US1192653A - Process of making gasolene. - Google Patents

Description

F. 8. LOW.

PROCESS OF MAKING GASOLENE.

APPLICATION FILED APR.24, 1913.

H I Fran/hilmu IN VEN T OR F. 8. LOW.

PROCESS OF MAKING GASOLENE.

APPLICATION FILED APR-24.1913. 1,1 92,653, Patented July 25,1916.

2 SHEETS- SHEET 2- Fm/M J. Low

IJ'YTNSSES l/V VLN TOR mum s. Low. on NEW 1 rnocnss or mnxme eAsoLEnn.

To all whom it may concern:

Be .it known that I, FRANK S. Low, a citizen of the United States, residing at New York, in the countyof New York and State of New York, have invented certain new and useful Improvements in Processes of Mak ing Gasolene, of which the following is a specification.

This invention relates to processes of making gasolene; and it comprises a method of making low-boiling hydrocarbons from higlpboiling hydrocarbons which comprises subjecting such high-boiling hydrocarbons while in a finely divided or atomized liquid state to suitable conditions of heat andpressure within a specially designed chamber as by spraying against a heated surface in a chamber of less temperature wherein a suit able pressure prevails and then withdrawing, coolin or condensing the products of the process for. subsequent distillation or purification; set forth and as claimed.

Crude petroleum on distillation yields a number of fractions of different boiling points, the amount of each fraction of course corresponding more or less closely with the amount originally contained in the oil. But the demand for the lower-boiling fractions, or the naphtha and gasolene fractions, is at present out of all proportion to the .demand a for the higher boiling fractions, the kerosene, spindle oils, fuel oil, etc.; this of course being largely due to the great use of internal combustion engines. By' cracking the oil during distillation the yield of low-. boiling. fractions may be somewhat increased; but the action is not as fargoing as can be desired. r

The object of the present invention is to provide a simple, cheap and ready method of increasing-the yield of low-boiling fractions at the expense of the high boiling.

To this end I may spray or atomize or otherwise momentarily contact liquid high-boiling oil against or with a heated surface at a temperature above the boilingpoint of-the particular oil, and preferably at a temperature rather far above, the action being under any desired pressure, above or below atmospheric, butgenerally above. This heated surface I maintain within a chamber of less temperature, so that the oil and the products of its decomposition on leaving'such surface Specification of Letters'ratent.

all as more fully hereinafter,

Patented July 25, 1916.

Application m April 24, 1913. Serial minaret. p

are cooled atonce below the decomposing temperature. For instance,- in treating a fuel oil or residuum I may project it against a surface maintained at a temperature ofsay 500 to 1200 F., this surface being so placed as to permit liquid oil to drip or fall off it at once. If I am endeavoring to make oily products of, a boiling point less than 212 F., in one form of my invention the chamber may advantageously be maintained at about 212 F. and a circulation of a gaseous carrier may be maintained from the chamber to and through appropriately cooled condensing means. In so operating, any gasolene formed .is at once removed from the sphere of reaction and high heat and can undergo no further c hange.- If the chamber and the liquid oil within it are at a temperature above 212 F., naturally such oil does not retain much or any of the lowboiling fraction. The oil dripping off the treating surface may of coursebe returned for re-projection or it may be removed and the low boiling bodies which have been formed and have dissolved in it may be dis-.

distillation of their gasolene and kerosene.

components. However, crude oil itself may be used. High-boiling .crudes are particularly suitable.

The petroleum oils consist for the most part of hydrocarbons in which many carbons are united in a chain-like arrangement In the high boiling'oils the chains may run from 15 to 25 carbon atoms. The

low boiling bodies which I desire to get in the present invention will run from 5 to 8 carbon atoms. The first influence of heat upon hydrocarbons of this nature is to break apart the union between the carbons; to form shorter chains by breaking apart the longer. If time enough be given the long chains will break down into 1, 2 and 3 carbon groups which are'gaseous bodies; and the effort in the present inventionis to restrict the breaking down to form bodies of somewhat higher complexity. This I have discovered I can attain by the described method of short-time contact. If the contact of the hydrocarbons with the heated surface, be long .continued, gaseous bodies are formed; and these gases in turn .may break down further to form tarry bodies,

coke, etc. This I desire to avoid.

The character of the heated surface is not a matter of indifference as each particular material exercises a specific effect. But forv the most purposes I desire to avoid any effect. upon the oil molecules. Nickel, espe- .cially if freshly reduced, exercises for most purposes too much of a similar effect. Copper coated with fine copper freshly reduced from the oxid is a catalyst intermediate between nickel and iron. The source of heating for the heating surface may be as desired. Electric heating is often convenient. Fire heating may also be employed.

In breaking down the complex high-molecule hydrocarbons, some fractions of the products obtained are unsaturated; and for some purposes the unsaturated gasolenes are not desired. In breaking down hydrocarbons by cracking since the. broken down products need a greater ratio of hydrogen to carbon to be saturated than do the original hydrocarbons and since the cracking is attended with. the production of more or less gas with a high ratio of hydrogen to carbon, cracking is always attended with the production of unsaturated bodies. Under the familiar laws attending dissociative actions, such as cracking, the tendency of gas to form is, in a measure, inversely as the prevailing pressure and by-maintaining as high a pressure as possible in the cracking chamber of the present device the percentage of saturated bodies in the resultant gasolene will be materially increased; this increase being due to the decrease in the amount of hydrogen-rich gas which can be formed. As in the present invention the high temperature necessary for. cracking is confined to surface of relatively small area in a chamber of relatively low temperature pressures within such chamber can easily be maintained at'a much higher point than is possible where the whole chamber is maintained at cracking temperature.

By a further development of my process, if desired, these unsaturated compounds may be converted into saturated. To do this, I employ an atmosphere of hydrogen the surrounding chamber.

or blue water gas in the treating vessel. and

use an active catalyst, such as nickel, cobalt,

. degree by iron and by copper, causes the union of hydrogen with the unsaturated hydrocarbons as they are produced and the formation of saturated hydrocarbons therefrom. A hot nickel surface in an atlilosphere of hydrogen or blue gas is particularly advantageous in causing the formation of saturated gasolene from heavy oils projected against such surface.

In the accompanying illustration I have shown, more or less diagrammatically thl ee embodiments of the many types of apparatus which may be used in the described process.

In this showing Figure 1 is a vertical section of an electrically heated type; Fig. 2 is a similar section of a fire heated device; and Fig. 3 is a similar view of a modification with electrically heated contact mass and operating in a somewhat different way.

In the showing of Fig. 1, element 1 is ment carried. on stem 6 of insulating material and supplied with current by 8 and 9.

sired temperature and is always hotter than Communicating with the chamber is a valved pipe 10 which may be used for adjusting the pressure in the retort or may be used to supply any suitable gas thereinto. Valved blow-off 11 allows venting the chamber when desired. Set immediately below this heating element is spray nozzle 12 supplied with oil under suitable pressure from pipe 13 and pump 14:. At its lower portion, the casing tapers to outlet 15 carrying a weighted valve 16 and leading into collecting reservoir 17 provided with draw-01f 18 and gas escape tube 19. This reservoir may be provided with cooling jacket 17*. Tube 19 may be, as shown, provided with a reflux condenser arrangement 20- c Another form of apparatus is shown in .Fig. 2. In this figure, 21 is acasing of any 23 which maintains it at a much higher temperature than the rest of the chamber. Oil is fed to the chamber through valved inlet pipe 29. This pipe may be supplied with steam from 30 or with gas under pressure from 31. At its upper end the chain her is provided with vapor and. gas outlet.

32 having a pressure valve 33 which may be set to any desired loading. This outlet is prolonged through condenser 34 and ends in collecting receiver 35. provided with vent 36 and draw-off 37 From it leads gas return pipe 38 to pump or fan 39. This fan or pump may supply gas to conduit 31 to operate the injector. Beyond the pump is a branch conduit 40 leading to the gas burner 23.

The device of Fig. 3 is substantially like that of Fig. 1, save that the vapors are removed from the residual oilas fast as formed. In this showing, 41 is a casing, 42 are temperature controlling coils, 43 is a valved inlet for oil, 44 an outlet for oil, 45 is an electrical heating surface against which oil picked up from the interior of the tank through 46 is projected by spray nozzle 47 supplied with gas by pipe 48 and pump 49. Vapors and gas pass outward through 50 and condenser 51, and condensed gasolene is collected in tank 52, whence it may be removed through outlet 53. Gas may be vented out through 54 or sent back through 55. 56 allows the introduction of gas from other sources, such as hydrogen, blue water gas, etc.

In the operation of the structure of Fig. 1, oil is continuously supplied through 14 and 13 to the projecting nozzle and is then' sent against heating element 5. This causes the formation of a greater or'less proportion of gasolene or kerosene which is dissolved by the unchanged heavy oil and falls to the bottom for escape through 15 into the tank 17. When a body of oil is kept in the tank cooling fluid may be used in the jacket or coils. The mixed oils from 17 may be removed to any suitable still (not shown) and distilled to regain gasolene and kerosene. Residual heavy oil may besent back. Condenser 20 returns any gasolene that may pass away with the gas through 19. If desired, hydrogen may be introduced through '10, and 5 may be covered with a catalytic metal.

In the operation of Fig. 2, production and removal of gasolene, or of gasolene and kerosene, are continuous, the chamber being kept at a temperature suitable to maintain these bodies in a vaporous condition. Oil is introduced from time to time through Coils 26 in the- This receiver is 24 to fo'rmabody of oil, and oil is picked up at 28 and sent against heated surface 22. The oildrips back for re-passage; The gasolene vapors formed are carried forward by the gas entering through 29 and, passing onward through 32, past 33 are condensed out' by 34 and accumulate in 35.

Some gas is always formed in the action and the excess of such gas as is formed may be vented through 36 but the temperature of 22 while of course maintained high enough to break down high boiling oils into low boiling oils, is not maintained high enough to cause the formation of any substantial amount of gas. A portion of gas is sent through 40 to maintain heat. Another portion of the gas may be sent through 31 to act as projecting means. Alternatively steam or hydrogen may be sent through 30.

The operation of Fig. 3 is much the same as Fig. 2, the difference being mainly in the substitution of electrically heated surface 45.

The apparatus may be worked under any pressure desired. Some pressure above that of the atmosphere is usually desirable; but of .course pressures below atmosphere may also be used for specific purposes.

What I claim is:

1. The process of converting high' boiling oils into lower boiling oils which comprises contacting such a high boiling oil in the form ofa spray against a localized heated element maintained at a suflicient temperature suflicient to crack said high boiling oils into low boiling oils while insufficient to form substantial amounts of gas, said element being in a chamber of less temperature, collecting the vapors and gases and condensing the vapors of low boiling products formed.

2. The process of converting high boiling oils into lower boiling oils which comprises contacting such high boiling oil in the form of "a spray against a localized heated element contained in a chamber under greater pressure than atmospheric and of less temperature than said element, said heated element being maintained at a temperature sufiicient to crack said high boiling oils into low boiling oils while insufficient to form substantial amounts of gas, collect ing the vapors and gases and condensing the vapors of low boiling products formed.

3. The process of converting high boiling oils into lower boiling oils which comprises maintaining a body of such oil in a still at a temperature elow that at which any substantial distillation or cracking of such oil will take place, maintaining a heated element within such still .at a temperature above the cracking temperature of such oil and continuously spraying oil from such body against said element while allowing unchanged high boiling oil to flow back to such body and removing vapors of cracked prodnets.

4. The process of converting high boiling oils into lower boiling oils which comprises maintaining a body of such oil in a still at a temperature below that at'which any substantial distillation or cracking of such oil will take place, maintaining a'heated element having a surface of catalytic material within said still at a temperature above the cracking temperature of such oil and continuously spraying oil from such body against said element while allowing unchanged high boiling oil to fiow back to such body and removing vapors of cracked products. v

5. The process of making gasolene and kerosene which comprises atomizing liquid high-boiling petroleum material by a gas comprising hydrogen underpressure against a surface heated to a temperature above the boiling point of such material and contained in a chamber of lower temperature than such surface and recovering low boiling oils thereby produced.

6. The process of making gasolene and kerosene which comprises atomizing liquid high-boiling petroleum material by a gas comprising hydrogen under pressure and projecting the atomized material against a catalytically acting surface heated to a temperature above the boiling point of such ma-v terial and contained in a chamber of lower temperature than such surface and recovering low boiling oilsthereby produced.

7. The process of converting high boiling oils into lower boiling oils which comprises maintaining a body of such oil in a still under pressure but at a temperature below that at which any substantial distillation or cracking of such oil will take place, maintaining a heated element within such still at a temperature above the cracking temperature of such oil and continuously spraying oil from such body against said element while allowing unchanged high boiling oil to flow back to such body and removing vapors of cracked products.

- 8. The process of converting high boiling petroleum oils into lower boiling oils which comprises establishing and maintaining a body of oil is a suitable chamber' under a pressure higher than atmospheric and at a temperature below the crackin point while maintaining the temperature 0 a heated 'element above such oil body and within such chamber at a materially higher temperature, a temperature suflicient to cause cracking decompositoin of oil, and continuously spraying oil from said body. against said surface and allowing unchanged liquid to now back to said body while removing and collecting produced cracked products. I

9. The process of converting high boiling petroleum oils into lower boiling oils which eon'iprises establishing and maintaining a body of oil in a suitable chamber at a temperature below the cracking point while maintaining the temperature ofa heated element above such oil body and within such chamber at a materially higher temperature, a temperature suilicient to cause cracking decomposition of the oil, and continuously spraying oil from said body against said surface and allowing unchanged liquid oil to flow back to said body while removing and collecting produced cracked products.

10. In the conversion of high boiling petroleum oils into lower boiling oils the process which comprises maintaining a body of suchhigh boiling oil in a still chamber at a temperature below its own boiling point while continuously spraying abstracted portions of said body of oil against a localized heated area located in said still chamber above said oil body and having a surface of catalytic material, said heated area being maintained at a temperature above the crackingpoint of said high boiling oil and recovering the low boiling cracked products formed.

11. The process of making gasolene and kerosene which comprises atomizing liquid high-boiling petroleum material by a gas comprising hydrogen under pressure against a surface heated to a temperature above the boiling point of such material, such surface being in a chamber under pressure above that of the atmosphere and such chamber being of lowi' temperature than such surface and recovering low boiling oils thereby produced.

12. The process of making gasolene and kerosene which comprises atomizing liquid high-boiling petroleum material by a gas comprising hydrogen under pressure and projecting the atomized material against a catalytically acting surface heated to a temperature above the boiling point of such material, such surface being in a chamber under pressure above that of the atmosphere and such chamber being of lower temperature than such surface and recovering low boiling oils thereby produced.

In testimony whereof, I afiix my signature in the presence of two subscribing witnesses.

. FRANK s. Low.

Witnesses:

GLENN I. WILLIAMSON, EDWARD P. HOPKINS.

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