US2345718A - Treating oils to produce antiknock gasolines or aromatic type liquids - Google Patents

Description

' J. S. WALTON TREATING OILS TO PRODUCE ANTI-KNOCK GASOLINES 0R AROMATIC TYPE LIQUIDS April 4, 1944.

Filed June 29 1940 CYCL owe .szrann 7'02 INJECTOR 5 TEAM INL T CATA I. YST Hawwen JA'PARA TOR ooezy o Patented Apr. 4, 1944 UNITED STATES PATENT OFFICE TREATING OILS T PRODUCE AN'I'IKNOOK GASOLINES 0R AROMA'I'IC TYPE LIQUIDS Jesse S. Walton, Westfield, N. J., assignmto Standard Oil Development Company, a corporation of Delaware Application June 29, 1940, Serial No. 343,130 4 Claims. (01. 260-468) ilns, and thereafter to dehydrogenate the cyclooleflns and cyclo-paraffins to form aromatic hydrocarbons. I a

It is a specific object of this invention to crack parafiinic hydrocarbons boiling within the kerosene and gas oil range by first vaporizing the 011, preferably in the presence of 12% water or steam where a catalyst is employed, and then subjecting the vapors to cracking conditions to form olefins and parafllns having from 6-8 carbon atoms, then treating the olefins and parafilns under such conditions as to form ring compounds and finally dehydrogenating said ring compounds to form aromatics.

Stated otherwise, it is an object of this invention to form from paraflinic hydrocarbons, arematic hydrocarbons which may be blended with gasoline or motor fuel of relatively low octane number to increase materially, the octane rating of the motor fuel.

Other and further objects will appear from the r ensuing description.

The single figure of the drawing represents dialine 6. The vapors, on the other hand, are withdrawn through line 10 and admixed in an injector l2 with a powdered catalyst, comprising clay or elements of the third and sixth group of the periodic system, including aluminum, chromium, and molybdenum or their oxides, or mixtures of these elements or theiroxides, withdrawn from some source It and dischargedinto th injector unvaporized product may be withdrawn through I2 through line H. The amount of catalyst admixed with the vapors may vary within rather wide limits. Good results are obtained by mixing from 2-5 lbs. of catalyst per cubic foot of oil vapors measured under the conditions of temperature and pressure prevailing in the injector It. The suspension is withdrawn from the injector I2 through line l8 and then passed through a reaction zone which may be inthe form of a tank, but preferably is in the form of a coil 2!! dis posed in the furnace setting 2| where more heat may be added to the suspension if desired. The

temperature prevailing in coil 28 should preferably be'within the range of from 800 F. to 975 F. andbest results are obtained by maintaining a pressure of about 40 lbs. per square inch gauge in this coil. The hydrocarbons undergo cracking in the coil to form substantially equalamounts of oleflnic and parafiinic hydrocarbons and under best conditions contain a large preponderance of hydrocarbons having from 6-8 carbon atoms.

From coil 20 the total product is withdrawn and passed into a third coil 25 disposed in a furnace setting 26 where the temperature of the vapors is increased to a temperature within the range of from 900 F. to 1050 F., the pressure conditions being about the same as in coil 20. In this furnace the principal reaction is one in which the olefins formed in coil 20 are converted into cyclooleflns or cyclo-parafllns, and the paraffins formed in coil 20 alon with unreacted feed stock are further converted into olefins, cyclo-olefins or cyclo-paraflins. From coil 25, the total product is withdrawn through line 28 and discharged into a fourth coil 29 disposed in a furnace setting 30, where the hydrocarbons are subjected to drawn through line 3| and discharged into'cyclone separator '32 where'the catalyst is removed from the vapors and passed by gravity into a baflle tower 35 having inclined baflies 36, as

' shown. Steam or some other gas, such as CO2,

nitrogen, flue gas, and the like, heated to approximately 825 F., more or less, may be introduced into the bottom of the tower through line 31 and permitted to flow upwardly against the downcoming catalyst to remove the volatile constituents.- The catalyst is then withdrawn from the bottom of the tower and may be delivered to a regeneration system (not shown) for revivification, according to known methods, for reuse in the process.

Meanwhile, the vapors are withdrawn over head through line ll and may then be passed to a fractionating tower to recover desired products.

namely, aromatic hydrocarbons.

It will be understood, of course, that instead=of using a powdered catalyst type of operation hereinbefore described, good results are obtained by using beds of stationary catalyst. that is to say, coils 20, 25 and 29 may be substituted by cylindrical chambers containing continuous beds or separated bodies of catalyst in granular or lump form supported on perforated trays. The vapors to be treated would .be caused to flow through the bed or beds of catalyst.

To recapitulate, the present invention relates to improvements in the production of hydrocarbons having relatively high octane ratings and which are particularly suitable for blending with motor fuels of relatively low octane value to produce a fuel of satisfactory performance. The particular advantages of this invention are believed to lie in the capability of controllin closely, the type of reactions which occur in each of the various steps and by thus controlling the temperature. time and pressure under which the reactions are carried out, it is possible to minithe product. In this treat, the temperature in coil .29 was from 800' F. to 950 F., and the time the material was-resident therein was about -15 seconds. In the operation carriedout in coil 28 the temperaturetherein was within the range of from 900 F. to 1050?? and the vapors were realdent therein for about 10 seconds. In the operation carried out in coil 29, the temperature there- Y in was within the range of from 925 F. to 1450' 1"., and the vapors were resident therein for about 8 seconds.

Many modifications of my invention within the spirit thereof will occur to those skilled in this art who have read the present disclosure.

The invention claimed is: 1. A process for the production of aromatic hydrocarbons from hydrocarbon oils predomiassure tained at a materially higher temperature of up to-lOiiD B. than was maintained in said first conversion zone, keeping said reaction mixture under superatmospheric pressure in said second conversion zone for a period sufllcient to obtain further formation of oleflnic hydrocarbons and cyclization of olefinic hydrocarbons, passing the reaction mixture from said second conversion zone into a third conversion zone maintained at a materially higher temperature of up to 1450 F. than was maintained in said second conversion zone, keeping said reaction mixture under superatmospheric pressure in said third conversion zone for a period sufiici'ent to cause conversion of the major portion of the hydrocarbons present into aromatic hydrocarbons and withdrawing conversion products and finely-divided catalyst from said third conversion zone.

3. A process for the production of aromatic hydrocarbons from hydrocarbon oils predominantly non-aromatic incharacter, such as kerosene or gas oil which comprises vaporizing said oil in a vaporizing zone, mixing the oil vapors with a finely-divided conversion catalyst selected from the group consisting of clay, elements of the third and sixth group of the perlodic system, and

oxides of elements of the third and sixth group of the periodic system, passingthe mixture of oil vapors and finely divided catalyst under superatmospheric pressure through an initial conversion zone maintained at an active conversion temperature of from about 800 F. to 975 F., keeping said mixture within said conversion zone for a period sufilcient to obtain a substantial conversion of the initial oil into parafiinic hydrocarbons of lower molecular weight and olefinic .hydrocarbons, passing the reaction mixture from said initial conversion zone to a second conversion zone maintained at a materially higher temperature of up to 1050 F. than was maintained in said first conversion zone, keeping said reaction mixture under superatmospheric pressure in said second conversion zone for a period sufiicient to obtain further formation of olefinic hydrocarbons the major portion of the hydrocarbons present nantly non-aromatic in character,'such as kcrosene or gas oil which comprises vaporizing said oil in a vaporizing zone, mixing the oil vapors with I a finely-divided conversion catalyst selected from maintained at an active conversion temperature.

of from about 800 F. to 975 F., keeping said mixture within said conversion zone for a period sufflcient to obtain a substantial conversion of the initial oil into paraflinic hydrocarbons of lower molecular weight and olefinic hydrocarbons, passin: the reaction mixture from said initial conversion zone to a second conversion zone mainbons.

into aromatic hydrocarbons, separating the finely divided catalyst from the conversion products and recovering a product rich in aromatic hydrocan- 3. The process as defined in claim 2 wherein the superatmospheric pressure maintained in the several conversion zones is about 40 lbs/sq. in.

4. A process for the production of aromatic hydrocarbons from a gas oil fraction having an A. P. I. gravity of 435 and boiling within the range of 300 lit-800 F. which comprises vaporizing said oil in a vaporizing zone, mixing the oil vapors with a finely divided conversion catalyst consisting of a mixture of chromium oxide and aluminum oxide, passing the mixture of oil vapors and finely divided catalyst through a first conversion zone maintained at .an active conversion, temperature of from about 800' I". to 975 F.,

keeping said mixture under a pressure of about 40 lbs./sq. in. in said conversion zone for about 15 seconds to convert a substantial proportion of the initial oil into paraiiinic hydrocarbonsof lower molecular weight and oleiinic hydrocarbons, passin: the reaction mixture from said initial conversion zone into a second conversion zone maintained at a materially higher temperature 01. up to about 1050 F. than was maintained in said first conversion zone, keeping said reaction mixture under a pressure of about 40 lbs/sq. in. in

said second conversion zone for about 10 seconds to eflect formation of additional olefinic hydrocarbons and cyclization of oleflnic hydrocarbons, passins the reaction mixture from said second conversion zone into a third conversion zone maintained at a materially higher temperature of up to 1450' 1". than was maintained in said second conversion zone. keeping said reaction mixture under a pressure of about 40 1bs./sq. in. in said third reaction zone for about 8 seconds to cause conversion of the major portion of the hydrocarbons present into aromatic hydrocarbons, withdrawing the reaction mixture from the third conversion zone, separating the flnaly divided catalyst from the reaction mixture and recovering from the conversion products a fraction rich in aromatic hydrocarbons.

' JESSE S. WALTON.

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