US1494191A - setzler - Google Patents

Description

May 13, 1924 1,494.19!

\ H. B. SETZLER PROCESS OF TREATING PETROLEUM AND PETROLEUM DERIVATIVES Filed Oct. 22 1915 Patented May 13, 1924.

UNITED STATES 1,494,191 PATENT OFFICE.

nom'rcn B.

stint-En; i? oorrEYvILLE, KANSAS, assmuon we ran NATIONAL marmmo com any, or CLEVELAND, 01110, aconronarxon or emo.

PROCESS OF TREATING- PE'IB/OLEUM AND PETROLEUM DERIVATIVE.

Application filed October 22, 1915. Serial No. 57,358.

To all whom it may concern.

Be it known that HORACE B. SnTzLnR, a a

citizen of the United States of America, re-

siding at Cofi'eyville, in the county of Montfl gomery and State of Kansas, has invented certain new and useful Improvements in Processes of Treating Petroleum and Petroleum Derivatives, of which the following is a specification.

This invention relates to an improvement in the art of distilling petroleum; preferably using distillates from petroleum containing natural or normal constituents, and which, under ordinary conditions, and 5 known methods, distill over between temperatures of 450 F. and 675 F. known as gas oil, having a specific gravity of 32 to 34 Baum. Primarily, my object is to obtain from said distillates, products which under ordinary conditions, distill between temperatures of 80 F. and 350 F. and have a specific gravity of 58 to 60 B.; the properties of which are dissimilar from the properties of the natural constituents. To this 28 end, I provide means for preventing the carbon, frebd during the operation, from settling, concentrating and depositing in a send-crystalline coke form, on the sheets of the still. V

Hitherto, the art of distilling petroleum, has consisted principally in separating its natural constituents, and grouping them into a series of products applicable for commerical use, gasoline, kerosene, gas oil, lu- 85 bricating oil and wax, when separated by distillation, and each product grouped separately, constitute natural constituents found in the original mass of crude oil.

Distilling under pressure has for its object, the production of 'low boiling point hydrocarbons; the properties of which are dissimilar from the properties of the by drocarbons from which they are obtained. Pressure distillation'therefore, must not be confounded with the normal atmospheric distillation, because the product sought in pressure distillation, is not a natural constituent of crude, but is a product obtained from the natural constituents. through its 0 subjection both to pressure and heat. Such roccsses are oundcd upon the well known act that h gum diLnder these comb; tions, may l we to permanen gases, liquids and wild carbon. Tcmperw .tures ranging from 700 to 800 F. are re- II quired for these breaking down re-actions; being those at which the afiinity between carbon and hydrogen usually is overcome. Consequently, the carbon must remain in thestill, or retort, while liquid or gaseous hydrocarbons pass off. In known methods, the carbon thus extracted from the hydrocarbon, by virtue of its gravity, settles to the bottom of.the still, and remains there; the particles growing in mass, concentrate 05 themselves in a layer over the entire bottom. Their presence is dangerous, because of the fact, that it is unsafe to operate a still under pressure with a cpating of carbon upon its bottom. Therefore, it is quite essential to the performance of such processes, that some device, or apparatus be rovided, whereb the carbon, which splits o is he 1:, from epositing and concentrating on t e sheets of the still, which fact previously, has been recognized.

My process involves the continued abrading and agitating action of a movable member, which I understand augments and continues a coloidal or suspended state of much of the carbon content, whereby the chemical reaction or cracking of the treated hydrocarbons is maintained by catal tic action, or by some action analogoust ereto, and the formation of deposited, coke-like carbon is avoided.

While my invention by no means is limited thereto, I may readily explain the practice thereof in the treatment of the commercial product of gas-oil; comprising a derivative hydrocarbon whose boiling point ranges between 450 F. and 675 F. with a specific gravity between 32 and 34 Baum, as obtained from mid-continent crude oil. This is selected as typical and explanatory I00 merely, since the temperatures and specific gravities of other derivatives, subjected to. my process and even other gas oils, necessarily will vary materially.

The improved process of my invention, 1 may best be explained in connection with the accompanying drawings, wherein: V

Fig. 1 is a diagrammatic view in side elevatioin'partially' broken away, showing apparatus adapted for the practice of my no 11 vention, an

Fig. 2 is a similar View in end elevation.

'Figs. 3 and 4 are cross-sectional views (4 stills illustrating the helicoidal cleaner and its adjuncts.

Throughout the drawings, similar parts are indicated by the same character reference.

In Fig. 1, a brick-enclosed furnace, is shown, wherei the firin -chamber 1, is separated by the ridge we 1 2, from the combustion chamber 3, from which a flue 4 leads to a stack 5, for the purpose of carrying off the products of combustion. The furnace 15 provided with a firing door 6, through which fuel is passed into the furnace, while the heat from combustion, is applied to the bottom of the cylinder-still 7 which is set over and supported by front and rear end walls, of the furnace and the combustion chamber. The still is provided with manhole 8, a pressure auge 9, and a thermometer (not shown? A charging inlet pipe 10, enters the still at its top, near the front end; the charging being controlled by valve 11, through which oil is pumped by means of pum 12, receiving its supply from a tank not s own. A vapor line 13, leaves the still near its rear end, and leads to a condenserbox 14, which contains condensing coils 15, and beyond the condenser box is a valve 16, connected to a pipe leading to the receiving tank 17 the pur ose of w ich equi ment is to carry off, con ense and receive t e products w ich distill over.

The still 7, is equipped with a rotating shaft 18, mounted in water-cooled stufiing boxes 19, and fitted with a driving wheel 20. Inside the still, there is attached to the shaft, a helicoidal cleaner 21 oflsuch diameter and length as to engage t e lower heated inner periphe of the still 7. This rotated abr mg mem er 21 preferably is equip ed M h lengths or loops of chains 34 whic en a e an conform to the bottom portions 0 e still. At the front and rear ends of said shaft respectively, are water pipes 22 2 leading fromia source (not shown) an en tering passages drilled in the ends of the shaft 18, a istance equal, at least, to the length of the shaft inside of the stuflinfi boxes. A discharge 23 is attached to the, sti at its bottom, near the rear end, and to which is connected outlet pipe 24, leading through valve 25, to a second condensing be 26, and thence-through the pipes 27, inssi e' the box, and out th rough a valve 28, to

a receivin tank 29. A motor 30' furnishes the wet or driving the wheel 20, connected to s aft- 18.

With this description of convenient apparatus' for practicing the same, I will now exlain, a process typical of my invention. e cylin or still 7, is charged with gas oil, we may assume, having the characteristics previously explained, and to approximately one half the ull volume or capacity of the cylinder; after which valves 11, 25 and 16 I condensed in the carbon,

are closed. Power is turned on the motor connected with driving wheel 20, which revolves the helicoidal scraper or cleaner inside the still. The still is heated by supplies of fuel passed from time to time through the firing-door 6, into the combustion chamber 3, the products of combustion being directed against the bottom of the still, so that the temperature of the contained oil, rapidly rises, untilit has reached about 700 at which temperature the pressure begins to rise, and is indicated on the pressure gauge 9. By the time pressure has reached 100 pounds,the temperaturewill have risen to approximately 7 30 F., at which temperature and pressure, carbon begins to split off from the heated hydrocarbons: thereby producing new hydrocarbon compounds dissimilar from the body of gas oil, and having boiling oints of to 350 F. and a Baum gravity of 56 to .58. It will be evident to those skilled in the art, that compounds having boiling poin of 80 to 350 F., cannot, by reason of their inherent pli'ysical roperties, remain indefinitel in the still at tlie tem rature referred to, ience they are permitte to pass out through the vapor line 13, and are coil 15 and thence conducted to the tank 17, b control of the valve 16.

I have found t at without the use of suitable cleaning, scraping, scouring or agitat' means, carbon, at the instant it is f from its plrx'levions combination; bein of amorphous c meter, and settling out of the mass of gas oil, seems to be attracted, or drawn to the heated bottom sheets of the still. Normally these particles of carbon growing together, and agglomerating over the bottom sheet, form a dense coating of resembling a semi-crystalline f rm, (which would have the dangerous re ults heretofore explained. By using a heliboid' cleaner, continuously revolving inside the stgll, and engaging the heated ower section 0 the inner periphery of the cylinder, or its equivalent, the carbon which has been freed from its combi ation, is kept in an amorphous conditi n, and suspended throughout the mass of oil. Any carbon, which by chance is attracted or becomes at tached to the bottom, cannot remain there, because the blade of the helicoid engaging on the bottom, sweeps the particles of carbon away in'its course of travel. Another important function of the helicoid is that of conveying the heat from the bottom sheets of the still, with which it is in constant contact, throughout the body of the hydrocarbon and the vapor s ace in the still above the lltfilld. Thisfurt ers the rocess in a marke d ree, by reason of t e fact that the helicoi through intimate contact with the still bottom, is very highly heated.

It is important that the still be only partially filled, so that an adequate pressure" s ace shall be afforded at all times above t e bod of hydrocarbons undergoing treatment referably the still is approximately half filled, and is so maintained during the process, inasmuch as it appears that considerable, if not a large proportion of the reaction takes place aniongvthe heatedva- As above stated, hydrocarbons can be degraded down to permanent gases and solid carbon, by the. influence of heat and ressure, and by the proper regulation of tie same, intermediate products between carbon and permanent gases, can be produced, but as far as I am aware, no device or apparatus previously has been employed to maintain the carbon in an amorphous condition, while the change is progressing. It is apparent then, that the degradation of hydrocarbons, necessarily means the extraction of carbon, which is-the clogging element in the successful performance of any'pressure operation. This I haveovercome by the means referred to.

In practicing my process, the gas oil or other hydrocarbon supplied to the still, is subjected to moderately high temperatures and pressures, and the chemical allinity of its elements being partially overcome, certain of the combined carbon atoms are split ott in amorphous condition, and are maintained in minute particles, in that condition by continued agitation. \Vhen the chemical aflinity between the carbon and hydrogen has been broken, the existing chain of hydrocarbonsis opened, and a new series is produced, which cannot remain in the highly heated still, because of the low boiling points, Consequently the new products are permitted from time to time, to pass out through the vapor line.

After the described operation has progressed, until approximately 10% of the volume of gas oil charged into the still. has been converted into other products boiling between 80 to 350 F., and theBaum gravityyof said products is found to range from 56 to 58, as indicated by the hydrometer with samples taken from the end of the pipe entering tank 18, the pump 12 is started. Gas oil thus is continuously pumped in through the line 10, regulated by and through valve 11, entering the still at the front end, at the sametime the new products referred to, are conducted off through the vapor line 13. Any convenient device may be used, such as meters 30,31 to establish the ratio of a constant quantity of gas oil. entering the still at the front end, and a corresponding quantity of converted products passing off, and collecting in the receivin tank 1 avin established the quantity entering andJeavmg the still, the operationis continued until a distillateapproximately 50% of the volume has been conducted olf, when the oil in the still will have reached approximately '24 Baum gravity. The valve 25, connected by a pipe to the trap on the bottom. near the near end of the still, is then operated for the purpose of drawing oil the contents, either continuously or periodically; measuring it through a meter 32. after the liquid has passed through the coils 27, submerged in the cooling box 26.

In the instance assumed, I have stated that when approximately 50% by volume has been conducted ofifthe Baum gravity of the oil in the still will have reached upproximatel 24, at which gravity I begin to drmy ofi at the rear end of the still, but I wish it understood that the gravity test referred to is not invariable. The figures were used merely to indicate the preferred mode of operation, and I have found, that with the gas oil referred to, I can go as low as 18 B. gravity in the still, with no apparent deposit on its bottom, if the agitatron be continued, and the operation proceeds regularly under these conditions.

From the foregoing it will. be seen that the described process is capable of indefinite continuation,depending somewhat upon the character of the hydrocarbons treated. The liquid condensed and collected in tanks 17, may be distilled in the ordinary manner, primarily for their gasoline content, while the heavier distillates therefrom, may be mixed with the contents of tank 29, and reintroduced into the still 7, for further treatment, if desired, after the carbon has been allowed to settle out. Connected at 33, is an automatic mechanism, which may be used for controlling the continued practice of the described-process, but as these steps form no part of my invention, they need not be further referred to herein.

It is apparent that the mechanism provided, serves continuously to agitate the contents of the still, and such agitation, moreover, is coupled with the repeated scouring and scraping of the bottom of said still; all of which contribute to the retention of the carbon in its amorphous form. and pre vent its adherence to the bottom plates in a copending application, Serial No. 58,720, filed October 29, 1915, form no es sential part of my present invention. I find, on the contrary, that in conducting my process under commercial conditions, it isnotnecessa to resort to an outside or foreign catalytic agents, due to t e combined aotion of the moving member and the colloidal or 'suspendedcarbon in the gas oil under treatment. The exact nature of such action is notclearl understood, but it is my belief that a mar ed catalytic property is obtained throu h maintaining the separated carbon in a co oidalstate. The continued abraiding and agitating action to which the inner still walls and still contents are subjected, obtain most favorable conditions for the formation of and preservation of this desirable sus ended or colloidal condition. The colloida carbon is substantially maintained in its state of suspension by the action of the moving member, and prevented from assuming its crystalline form wherein it would lose its properties as an agent to assist in the action upon the unchanged gas oil and would adhere to the bottom sheets 0 the still. Fi 3 and 4, resfiectively, are cross-sectiona views which i us trate certain specific auxiliary apparatus for augmenting the a itating and scouring means afforded by. t e

helicoidal blade. In Fig. 3,-said blade and supporting shaft areshown mounted slightly eccentric to the axis of the still, for the purpose of scraping only the heated bottom ortions; said blade being given some play y reason of its looseattachment to the shaft. In Fig. 4, the action of the plate 21, is augmented by-chains 34, attached thereto at 'in'tervals, thereby permitting its loops to drag over the heated bottom. The shaft may be concentric, if desired, but sufficient play is provided with respect to the scrapmg, scouring or agitating members, so that the heated bottom portions of r the still, in any event, are subjected to such action as will prevent the deposit of the separated carbon particles. Obviously, other means may be employed for accomplishing these tions or functions, and my process or method of treating hydro-carbons ma properly be said to e independent of suc means particularly shown and set forth herein.

Having now described the preferred method for practicing said .invention, I claim as new, and desire to secure by Letters Patent, the following .l

11. A process for treating petroleum or its derivatives, which consists 1n introducing the same to a sealed retort, establishin and maintaining therein a tem rature an ressure for crackin a gasoline content t refrom, and meantime subjecting the interior 9 of the retort to the action of an abradiug derivatives which consists in conductinfi and agitating movable member, whereby carbon is separated and maintained in a suspended state and the reaction is furthered, substantially as set forth.

2. A process for treating petroleum derivatives of relatively high boiling points, which consists in conducting ressure dis: tillation, under conditions of high temperature, suificient partly to. split out the carbon atoms, subjecting the same meantime to mechanical action and the sealed container to continual abrasion for preventing the deposit of said carbon and efl'ectin the even distribution of heat, substantiafiy as set forth. u

3. A process for producing gasoline from gas oil which consists in heating the liquid at temperatures approximating 700 F. under moderate ressures in a sealed still structure; meantlme maintaining the freed carbon in a state of suspension and sub'ecting the liquid and the pressure space a ve it to the action of a highly heated moving member, withdrawing the newly formed bydrocarbons and supplying pro ortionate ualiitities of gas oil, substantia ly as set ort 4. A process for treating petroleum or its derivatives, which consists in conductin pressure distillation thereof under conditions insuring a relatively large pressure space in the container, meantime maintaining the freed carbon in finely divided state and suspension, while subjecting the treated derivatives and the container to the action of a scouring moving member and withdrawing the newly formed hlydrocarbons from the container, substantia ly as set forth.

5. A process for treating petroleum or its pressure distillation thereof in a sealed st maintained substantially half full of the hydrocarbons undergoin treatment, meantime maintaining any f carbon in suspension while subjecting sai hydrocarbons'and the heated portions of th still to the action of a moving member, withdrawing the products of pressure distillation, and introducing to the still from time to time, corresponding Tuantities of said hydrocarbons, substantial y as set forth. I

6. A process for extracting carbon I gas-oil to produce gasoline, wh ch consists in subjecting the gas-oil to press re-d stillation in a volume maintained substantially constant under conditions involving a pres- ,t sure of from 50 to 100 pounds, tempera. c tures of from 700 to 750 F., within a.

highly heated ressure space approximately double the V0 ume of gas-oil under treatment; meanwhile subjecting the gas-oil and its vapors within the pressure space to a moving and highly heated member, and scouring the bottom of the containing still,

substantially as set forth. 13o

7. A process for treating petroleum or its derivatives, which consists in introducing the same to a sealed retort, in volume ap roximately one-half its total contents, esta lishing and maintaining therein a temperature and ressure for cracking a gasoline content t ierefrom, and meantime subjecting the interior of the retort to the action of an abrading and agitating movable member whereby carbon is separated and maintaine in a sus ended state and the reaction is furthere substantially as set forth. 8. A process for extracting carbon from troleum derivatives to produce lighter i5 istillates thereof, which consists in heating said derivatives above 700 F., under pressure within a relatively large pressure space, meantime maintaining the freed carbon in a state of suspension, scouring the heated portions of the still, and supplying fresh cpiiantities of the petroleum derivatives as t e lighter distillates are withdrawn, substantially as set forth.

9. A process for extractin carbon from gas-oil to produce lighter istillates such as gasoline, which consists in heating said gas-oil to temperatures ranging from 700 to 750 F., under pressure approximating 50 to 100 pounds within a free pressure space roportioned to the volume of liquid treated meantime maintaining the freed carbon in finely sub-divided' sus ension, scouring the heated portions of t e still, and an plyin fresh (iuantities of the gasoil as are lig ter disti lates are withdrawn, substantially as set forth.

10. A process for producing gasoline, which consists in sub'ecting suitable hydrocarbons of higher i ing points to pressure distillation under conditions of pressure approximating 100 pounds per uare inch and temperatures ranging from 00 F. to 750 F., within a pressure space aflording material expansion for the vapors, meanwhile subjecting the hydrocarbons and vapors to a moving highly heated member and scouring the directly heated portions of the container to prevent adhesion of extracted carbon, substantiall as set forth.

In testimony whereof I 0 now afiix my signature in the presence of two witnesses.

HORACE B. SETZLER. [1,. 5.] Witnesses? Famx B. Fnamn, ALBERT LYNN LAWRENCE.

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