitrogen in the presence of carbon. a.

18. In a process of producing cyanogen compounds and the like, the step which includes effecting areaction in which the elements lithium, nitrogen and carbon participate, in a mass of molten matter comprising said elements.

In witness whereof I subscribe my signa-4 ture, in the presence of two witnesses.

CHARLES E. ACKER. Witnesses: Wanne M. OHAPIN,

WILLIAM C. LARY.

Copies of this patent may be obtained for ve cents each, by addressing the Commissioner of Patents,

' Washington, D. G.

Images