US1577871A - Process of continuous catalytic distillation - Google Patents

Description

' March 23 ,1926.

G. L. PRICHARD ET An.

PROCESS oF CONTINUOUS GATALYTIQ DISTILLATION Filed Feb. 14, 1922 5 Sheets-Sheet 1 mi.' @Hon/wg March .z3-,1926. 1,577,871

G. L. PRICHARD ET AL PROCESS OF CONTINUOUS CATALYTIC DISTILLATION Filed Feb. 14, 1922 3 Sheets-Sheet 2 March 23 14926. 1,577,871

G. l.. PRICHARD ET AL PRocEss 0F CONTINOUS GATALYTIC DISTI'LLATION Filed Feb. 14, 1922 s sheets-shi s Patented Mar.'23, 1926.

, l UNITED STATES PATENT OFFICE..

GEORGE L. PRICHARID AND HERBERT HENDERSON, rOIF PORT -ARTHUR,' TEXAS, AS- SIGNOBS T GULF BEFINING COMPANY, 0F PITTSBURGH, PENNSYLVANIA, A COR- PORATION 0F TEXAS. 4

rnocnss or CONTINUOUS CATALYTIC DISTILEATION.

Application led February 14, 1922. Serial No. 536,503.

To all whom t may concern:

-Be it known that we, GEoRcE L. PRICHARD and HERBERT HENDERSON, citizens of the` United States, and residents of Port Arthur, in the county of Jeierson and State of Texas, have invented certain new and useful Improvements in -Processes of Continuo-us Catalytic Distillation, of which the l following is a specification. 1U This invention relates to processes of oo ntinuous catalytic distillation and it comprises distilling higher boiling hydrocarbons such as gas oil and the like-in the presence of a catalytic chemical such as. anhydrous aluminum chlorid advantageously at progressively rising temperatures and under certain conditions ensuring the maximum yield of lower boiling hydrocarbons with a maximum utilization of heat units and with 2 0 economy in time; all as more fullyA hereinafter set forth and as claimed.

In the Adistillation of higher boiling hydrocarbons withI catalytic chemicals, such as aluminum'chlorid, the aluminum chlorid is mixed with a higher boiling oil and the mixture is brought to distillation temperature',-

-usually in the case of gas oil, to a temperature around 500. to 550 F. In practice, the vapors from the stills are allowed 'to 30. pass to o ne or more air or other cooled con 'densers which serve not'only to condense the higher boiling oils vaporized, but also the.

aluminum chlorid and the aluminum chlorid combinations with the oil. The condensates in the condensers are usually backtrapp'ed to the still, from which they come andthe vapors of lower boiling oils,.such as gasoline, 'are allowed to.flow fromthe. air cooled condensers 'to nal or water cooled l .40 condensers and thence tofstock.. At temperatures not substantially 'above 350 1 the aluminum chlorid and: its combinations 'with higher. boiling oils' condense and thus'can be back-trapped to lthe stills, while the-vapors of lower boiling hydrocarbons lmostly of. the

.its

' natureof gasoline, will not condense at such temperature and therefore How onward to the final orthe water-cooled condensers.

the yvapors reaching the preliminary or air'- cooled condensers 1n distillation :processes We havefound in actual operation, .thatv lower boiling oils,f which are'condensed and-65 returned. In other words, the back-trapping of the aluminum chlorid and its hydrocarbon compounds under the conditions noted, also results in back-trapping to the stills, lower boiling hydrocarbons, very much like gasoline, and such as kerosene and thelike. Inbeing vback-trapped, the lower vboiling hydrocarbons must necessarily be again heated, since they have undergone cooling and condensation in the preliminary condensers, 65. and this. is disadvantageous because there is a tendency foraluminum chlorid to perform what we call the reverse action, and convert lower boiling hydrocarbons into higher boiling hydrocarbons.' Aluminum chlorid 7U has the power not only of building up,` but of breaking down hydrocarbons.

Among other objects of our invention is the provision of ways and means for utilization of lower temperatures (with consequent less resultant deterioratlon of the aluminum chlorid) i"and consumption of less heatunits than is pdssible by -hitherto 'known processes; and the provision of a distillation system whereby all the aluminum chlorid is utilized for thebreaking down reaction rather than the building reaction, and whereby products with narrow range between their initial and end boiling points maybe easily Figure 1 is a. segmental view partly'in section and partly/in elevation ofour. distil.

` lation plant;

` Figure 2 is adiagrammatic-view showing the dlerent vapor llnes, condensers, etc.; M

- and Figure 3 is a top plan view of the diagrammatic showing of Figure 2;

Fig.' 4e is a, diagrammatic View, partly in section showing twoadjac'ent stills. 1.00 Referring to vthe 4drawings and vpartcularly Figure 1, we .have shown a plurality of `lstills lettered A to I inclusive, stills D,

E, G and H. being omitted for clarity of presentation.A The diagrammatic viewsA of 10i 'Figures 2 and.3 show', all thestills; Each still comprises the tank ljhaving the con ical shaped. .bottom or sump 2,- anlan lntenor draft tube 3, provided with theenclosed shaft Il, havingthe propeller 5' at the lower' the pinion 8 on shaft 9 driven from a source of power (not shown). Since aluminum chlorid tends to settle and form'- an under-l '.lying layerunder the body of oil undergoing distillation, this stirring means is particularly advantageous. The apparatus described results in a circulation upwardly in the tubev and downwardly around the outsidethereof. The conical shaped bottom or sump 2 provides a settling basin for the. exhausted or partially exhausted sludge of oil .and aluminum chlorid which may be withdrawn continuously or from time to time as the exigencies of any particular case demand.

In the embodiment shown, the higher boiling oil is .heated in the tubular boiler like arrangement 10, mounted in the furnace 11, provided with the oil or oil and gas burner 12 and is setvby means of pump 13 through line 14 to the still, preferably, to a point near the bottom thereof -by lpipe 15 extending toward the lowerv end of the Still.v The higher boiling oil in admixture with aluminum chlorid is removed .from the still by line 16 and sent tol the heater 10 by means yof the pump 13. This provides for a continuous circulation of the oil and mixture in the still l and not only assists in the stirring but is `particularly advantageous in preventing localized heating of the still kwith consequent baking on of aluminum lchlorid and coky residue(v The circulating system is not specificallyy herein claimed, it forming part of our application, Serial No.

`516,596, filed'. November 21, 1921, matured into Patent No.l 1,476,219.

'i 17.leading to the trap 18, which comprisesv Each still is provided with the vapor line a sleeve or envelope sealed at both ends with the` vapor line terminati-ng short of the far end. Condensates in thistrap 'flow by line 19 either to still B or to another point of disposition and use through the line 20, the valve on line21 leading to still B being open andthe valve on line 2() being closed in the first instance, and vice versa. `This condensate from the trap 18 will contain relatively large.' quantities of aluminum chlorid and .aluminum lchlorid hydro-r Vcarbon compounds, together with some relatively lower boiling oils and higher boiling oils.

The condensate taken from line' 2O may be filtered through ordinary filtering apparatus such as the tank '2OA containing filtering material and having outlet 20B for y filtered oil, outlet 2OC for aluminum chlorid and closure v'20D for placing and removing the ltering medium. The aluminum chlorid thus recovered is sent to any one of I disposition.

another still. The trap 18 is provided With thermometer 22 for observation of temperature. Leading from the trap 18 is the' vapor line 23 terminating in an air cooled condenser of special design. This condenser 23 is annular in cross section and isprovi'ded with the preferably central flue or air space 24 for the purposes of insuring maximum cooling surfaces. `The vapors from line 23 pass in the annular space against the spiral.`

bale 25 and thence out of the vapor line 2.6 to final or water cooledv condensers (not slhown). Condensates in the air cooled conens the still B. through line 28 or to other points of use through line 29, the valve on these two I astmentioned lines being adjusted depending upon the disposition of such con-V densates. The aluminum chlorid may be fed into still A through the line 30 or 30',l

and this is best done by heating oil and aluminum chlorid and pumping it through saidv line, or the mixture of oil and aluminum chloiid may be admitted to the line 16 through line 31 and sent to the furnace 10.`

.The other stills in the series are similar in construction to the still described and are described dow by line 27either to ing device illustrated. Of course, any other hea-ting device or any other process of heati 'ing may be employed. It vis advantageous to provide thermometers 32 for each of the air cooled condensers.

From the apparatus and operation described,it will be noted -that the condensate from the trap 18 goes either' to the next succeeding still or 'may be removed for other Howevemwhen a plurality of stills are used, at some point in the system, it is advantageous to send this vheavy condensate to a still.y further alon in the system. This may be accomplished t rough the con-- struction lshown beginning at still F. The line 19, leading. from the trap 18, may be .provided wit-ha branch 33 tapping into any one of the succeeding stills and the line 27 from the preliminary air cooled condensers may be provided'with a line 341v leading to.

anyv one of the succeeding stills. For purposes of illustration, we haveshown these lines 33 and 34: leading to thelast still I in series, but it is to be understood that they may lead to any one of a number of stills between F and I. Thisl construction may be used for all of the stills.

The last still in the series, represented by I, may. be provided with return back- trap lines 35 and 36 leading respectively from the trap 18 and the L.ir cooled condenser 23; back tothe still.

The etrangeres@ Cissrbed Permits Operathe oil in admixture with aluminum chlorid used on lower boiling hydrocarbons in still from4 any one still to another in the-'series and in order that wemay accomplish-this result, wel provide what We call a continuous oil main 37 tapping all the stills. Thisv main is provided with branches 38 and 39 at eachA still. For instance, the contents of stills A or a portion thereof may be sent to any one or more of the succeeding stills and the contents of still B or any portion thereof may bel likewise transferred to one or more'of the succeedmg stllls.

With the apparatusJ in operation as de-V scribed, the most highly active aluminum chlorid may be used in the first still A, with the .rela-tively higher boiling hydrocarbon and the vused aluminum chlorid trapped from the traps 18 and condenser-23 may be B and so on, with the possibility of changing the specific character of theoil in any one of the stills through the oil main 37, described.

As the trapped Valuminum chlorid gradu ally loses itsv activity, fresh aluminum chlorid may be-,added to any of the stills through the line 30 or through the line 31 leading to the heating apparatus.4 As the aluminum chlorid passes from still` to still it gradually loses its activity so that particularlyin the last few stills of the series it may be in a-Ycondition where it is masked, so to speak with carbon or coke, which has been formed.-A

lVe therefore provide means for reco-vering the aluminum chlorid, particularly from the last four stills in the series, although we, of course, mayuse the recovery apparatus,'to be described, with any ofthe stills. y. Thev recovery apparatus shown in Figure l may be of the type-,described and claimed in our copending pplica-tion, -Serial N o. 518,197, filed November 28, 1921.

Leading from the sump of the still is the pipe 50 suitably valved as at 51 and Ysuch pipe communicates with themam 52, havrng valved branches 53 leading to retorts 54 mounted .in the furnaces 55. 'Vapors of hy# drocarbon first distilled off from these residues may go by Gines 56 to the pipe 57 leading to a condenser (not shown) or to. one or more the stills'and the volatilized aluminum chlorid resulting `from further heating to -a higher 'temperature may go by lines'- 58 to pipe 59 lea-ding' toan aluminum chlorid condensing apparatus (not' shown) from which the aluminum chlorid may he pumped to inlet 30 of the stillhAfand'inlet 31 of the lstill A or the vpreheating appa-A ratus.

`According to a specific embodiment of our invention high'boiling oil is char ed by apump 13"throu gl1the 'heaterllnto still In some cases laluminum chlorid va?A pors may be sent direct to a still.

-line 30. Pump 13 withdraws oil from still A through line 16 and discharges it through heater 10 intol the bottom'of still A through line 14. The vapors pass from still A through vapor line 17 andthe still is controlled by thermometer 22 placed in line 17. That is to say, the degree of heat in the preheater is regulated in accordance with the temperature of the vapors at this point. The vapors'then pass through the trap 18 andl around the pipe located therein. The aluminum chlorid sludge is trapped from the bottom of this trap 18 through pipe 19 and by opening the 4valves on line 21 the mixture of aluminum chlorid andv oil is trapped to still B. If it is desired to trap the mixture out at this point valve on line 21 is clos-ed and valve on line20 is opened,

thus trapping the mixture out to a recovery plant or through a filtering device as previously described. This mixture of aluminum chlorid sludge may be trapped ofi after it -ha's line. l

The vapors from this trap 18 pass through vapor line 23 into the dephlegmator -tower or air cooled condenser 23 and the vapors passed through any still down the i from this dephlegmator pass through line 26 to a final or water cooled' condenser (not shown).

The heavy oil and aluminum chlorid sludge from y this' dephlegmator 23 are trapped through line 27 into the second still B or, -if found desirable, they may be trapped Aout either to a filter and recovery Aplant or direct. to. the recovery plant through valved line 29, the valves on these lines being suitablyregulated as will be well understood. The higherv boiling condensed hydrocarbons and the aluminum chlorid are 'sepa- -rated and *then either vor both sent to any one ofv the succeeding stills through themain 37. K Y Y Oil main 37 is .connected to all the stills so that the oil can when occasion requires be equalized throughout the entire battery.

ample-z-the -valve 37 in line 37 is closed and valve 38 opened,xallowing the( oil to flow to one side of the still and valve inline 39 .is' opened allowing-the oil to'ilow from the stillbaok intothe equalizing line 37. If a dephlegmator from still E may trap into still G, by-passing still F. This `arrangement,iof course, Imay be adopted for any 'of-the, s'tills'n the series. In other words,

v1220 stillis cut out ofthe linev for repairs or'for v' `any other purpose, valve 37 is opened and Valves on'lincs 38- and l39` are closed, allowma or any group of stills in the battery ma be cut out, either as regards the flow of 011 or as regards trapping arrangements, The trap lines may be cut out entirely and recovering of the residue resorted to.

The last group of stills in the battery commencingl with F is equipped with a battery of batchretorts or stills'referred to as a recovery apparatus. The sludge is drawn from the still ythrough line 50 to any one of the recovery apparatuses or retorts 54, and they oil vapors driven oi are conducted through lines 56 and 57 to a condenser (not shown). After all the oil vapors have beenl driven oii, the valves on line 56 are closed,

' and valves on lines 58 are opened, thus al- `lowing the volatilized and recovered aluminum chlorid vapors to pass through line 59 to the condenser (not shown) from whence the aluminum' chlorid may be pumped back to still AJ a It' found desirablegall-the sludge may be trapped od from any one of the condensers by closing valve in line 2l and opening valve in line 20, also by closing valve in line 2S and opening valve in 29, thus trapping the sludge from this point to the batch still or retorts 54; and a certain amount of fresh aluminum chlorid may be charged into the high boiling point oil inline 37 through pipe 37A '(Fig. 4) to make up the supply.

It vwill be seen that in operation all the vapors andy oil thatcome over from vany individualstill unit'may :be taken-out; that is, the vapors consisting of low boiling point oil vapors, high boiling point oil vapors and aluminum chlorid 'may be removed. The low boiling oint vapors, after passing through the a uminum chlorid'trap 18 and dephlegmator 23, go to the final condensing coil. The high boiling point oil vapors and the aluminum chlorid are either trapped to ,the next succeeding still in line or are trapped out and the higli boiling point oil and aluminum chlorid (or aluminum chlorid sludge) are filtered through any filtering medium found best. We may use canvas or asbestos paper if the filtrati-on is done hot, in which case the high boiling point oil which passes through the filtering medium may be trapped int-o the Vnext still line or may be sent to storage to be used over again or for some other purpose. The aluminum chlorid remaining on the filtering medium is either trapped into the next succeeding still in line or is drawn off to a recovery plant,

If the battery of stills is run continuous, trapping-from the first to the second, secon-d to third, and so on, atsome 'point down the line of stills, (at F, for instance), the

valuminum chlorid sludge would be lspent or practically spent and may be recovered in the manner described, or the last still may be run to dryness,

In. one mode of operation, still A may be run witha vapor temperature in the vapor line of approximately 150 F. as indicated by thermometer 22. The vapor temperature in the vapor line of the last still, or still I, may be run as high as 500o F., with the temperatures in the vapor lines of the stills in between gradually stepping up and ranging from 150 F. for still A to 500 F. for still l. The temperatures of the mixtures in the stills are determined by the vapor temY peratures. This permits of' greater production of low boiling point oils because we are able to keep each individual still at a uniform temperature. l

In prior practice, the still is heated to a gradual increasing temperature and where fresh aluminum chlorid is charged the teniperature is lowered temporarily because there is sudden production of lower boiling point oilu We are not confronted with this diiiiculty. f

.Of course, the temperature to which the oil in any ,still must be heated to insure converting action. of the aluminum chlorid on the oil, depends upon the nature ot' the distillate or the higher boiling oil in the particularly still, and since these distillates may be constantly changed not only by the eharacter ofthe condensates 'sent to them from thetrap and dephlegmators, but also by the introduction or' fresh oil either continuously or from time to time, it is difiicult to state the exact temperature necessary to j run each still. In a general way, the oil in the first still, gas oil, for instance, in admixture with aluminum clilorid may be heated to about 350 to 400' F. and the mixture in the last still may be heated from 500o to 600 F., with a' gradual rise in temperature 4from the second to the eighth still in the series. The highly active aluminum chlorid in the first still under the temperaltures noted will produce considerable gasoline and large quantities of partially converted and saturated higher boiling oil. These in going to the second still are acted upon by the aluminum chlorid which has already exercised some of its converting action, and unless new aluminum clilorid is'1 supplied to the second still, the temperature therein should be slightly in excess ofthe temperature in the .first still, and so on down the series. Since We provide individual `heating plants for cach still1 vthe heating vapors in them. atany given time; and the volume of these vapors, or the rate of distillation, in other words, may be controlled by plants furnishing het oil to the still or the converting chambers.`

It is possible with the arrangement described t-o produce continuous Iflow of good gasoline vapor from thedephlegmators all along the series while reduxing froml still to still through the traps and dephlegmators the condensates including aluminum chlorid;

and when -the exigencias of any particular case demand, hydrocarbons having somewhat higher boiling points than gasoline, but lower boiling points than the oil undergoing distillation, may be trapped o ut along the line, lterediree of aluminum chlorid or distilled.

Ve have secured gasoline from the vapor line of the dephlegmator having end boiling -point as'low as 300 F. and we Vhave secured Afrom the traps' and dephlegmators condensate having end boiling point as low as 400 F. and 450 F. By proper manipulation-this may be done anywhere along the lor exhaustionas. the case maybe. For eX- ample, -fresh aluminum chlorid is charged -into still A and the still may be run at the yrate of two-tenths` gallons of distillate per poundaluminumchlorid charged and the valuminum chlorid sludge .trapped into another still. This aluminum chlorid sludge upon'being 'trapped into the second stilldoes the further work of two-tenths gallns y.per pound of the chlorid making thewtotal work it has donethrough this stage fourtenths gallons of distillate per. pound and so o n down the line. which is :trapped from the eighth still to the ninth still has done the work of one and sixth-tenth gallons .per pound of aluminum simply by .way of-explanation.

chlorid 'chargedf 'llhese figures 'are used By removing the condensates from 'the traps and dephlegmators, as described, we are enabled to obtain good, sweetfsaturated kerosene, and other"hydrocarbons having The aluminum chlorid ranges betweenl their. end and initial boiling pomts.

.. Referringto the diagrammaticshowing or Figures 2 and 3, the operation :is the samel --as.de: cr1bed wth regard to Figure .1, and

these diagram-matic showings are self-'explanator vWhat we claim is 1. The process of producing lower boiling hydrocarbon from higher boiling hydrocarbons which comprises distilling a body of higher boiling hydrocarbons in the presence ofa catalytic chemical ofthe na-Y ture of 'aluminum chloridcondensing vapors of higher boiling hydrocarbons and the cata ytic chemical, maintaining asecond body of higher boiling hydrocarbon, and the catalytic chemical undergoingv distillation,

delivering said condensate to said secondbody, and delivering for inal .condensation l vapors 'of lower boiling hydrocarbon produced in the first: distillation. 2. The process of catalytic distillation which comprises maintaining a series of bodies of hydrocarbon and catalytic chemical of the natureof aluminum chlorid at distillation temperatures, preliminarily condensing higher boilinghydrocarbons and the catalytic chemical from each distillation and delivering the condensates 'from each such distillation to a succeeding body in the series, while-separately and finally condensing vapors of lower. boiling hydrocarbons from each such body.`

e. The process of catalytic' distillation.

which comprises maintaining a plurality of bodies of hydrocarbons and catalytic chemical of the nature of aluminumfchlorid at distillation temperatures, preliminarily con` densing higher boiling hydrocarbons hav-K ing boiling points higherfthan that of gasoline and preliminarily condensing the cataloo . lytic chemical from each such. distillation,`

while separately collecting and condensing the 'condensed kerosene and higher-'boiling hydrocarbons together with'such catalytic vapors of gasoline formed and delivering llo chemical from each such body `undergoing distillation to a succeeding body undergoinlg,l

distillation.

which comprises maintaining a .plurality of 4. The process-0f catalytic ais-finitionbodies of hydrocarbons and catalytic chem y .I

ical of the nature 'of aluminum: chlorid at distillation temperatures, preliminarily conv the catalytic chemical from each such di'stillation, whilel separately collecting. andcondensing higher boiling hydrocarbons :and

'densing vapors of lower boiling hydrocarf bons formed, separating the hi her boiling narrow ranges between their initial and end/*n hydrocarbon condensates` an Q 'catalytic 125 .boiling points,vwhil'e continuously produc-4 ing sweet, saturated gasoline, and l'lowerboiling hydrocarbons with. slmilarily narrow chemical from each othe/r and returning one of them to. a succeeding body undergoing distillation'. i

g5. The process of catalytic distillation which comprises maintaining a lurality of bodies of hydrocarbons and cata ytic chemical of the nature of aluminum chlorid at distillation temperatures, preliminarily condensing higher boiling hydrocarbons and turning one of them to a succeeding hydrocarbon the catalytic chemical from each such disdensing higher boiling hydrocarbons and the .catalytic chemical from each such distillation, while separately collecting and condensing vapors of lower boiling hydrocarbons formed, separating the higher boiling condensates and catalytic chemical from each other and returning the higher boiling hydrocarbon condensates to a succeeding body undergoing distillation.

7. The process A of catalytic distillation which comprises maintaining a plurality of bodies of hydrocarbons and catalytic chemical 'of thenature of aluminum chlorid at distillation temperatures, reliminarily condensing higher boiling hy rocarbons andthe catalytic chemical from -each such distilla tion, while separately collecting and condensing vapors of lower boiling hydrocarbons formed, separating theA higher boiling hydrocarbon condensates chemicalfroin each other by filtration and returning the higher boiling hydrocarbon condensates to a succeeding body undergoing distillation. l

`8. The process of catalytic distillation,-

which comprises maintaining a' plurality of bodies of hydrocarbons and catalytic' chemical of the nature of aluminum chlorid 'at distillation temperatures, reliminarily condensing higherboiling v ydrocarbons and catalytic. chemicalfrom each such distilla- -tion in a plurality'of stages, while separateundergoing distillation.

. l gi l catalytic...

ly collectin and condensing vapors off lower boiling hy rocarbon formed and delivering the. condensatev of higher boiling hydrocarbons and catalytic chemicalfrom one .of said f condensation stages to 'a succeeding body 9. The -proces's of catalyticf'distillation,

.60; 'which comprisesmaintaining a lurality of bodies of hydrocarbons and cata ytic chemical of the nature of aluminum chlorid -at distillation temperatures, preliminarily condensin higher boiling hydrocarbons and cheiriical from each such distillation in a plurality of stages, while separately and catalytic boiling hydrocarbon formed and delivering the condensate of higher boiling hydrocarbon 'and catalyticl chemical from all of said stages of said condensationpto a succeeding -body undergoing distillation.

collecting andA condensing vapors ofV lower v `10. The process of catalytic distillation, i which comprises maintaining a plurality of bodies of hydrocarbons and catalytic chemical of the nature of aluminum chlorid at .distillation temperatures," reliininarily condensing. higher boiling ydrocarbons and catalytic chemical from each such distillation in a plurality of stages, while separately collecting and condensing vapors ofv lower' boiling hydrocarbon formed and delivering the condensate of higher boiling hydrocarbon and catalytic chemical .tromv one of said stages of condensation to a succeeding body undergoing distillation, and separating the mixture of higher boiling hydrocarbon condensates and catalytic chemical from another of said stages of such condensation from each other.

soI

ll. The process of catalytic distillation',

which comprisesmaintaining a, plurality of bodies of hydrocarbons and catalytic chemical of the nature Iof aluminum chlorid4 at distillation temperatures, preliminarily condensing higher 'boiling hydrocarbons and catalytic chemical fromV each such distillation in a plurality of stages, while `separately collecting and condensing vapors of lower yboiling hydrocarbonformed and delivering the condensate of higher boiling hydrocarbon and catalytic chemical from one of said sta es of condensation to a succeeding body un ergoing distillation, and separating the higher boiling hydrocarbon condensates and catalytic chemical from one of said stages of condensation from each other and return- Aing one of the so separated products to one of said bodies other than the one from which v it was derived.

12. The process of catalytic distillation, 'Y

which-comprises maintaining' a plurality 0I bodies of hydrocarbons andv catalytic chemical of4 thenature of aluminum chlorid atl distillation temperatures, preliminarily coiidensing higher boiling Yhydrocarbons and. catalyticv chemical from each such distillation in a pluralitylof stages, while se arately collecting and condensing vapors o lower boiling hydrocarbon formed and delivering the condensate of higher boiling hydrocarbon andV catalytic chemical from one r'ofV said stages of condensation to a succeeding body undergoin distillation, land separating the higher boi ing hydrocarboncondensates and catalytic chemical from another vof said stages of condensation.' from eachother and returning the higher boiling hydrocarbon so separated toone of said bodies other than the one from which \it was'derived.

13. Thefprocess lof catalytic distillation, which comprises maintaining/a plurality of other other cal of the 'nature' of aluminumr chlorid at distillation temperatures, preliminarily condensing higher boiling catalytic chemical from eachsuch distillation in a plurality of stages,.while separately collecting and condensing vapors otlower boiling hydrocarbon formed and delivering the condensate of higher boiling hydrocarbon and catalytic chemical from one of said stages of condensation to a succeeding body undergoing distillation, and separat-l ing the higher boiling hydrocarbon conden- Sates and catalytic ciemical from another of said stages ot' condensation from each by filtration and returning one of the separated products to one of saidv bodies than the one from' which it was derived.

reliminarily conrately collecting and condensing vapors of lower boiling'hydrocarbon formed fand def livering the condensate of higher boiling hydrocarbon and catalytic chemical from one of said stages of condensation to a succeeding body undergoing distillation, and separating the higher boiling hydrocarbon condensates and catalytic chemical from another of said -stages .of condensation from each other by filtration andreturning the higher boiling hydrocarbon so separated tc one of said bodies other than the one from which it was derived. l

15. The process of catalytic distillation which comprises maintaining a plurality of bodies of hydrocarbon and catalytic chemical of the nature of aluminum chlorid at distillation temperatures, preliminarily condensing higher boiling hydrocarbon and the catalyt1c' chemical from each such distillation, while separating, collecting and con- I l tion. i

densiiig vapors of lower boiling hydrocarbon formed, and delivering the condensed higher boiling hydrocarbon and catalytic" chemical from each suoli distillation to a succeeding body undergoing distillation whilesupply' V higher boiling hydrocarbon from one of the bodies undergoing distillation to another of the bodies undergoing distillaj .16. The -proce'ssof catalyticn distillation, which comprises maintaining a g bodies of hydrocarbons and `cata ytic chemical of the nature of aluminum ilorid at distillation temperatures, relimina ily condensin `higher boiling'hy rocarbons andthe cataly/ic chemical from each such distillation while separately collecting and condens hydrocarbons and 'f body undergoing distillation 14. The process of'catalytic distillation,v plurality of lurality of'.

tillation.

ing vapors of -lower boiling hydrocarbons v formed and delivering the condensed higher boiling hydrocarbon and catalytic chemical rom each such distillation to a succeeding while supplyingAv liquid higher boiling hydrocarbon and catalyticl chemical from one of the bodies undrgoing dstillation to another of the bodies undergoing distillation.

17. The processbf catalytic distillation, which comprises maintaining aplura-lity of bodies of 'hydrocarbon and catalytic cheinicalof the nature of aluminum chlorid at distillation temperatures, prelin'iinarily condensing higher boiling -liydrocarbons and catalytic chemical bons formed, separating the condensed highei' boiling hydrocarbons and the catalytic from cach such distillation, while separately collecting and colidensing vapors of lower boiling hydrocarchemical from each other delivering one.of

them to a succeeding body undergoing distillation and supplying liquid higher boiling hydrocarbonsv 'from one of the bodies undergoing distillation to another of the bodies undergoing distillation.

.18. The process of batalytic distillation,

which comprises maintaining a plurality of bodies of hydrocarbon and catalytic chemical of the nature of aluminum chlorid at' distillation temperatures, preliminarily condensing higher boiling hydrocarbons and catalytic chemical from each suoli distillation, while separately collecting and condensing vapors of lower boiling hydrocarbons formed, higherv boiling lytic chemical from each other,l delivering one of them to a succeeding body distillation while supplying liquid. higher boiling hydrocarbon and catalyticcheinical from one of the bodies undergoing distillation to another of the bodies distillation. n

1.9. The process lof catalytic .distillation which comprises. maintaining a, plurality of separating the condensed. hydrocarbons and the cataundergoing l undergoingv bodies of hydrocarbon .and catalytic che-in-v catalytic chemical from .each suoli ;dist'illa-l l tion,` whilegseparately collecting .and con-f.' i densing vapors .of lower boiling' hydro'car v sepzirating the condensed-'fr higher boling hydrocarbons and, catalytic bons formed,-

chemical from each ';other,

the nature ofalum'inum chlorid at rati. delivering Vthe condensed higher .boiling4 hydrocarbon to; a

'succeeding body.undergoingmdistillationand supplying liquid higher boiling hydrocarbon" from one of the bodies undergoing distilla-,f

undergoing disl'.

tion to another of thebodies 20. The

which comprisesmaintainingl a plurality of prc'ices-sf-fof` catalytic distillation bodies o fhydrocarbon and catalytic chem-i ical of the nature ofalu'In-iniim chlorid at distillation temperatures, preliniin'arily con.- densing higher boiling hydrocarbons and catalytic chemicaliroln each such distillation, While separately collecting and condensing' vapors of lower boiling hydrocar-4 bons formed, separating the condensed v higher boiling hydrocarbons and catalytic each body being higher thanthe temperature of the one preceding it in the series, preliminarily condensing 'higher boiling hydrowhich comprises 1 of bodies of hydrocarbon -and catalytic cai-bons and the catalytic chemical from each distillation and delivering the oondensates from each such distillation-to a body in the series maintainedfatla temperature higher than the 'temperature of tle body from which said condensates were derived, While separately and finallycondensing vapors of lower boiling hydrocarbons from each such body.

2Q. The. 'process of cat alyticl-I distillation maintaining a. series chemical of the natureof aluminuinchlorid at distillation temperatures, the tempera. ture of each body being higher than the' temperature of the one preceding itin the series, preliminarily condensing higher boiling hydrocarbons and the catalytic chemical from each distillationand delivering the Dcondensates fromeach such distillation to a` body in the series maintained at a' temperature higher than the temperature; of the body from which said oondensates were clerived, separately and finally condensing vapors of lower boiling hydrocarbons from each such body, and supplying higher boiling hydrocarbon fronione of the bodies'to another of the bodies maintained at a higher.

temperature.

a. The sfv catalytic *astanti which comprises maintaining a 'series' or' bodies of hydrocarbon and 4catalytic chemical of the nature of aluminum chlorid at distillation temperatures, thentemperature'" of A' each bodybeing higher than thetemperature of theone preceding it in' the series, preliminarily condensing higher boiling hydrocar bons andv the-catalytic chemical -from veach,`

distillation and delivering the condensates l from each such distillation toA a'bodyfinthe 4series maintained "at atemperaturelhigher than the vtcinperatnre of the body from which saidgcondensates'ivere derived, separately ad'linally'cndensing vapors of lower:

boiling hydrocarbons from each'bod'y, and

supplying liquid higher boilinglhydrocarbon and catalyticl chemical :from one of the a higher temperature. v

In testimony w signedl our names at Port Arthur, this 9th dayof February, i922. v

bodies to another of the bodies'imaiitained at hereof we have herenn'to `Texas,

GEORGE-L; Parona-ED(- HERBERT HENDERSON.

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