US1862003A

US1862003A - Process for treating hydrocarbons

Info

Publication number: US1862003A
Application number: US235502A
Authority: US
Inventors: Carlisle Paul Johnson; Harris Charles Roberts
Original assignee: Roessler and Hasslacher Chemical Co
Current assignee: Roessler and Hasslacher Chemical Co
Priority date: 1927-11-25
Filing date: 1927-11-25
Publication date: 1932-06-07
Anticipated expiration: 1949-06-07

Description

June 7, 1932- P. J. CARLJSLE ETAL PROCESS FOR TREATING HYDROCARBONS Filed Nov. 25, 1927 2 Sheets-Sheet 2 filPfwiji '35 a o 7 2 O 7 v o Q 7 a 43 26 2a fi m/V6 Z5- 22 L 17 mm INZIENTORS BY W ATTORNEY Patented June 7, 1932 U ITED STATES PATENT oFF cr.

h drocarbons,

rant aomvsou oanmsLn Am) cnnnnas nonnars Hams) NIAGARA m new Yonx, assrenons nr missus ASSIGNMENTS, cnnmrcan comranzor new Yon r, 1v. Y.,IA

raocnss ron 'rnna'rrne rrrnnooansous Application tiled November 25,

This invention These hydrocarbons may. e tained from any source, tion of crude petroleum, hydrocarbons, tion or extraction'of oil shale, gasoline, etc.- Our invention is also. applicable to the individual hydrocarbons as well as to mixtures. These untreated products are usually undesirable for use ecause of the presence of substances, such as certain sulphur compounds and unstable hydrocarcracklng of heavy bons, which have an unpleasant odor, whiclr resinifyon standing, etc. Thus in gasoline for motor usethese undesirables must here-- duced to render the product stable and saleable. In the succeeding specification our 1n-,/

vention will be particularly described with reference to, what is commonly known as gasoline, but we do not wish to be limited thereto since our invention is applicable to the treatment of hydrocarbons in general.

The treatingof; crude gasoline usually results in the formation of certain solid and liquid by-products which may be polymers of unsaturated compounds in the gasoline-or treating agent i ation, and may may be compounds of certain constituents of the gasoline, or both. In general, such by-products are troublesome since they tend to r'oul thetreating apparatus and the treating agent. In many cases it is necessary for economic reasons to recover the from its mixturevwith the of course, adds an. extra operproducts; this,

be attended with considerable difficulty and expense; This prohibits j the use ofrelatively expensive treating baths or a process whereby treating agents cven though theyproduce asuperior product.

' Thusfior example, suchdiiiicultiesform one of the principal reasonswl y alkali metals have not bccnused commercially in treating .crude gasolines even though .itis known that the treated product is of excellent quality.

. Theobject of this invention is to provide the excessive fouling or the accumulation of treatment lay-products in media for hydrocarbons is avoided. A further object is to provide a process whereby alkali metals may be used as treating agents undcrsuch conditions that relates tothe treatment of such s the distilla-V hydrogenation of coal, distilla- I able.

the treating agent with a we do not wish CORPORATION i OF DELAWARE 1927. Serial N... 235,502.

without additional treating agent,and alsoremoving some suspending liquid and contaminating by-products with it; these by products may be in suspension or solution or both. Thus, for example, the suspending liquid may be a hydrocarbon of characteristics, boiling range, etc., similar to the product removed as vapor but having a boiling point curve higher than that of the vapor fraction (temperature as abscissae, volume as ordinates) such a sus pending liquid would be formed from higher boiling constituents of the gasoline being treated. Other suspending liquids of proper physical and chemical characteristics are suit- Thus, liquids, such as heavy oils, having much higher boiling ranges drocarbons being treated would be suitable; so also, individual hydrocarbons of proper boiling point maybe used.

A great variety of treating agents may be used in our process; some of these arealuminum chloride, sodium,potassium, or alloys such as sodium alloys with other alkali metals or .with alkaline earth metals, or with heavier metals as lead, mercury, and the like. We have'obtained excellent results with, for example, aluminum-chloride, sodium metal ro THE nonssnna a nassnacrmn than the hy- (solid and liquid), sodium amalgam and sodium lead alloy.

In this specification. we speak of a suspension of the treatin to be limited to the physical condition of the medium that this may imply. \Vc donot know whether-the success and particular cfiicacy of our method in producing excellent products is due to the contact with undissolrcd agent in the liquid or to contact ble that with dissolved agent. It is even possi some reaction product of component of the the agent and a liquid, or that certain subagent in liquid, but

stances produced by the treating process and included in the term polymer or by-prodnot as used herein, may either in solution or suspension, or both, contribute to the suc- 5 cess of the process. In any event we intend e expressions treating agent ina liquid treating agent in liquid hydrocarbon or suspension in a liquid, etc., to cover all these possible mg medium is meant th of which may be organic compounds, some compounds of alkali metals, and some sulproduced from hydrocarbons from different sources or from the same source at different times.

Our preferred application of this general gsprinciple comprises passing the hydrocarbons into contact with alkali metal in liquid hydrocarbon and effectbe atomized or hydrocarbon f vapors. mist, The treatment he main portion thereof will remain in 5 the reaction vessel. Therefore, we donot limit ourselves toany particular method of contacting the hydrocarbons ing medium becausethis can be done inmany i consisting of sodium in liquid hydrocarbons.

condensinga part of the high boiling constitthe suspending liquid, re-

treating lots or other impurities reatment.

Figure I illustrates one form of apparatus physical conditions. By treat e mixture of liquid tator may, under posed we will describe in th iis invention which comprises suitable for applying the principles of this invention.

Figure II illustrates further adaptations of our inventionwith special reference to the ydrocarbon are introduced through the pipe 1, which may carry a condenser 2, through the opening treating mediuin 4, with level at 5, and contained in a vessel or reactor 6. The vessel may be equipped with an agitator 7. driven by the pulley 8 through the shaft 9. The agicertain conditions, be omitted, the agitation being supplied by the va- H pors entering the treating medium. The vesse is equipped with a acket or a coil 10, W ich is used either for heating or for cool- "alve .12 and pipe 13.. I

A fraction, depending upon the treating temperature, of the hydrocarbon vapors enteringthe vessel 6 is condensed. This con- 'fraction leaves battle separator 14 and pipe 15, and b a devicesuc as siphon 16, an approximate y constant level 5 of the medium is maintained. This liquid is run through pipe 17 and disof inv various Ways.

The portion of the hydrocarbons leaving the reactor as vapor passes through the pipe 18, which may be equipped with a fractional condenser 19 to'con ense out, if desired, an higher boiling constituents. The liquid thus condensed can be passed into the treating vessel through valve 50 and pipe 51 or it can be removed through valve 52 and pipe 53 and any desired way.

suitable recovery system, not shown here.

Exchanger 2 has been referred to as a condenser. Both 2 and the coil 10 can be used either as treating temperature.

The liquid leaving the reactor by Way of separator 14 and pipe15 consists of the heavier ends, that is, the higher boiling constituents of the gasolines or hydrocarbons treated. This'liquid efliuent carries with it Inasmuch as the alkali metals are relatively light it is advisable to provide a separator,

' bafiles as at 14, which will 7 r I Y from the liquid efiluen The liquid eflluent may be handled in a number of ways. For example, with reference to Figure II, it may be sent by Way of valve of valve 42 and pipe 43, or, by way 37, to aproper point for evapora- 36 and pipe tion. cracking, etc. Or, the effluent in pipe 17 can be passed through valve 44 and into a separating device 25 and subjected to or other method of 130 fuging, filtering,

separation,

flowing into a container28 which acts as a feed reservoir for pump Treatment by-products are shown as leaving the separating device at 26. The clarified liquid leaves by way of pipe 27,

30, the latter driven bymotor31. The pump receives the liquid through pipe 29 and can deliver it through i pip liquid canbe caused to vessel, thus making tmuous operation .32 to any point desired. Thus, the flow through

valves

33, 38, and -10, and pipe 39, into the treating it possible with conand proper temperature control: to remove from the treating as treated gasoline practically allot the gasoa jected to distillation,

polymerresidue 1 and the suspension 25 i those skilled in The metal might cept that lost b line fed ex operation and as polymer.

disposed of as. desired. It is to be noted that the efiiuent has also been subjectedto the treating action.

The alkali metalcan be fed to the reactor inany convenientmanner. It may be prepared as-a suspension in liquid hydrocarbon added to. the reactorby way of hopperll or the metalmay he adde in solidfo-rm such as bricks andagitation" in the reactor will serve to subdivide it on be applied by handling. such materials.

melting. Other methods may be added as a liquid or asa finely divided metal in suspension. method of making and applying colloidal sodiumconsists in passing a condensed electric sparkbetwen two sodium electrodes a suitable distance from each other placed at liquid suchas ether, xylene, etc.:

under a Such a colloidal suspension isthen introduced directly into the treating vessel. It is also possible. toy make the colloidal suspension directly in the treating vessel itself.

The percentage of the hydrocarbons fed to 1 the treating apparatus which leaves the reactor asliquid is regulated, in general, ac-

hydrocarbons so line as liquid and finished product. y 6 hydrocarbons are removed almostentirely a same time a higher temperature of'treatjment? p can be maintained,

stantially all 56 cording to the amount oi polymer formed.

removedto carry away Enoughsuchliquid must be condensed and the polymer at a satisfactory rate.

In some cases substantiallyall of the maybe removed as liquid.

There would be little point in doing thisif gasoline vapors are being gasoline is introduced into as liquid it is entirely feasible to removesub boiling constituent-s which might compose say up to 15Vpercent of the material) ofthe gasodistil it for recovery of the being treated, for example, lubricating oil stock, the hydrocarbons canbe as liquid and at the if desired. The efliu'ent liquid may be distilled or treatedby such methods as centrifuging, agitating with ab- Further, the e uent may be sub: and the distillate and to a spare unit if d V metal collect-s One . Thus, referring treating vessel.

treated, but if the the treating vessel (except perhaps the very lowest boiling liquid,

If higher. boiling liquid mcnt of hydrocarbon --va pors'; the

peratures even though at higher temperatures the treating medium fouls more quickly per unit of hydrocarbons treated and the polymer has more objectionable physical properties than at lowertemperatures.

Operations utilizing higher temperatures may be carried outin at least three ways. Thusat intervals operation may be switched the first has become excessively fouled. Then, because thealkali metals (except lithium) settle more rapidly than the polymer, a large part of the alkali in the lower end of the conical bottom of the treating vessel asat and day be drawn oil by valve '21 andpipe '22.

r bulk of the polymer which is suspendedin the medium settles down just above the alkali metal most of thepolymer canbe removed,

along with a portion of the liquid medium, throughthe pipe 23 andvalve 24;, after which the treating vesselis ready for further use. According to the second method the polymer may be removed from the treating medium by effecting a flow, circuit, of higher boiling hydrocarbon. to Figure II, higher boiling liquid in supply tauk 35 may be, caused to flow through valve fll'and pipe 47 into the treating vessel at a given rate and be removed through pipe 15, with the polymer,

the polymer separated from the liquid by filtering, centrifuging or other 25 and the liquid returned by pump through pipe 32 and valves 33 and 34 to the supply tank 35 and'then to the It is obvious that the higher boiling liquid neednot necessarily be returned to the circuit, butyinstead, since it settling, means as at has been treated once 1t may be utilized, per

se, for finished products. In such cases fresh crude higher boiling fractions are introduced vessel. Some of the higher depending upon its vapor ressure, leaves the trcatingvessel with the treated hydrocarbon vapors and, if necessary,1may be recovered by subjecting the treated hydrocarbon vapors to-a partial coninto the treating ossihle to operatc nhaler pressure. I

Our invention,1s'not lin1ited to the treatapparatus may be utilized for-"liquid treatment. "For instead of removing the metal, since the so to speak, in a separate nsationgprocessii.-Asia third method it is instance, liquid hydrocarbons can be introduced through pipe 1. In this case the coil can-be used as a heater. The same treating temperature can be used which would be employed if the same hydrocarbons fwereintroduced as Vapors in which case the greater part of the treated hydrocarbons leave the drocarbons of 14 and reactor as vapor through 18. Or, if desired, a lowertreating temperature can be used, such that substantially all of the treated byleave the reactor as liquid by way 15; the liquid passing, for example, directly to a still from which a final product of good qualitygis obtained.

3.5 grams of sodium in 350 cc.

fluent or heavy ends froma previous run,

Ea'ampZe.This example serves as a spe cific illustration of this invention. The hydrocarbon mixture treated was crude, cracked gasoline made by cracking certain fractions of Pennsylvaniacrude petroleum. 87.15 liters of this liquid crude cracked gasoline was passed as vapor into a dium consisting initially of approximately at an average rate of about 1.0 liter per hour.

7 The temperature of the treating medium was maintained at 150.155 At intervals of about, 8 hours of running time additional sodium was added to the treating medium. These additions consisted of 2 to 3 grams of the metal in the form of sodium shot. tinned the treating lent condition and a medium was in excelhigh quality of product I was still being obtained.

69.865 liters of refined gasoline and 15.07 liters of liquid-polymer fractionwere recovered. The; loss of hydrocarbons was 2.215 liters or about 2.54 .percent by volume of the'feed. The 15.07 liters of liquid of: fluent amountedto about 17.3 percent of the feed. Approximately90 percent by volume ofthis liquid to that of the was gasoline of end point equal crude gasoline before treatment as shown in the distillation data of Table I.

The total weight of sodium introduced into thetreating medium for the Whole run was 39.5 grams. At the end of the run 12.25 grams of sodium" remained in the treating vessel. The sodium consumer, therefore, was 27.25 grams which corresponds to about 0.313 grams per liter or about 0.11 pound per barrel (42 gallons) of crude gasoline fed.

Table I shows the distillation data for the the reaction medium is. poscertain cracked gaso treating meof liquid ef- WVhen the run was discon- 1. e., sodium, potassium,

' or with other vapors leaving'the treating crude cracked gasoline before treatment, the

Crude cracked gasol Refined gasoline Liquid emuent 1 I Percent Temp. i Percent (115- Temp. distilled F. tilled F.

Residue 1% Residue Loss L Residue 10% Table 11' Crude gasoline g gaso- MR "Unsaturated" hydrocarbons 12. 33% 10. 5 Aromatic hydrocarbons 24. 3% 24. 9% Naphthenio hydrocarbons 31.1% 32.8% Paraffin hydroearbons 32. 27% 31. 8% Sulphur (lamp method) 0' 0195% 0.007% Doctor test 1 Positive Negative. Copper strip corrosion test Positive. Negative. Odor f "Sulphurnus Sweet. Color About 18. Water-white.

The excellent color stability of the refined gasoline fraction is shown by the factthat subjected to sunl'ghtifor 7 days the color changed from 30 to 25; other samples placed in a window for 7 days changed in colorfrom -30 to 28; other samples exposed to darknessfor 7 days suffered no appreciable change in colon.

In order to avoid ambiguity and a multiplicity of claims the following definitions of' the terms used in the claims are here given: The term alkali metal etc., singly or in various combinations or mixtures with each other metals such ascalcium, mag nesium, mercury, lead. tin. etc., in any applicable physical state. The term by-products covers all of the substances that are formed in the treating medium and that are not removed with the treated hydrocarbon vessel. The

term hydrocarbons stands for mineral oils,

rials that may gasolines, and any other be improved hydrocarbon mateas herein described. liquid is meant bons substantially as 3 medium com rising sodium suspended inliqproducts ,bonsintoa treatin metal suspended unreacted alkali q 2. Process comprising passing hydrocar- 1 ed hydrocarbon 1; Process comprising contacting hydrocarbons liquid atthe reaction temperature with a treating medium comprisin an alkali liquid hydrocarbon,

metal suspended in washing contaminating by-products from said alkali metal by agitation with the suspending medium, and removing treated hydrocarbonifromthe treating medium as liquid effluent, after uid hydrocar on, washing contaminating byfrom said sodium by agitation with the suspending medium, and removin treatr'rom the treating me ium as liquid efliuent. i q 4:. Process comprising passing hydrocarmedium comprising alkali in liquid hydrocarbon having a boiling point curve higher than that metal from an efiiuent portion,

of the hydrocarbon introduced, removing treated hydrocarbon from the treating medium as vapor, washing contaminating byproducts from said alkali metal by agitation with said higher boiling hydrocarbon flowin throughthetreating vessel, separating su stantia ly all washed unreacted alkali and discharging suspended contaminating byaproducts byagitation with 0 carbon, separating from the treating vesselsuspende in said efliuent before fouling quantities accumulate.

a 5., Process comprislng passing hydrocarbons substantially as vapors into a treating medium comprising suspended sodium in liqui'd hydrocarbon having a boiling point curve higher than that of the hydrocarbon introduced and removin treated hydrocarbon from the treating me ium as vapor, washing contaminating by-products from saidsodium said higher boiling hydrosubstantially all unreacted sodium \from a portionof sai hydrocarbon, flowing said portion from the treating vessel vat such; a rate that suspended contaminating by-products are discharged from the treating vessel before fouling quantities accumulate.

y such treatment comprising alkali metal suspende dium partially as vapor,

*6. Process comprisin passing hydrocarbons at least partially diquidunder the reaction conditions into a treatin medium d in liquid hydrocarbon, washing said alkali metal by agitationwith said liquid and removing treated hydrocarbon from the treating meand partially as liquid eflluent, separating substantially all unreacted alkali metal from said effluent before discharging it from the treating vessel.

Process comprising passing hydrocarbons substantially as vapors into a treating medium comprising sodium suspended in liquid hydrocarbon, washing said sodium by agitation with said liquid hydrocarbon and removing treated hydrocarbon from the treating medium partially as vapor, and partially as liquid effluent, while separating substantially all unreacted sodium from said effluent before discharging it from the treating vessel.

8. Process comprising contacting hydrocarbons at least partially liquid under the reaction conditions with a treating medium comprising alkali-metal suspended in liquid hydrocarbon having a boiling point curve higher than that of the hydrocarbon introduced and removing treated hydrocarbon from the treating medium partially as vapor and partially as liquid efiluent, separating substantially all unreacted alkali metal from said efiiuent before discharging it from the treating vessel, and removing treatment byproducts from the medium with said liquid efliuent. Y i

9. Process comprising contacting hydrocarbons at least partially liquid under the reactionconditions-with a treating medium comprising sodium suspended in liquid hydrocarbon having a boiling point curve higher than that of the hydrocarbon introduced and removing treated hydrocarbon from the treating medium partially as vapor and partially as liquid efiluent, separating substantially all unreactedsodium from said eflluent before discharging it from the treating vessel, and removing treatment by-products from the medium with said liquid efiluent.

10. Process comprising passing hydrocarbons substantially as vapors intov a treating medium comprising a treating agent suspended in liquid hydrocarbons having a boiling point curve hi her than that of the hydrocarbon introduced; removing treatment byproducts from themedium with a liquid effluent continuously-flowing from said treating medium at such rate that fouling quantitles of said by-productsdo not accumulate within the treating vessel, while continuously separating substantially all unreacted treating agent from said effluent before discharging from the treating vessel, said treating agent being continuously retained suspended in the said hydrocarbons and withinthe treating vessel.

I introduced; washing treatment by-products from said alkali metal by agitation with said suspending liquid; removing treatment byproducts from the medium with a liquid effluent continuously flowing from said treating medium at such rate that fouling quantities of said by-products do not accumulate within the treating vessel, while separating substantially allunreacted alkali metal from said effluent before discharging from the treating vessel.

12. Process comprising bons substantially as vapors into a treating medium comprising sodium suspended in liquid hydrocarbons having a boiling point" curve higher than that of the hydrocarbon introduced; washing treatment by-products from said sodium by agitation With said suspending liquid removing treatment by-products from the medium with a liquid eii'luent continuously flowing from said treating medium at such rate that fouling quantities of said by-products do not accumulate within the treating vessel, while separating substantially all unreacted sodium from said effluent before discharging from the treating vessel.

13. Process comprising contacting hydrocarbons at least partially liquid under the reaction conditions with a treating medium comprising alkali metal supended in liquid hydrocarbon and removing treated hydrocarbon from the treating medium partially as vapor and partially as liquid effluent, separating substantially all unreacted alkali metal from said efiluent before discharging it from the treating vessel, and removing treatment byproducts from the medium With said liquid effluent.

14. Process comprising passing hydrocarbons substantially as vapors into a treating medium comprising alkali metal suspended in liquid hydrocarbon and removing treated hydrocarbon from the treating medium partially as vapor and partially as liquid effluent, separating substantially all unreacted alkali metal from said efiiuent before discharging it from the treating vessel, and removing treatment by-products from. the medium with said liquid efiluent. 1

15. Process comprising contacting hydrocarbons, at least partially liquid under the reaction conditions, with a treating medium comprising a treating agent suspended in liquid hydrocarbon, removing'treated hydrocarbon from the treating medium partially as vapor and partially as liquid effluent, continuously discharging treatment by-products suspended in said effluent from the treating vessel, while simultaneously separating subpassing hydrocan' stantially all unreacted treating agent from said eflluent before its discharge from the treating vessel and continuouslyretaining saidagent suspended insaid liquid hydrocarbon in said vessel.-

16. Process comprising-passing hydrocarbons substantially as vapors into a treating medium comprising alkali metal suspended in liquid hydrocarbon and removing the treated hydrocarbon from the treating medium partially as vapor and partially as liquid eflluent, separating substantially all unreacted-alkali metal from saidefiluent before discharging it from the treating vessel, removing treatment by-products from the medium with said liquid effluent and separating the by-products from said liquid.

17. Process comprising contacting hydrocarbons atleast partially liquid under the reaction conditions with a treating medium comprisinga treating agent suspended in liquid hydrocarbon and removing treated hydrocarbon from the treating. medium partially as vapor and partialyfas liquid efiuent, separating substantially all unreacted treating agent from said efliuent before discharging it from the treating vessel, removing treatment by-products from the medium with said liquid etiiuent, separating'the byproducts from said liquid and recycling said liquid through the treating vessel.

18. Process comprising passing hydrocarbons substantiall as vapors into a treatin medium comprising alkali metal suspended in liquid hydrocarbon andremoving treated hydrocarbon from'the treating medium partially as vapor and partially as liquid eflluent, separating substantially all unreacted alkali metal from said effluent before discharging it from the treating vessel, removing treatment by-products from the medium with said liquid effluent, separating the by-products from said liquid and recycling said liquid through the treating vessel.

19. Process comprising contacting hydrocarbons, at least partially liquid under the reaction conditions, with a treating medium comprising a treating agent suspendedin liquid hydrocarbon having a boiling point curve higher than that of the hydrocarbon treated, washing said treating agent by agitation with said suspending hydrocarbon, continuously removing treated hydrocarbon from the treatingmediums partially as vapor and partially as liquid cfiluent, continuously discharging treatment by-products suspended in said liquidetfiuent, while simultaneously separating substantially all unreacted treating agent from the efiiuentbefore its discharge from the treating vessel, and continuously retaining said agent suspended in said liquid hydrocarbon withinsaid vessel, and thereafter separating by-products from the liquid effluent. 1 7

20. Process comprisingcontacting hydrocarbons at leastdpartially liquid under the naction conditions with a treating. medium comprising a treating agent SIISPOndGd in U liquid hyt'lrocarbon' having bon from the treatingmedium, partially as {I vapor and partially as liquid efiluent, sepavessel, separatingthe rate that fouling rating substantially all unreacted treating agent troin said efiiuent before discharging it from the treating vessel, removing treat meut by-products from the medium with said liquid eflluent, which is flowed out at such a quantities do'not accumulate within the treating medium and treating by-products from said liquid and recycling said liquid through the i with a treating medium comprising sodium treating vessel.

21. Process comprising contacting hydrocarbons liquid at the reaction temperature suspended in liquid hydrocarbon, washing contaminating by-products from said sodium by agitation with said liquid hydrocaring vesseLand bon, and removing treated hydrocarbon from the treating medium as liquid efliuent,

separating substantially all unreacted sodium before discharging said efiluent from the treating vessel. i

' 22. Process comprising contacting hydrocarbons at least partially liquid under the reaction conditions with a treating medium comprising sodium suspended in liquid bydrocarbon and removing treated hydrocarbon rfrom thetreating medium partially as as liquid effluent; sepaall unreacted sodium before discharging said eflluent from the treatremoving treatment by-prod ucts from the medium with said liquid efiiuent. i

28. Process comprising contacting hydrocarbons at least partially liquid under the eiiiuent, separating said by-products from reaction conditions with a treating, medium comprising sodium suspended in liquid hy-' it drocarbon and removing treated hydrocar bon trom the treating medium )artially as vapor and partially as liquid e uent; sepad rating substantiallyall unreacted sodium be- 5 fore discharging said efiluent from the treat-- ing vessel, removing treatment by-products from the treating medium with said liquid said liquid and recycling said liquid through the treating vessel.

24. Process comprising passing hydrocarbons substantially as vapors ntoa treating medium comprising a treating agent suspended in liquid hydrocarbons having a boiling point curve higher than that of the hydrocarbon introduced, continuously condensing a sufiicient portion of introduced hydrocarbon to suspend and remove treatment byproducts with the overflow of said liquid from the treating vessel, and simultaneously and continuously separating substantially all unreacted treating agent from said overflow unreacted alkali metal from said overflow.

26. Process comprising passing hydrocarbons substantially as vapors into a treating medium comprising sodium suspended in liquid hydrocarbon"having a boiling point curve higher than that of the hydrocarbon introduced, condensing a suiiicient portion of said hydrocarbon vapors insaid medium to suspend and remove treatment by-products with overflow of said liquid hydrocarbon from the treating vessel while separating Within the treating vessel substantially all unreacted sodium from said overflow.

27. Process comprising passing hydrocarbons substantially as vapors into a treating medium comprising alkali metal suspended inliquid hydrocarbon under such conditions that a part of the introduced hydrocarbpns leaves the treating medium as vapor and a sufficient part is condensed in the medium to wash contaminating by-products from said alkali metal and by its outflow to remove byproducts at such rate that fouling quantities do not accumulate within said medium.

Process for treating hydrocarbon vapors which comprises subjecting them' to fractional condensation in a treating medium, comprising alkali metal suspended in liquid previously produced by such condensation and washing contaminating by-products from i substantially all unreacted alkali metallicfore discharging said efiiuent. t

30. Process for treating hydrocarbonvapors which comprises subjecting them to fractional condensation and treating them in a treating medium compr sing alkali metal vaporswith a medium suspended in liquid previously produced by such condensation, said medium being maintained at such temperature as to maintainas tl -hq1nd substantially all the condensate pre viously produced, and flowing out a portion of said condensate carrymg treatment by- 7 products after separating therefrom substantiallyall unreacted alkali metal.

Process for treating hydrocarbon vapors which comprises fractionall'y condensing a portion of said hydrocarbons and passing thevapors remaining into a medium formed by suspendin r alkali metal in ahydrocarbon liquid obtained by such fractionation, removing contaminating b'y-products from said alkali metal by agitation with said liquid and discharging by-products suspended in a portion thereof after separating substantially all unreacted alkali metal therefrom. I

32: Process for treating hydrocarbon vapors which comprises passing them in contact with alkali metal suspended'in liquid hydrocarbon maintained at such a tempera ture that a sufiicient fraction of said vapors is condensed in said liquid hydrocarbon, to

from the treatin Niagara and uent and recoverin Signed at Niagara Falls, State of New day of November, A. D. 1927. 1

PAUL JOH CHARL discharge contaminating by-prod'ucts suspended therein at such a rate that fouling amounts do not accumulate within said contacting liquid. ,s v

33. In a process for treating hydrocarbon vapors with alkali metal, the step which comprises removing solid treatment by-products from said alkali metal by means of liquid hy- 'drocarbon, while separating and retaining unreacted metal within the treating vessel and discharging said by-products suspended in an efliuent portion of said liquid.

34. In a process for treating hydrocarbon I vapors with alkali metal, the step which comprises removing solid treatment by-products from said alkali metal by means of liquid hydrocarbon obtained by condensing a portion of said hydrocarbon vapors, while separating and retaining unreac-ted metal within the treating Vessel'and discharging said by-products suspended in an efiluent portion of said liquid.

35, In a process for treating hydrocarbon consisting of alkali metal suspended in liquid hydrocarbon, the step which comprises fractionally condensing a suflicient portion of saidvapors to furg zone after separating substantially allunreacted' sodium from this'ef g treated hydrocarbons. in the county of York, this 19th NSON CARLISLE. as ROBERTS HA'RRIS.