Patented Dec. 10, 1946 2,412,371 ' UNITED STATES PATENT OFFICE, MANUFACTURE OF GASOLINE John W. Teter, Chicago, Ill., assignor to Sinclair Re?ning Company, New York, N. Y.-, a corpora tion of Maine No Drawing. Application December 19, 1940, Serial No. 370,837 6 Claims. (Cl. 19.6—54) 1 2. This invention relates'to improvements in the manufacture of gasoline by a cracking process of the catalytic type. More particularly the inven tion relates to an improved catalytic cracking process of the class wherein the cracking catalyst is of the type which functions by adsorption, activation and desorption as distinguished from or oil vapors and the mixture, passed through a heating zone in which the desired temperature clays, acid-treated clays and synthetic catalysts only when supplied in the anhydrous state. is maintained. ‘ ' Aluminum?uoride is quite stable and has a melting point of 1040° 0., far in excess of the temperatures at which it is'most effective. How= ever, when supplied in the anhydrous state it cracking catalysts which, like anhydrous alumi appears to have little catalytic activity. In these num chloride, function in the Friedel-Crafts type respects it differs from aluminum chloride which of reaction. Examples of cracking catalysts of 10 sublimes at a temperature of approximately 179° the type ?rst mentioned are naturally occurring C. and which has signi?cant catalytic activity comprising silica and alumina, or silica and alu The following examples illustrate the effect of mina together with other metal oxides. my aluminum ?uoride catalyst, as compared to Prior to the discovery of the invention herein 15 thermal cracking and to the effect of the syn described, the most active of the catalysts of the thetic silica-alumina catalyst previously de ?rst type known to me was a powdered synthetic scribed. In each of the following operations the catalyst composed of 90% silica and 10% alumina charging oil was a Pennsylvania gas oil having by weight, prepared by precipitating aqueous so the following characteristics: dium silicate with hydrochloric acid in the pres 20 Gravity ____ _'_ _____ A ____________ __°API__. 37.8 ence of added sodium chloride, adding aluminum Distillation: ' , chloride solution and precipitating with ammo Initial __________________________ __°F__' 4'72 nium hydroxide, washing, drying at 250° F., 10% ____________________________ __Y_°F__ 572 crushing and sizing. Cracking in the presence 50% ____________________________ __°F-_ 598 of this catalyst has been found to produce a 90% ___________________________ __°F__ 648 marked improvement both‘ in the anti-knock End point ______________________ __°F__~ 674 value of the gasoline produced and in the gaso line yield, together with a substantial decrease in In each operation the oil, alone or admixed with the amount of gas formed. _ a. predetermined percentage of catalyst by weight I have now found that crystalline aluminum based on .the oil, was passed through a heating ?uoride, either by itself or together with metal coil of the same length and at substantially the oxides such as alumina, is an active cracking cat same feed rate. During passage therethroug'h alyst of even greater activity than the most active of the synthetic silica-alumina catalyst hereto fore employed. The aluminum fluoride employed the oil was ?rst heated to, and then maintained in the process of my invention is used in pow dered form and may contain varying amounts of combined and uncombined water. It may be rep resented by the formula AIFS‘XHZO. In the cracking process of my invention I merely subject the oil to be cracked, in the presence of the aluminum ?uoride catalyst. to a temperature ap~ proximating 900—1050° preferably about 1000° F., for a period of time sufficient-t0 effect a sub stantial amount of cracking. Substantial super atmospheric pressure may be applied to the oil during treatment if desired. However, I prefer at, the desired predetermined temperature. ; Pressure was controlled to maintain the desired predetermined pressure at the outlet of the heat ing coil. The total products discharged from the coil were cooled to condense all normally liquid hydrocarbons ‘in the form of a synthetic crude. After separation of the catalyst, by hot ?ltration, the ‘gasoline fraction was recovered from the syn thetic crude by ‘distillation and stabilization. Thus the gasoline yields are those obtained, by a single once-through treatment, all recycling being avoided in order to eliminate errors in Oh taining comparative results. rd Three operations with no catalyst were ?rst to use a pressure not substantially above thirty carried out at temperatures of 950° F., 10009 F. pounds per square inch asthe use of higher pres and 1050" F., respectively, and with a coilloutlet sures impairs the anti-knock properties of the 50 pressure of 30 pounds per square inch to cali resultant gasoline. The aluminum fluoride cat alyst may be arranged in a ?xed bed and the oil brate the apparatus for thermal cracking with respect to the particular oil used. Three similar additional operations were then‘ carried out ‘un to be cracked vaporized and passed therethrough at the desired temperature, or the catalyst in der the same three sets of operating conditions powdered form may be dispersed through the oil 55 but with 1% by weight of ?nely divided crystal 2,412,371 3 . line aluminum ?uoride of reagent grade admixed amount of gas produced as compared to the sil with the oil. A fresh sample of the crystalline ' aluminum ?uoride catalyst used in these oper ations was completely dehydrated in a mu?le furnace and the weight loss indicated an original water content of 2.35 Hzo'AlFs. The octane number of the produced gasoline was determined in each instance both by the motor method ica-alumina catalyst. (M. M.) and by the research method (Res. M.). The following table gives the results obtained: ‘ Temperature ________________ __° F_- 950 Pressure ______________ _ .pounds. _ 30 Gasoline yield pe Thermal. 1, 000 ‘ 1,050 30 cent on charge: . 21.0 17. 5 23. 2 991 1, 632 r " " . Thermal . __.._ . ._____ 363 M.): _ _ _ __ _ _ _ __ ‘ 2, 686 906 2, 340 67. 7-80‘ 0 69. 5-822 ' 63. 7-74. 4 ‘ 24.6 _ Octane number (M. 10 with 1% of this heterogeneous aluminum ?uoride catalyst. dispersed in the oil. The results ob tained, together'with those obtained under 'sim-' ilarconditionsbut using the reagent grade of (aluminum ?uoride as the catalyst, are given'in a 28.8 Gas, cu. ft./bbl. of gasoline: a1 ______________________ __ scribed, was made at a temperature of 1000" F. and at a pressure of 30 pounds per square inch . . 11.8 v aqueous hydro?uoric acid to yield a 50:50 mix- 7 _ ture of AlFsZAlzOa. A test, using the same charg ing oil and same procedure as previously de- " 30 ' ____________________ __ 1% AIFa-XHzO _______________ __ ' A heterogeneous aluminum ?uoride catalyst was prepared by treating alumina with su?icient 15 the following "table: 1 . 1%A1F3-XHgO _______________ __ 76. 9-89. 5 76. 1-90. 0 72. 4-85. 4 Gasoline Gas‘,7 ' Octane number 7‘ ' cu‘ pcrbgent perobbl. (M‘ MrReS' M_) Catalyst Another operation with the same charging oil ' 20 volume was carried out at 1000?;F. with 1% of the crys talline aluminum ?uoride" catalyst but with a coil discharge pressure of -'75 pounds per square inch. _ The following results were obtained; gasoline ' mrrxmmreagcnt grade); 7 23. 2 V 1 toe 76.1-90.0 iMF3:AlzOs(50I50) _________ _. 25. 5 '936 76. 2-89. 1 ‘ It will be noted that the heterogeneous aluminum Gasoline yield __‘__t;__r_ _____ _____per cent" 28.5 Gas, cubic feet per barrel of gasoline_r_____ 1,240 25 ?uoride catalyst produced a greater gasoline yield than did the reagent grade aluminum ?uoride Qctanenumber 1M. M.—~Bes. M.)____ 73.2-86.0 catalyst, the anti-knock value of the gasoline be Comparison of these results with those obtained ing substantially the'ws‘ame' in both instances. Yet at a pressure .of‘30 pounds per square inch but alumina alone has very little activity as a crack at the sameoperating temperature shows that 30 the increase in gasoline yield obtained by in I claim: creasing the operating pressure is accompanied 1. The improvement in cracking hydrocarbon‘ ' by a decrease in the anti-knock value of the gas oils for the production of high anti-knock gaso lines which comprises subjecting the oil to crack Two additionaltests were carried out at pres 35 ing temperature in the presence of ?nely divided ing oline.i . 1. > I catalyst. ’ ' - ‘ . ' ' l > . sures of'30 pounds per square inch and at tem peratures of 950° F. and 1000° F.,' respectively, crystalline aluminum ?uoride. ' 2. The improvement in cracking hydrocarbon with‘i1% of the previously. described synthetic oils for the production of high anti-knock gaso silica-alumina catalyst dispersedin the oil. The line which comprises subjecting the oil to crack charging oil and the pressure employed were the 40 ing temperature in the presence of ?nely divided‘ sameas in vthe tests previously described.- The aluminum ?uoride containing combined moisture. results obtained, together with those obtained ‘3. The improvement in‘. cracking hydrocarbon underisir'nilar operating conditions but with 1% oils for the production of high anti-knock gaso of the aluminum ?uoride catalyst, aregiven in line which comprises dispersing a, small amount the permeable i1 1 of a ?nely-divided crystalline aluminum ?uoride Temperature: _______ _7 ___________ ___‘______° F_. 950 n 1,000 in the oil tolbe cracked ‘and subjecting the mixture Pressure . . ______ _‘_ _____ ._' ________ __pounds_. “30' 3O Gasoline yield per cent on charge: ‘ r ‘ "1% silica-alumina catalyst.‘ ___________ _- 1% aluminum ?uoride catalyst . _ _ _ _ _ _ _ __ 20. 9 for a period of time su?icient to convert a sub 17. 5 23. 2 stantial proportion of the oil into high anti-knock 576 1, 234 363 906 Gas cu. l'tJbbl. of gasoline: ~ " 1% silica-alumina catalyst _______________ _; ; 1% aluminum ?uoride catalyst; _________ __ Octane M. M. and Res. M.: . . , to a temperature approximating 950° F.—1000° F. 13.9 ' _ gasoline. ' . ' 7 , I > . I 4. ‘The, improvement in cracking ‘hydrocarbon oils for the production of high anti-knock gaso line which comprises dispersing a small amount -~ As the foregoing tests illustrate, the results of ?nely+divided crystalline aluminum ?uoride in obtained with the aluminum ?uoride catalyst are 55 the oil to be cracked and subjecting the mixture markedly superior to those obtainable with ther to a temperatureapproximating 9v5_0r°—l000° F. at ' mal cracking at temperatures ranging from be a pressure not substantially. exceeding 30 pounds low. 950° F. to upwards of 1050° F. from the stand per square inchfor a period of time su?icient to‘ point or“ the gasoline yield, the amount of gas convert a, substantial proportion of the oil into produced'and the anti-knockvalue of the gas 60 high. octane gasoline. ' 'l ' oline. However, when the temperature substan 5. The improvement in'_ cracking hydrocarbon tially'e'xceeds 1000° F. the» resulting increase in oils for the production of. high anti-knock gaso gasolinefyield isobtained only at the expense of line which comprises subjecting the oil to a cracka substantial increase in gas production and a 65 ing temperature‘ in the presence. of a finely-di vided catalyst comprising alumina and crystalline reduction in the anti-knock value of the gaso ’ ~-1%'silica-alumina catalyst. ,_-.;_ _ ; .7. ._ __,-; 76. 5-89. 7 75. 7-87. 9 V 1% aluminum ?uoridecatalyst __________ .4 76. 9—89. 5 76.1-90.0 line. The tests further illustrate the fact that aluminum ?uoride. j . . ' ‘ r * ‘ v6.'The improvement in cracking hydrocarbon oils for the’ production of high anti-knock‘ gaso ?uoride catalyst are as good or better than those 70 line whichcomprises subjecting the oil to crack ing temperature in thenpresence vof aluminum obtainable with the synthetic silica-alumina ?uoride containing combinedmoisture.;; ' ‘ catalyst, while With the aluminum ?uoride cat within the preferred operating range the anti knock values obtainable with the aluminum alyst there is a substantial increase in the gas oline yield and a substantial decrease in the ' ' JOHN ‘W. TETER.