US1407339A - Apparatus for cracking mineral oil to produce gasoline - Google Patents

Description

B. VAN STEENBERGHL APPARATUS FOR CRACKING MINERAL OIL T0 PRODUCE GASOLINE.

APPLlcATIoN man 05016. 1920.

1,407,339. Y v- Patented Feb. 21, 1922..

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Hot ou zwaven 43 B. VAN STEENBERGH.

APPARATUS EUR CRACKING MINERAL oIL ToPRoDUcE GAsoLlNE.

APPLICATION FILED DEC. I6. 1920.

1,407,339. Y Patented 2610.21, 1922.

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BURHANS VAN STEENBERGH, 0F GOSHEN, NEW YORK.

Specification of Letters Patent.

Patented Feb; ai, 1922.

Original application filed April 20, 1918,|Seria1 'Na 229,707. Divided and this application filed December 1e, 1920. serial No. 431,279. r

To all whom t may concern.' f

Be it known that I, BURHANS VAN STEEN- BERGH, a. citizen of the United States, residingA at Goshen, in the county of Orange and State of New York, have invented certain new and useful Improvements in Apparatus for Cracking Mineral Oil to Produce Gasol-ine', of which the following is a speciication.

.This invention relates to an apparatus adapted for increasing the yield o-f low boiling point hydrocarbons, commonly known as gasoline, from petroleum or heavy distillate products by decomposition or cracking of the higher boiling point oils.

The principal object of my invention is to provide an apparatus adapted for carrying out a continuo-us process for dissociating or cracking heavier oils into oils of lighter gravities by spraying heavy oil into contact with an electrically heated surface or numerous heated surfaces spaced apart, and

repeatedly subjecting the resulting mixtures of cracked and uncracked vapors to contact with spaced-electrically heated surfaces at a temperature to produce decomposition or cracking into vapors of lower boiling point oils with the maximum production of vapors of lower boiling point oils and the minimum production of fixed gas by destructive decomposition of the oil.

Another object of my invention is to provide for pre-heating and superheatin or oil and water or oil and steam by circulating under pressure through a coil, or a serpentine arrangement of pipe in a heating furnace and then injecting and spraying the heated oil and vapors into contact. with heated surfaces at a cracking. temperature in a generating chamber.

Another object of my invention is to pro.

vide a plurality of catalytic .agent coated surfaces adapted to be electrically heated to a temperature to decompose the oil into lower boiling point oils and means for bringing free hydrogen o-r a hydrogen carr 'ng gas or vapor into contact with said surfalces for hydrogenating the unsatuarted hydrocarbons and carrying them away from .the heated surfaces and out of the generator to prevent over-cracking or destructive decom-l position and formation of fixed gases and carbon.

Another object of my invention is to provde for generating hydrogen carrying gas .transverse section of an electric heater by contact of steam andoil Aor steam in the presence of carbon, with surfaces heated approximately to 2,0000 F. in the lower part of zone so' thatit will not be baked as hard carbon or lampblack upon the heated surfaces.

The cata-lytic agent coatings which form the heated surfaces serve the useful purpose of preventing the deposit and accumulation of carbon on the heaters; also the purpose of'making gasoline of sweeter odo-r and better quality.

I preferably employ electric heaters for Constantly maintaining the exact temperature, between 650o and 85001?. in the main and upper part of the generator, for best effecting the cracking operation. depending upon the quality and gravity of the oil being treated. The lower heaters are preferably heated to a higher temperature and may be heated to atemperature between 1,800"v F. and 2,0000 F.'to serve as steam decomposing surfaces and for cracking heavier portions of oil which may ow down over them for final deposit of residual Oily 'or tarry matter in a receiving chamber below or outside fof the heatingzone..

'My apparatus, adapted for carrying out the above indicated process is illustrated in the accompanying drawing, in. which: IFigure 1 represents a sectional elevation,

showing part of the electric heaters in longitudinal section antipart in cross section.

, Fig. 2 represents a' top plan view.

Fig. 3. represents, on enlarged scale, a

transverse section of an electric heater, such as shown in Fig. 1.

Fig. Uf represents, on enlarged v.seal-e, a f

eodied Generation'.

Fig. 5 represents a sectional elevation of an electric furnace showing a serpentine arrangement of steam or superheating pipes.

T have discovered that cracking of high boiling point oil can be most economically and rapidly effected by direct contact with a heated surface and preferably provide that the surfaces in my apparatus shall be a few inches apart, and so arranged that the currents of mixed oil vapor and steam shall be repeatedly deflected and caused to impinge on numerous heated surfaces. Tn this arrangement T heat the contact surfaces only to that temperature which will decompose or crack the oil into lower boiling point fractions which are condensableto gasoline, and with the least possible destructive decomposition to fixed gas and fixed carbon. heated surfaces are too close together the hydrocarbon will be held too long in contact and will result in destructive decomposition and deposit of carbon. Tf the surfaces are too far apart the vapors are apt to flow past them too fast and escape proper cracking. The tendency, then, is for the operator to more highly heat the surfaces, with the result that those hydrocarbons brought into direct contact with the surfaces will be overhe-ated and caused to deposit fixed carbon and make fixed gases, instead of the desired gasoline.

l preferably-employ internally heated or electric heaters for maintaining a large external heating surface at the exact degree required for the most economical and effective operation. cracking operation, T preferably preheat oil and water or steam under pressure to approximately 800O or 1,0000 F. before subjecting them to contact with the catalytic agent coatings of the electric heaters where cracking is effected. The oil and water will preferably be preheated in coils or a serpentine arrangement of pipes in any desired heating furnace outside of`my generator, but T also arrange -coils or serpentine folds of pipe between the electric heaters in the generator. They thus act as heating surfaces and serve to deflect hydrocarbon vapors and steam into contact with the catalytic agent coatings of the electric heaters and to intermingle the cracked and uncracked vapors, so that a larger percentage of uncracked vapors will be caused to make contact with the heated surfaces and be cracked.

Referring to the drawing, the treating chamber or generator 1 is preferably constructed with a double plate iron shell 3 and 5, between which is placed a filling of nonconducting material t,l which may be of asbestos, mineral wool, ashes or brick. Tf brick is used, the outer metal shell may not be required. The top is closed by a cover 2, having a dome 6, and from the latter leads the vapor escape pipe 6a which connects with the first condensing coil 6b in a water tank 9.

If the In order'to expedite the- The coil 6b terminates in an outlet pipe 6c which extends down into a seal-box 9", where its opening is sealed in the liquid. An outlet vapor pipe dirises from the box and con ects with the second condenser coil 10 in water tank 10a, and this coil terminates in an outlet pipe 10c having a valve k and extending down into a seal-box 10d. This box is provided with a draw-off pipe and valve g for gasoline. A gas outlet pipe 10b rises fromthe outlet end of coil 10 and is provided with a valve f to control the outflow of gas to a holder or a place of immediate use. The seal-box 1()d is not intended to serve as a reservoir, but merely as a trap or seal to prevent back flow of air into the condenser. The box may be filled, or partially filled, with liquid and a vent g provided at the top in a well known manner. diagrammatic, but will be understood, and the apparatus will be made operative by those skilled in the art. A return pipe 10e, having a valve c, connects with Vapor pipe 10e and with seal-box 9b for returning any desired portion of oil to be again run through the treating apparatus.

A safety valve 7 and a pressure gage 8 are preferably applied to the dome 6.

In making my electric heater T may use an exterior iron tube'11, into which is insei-ted the electric heater proper, constructed as follows: A cardboard cylinder 14 is coated externally with insulating material, consisting of finely ground silica and finely ground carbonate of lime mixed with sodium silicate diluted with water to form a paste'. This paste is moulded around the c linder 14 and forms a coat or jacket 15. he tube thus formed is partially filled with granular carbon 16, and then carbon electrodes 17, 17a are thrust into the ends of the tube making a tight fit so as to compress, the

carboni into the tube and form a resistance connection between the ends of the electrodes 17, 17a. A

The tubes 14, after the insulating jacket has hardened, is inserted in the outer 'iron tube 11 and the latter is placed n openings in the wall of the generator, extending at both ends beyond the same. The ends of the tube are screw threaded. Washers 13, provided with horizontally concave inner faces, are slid over the endsof the tubes and fit against the curved `wall, and nuts 12 are then screwed onto the tubes'so as to clamp them Securely in place. lBefore the iron tubes are fitted into the generator walls they are covered with a coating or jacket of a catalytic agent containing a metallic oxide, such as oxideof calcium and oxide of magnesium mixed with diluted silicate of sodium. These are made into a paste which is applied as a coating or jacket 18 to each tubell beforeit is secured in place. This coating aids by catalytic. action in cracking the oil into lower boiling point products, and also prevents deposit of carbon.

lVhen the elect-ric current is passed through -the heaters the cardboard tubes will be carbonized, forming in effect part of the resistance material of the heater.

A modified form of elec-tric heater shown in Fig. 4, in which a fire clay tube baked at a temperature of about 3,000o F. is used instead of the iron tube 11. This also makes unnecessary the inner pasteboard tube and its insulating coating, since the fire clay tube acts as anI insulator. The catalytic agent coating 18 may be applied to the outer surface of the fire clay tube.

The body of granular carbon 16 compressed between the ends of the electrodes 1T, 17a forms a resistance, by means of which a succession of small or short electric arcs are produced, thus converting electric energy into heat, whereby heating the tubes at that part filled with granular carbon from the inside to the surface.

The heat will be largely confined within the space between the walls of the generator, by reason of the heat insulating material in the walls. Since the granular material offers a much greater resistance to the electric current than is offered by the electrodes, heat will be generated principally in the parts of the heaters located between the inner walls of the generating chamber. Such localized heat is imparted to the preheater pipes 20 and the intervening space between them and the heaters.

Though I have shown and described a special construction of electric heater, I wish it to be understood'that my invention of apparatus is not confined to this specific construction. Modifications in details of construction may be effectively used to carry out my process. Other kinds of electric heaters may be used. In my apparatus I am not limited to the particular catalytic agent coating above described, but other catalyticv agents may be successfully used in hydrogenating oils, and particularlycra'cked hydrocarbon oils for saturating and making them sweet.

Within the generator chamber' I arrange a series of pipes 20 in the form of a serpentine,'as indicated by dotted lines in Fig. 2, betweeri the electric heaters, Fig. A1, thereby forming numerous defie'ctors and Jtortuous passages.' They also become highly heated and effective as decomposing surfaces, and ll the wider spaces between the electric heaters so as to deflect the oil vapors into con-- tact with lthe catalytic agent coatings of the electric heaters. A mixed fluid, composed of approximately eighty per cent oil and twenty per cent of water may be forced-,into the pipe 20 at the top through a feed pipe 23, having a valve d, by a proportioning force pump 22 of a kIlOwn kind. This pump connects by a pipe 25, having a valve e, with the oil reservoir 27, and by pipe 26, having a valve lc, with a water supply, not here shown. An outlet pipe 24 connects at the bottom of theigenerator with the prehe ter pipe 20 and connects by branches with the injector spray pipes 21, 21a, located at different heights in the generator. The injectors have` contracted nozzles a, a and valves b, b. For the purpose of preheating or superheatin the mixed oil and water to a temperature o? approximately 1,0000 F., or any desired temperature, I provide a separate heating furnace 40, Figs. 1 and 2, having Ia preheatin coil 41, and heat the same with. a coal or oil fire in a well known manner, or I may use an electric furnace, Fig. 5. The, mixing and forcing pump 22 will serve for supplying mixed oil and water to the preheating coil 41 by the pipe connections shown. A discharge pipe 42 having a valve d for mixed oil and water leads from the discharge pipe 23 of the pump below its valve d and connects with the preheating coil 41. A discharge pipe 43 having a valve 1' leads from the bottom of coil 41 and connects with pipe 23 which leads to the serpentine pipe 20 in the generating chamber 1. A branch pipe 44 having a Valve P connects pipe 43 directlywith the injector spray pipe or nozzles 21, 21S.

The oil reservoir 27 has a supply opening and cover m. A return oil pipe 28, having a valve n, leads fromA the seal-box 9b into reservoir 27, for the return of heavy oil.

At the bottom, the chamber of the generator is provided with a settling pocket 5a, having a draw-off faucet p for any heavy oil or tarry matter which may collect.

The electric heaters which are parallel and lying at different levels are connected bybus- bars 30, 31 and 32, 33, respectively, which bars are connected in circuit wit a source of energy 34; and a switch 35 controlsV the circuits. An automatic device, such as a thermostat 36, may be located at the outletl of each electric heater, or at suitable points in the wall of the generator to control'the temperature by cutting out or cutting in the circuit, according to variations in the temperature. The temperature may thus be kept within fixed limits and practically uniform, and so long as the proper quant-ity of preheated oil or vapor and superheated steam is supplied the process will be continuous.

A rheostat 37 is preferably connected with each pair of electric heaters for controlling the electro-motive force, and consequently the temperature in each set of heaters. The heat will thus be regulated and controlled tothe exact degree required for cracking'the heavier hydrocarbon yinto lower boiling point hydrocarbons to make gasoline.v i The mixed stream of oil and water may be superheated in a detached coil 41 in a separate chamber 40 which may be heated in any well known manner, and passed therefrom to the spraying injector devices 21, 21a, or first into the pipe 20 and then into the injectors, as above described.

lfn Fig. 5 T have shown a preheating pipe 410 for oil or oil and water arranged 1n the form of a serpentine, or oppositely inclined sections of pipe, having end connectionsr in an electric heating furnace 40EL mounted on legs X. A liquid inlet pipe 42a connects with an upper pipe section 41a and a discharge 4:3 connects with the lower end of the serpentine. A switch board will be provided with any desired number of switches 35a, connecting with a rheostat 37a. The pipe sections 41a may be composed of chromel, an alloy of nickel and chromium and well insulated in a well known manner. Oil and water may be preheated in this serpentine to the required temperature, as above described by reference to the furnace 40 and coil 41.

The operation is very simple and can be readily carried o-ut by any one skilled in the art of distilling and refining oil. It will be simply necessary to turn on 4,the electric current at the switch 35 and heat the electric heater 5 to the proper degree of temperature, between 6500 and 8500 F., and maintain them at that temperature durin the cracking operation. The pump will e so set as to draw in about 80 per cent of oil and 20 per cent of water by volume. This mixture will be forced into a preheating coil, preferably in the outside furnace 4:0 or a furnace 50. The temperature in the preheater coil 4:1, or in a serpentine 41a, Fig. 5, will be maintained at about 8000 or 1,0000 F. and the mixed oil and water and their vapors will be forced under pressure into and throu h the preheating coil or serpentine 20. y maintaining the fluids under pressure they will remain in a liquid condition and thus be more readily preheated. 0f course, when the compressed liquids escape from the spraying nozzles of the supply pipes 21, 21a, they expand and lose part of their heat, but are immediately brought into contact with the heated catalytic coating surfaces of the electric heaters, where decomposition or cracking is effected. This reduction of pressure on the oil and vapor in the generating chamber is important, as it permits them to expand and separate more or less? from the water vapor and be impinged directly upon the heated surfaces where decomposition or cracking is eected at a lower temperature than would be possible under the pressure maintained in the preheating or superheating coils 41 or serpentine 51 and serpentine 20. Decomposition of comparatively heavy oil into vapors ofD lower boiling point oils is, therefore, very neef/,eee

rapid in the generating chamber. Owing also to the low pressure or lack of pressure in the generating chamber and to the fac-t that hydrogen is labeing passed up through the chamber, the vapors of freshly cracked oil will be quickly carried out of the chamber, so as to prevent destructive decomposition by too long exposure to the heated surfaces.

Hydrogen for exercising a hydrogenatlng effect by contact with the catalytic agent coatings and the vapors at the moment of' admitted by pipe 21b will pass up through' the generator and act as the hydrogenatmg agent to combine with the unsaturated hydrocarbons and make a pleasant, sweet odored gasoline. The carbo-n monoxide with other permanent gases will eventually pass off through the pipe 10b to a holder. Thelower group of electric heaters being more highly heated, as described, will cause heavy oily matter which may fiow down over them to be cracked and converted into gasoline, so that very little tarry matter will pass into the pocket 5a. llt will be understood that most of the heated oil which is sprayed into the generator by the upper injectors 21a vwill be vaporizedand cracked by contact with the heaters above, but that, after suchl cracking operation, some of the remaining heavier oil will drop down and pass over the more highly heated surfaces below -and become cracked or decomposed into oils of lighter gravity.

Any heavy uncracked oil, remaining after the cracking of oil in contact lwith the heaters above, willflow down over the more highly heated surfaces, between 1,8000

and 2,0000 F., below and be cracked into vapors of lower boiling pointl oils, and the residual heavy oil or tarry matter will pass down into the receiving chamber or pocket 5a outside of the heating zone.

yso

The apparatus can be operated with very little attention or manual Vlabor and will be rapid and economical in operation- This is a divisional application of my ap-f` plication, Serial No. 229,707, filed pril 20, 1918.

Having described my invention, what T the combination with a generating chamber,

of a plurality of spaced'heating surfaces adapted to be internally heated, means for heating them to a temperature for cracking oil, spray pipes in the walls of the chamber, means for preheating oil and means for forcing said oil therethrough and to said spray pipes to discharge upon the heating surfaces. v

2. In apparatus for producing gasoline, the combination with a generating chamber, of a plurality of spaced heating surfaces, adapted to be interiorly heated, means for heating them to a temperature for cracking oil, means between the heaters for deiecting vapors in contact with the heater means for preheating oil, an oil forcing device connecting therewith and a discharge pipe leading from said means and connecting with the generating chamber for spraying oil on said heating surfaces.

8. In apparatus for .producing gasoline, the combination vwith a generating chamber, of an electric heater therein having suitable electrical connections, an oil spray pipe adapted to discharge and spra oil upon said heater, means adjacent to said heater in the generating chamber for preheating oil and deecting the resulting vapors and means for forcing oil to said spray pipe.

4. 'In apparatus for producing gasoline, the combination with a generating chamber, of a plurality' of spaced heating surfaces,

adapted to be internally heated, oil preheating pipes between said heating surfaces to deflect vapors in contact therewith, an oil spray pipe connecting with the oil preheating pipe, adapted to spray oil in contact with said heated surfaces, and means for forcing oil under pressure into said preheater pipes.

5. In an apparatus for producing gasoline, a generating chamber -having nonconducting walls, a vapor dome, an o1l receptacle at the bottom below the heating z'one, a plurality of electric heaters extending ings of catalytic material, means between said heater pipes for deiecting vapors into Contact with the pipes, means for spraying oil on the heater pipes and means for admitting hydrogen to contact with said coatings, whereby the oil vapor, as cracked, may be hydrogenated.

7. In an apparatus for producing gasoline, a generating chamber having nonconducting walls, a vapor escape pipe at the top and a receptacle at the bottom outside of the heating zone for residual oil, spaced pipes extending through the walls having interior electric heaters and exterior coatings of catalytic material, a pipe .for admitting hydrogen at the bottom of the generating chamber, and means for spraying oil on the heater pipes.

8. Apparatus for producing gasoline, comprising a generating chamber, a plurality `of spaced heating surfaces adapted to be heated to a temperature for ,cracking oil, delecting pipes between said heating surfaces,'means for preheating oil outside of the generating chamber and means for connecting therewith ada ted for spraying oil upon said heating sur aces.

In testimony whereof I aix my signature in presence of two witnesses.

BURHANS VAN STEENBERGH.

Witnesses:

JOHN B. Lnnolmn, ALFRED ADAMsEN.

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