US2202463A

US2202463A - Method of thermolyzing liquids

Info

Publication number: US2202463A
Application number: US448704A
Authority: US
Inventors: Oberle Grace
Original assignee: Individual
Current assignee: Individual
Priority date: 1930-04-30
Filing date: 1930-04-30
Publication date: 1940-05-28
Anticipated expiration: 1957-05-28

Description

May 23, 1940-. OBERLE 2,202,463

METHOD OF THERMOLYZING LIQUIDS Original Filed April 30, 1950 1;, Well as in the vapor phase for the indirect transchamber 4, valve 5 being open and valve 6 closed.

skif I In the known cases in which the heated mercondenser coil through; pressure release valves $150 separate coils and under pressure in a furnace, I9 into the tower 4.and against the baflie plate 20. 1

Patented May 2 1940 i s s 2,202,463

" ,2,202',463'f, r l v METHOD OF Tl-IERMOLYZING LIQUIDS Alfred Oberle, Washingtom l). 0.; Grace OberIe.

administratrix' of the "estate of said .Alfred Oberle, deceased Application April 30, 1930,=:Serial No. 448,704

Renewed August 14, 1935 i p I 28 Claims. ((Jl.196 -'58) This invention relates to a method of thermovaporization, separation: and fractionation take lyzingfluids, liquid substances, oils or substances place, preferably still under elevated pressure, which may be liquefied by heat. although atmospheric pressure or vacuum may v The objects of they invention are to provide a be employed, and from which the volatileip'rodprocess wherein the heat required for the changes ucts, unvaporized residue and the mercury, can-f- I involved in the process are in partprovided-by be removed for further treatment, diverted or transfer from a medium, heated to a very high returned to thesystem as seemsodesirable or temperature, with which the substance comes necessary. into intimate contact, in such a manner as to The, details and advantages of the process will 10 cause the desired changes without danger of bebest understood with theaid'of the diagrams-mt superheating and the consequent excessive undeshown in the drawing.

sirable changes, the conditions of temperature The substance to/be treated is forced into the and pressure being controlled throughout. system by pump l throughp'line 2.v It may be The use of heatedflmercury in the liquid'as preheated in the coil 3 in the vapor space of fer'of. heat to liquids to be distilled or heatedf From coil 3 in the vapor space in the chamber for other purposes is well known, in the prior 1 4 the preheated oilpasses through valve 1 (valve art. It should benoted, however, that in the 18 in auxiliary feed or discharge line 8; being prior art processes the heat is transferred closed) valves 9 and 10, line H, valve l2, pump though the walls of a heatexchanger, only, and. is l3, coil 14, valve 15, line l6, valves 84 and I1 ande not directly transferred as in the .process of this into coil 18 whereit is intimately mixed with application, by the intimate mixture of the heated mercury (and may be further heated exheated mercury with the other component. ternally before it passes into the chamber 4).

Where mercury has been usedfor directheat The mixture of oil and mercuryis then passed transfer to the oil to be treated, the'two liquids through the pressure release valve I9, and im were kept at pressures below atmospheric or else pinges (together with the mercury) on the battle the difference in the temperature of the mercury 'plate '20. Vapors given off in chamber of deand the tool oil used was so great that much heat .;phlegmator, 4 are fractionated in the upper porcarried by the mercury was expended long before tion thereof and the uncondensed vapors leave the temperature of the oil reached a point high by line 21 equipped with pressure valve 2|, and-.

enough for the desired changes, and thus the are cooled in coil 22 of condenser 23.

quantity of mercury was of necessity very large. The condensate formed heremay be returned The initial heating of the oil by ordinary means, to the system throughvalve 24 and line 25.

prior. to the mixing is proposed in this applica- Uncondensed vapors and, if desired, the (modem tion. o sate together with uncondensed vapors leave the 1 cury vapor was mixed with hotoil vapors, con-, .26 and 26' and may be withdrawn for further trol of the temperature and pressurejof ithe oiltreatment through valve 26, or returned to Y and mercury vapors, during theheat exchange chamber- 4, by means of lines and -41 and was not provided for. Due to, the-fact that -in valves48 and 46 bymeans of a pump not show-m the process disclosed here, the oil and mercury Mercury enters the system by line 21 through are heated under pressure prior to mixing and valve 28, charging pump 29, line 30, high'presare still under pressure when mixed in a tube sure pump 3|, line 32, and is heated in coil 33, which may .receive'additional external heat, the passes through pressure'release valve'34' into thev 21:3 temperature of the mixture as well as the duraenlarged (thermolyzing') coil 18, and mixes inn 5 tionof the contact and the velocity of the flow mately with the oil which enters this coil, at a of the mixture may be controlled. point at or near valve 34 and at such an; angle In the process here disclosed-the oil or other as to insure proper mixing. From coil .18, as fluid substance and the mercury are heated in' above stated, the mixture passes through valve combined in a thermolyzing tube, still under Unvaporized oil and the condensed mercury pressure, though reduced, in such a manner as settle to the bottom of the chamber 4 in two to insure intimate mixing and efiicient heat layers. Any excess of the hot jmercury layer 35 transfer, passed into -a reaction chamber or below, may be continuously withdrawn through 1:55 vaporizer where changes are continued and line 36,-valve 31, to be returned to the beatings 'and valve 57 (valve 58 closed). pumped through coil 33 by means of pump 29,

system by pump 3|. The residue which collects on the top of the mercury pool in the bottom of the tower 4 is withdrawn through line 38, and may be discharged into the flashing chamber 39 through pressure release valve 40, or may be withdrawn through valve 4|, pipe 42. Gauge 43 indicates the mercury level in pool 35 (or chamber 4). Vapors given ofi from the residue in tank 39 are withdrawn through valve 44 in line 45, and may be combined with the vapors passing through valve 26 or they may be returned. to the chamber 4 through valve 46, line 41, or they may be withdrawn from the system through valve 26". The residue formed in tank 39, is solid, can be removed through manhole 49. Tank 39 is provided with a gauge glass 50. Line 5| serves to introduce steam into the bottom of chamber 4 through valve 53. The residue collected in the bottom of tank 39 may be diverted from the system through line 54, valve 55, connection 56, Or it may be with valves 55 and 58 open and valves 61 and 28 closed.

The condensed oil or any mercury carried over into the vapor line 2! may be returned to the chamber through valve 24, line 35, valve 59 and line 6.3. The condensate formed in the coil .22 maybe returned to the upper part of the dephlegmator through line 5!, valve 62, pump 62', line 63 and anyone or more of the valves 54, Gila, 6th, Me, or it may be returned to the heating system through line 93, valve 63'', and line H. Provision is also made to return the corn densate from coil 22 into the bottom of chamber 4, 'forcing it through the mercury 35 by means of pump 69 in line 6|, then valves 98 and ill. In order to control the fractionation in chamber 3, provision is made for the introduction of cool or preheated charging stock into the dephlegmator through line '51, valve 12. Two auxiliary pumps "13 and 14 are provided in

lines

13 and 13.

For the introduction of cold or preheated charging stock into coil 59, line 15, valve 16, line 18 and valve 59 can serve. An extra amount of oil (simultaneously with the charge entering through line 2) may be introduced through line 8 by means of pump l. The pump 1 will furnish the pressure necessary to force the charging stock through valve 15, lines "i5 and iii and valve 79 to enter the thermolyzer l3 together with hot oil from coil is, through pressure reduction valve ll. By means of valve 86 in bypass 88, oil may be diverted from the system, or introduced by suitable'connections. Hot oil may be diverted from the heating coil I4 through valve 19 or by-pass8ll and reintroduced into the heating system through line 85 and valve 15 thus reentering line H, or it may be introduced into the dephlegmator 4 through by-pass (not shown in the diagram) connecting lines l5 and F! (with a valve interposed).

Provision is also made for the introduction of the heated oil and the heated mercury through separate line 32, valve 83, and coil i8, and valve l9, respectively, into-the vaporizer a (valve 84 being closed). By means of valve 85 in line ll, it is possible to send the entire charging stock, or part of it, together with the mercury, through coil 33. Valve 86 is in a line connecting coil 33 with lines '38 and F5.

The charging stock or oil from coil E4,,after entering the dephlegmator 4 by line H and being stripped therein, together withithe reflux, may

pool of hot liquid be returned to the charging line H by means of line 73, pump 13" and valve 14.

Line 32 represents a by-pass by which mercury can be sent into heating coil 14 instead of 33, so that use of the coils is reversed. To do this, valves 30 and 12 must be closed and 39" and B5 opened to admit the charging stock to line 32 and coil 33 through pump 3|.

The pumps may be of any conventional type and supplied with by-passes for the reversal of the direction of the flow of oil in the lines to which they are connected, or the by passes may serve to eliminate the pumps entirely or termporarily.

The drawing is only diagrammatic and the dimensions of the various parts may be altered, especially those of. the heating and thermolyzlng coils. Pyrometers, pressure gauges, and various devices for control and safety may be introduced as and wherever desired.

. The underlying principles of the invention can be further explained to advantage byway of an example illustrating one practical embodiment of the process and of apparatus suitable for carrying it into effect.

In a typical operation, the oil to be thermolyzed is charged intothe system by pump 1,

through line 2, valve 5, preheating coil 3, valve 1 (with valves 9 and 8 closed) through valves 9 and I9 (valve's'lZ and 16 closed), line H,.valve l2, (with valve 85 closed), high pressure pump l3,

heating coil l4, valve i5, (valve 83 closed), line i6, valve 84, (valves '19 and ti closed), and pressure reducing valve l'i. Here the heated oil enters the thermolyzing coil 8 at an angle, and

imparts a centrifugal or turbulent motion to the mixture which it forms with the mercury which also enters the thermolyzing coil. The mercury is charged intothe system on the suction side of charging pump 29 through line 21 and valve 28. It passes through line 30, valve 39 and is forced through line 32 by high pressure pump 31 and into heating coil 33 in which it is heated to its maximum desired temperature. It-thenpasses through pressure reducing valve 34 into the .thermolyzing coil 18, which is preferably of largcoil i8 is located. It is possible to keep the coil 18 at such atemperature that practically no heat transfer between the mixture in the coil and the line gas takes place, or the temperature in this part of the furnace may be adjusted so that a slight. heat exchange in favor of thermolyzing coil 18 may take place or vice versa. This ieature of regulating the temperature at which the thermolyzing coil is kept, somewhat independently of the temperature of the mixture of the oil .and mercury entering therein, is important.

Any desired pressure may be maintained on the oil in heating coil M as well as inthe connecting lines 16, by means of the high pressure pump l3 and valve l7. Any desired high pres: sure, independent of the pressure maintained on the oil in coil l4, may be maintained on the mercury in heating coil 33.. This pressure on the oil,

' as well as on the mercury, is reduced at, or near the point where these-two-liquids are discharged;

vturnedtothe charging stock in line I I by means or. sprayed tangentially into the common thermolyzing tube l'8. By means of the pressureireduction valve l9, a pressure may be maintained in the, thermolyzing coil, notwithstanding the fact that a pressure drop of..300 lb. per square inch mayhave takenplace where the twoliquids entered the thermolyzing tube. Through this pressure reductionvalve IS, the oil andmercury mixture (substantially in the form of a mist) enters expansion or vaporization chamber 4.

. Near the. point where the mercury and oil mixture enters chamber 4, a baffle plate is so arranged that it gives the mixture a rotatingmotion, thus'aiding in the separation of the various constituents.

1 well as the non vaporizedparts of the oil will "settle to the bottom of this chamber 4 where the mercury forms pool 35 over which the non-vaporized parts of the oil Will collect in fluid form'to' be continuously or intermittently withdrawn" from the system through line 38. Gauge glass 43 serves to'indicate" the level of the mercury pool 35. Any loss of mercury in the system may be made up by the introduction of equivalent quantities through line 21, connected ,to a source of mercury supply, valve 28 and charging pump 29, which is otherwise usually idle during the run after the necessary amount of mercury has been introduced into the system.

The volatile parts which separate in the tower 4 are fractionated inthe upper part of this tower which may contain any fractionating or rectifying device as bubble plates, perforated bafiies or the like for intimately contacting liquids or vapors. The temperature in the upper part of the vaporizer 4 can be regulated by means of the amount of cool charging stock allowed to flow through coil 3 which in turn can be controlled by manipulation of valves 5, 5,1 and 8. By means of linell and valve'lZ, cold or preheated charging stock may also be admitted into the upper part of chamber 4 whichacts as a fractionator or dephlegmator.

Provision is made for the withdrawal of the reflux condensate from the 'tower'at different heights through lines 13 and 13' which lines may be provided with auxiliary pumps 13" and 14' andvalves l4 and 14. This condensate to gether with any unvaporized charge-introduced through line H may be returned to the charg ing stock in line II. The uncondensed vapors leave chamber 4 through pressure reduction valve 2|, line 2| and pass into a [condensing coil 22 in cooler 23. In this coil, any mercury which may have been carried over will be condensed andreturned by gravity through valve 24 into,

line 25 to chamberd,

through valve 591and line 60.

The condensate formed in the cooling coil 22 may be returned to the upper part of chamber 4 by means of line 6!, valve 62, pump 52', line 63, and Valves 64, 64a, 84b, and 64c, or to the I bottom of chamber il by means of valve 68, line 6|, pump 69 and valve HL'and be forced through the heated mercury pool to be reboiled, the

volatile parts escaping to be refractionated while the heavier constituents will mix with the reflux.

and residue which has collected on the top of the mercury pool 35, to be withdrawn therefrom The condensate from coil 22 may also bere- The condensed mercury as-'- lowing:

of line 63' and valve63". These vapors from flashing chamber 39 may be returned wholly or partially to chamber 4 or combined with the va-.

pors and condensate passing-through valve 26, to be withdrawn through valve 26' for further cooling or treating, or they may be withdrawn through valve 25". Any mercury flowing over into the flashing drum 39 and also the residue may be returned to the system by line 54, valves and 58 (valves 5'! closed). I

' Depending on the character of the oil and the mode of operation it may be desirable to have the level ofthe mercury pool 35 so high that enough not mercury fiOWs over into the flashing' drum 39 together'with the residue, to form a pool-of hot mercury in the bottom of thistank also, the level of the mercury here being controlled by line 54, valve 55, and either valve 5'! or 58 in line 56 by means of which it may be withdrawn from or reintroduced into the system. This hot mercury pool in the flasher will aid in vaporization cfthe oil, especially if steam also is injected through the mercury, and also in preventing the residue fromclogging the flasher.

The residue from-the flashing drum 39 may be withdrawn from the system together with any mercury present b'y'means of line 54 and valves may beremoved through manat any desired value,.above, at, or below atmospheric. s

Pressure reducing valve 2| is used principally for regulation of pressures above atmospheric, valve26 for atmospheric. For pressures below atmospheric;

valve

26 or 26", or both,vare used connected to a source of.,vacuum.

The chief features of the process are the fol- The charge oil' is thermolyzed by a very brief contact with the hot mercury. The thermolyzing tube is kept at such a temperature that heat loss therefrom is I of the hot oil is brought into intimate contact with atomized, highly heated mercury in such a manner that every molecule ofthe walls of the tube to cause skin cracking, cok- -f0re they are atomized into the thermolyzing oil.

The return of the hot mercury to the system from the bottom of the chamber 4 is an economy in heat. r

If the oil and'mercury mixture entering the vaporizer is too hot; it may be cooled by admit.- ting oil from line 'BZthrough valve 83 which will, be mixed with the oil and mercury mix; ture as it impinges upon the baffle plate 20.

Due tothe fact that: the mercury is nonein flammable and non-combustible, there isa great reductionofflre and explosion hazard. The mer-I cury has a catalyticieffect on oil. Other features are the reheating and purifying of the re flux condensate by, passing it through the pool oihot mercury in the bottom of the vaporizer 4.

Further details of the apparatus and special modifications thereof are as follows:

As the chief purpose of the furnace is the heating of the mercury and the amount of the mercury is so small in comparison with that of the oil treated, the tubes can be small, and the furnace itself can be relatively small, and needs no special construction such as is necessary when cracking of oil is accomplished by the transfer of heat from the furnace through the walls of cracking tubes.

The mercury is heated in the hottest part of the furnace. The coils for heating the oil nearly to cracking temperature may be placed in a cooler part of the furnace.

As the thermolyzing coil needs only slight heating, ii any, it can be placed in the flue nearest where the flue gases leave the furnace. Although the direction of flow of oil in the thermolyzer is preferably from top to bottom, it might be desirable the direction be reversed. To do this, slight alterations in the connections of the mercury and oil coils with the thermolyzing coil would be necessary. In addition to the control of temperature in the thermolyzer by dampers in the flue, temperature of the oil and mercury from the coils, pressure alterations and so forth, further regulation of temperature can be accom-- plished by the introduction of cool oil into the system near the pressure reduction valve by means of valves 86 or 19.

Due to the high velocity with which the intimate mixture of the two liquids is passed through the thermolyzing tube, it is possible to use mercury heated to a very high temperature before it enters the thermolyzing tube thus insuring very effective, although brief, contact of the highly heated mercury particles with the oil to be treated before they are expanded in the vaporizing chainber.

There is flexibility in the operation due to the fact that the heat stored in the mercury is made available in parts of the system, entirely outside of the furnace. This allows for an exceptionally fine control of conditions of temperature, pressure and time for the reactions.

At the point where the oil and mercury mixture enters the vaporizing chamber, a baflie plate or other device is so arranged as to give the mixture whirling motion downward, as well as upward, which will aid in the separation of the light oil from. the heavy oil and mercury. Provision is made in the upper part of the vaporizer to fractionate the vapors by means of well-known balile plates or similar fractionating equipment. Provision is also made for the condensation,-separation, and return of the mercury carried by the oil into the upper part of the vaporizer.

The temperature of the vaporizer can be controlled by the introduction of cold or preheated charging stock, reflux condensate, or condensate with steam, either wet or superheated, into the chamber as well as by indirect contact with the charging stock in preheating coil 3.

Hot oil from coil i l, together with charging stock, can be introduced into the chamber through line it,

valves

84 and 19, line 15 and by-pass (not shown) around valves 16 and T2 (or through valves it and T2) into line "ll, and then be returned to the heating system through line 3.

auxiliary pump l3, valve Hi and line H. The injection of steam from line 5i through valve 53. mercury pool 35, and the residue above the mercury also aids in thevaporization and separation.

Also, if desired, the hot mercury and hot oil may be sent from the coils into chamber a without first combining them in the thermolyzing coil, that is, the oil can go directly from heating coil i4 through valves I5 and 83, with valve 8% closed, and the mercury pass through the thermolyzing coil and enter the chamber through valve i9. The bafiie plate or other appropriate device serves to aid the mixing of the vapors and to give the desired whirling motion in the chamber.

The use of mercury in this process and apparatus has many advantages, among which are: It is technically possible to heat it to a very high temperature; it gives up its heat very rapidly,

especially if atomized or vaporized, because of the.

intimate contact that it can make with the oil, without however, being soluble therein; both skin cracking and supcrheating of the oil are avoided; the amount of mercury and the temperature to which it must be raised are readily determined and controlled; also, because of its liquid state and its high specific gravity, it can be readily fed and transported with the aid of appropriate reservoirs and pumps; it separates from the oil and residue very readily, and (because of its heated. condition) aids in keeping the collecting oil resi-,

due in the chamber fluid, and in vaporizing the more volatile constituents.

Furthermore, its use is economical, because it can so conveniently be raised to the maximum temperature desirable in oil treatment, the amount needed is not large, its recovery is practically complete, and it can be returned to the system at a relatively high temperature; due to its specific gravity, it aids in causing turbulence and prevents clogging.

By careful manipulation of the pressures after the mercury leaves the heating coil 33 at its maximum temperature and pressure, it is possible to have a pressure in the thermolyzing coil i8 such that an appreciable amountof the mercury which tends to vaporize on entering therein, (due to pressure reduction), will give up its heat of vaporization to the oil and be again chiefly liquid as it reaches the pressure release valve is to enter the expansion chamber 4. With the c decrease on entering the chamber, it will again tend to become vapor but with a lower temperature. There will then be the same phenomenon as already described in the thermolyzing coil. Appreciable heat will be transferred from the mercury to the oil at a temperature hi h enough to permit continued reaction and, at the same time, a high degree of vaporization of the oil. The heat remaining in the liquefied mercury which collects in the pool is partially spent in vaporization of the residue in the ell-amber or later in the flashing chamber 39, and partially reserved in the mercury which is returned in a still heated condition to coil 33 to be used over again.

It is readily apparent that the process, described above with its various suggested modifications, may be applied to various kinds of crude oil, residues, hydrocarbon oils, carbonaceous material containing hydrocarbons, and other substances which are fluid at ordinary temperatures or readily liquefied by the application of heat, in cases where controlled heating followed by the vapor ization of some of the products is desired.

Instead of using mercury as a heat transfer media, an alloy with a very low melting point such as, for example, Rose or Wood metal may be used. It is also understood that instead of mercury, a mercury amalgam which is liquid at temperatures such employed in this process may be used.

In order to start up the process when a low uid mercury heatedunder pressure to atem- I perature high enough to bring the mixture of hydrocarbons and mercury to conditions sufiicient'to convert the hydrocarbons, passing the mixture through a thermolyzing zone in .a stream of restricted cross-sectional area, introducing the mixture into a zone of reduced pressure,..distilling off the hydrocarbon vapors and collecting the mercury in a pool, withdrawing volatile, liquid and solid material for further treatment.

2. A method of converting hydrocarbons comprising intermingling the hydrocarbons with liquid mercury heated under pressure to a temperature high enough to bring the mixture of hydrocarbons and mercury to conditions sufficient to convert the hydrocarbons, passing the mixture through a thermolyzing zone where primary cracking takes place, in a stream of restricted cross-sectional area introducing the mixture into a zone of ,reducedpressure,where secondary cracking takes place, distilling off the hydrocarbon vapors, condensing the, vapors, collecting the mercury in a pool and reintroducing the condensate or pressure distillate into the zone by injecting the same into the pool of highly heated mercury, withdrawing volatile, liquids and solids for further treatment. 3. A method of converting hydrocarbons, comprising intermingling the'hydrocarbons heated.

to a temperature just below the point of decomposition with a metallic liquid heated to a temperature high enough to bring the mixture of hydrocarbons and liquid metal to conditions suf-' ficient to convert the hydrocarbons, forcing the mixture thru 'a thermolyzing zone in a stream of restricted cross sectional area under conditions of high velocity and turbulence to bring about conversion without appreciable carbon formation, introducing the mixture into azone of reduced pressure, distillingoff the volatile hydrocarbons, collecting the unvaporized and condensed material in a pool and withdrawing volatiles, liquids and solids for further treatment.

4; A method of thermolyzing hydrocarbons,

comprising heating the hydrocarbons close to a temperature at which thermal decomposition of the higher boiling constituents would occur at atmospheric pressure, heating mercury to a higher temperature and forcing said heated by- 5. Amethod of converting hydrocarbons, comprising heating the hydrocarbons close to the limit of molecular stability of the higher boiling point constituents, mixing said hydrocarbons with a metallic liquid, heated under superatmospheric pressure to a temperature above that of the aforementioned hydrocarbons substantially in the liquid phase, passing the mixture thru a thermolyzing coil in an elongated stream of restricted cross sectional area under conditions of velocity, turbulence and temperature to bring about conversion of the hydrocarbons without substantial carbon formation, expanding the mixture into afractionator, withdrawing vapors and gases, collecting the unvaporized and condensed hydrocarbon and metallic material in a pool, removing the unvaporized and condensed hydrocarbons from the surface of the pool, flashing same into a separatechamber, injecting steam into said chamber and withdrawing the volatile,

liquid and solid material from the system;

' 6. A-method of convertinghydrocarbons,comprising intermingling. the-hydrocarbons with a metallic liquid heated under pressure to a temperature high enough to bring the mixture of ized and condensed hydrocarbons in a pool and flashing said unvaporized and condensed hydrocarbons collecting on" the surface of the highly heated liquid metal intoa separate chamber and withdrawing volatiles,liquids and solids from the system.

'7. A method of converting hydrocarbons, comprising intermingling the hydrocarbons with liquid mercury heated under pressure to a temperature highenough to bringthe mixture of hydro carbons and mercury to conditions sufiicient to convert the hydrocarbons. passing the mixture thru a thermolyzing zone in a stream of restricted cross sectional area,introducing themixtureinto a zone of subatmospheric pressure, distilling oifthe hydrocarbon vapors and collecting the mercury in a pool, withdrawing volatile, liquid and solid material.

-8. A method of thermolyzing hydrocarbons, comprising heating under pressure, a continuously advancing stream of liquid metal to a tem perature above the cracking temperature of hy drocarbons heated to a lesser degree introducing these two streams of heated metal and hydrocarbonssubstantially in the liquid phase into a thermolyzing zone of restricted cross sectional area, advancing this'stream of oil and metal in a rotating motion thru the thermolyzing zone and introducing same into anexpansion chamb'er under pressure reduction, distilling off and removing thevapors and collecting the liquid metal and residual and condensed hydrocarbons in a pool in the bottom part of the expansion chamber, withdrawing part of the highly heated metal and the residual hydrocarbons from the aforementioned pool-"and flashing the same into a separate chamber under a pressure sufii'ciently low to bringabout copious evaporation of the hydrocarbons in presence of the highly heated I metal and over a pool of highly heated metal and withdrawing volatiles, liquids and solids.

=9. A method of converting hydrocarbons ac-' cording to claim 1, further characterized in that the oil is thermolyzed under reduced pressure by means of heated mercury, at a reduced pressure while passing substantially in liquid phase into the zone of reduced pressure, in distilling off and fraetionating the vapors and collecting residual hydrocarbons, liquid mercury and condensed material in a pool, flashing the residum hydrocarbons and condensate and part of the highly heated mercury into a separate chamber under a pressure suificiently low to bring about copious vaporization of the hydrocarbons, introducing steam into the pool in the base of the fractionator as well as into the flashing chamber and with drawing volatiles, liquids and solids from the system.

10. A method of converting hydrocarbons according to claim 5, further characterized in that the vapors removed from the fractionator under pressure are condensed under reduced pressure and part or all of the condensate is returned to the fractionator by forcing it thru the pool of highly heated metallic liquid and residual and condensed hydrocarbons and the residue in the flasher is Withdrawn for further treatment.

11. A method of converting hydrocarbons according to claim 3, further characterized in that the volatile hydrocarbons distilled ch in the zone of reduced pressure undergo dephlegmation in the upper part of this zone, the uncondensed vapors being removed under reduced pressure and condensed and part of the condensate is re turned to the dephlegmating zone while part of the condensate is returned to the zone of reduced pressure by forcing it thru the pool of metallic liquid in the base of the zone of reduced pres sure.

12. A method of converting hydrocarbons according to claim 1, further characterized in that part of the hydrocarbons to be treated are introduced into the top of the zone of reduced pressure before coming into contact with the heated mercury, flowing countercurrent to the ascending vapors and contacting with the heated mercury and residual hydrocarbons.

13. A method of thermolyzing hydrocarbons according to claim 4, further characterized in that the uncondensed vapors from the expansion chamber are condensed under reduced pressure mt still above atmospheric pressure and part of this condensate is forced back into the fractionator under increased pressure mingling in the top of the fractionator with part of the untreated charging stock to be withdrawn from the fractionator together with reflux-condensate and forced back into the charging stock, in order to be rethermolyzed.

14. A method of thermolyzing hydrocarbons according to claim 4, further characterized in that the heated mercury and the oil each enter the thermolyzing zone under pressure reduction, impinging upon each other at such an angle that the mixture is given a forward rotating motion whereby the mercury and oil are churned and intimately mixed, toavoid skin-cracking and carbon formation, whence the stream of this mixture enters the expansion chamber, under further reduction of pressure, at or near the point where part of the oil from the charging stock enters the expansion chamber under pressure reduction, both streams impinging on a baflie plate in the expansion chamber, whereby the thermolyzed oil is mixed with the cooler oil at the time when expansion occurs.

15. A method of thermolyzing hydrocarbons according to claim 4, further characterized in that the uncondensed fractionated vapors are withdrawn from. the expansion chamber and condensed under reduced pressure, and part of the condensate is forced back into the charging stock for retreatment and another part of the condensate is forced thru the pool in the base of the expansion chamber, while steam is simultaneously forced thru the aforementioned pool.

16. A method of converting hydrocarbons according to claim 1, further characterized in that part of the hydrocarbons to be treated are introduced into the top of the zone of reduced pressure before coming into contact with the heated mercury, flowing countercurrent to the ascending vapors and contacting with the heated mercury and residual hydrocarbons, reflux condensate is withdrawn from the top of the dephlegmator at a point above that where the split feed is introduced, and returned to the charging stock for further treatment.

17. A method of thermolyzing hydrocarbons according to claim 4, further characterized in that the uncondensed fractionated vapors are withdrawn from the expansion chamber and condensed under reduced pressure and part or all of the condensate is forced back into the charging stock for retreatment.

18. A method for converting hydrocarbons according to claim 1, further characterized in that the vapors and gases are removed from the zone of reduced pressure for further treatment; the mercury and unvaporized cracked residue is collected in a pool into which superheated steam is introduced to contact and mix with the highlyheated mercury and cracked residue; the residue and part of the hot mercury are flashed together 7 into a flasher kept under a subatmospheric pres of the zone of reduced pressure, whence it flows,

countercurrently to and in intimate contact with the ascending vapors, into a pool of residual, feed and condensed hydrocarbons, collecting over a pool of highly-heated mercury, forcing pressure distillate thru the pool of highly-heated mercury and into the overlying pool of liquid hydrocarbons, continuously withdrawing residual hydrocarbons from the surface of the mercury pool for further treatment, continuously removing vapors and gases from the zone of reduced pressure for further treatment.

20. A method of converting hydrocarbons according to claim 5, further characterized in that the vapors removed from the fractionator are condensed under pressure in open communication with the fractionator.

21. A process for cracking oil which comprises intimately mixing oil and heated molten metal in a confined stream, maintaining said mixture in said confined stream to cause cracking of said oil, separating oil vapor from said metal and residual carbonaceous matter from said oil in a separating zone, reheating said separated molten metal, returning said reheated molten metal to 26. An apparatus for crackingoil which com-,

said confined stream, withdrawing a portion of said molten'metal and carbonaceous matter from said separating zone, treating said withdrawn molten metal and said residual carbonaceous matter in a treatment zone and returning said molten metal to said separating zone. g

22. An apparatus for cracking oil which comprises means for heating oil under pressure,

means for expanding said oil, means for intimate-.

1y mixing said oil with hot molten metal to crack said oil, means for separating said hot molten metal from said cracked oil, means for reheating said separated molten metal, and means for'returning said reheated molten metal to saidmix ing means.

23. A process for'cracking oil which comprises heating oil under pressure, expanding said heated oil, intimately mixing said oil with hot molten metal to crack said oil, separating said hot molten metal from said cracked oil, reheating said separated molten metal, and returning said reheated molten metal to the cracking cone.

24. An apparatus for cracking oil which comprises means for heating oil' under pressure, means for releasingthe pressure on said heated oil, means for intimately mixing said pressure,

released oil with hot molten metal to effect cracking of said oil, means for separating said hot molten metal from said cracked oil, means for reheating said separated molten metal, and means for effecting a cyclic circulation of said molten metal through said mixing, separating and reheating means. I v

25. An apparatus for cracking oil'which comprises means for heating oil under pressure,

means for releasing the pressure on said heated oil, means for mixing said oil with hot molten metal to crack said oil, means for separating said molten metal from said crackedoil, means for reheating said molten metal, and means for eifecting a cyclic circulation of said molten metal through said mixing, separating and reheating means.

prises means for intimately mixing oil with hot molten metal in a confined stream to crack oil,

means for separating said hot molten metal and residual carbonaceous matter from said cracked oil, means for reheating said separated molten metal, means for returning said reheated molten metal to said mixing means, means for withdraw-' ing a portion of said molten'metal and residual carbonaceous matter from said separating means,

- means for treating said withdrawn molten metal and said residual carbonaceous matter, and means for returning said treated molten metal to said separating means. I

27. An apparatus for cracking oil which comprises means forintimately mixing oil with hot molten metal at a temperature sufiicient to crack said oil, means for separating said hot molten metal and residual carbonaceous matter from said cracked oil, means for reheating said separated molten metal, means for returning said reheated molten metal to the mixing means, means for withdrawing a portion of said molten metal and residual carbonaceous matter from means for withdrawing a portion of said molten metal and carbonaceous matter from said separating means, means for treating said carbonaceous matter and molten metal, means for reheating-said treated molten metal, and means for returning said reheated molten metal to. said cracking coil.

ALFRED OBERLE.